Award type：Award from publisher, newspaper, foundation, etc.  Country：Japan

Country：Japan

Country：Japan

Award type：Honored in official journal of a scientific society, scientific journal  Country：Japan

Award type：Award from Japanese society, conference, symposium, etc.  Country：Japan

Country：Japan

Award type：Award from international society, conference, symposium, etc.  Country：Japan

Award type：Award from publisher, newspaper, foundation, etc.  Country：Japan

Country：Japan

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/anie.201610041

Language：English   Publishing type：Research paper (scientific journal)  

The first 4-position-selective C-H perfluoroalkylation and perfluoroarylation of six-membered heteroaromatic compounds were achieved using nucleophilic perfluoroalkylation and perfluoroarylation reagents. The regioselectivity was controlled by electrophilically activating the heteroaromatic rings, while sterically hindering the 2-position, with a sterically bulky borane Lewis acid. The reaction proceeded in good yield, even in gram scale, and by a sequential reaction without isolating the intermediates. This reaction could be applied to late-stage trifluoromethylation of a bioactive compound.

DOI： 10.1021/jacs.6b01753

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/anie.201511117

Language：English   Publishing type：Research paper (scientific journal)  

Regioselective C-H bond transformations are potentially the most efficient method for the synthesis of organic molecules. However, the presence of many C-H bonds in organic molecules and the high activation barrier for these reactions make these transformations difficult. Directing groups in the reaction substrate are often used to control regioselectivity, which has been especially successful for the ortho-selective functionalization of aromatic substrates. Here, we describe an iridium-catalysed meta-selective C-H borylation of aromatic compounds using a newly designed catalytic system. The bipyridine-derived ligand that binds iridium contains a pendant urea moiety. A secondary interaction between this urea and a hydrogen-bond acceptor in the substrate places the iridium in close proximity to the meta-C-H bond and thus controls the regioselectivity. 1 H NMR studies and control experiments support the participation of hydrogen bonds in inducing regioselectivity. Reversible direction of the catalyst through hydrogen bonds is a versatile concept for regioselective C-H transformations.

DOI： 10.1038/nchem.2322

Language：English   Publishing type：Research paper (scientific journal)  

Successful benzylic C(sp³)-H trifluoromethylation, pentafluoroethylation, and heptafluoropropylation of six-membered heteroaromatic compounds were achieved as the first examples of a practical benzylic C(sp³)-H perfluoroalkylation. In these reactions, BF₂C_nF_2n+1 (n=1-3) functioned as both a Lewis acid to activate the benzylic position and a C_nF_2n+1 (n=1-3) source. The perfluoroalkylation proceeded at both terminal and internal positions of the alkyl chains. Perfluoroalkylated products were obtained in moderate to excellent yields, even on gram scale, and in a sequential procedure without isolation of the intermediates. By using this method, trifluoromethylation of a bioactive compound, as well as introduction of a CF₃ group into a bioactive molecular skeleton, proceeded regioselectively.

DOI： 10.1002/anie.201505335

Language：English   Publishing type：Research paper (scientific journal)  

We achieved a palladium-catalyzed C-H activation/C-C coupling reaction between arenes with a pyridyl, aminoquinolinyl, imino, or amide directing group, and oxiranes. The reaction proceeded at room temperature without any additives and tolerated a wide variety of functional groups, and the products were obtained in good to excellent yields, even on gram scale. This is the first example of a transition-metal-catalyzed intermolecular direct coupling reaction between a C-H bond of aromatic compounds and a carbon atom of oxiranes via C-H bond activation. By using N-methoxybenzamide as a substrate, we obtained 3-substituted isochroman-1-ones in one pot. The coupling reaction proceeded with stereoretention. Kinetic isotope effect experiments suggested that C-H bond activation is the rate-determining step.

DOI： 10.1021/jacs.5b02435

Language：English   Publishing type：Research paper (scientific journal)  

The first copper-catalyzed intramolecular C(sp³)-H and C(sp ²)-H oxidative amidation has been developed. Using a Cu(OAc) ₂ catalyst and an Ag₂CO₃ oxidant in dichloroethane solvent, C(sp³)-H amidation proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various β-lactams were obtained in excellent yield, even on gram scale. Use of CuCl₂ and Ag₂CO₃ under an O₂ atmosphere in dimethyl sulfoxide, however, leads to 2-indolinone selectively by C(sp²)-H amidation. Kinetic isotope effect (KIE) studies indicated that C-H bond activation is the rate-determining step. The 5-methoxyquinolyl directing group could be removed by oxidation. Silver ox: By using a Cu(OAc)₂ catalyst and an Ag₂CO₃ oxidant in dichloroethane solvent, C(sp³)-H amidation proceeded at a terminal methyl group as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various β-lactams were obtained in excellent yield, even on a gram scale. Use of CuCl₂ and Ag₂CO₃ under an O₂ atmosphere led to 2-indolinone selectively synthesized by C(sp²)-H amidation. DMSO=dimethylsulfoxide.

DOI： 10.1002/anie.201311105

Language：English   Publishing type：Research paper (scientific journal)  

Many important drugs, agrochemicals and their lead compounds contain trifluoromethyl group(s). Most processes currently used to access trifluoromethyl group-containing molecules are performed by substitution of the carboxy or trichloromethyl groups using hazardous fluorinating reagents under harsh reaction conditions. Cross-coupling reactions between organohalides or boronic acids/esters and trifluoromethylating reagents are also used. Direct C-H trifluoromethylation of organic molecules, however, is the ideal method of introducing trifluoromethyl group(s). Despite the recent advances in C-H trifluoromethylation of N-heteroaromatic compounds, regioselective C-H trifluoromethylation of six-membered heteroaromatic compounds has yet to be achieved. Herein we present a general and reliable method for the synthesis of trifluoromethyl group-containing N-heteroaromatics through highly regioselective addition of a trifluoromethyl nucleophile to pyridine, quinoline, isoquinoline and two or three heteroatom-containing N-heteroaromatic N-oxides activated by trifluoromethyldifluoroborane. The C-H trifluoromethylation proceeds under mild conditions in gram scale with high functional group tolerance. This method will be useful in both laboratory and industrial processes.

DOI： 10.1038/ncomms4387

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of 2-phenylpyridines with amino(1,3,2-dioxaborolan-2-yl) diphenylsilane produced fluorosilylated 2-phenylpyridines in good to excellent yields under palladium catalysis. This reaction is the first example of Ci-H fluorosilylation. Single-crystal X-ray structure analysis revealed a Lewis acid-base interaction between the silicon and nitrogen atoms, and the obtained fluorosilylated products are silafluorene equivalents. The fluorosilylated products showed stronger fluorescence than the corresponding silafluorene derivative. Treatment of 2-phenylpyridines with amino(1,3,2-dioxaborolan-2-yl) diphenylsilane produced fluorosilylated 2-phenylpyridines in good to excellent yields under palladium catalysis. This reaction is the first example of Ci-H fluorosilylation. A Lewis acid-base interaction exists between the silicon and nitrogen atoms, and the obtained fluorosilylated products can be regarded as silafluorene equivalents.

DOI： 10.1002/anie.201310293

Language：English   Publishing type：Research paper (scientific journal)  

Polyimide solution: Synthesis of the title compounds from aromatic imidates and isocyanates in good to excellent yields by a rhenium-catalyzed C-H bond transformation is described. The reaction also proceeded in high yield on gram scale and could be applied to the synthesis of polyimide derivatives (see figure), which are highly soluble in organic solvents.

DOI： 10.1002/anie.201306360

Language：English   Publishing type：Research paper (scientific journal)  

Boron delivery: C-H borylation at the ortho-position of aromatic compounds is promoted by the treatment of 2-phenylpyridine, or its derivatives, with 9-borabicyclo[3.3.1]nonane in the presence of a palladium catalyst. This reaction proceeds at room temperature and can be conducted without the palladium catalyst at higher temperatures. In both cases, the regioselectivity is controlled by Lewis acid-base interaction between the boron and nitrogen atoms.

DOI： 10.1002/anie.201210328

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Si goes chiral: Treatment of a bis(biphenyl)silane with a catalytic amount of a rhodium complex gave a spirosilabifluorene bearing a quaternary silicon atom. By using a rhodium catalyst with a chiral phosphine ligand (see scheme), asymmetric dehydrogenative cyclization proceeded to give chiral derivatives in good yields and enantioselectivities.

DOI： 10.1002/anie.201207723

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Singled out: Treatment of ketones with carbodiimides in the presence of a catalytic amount of either [{HMn(CO)₄}₃] or [Mn ₂(CO)₁₀] gave amides in good to excellent yields. In this reaction, the carbon-carbon single bond of a ketone is cleaved efficiently. The reaction also proceeded by using isocyanates instead of carbodiimides.

DOI： 10.1002/anie.201104704

Language：English   Publishing type：Research paper (scientific journal)  

The rhodium-catalyzed synthesis of silafluorenes from biphenylhydrosilanes is described. This highly efficient reaction proceeds via both Si-H and C-H bond activation, producing only H₂ as a side product. Using this method, a ladder-type bis-silicon-bridged p-terphenyl could also be synthesized.

DOI： 10.1021/ja107698p

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) Treatment of phenol derivatives with terminal alkenes in the presence of a catalytic amount of a rhenium complex, Re ₂(CO)₁₀, gave monoalkylated phenol derivatives in good to excellent yields. This reaction proceeds at the ortho- or para-position of phenols regioselectively.

DOI： 10.1021/ja904360k

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) Come on allene: Commercially available [Re₂(CO)₁₀] as a catalyst provides five-membered carbocycles in moderate to excellent yields with high stereoselectivity (see scheme). The configuration at each of the three sp³ carbon centers of the ring is defined. The reaction proceeds at the β, γ, and adjacent methylene positions of the allene; previously, similar reactions usually occurred at the α, β, and γ positions of the allene.

DOI： 10.1002/anie.200803350

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Treatment of an α,β-unsaturated ketimine with an α,β-unsaturated carbonyl compound in the presence of a rhenium complex, Re₂(CO)₁₀, gave a cyclopentadienyl-rhenium complex. This reaction proceeds via rhenium-catalyzed C-H bond activation of an olefinic C-H bond, insertion of an α,β-unsaturated carbonyl compound into a Re-C bond of the alkenylrhenium intermediate, intramolecular nucleophilic cyclization, reductive elimination, elimination of aniline to give a cyclopentadiene derivative, followed by the formation of a cyclopentadienyl-rhenium complex from the cyclopentadiene derivative and the rhenium complex.

DOI： 10.1021/ja805921f

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) Retro-aldol reaction: Indium-catalyzed reaction of a 1,3-diketone with an alcohol proceeds under solvent-free conditions by nucleophilic attack of the alcohol on a carbonyl group of the 1,3-diketone and carbon-carbon bond cleavage by a retro-Claisen condensation to give an ester in high yield (see scheme). Using water and an amine as nucleophiles instead of an alcohol gave the corresponding carboxylic acid and amide.

DOI： 10.1002/anie.200702798

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) Mn gets in the game: In the presence of a manganese catalyst and a stoichiometric amount of hydrosilane, aldehydes insert into C-H bonds of aromatic rings of compounds with directing groups (see scheme). This first example of a manganese-catalyzed chemical transformation through C-H bond activation gives silyl ethers in good to excellent yields and can also be applied to asymmetric transformation.

DOI： 10.1002/anie.200702256

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) Very couply! Coupling reactions of propargyl or benzyl alcohols with allyl- or alkynylsilanes proceed efficiently using [{ReBr(CO)₃(thf)}₂] as catalyst. Additionally, diethynylmethane derivatives were obtained by the reaction of aromatic aldehydes with trimethyl(phenylethynyl)silane in the presence of both the rhenium complex and AuCl (see scheme).

DOI： 10.1002/anie.200700183

Language：English   Publishing type：Research paper (scientific journal)  

A rhenium complex, [ReBr(CO)₃(thf)]₂, catalyzes the reaction of a 1,3-dicarbonyl cyclic compound with an acetylene to give a medium-sized cyclic compound in excellent yield. By using isocyanide as an additive, the catalytic activity of the rhenium complex changes dramatically, and the insertion of acetylenes into a carbon-carbon single bond occurs under mild conditions. A plausible mechanism is that the reaction proceeds via the formation of a rhenacyclopentene intermediate, ring opening by a retro-aldol reaction, isomerization, and reductive elimination.

DOI： 10.1021/ja064022i

Language：English   Publishing type：Research paper (scientific journal)  

A rhenium complex, [ReBr(CO)₃(thf)]₂, catalyzed reactions of aromatic ketimines with aldehydes to give isobenzofuran derivatives in good to excellent yields. In contrast to ruthenium and rhodium catalysts, aldehydes, which are polar unsaturated molecules, inserted into the C-H bond after activation by the rhenium complex.

DOI： 10.1021/ja065643e

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) Several reaction steps, including C-H activation, lead to indene derivatives in good yields in the rhenium-catalyzed reaction of aromatic ketimines and ethyl acrylate. Indene derivatives can also be obtained by the reactions of aromatic ketones with α,β-unsaturated esters in the presence of a catalytic rhenium complex and p-anisidine (see scheme).

DOI： 10.1002/anie.200503627

Language：English   Publishing type：Research paper (scientific journal)  

A rhenium complex, [ReBr(CO)₃(thf)]₂, catalyzes the reaction of an aromatic aldimine with an isocyanate and an acetylene to give a phthalimidine and an indene derivative in a quantitative yield, respectively. The reactions proceed via C-H bond activation, insertion of the isocyanate or the acetylene, Intramolecular nucleophilic cyclization to the aldimine of the generated amido- or alkenyl-rhenium species, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are usually employed in this type of reaction, the rhenium catalyst promotes the insertion of a polar unsaturated molecule. This occurs more easily than the insertion of a nonpolar unsaturated molecule.

DOI： 10.1021/ja054216i

Language：English   Publishing type：Research paper (scientific journal)  

A rhenium complex, [ReBr(CO)₃(thf)]₂, catalyzes the reaction of an aromatic aldimine with an acetylene to give an indene derivative in a quantitative yield. The reaction proceeds via C-H bond activation, insertion of the acetylene, intramolecular nucleophilic cyclization, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are usually employed in this type of reaction, the rhenium catalyst promotes the intramolecular nucleophilic cyclization of the alkenylmetal species generated by insertion of the acetylene.

DOI： 10.1021/ja0528174

Language：English   Publisher：Journal of Organic Chemistry  

We successfully developed a method for the site-selective C(sp³)-H fluorination of saccharides. When saccharides were treated with Selectfluor under 405 nm light irradiation, fluorination selectively proceeded at the weakest C(sp³)-H bond. Conversely, when the same saccharides were treated with N-fluorobenzenesulfonimide in the presence of a sodium decatungstate catalyst under 365 nm light irradiation, the reaction site could be switched and fluorination occurred at the C(sp³)-H bond with less steric hindrance.

DOI： 10.1021/acs.joc.5c00676

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Publisher：Organic Chemistry Frontiers  

An iridium/electron-deficient bipyridine-catalyzed selective α-Me-C(sp³)-H borylation of methyl sulfides was disclosed. The reaction exhibited high site-selectivity at the C(sp³)-H bond of the α-methyl group when aryl methyl sulfides were used as substrates (up to 65% yield with a 99 : 1 rr ratio). In contrast, the borylation mostly occurred at the aryl ring and gave C(sp²)-H borylated products when using 4,4′-di-tert-butyl-2,2′-bipyridine as a ligand (up to 76% yield with a 5 : 95 rr ratio). DFT calculations revealed that the C-H bond cleavage step of this reaction is the rate-determining step; the electrostatic interaction (π-π stacking) between the substrate and the electron-deficient bipyridine ligand contributing to the energy difference between the major sp³ pathway (19.4 kcal mol⁻¹) and the minor sp² pathway (23.7 kcal mol⁻¹) is the key factor for controlling the unique site-selectivity. This selective α-Me-C(sp³)-H borylation was applicable to many aryl methyl sulfides, as well as aliphatic methyl sulfides, displaying high functional group tolerance and good yields. Furthermore, the boryl group of the borylated product was readily transformed into other functional groups, which demonstrates the applicability of this methodology.

DOI： 10.1039/d5qo00231a

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Language：English   Publisher：Organic Letters  

1,2-Difunctionalization of alkynes is an attractive synthetic protocol, because it can achieve a high step economy and provide various complex organic molecules. This study demonstrates the visible-light-induced carbamoylarylation of terminal alkynes using N-aryl oxamic acids as bifunctional reagents. The transformation involves the addition of carbamoyl radicals to alkenes, resulting in 1,4-aryl migration via C(aryl)-N bond cleavage to afford the corresponding arylacrylamides in moderate to good yields.

DOI： 10.1021/acs.orglett.5c00866

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Organic Chemistry Frontiers  

The great potential of transition metal-catalyzed C-H functionalization lies in its ability to selectively target specific C-H bonds in complex molecules. Therefore, the development of enantio- and site-selective C-H functionalization is a long-term pursuit in this field. Herein, we disclose a ligand-enabled enantio- and site-selective remote C-H arylation of 2-(2-phenylpropyl)pyridine derivatives. The combination of an acetyl-protected aminoethyl phenyl thioether (MPA-thiol) with aryl iodides is found to enable γ-C(sp3)-H arylation, whereas l-pyroglutamic acid (l-pGlu) promotes δ-C(sp2)-H cross-coupling with various aryl-Bpin moieties. Notably, both C-H arylations proceed with high enantioselectivity and good yields. The results of DFT calculations support the enantioselectivity and site-selectivity of these two C-H arylations. Moreover the utility of this transformation was demonstrated by derivatization of a harmane alkaloid, a gram scale reaction and the successful removal of the pyridyl directing group.

DOI： 10.1039/d4qo02236j

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Language：English   Publisher：Cambridge University Press  

We successfully developed a para-selective C–H borylation of aromatic compounds using iridium catalysts with bulky bipyridine-type ligands. The key to success is the introduction of bulky substituents (m-terphenyl groups) at the 4- and 4′-positions of the bipyridine-type ligands to sterically protect both sides and back of the catalysts, thereby efficiently preventing substrate orientation that gives ortho- and meta-borylated products. Using these ligands, higher para-selectivity was achieved compared to the conventional iridium-catalyzed para-selective C–H borylation. Interestingly, high para-selectivity was achieved even when using aromatic compounds with small substituents such as ethyl or isopropyl groups on the aro-matic ring.

CiNii Research

Language：English   Publisher：Cambridge University Press  

The site-selective transformation of aromatic compounds remains a challenge in organic synthesis. Conventional methods for controlling site-selectivity often use directing groups, which limit substrate availability owing to the need for coordinating functional groups. Herein, we report a strategy in which the cyclic moiety of a catalyst recognizes and traps the substrate via host-guest interaction between the catalyst and substrate, allowing the catalytically active site to preferentially approach the desired reaction site, thereby enabling site-selective reactions. This catalyst can be used to control the site-selectivity of substrates that lack functional groups, which are essential in conventional methods. These results have the potential to extend the substrate scope and provide new catalyst designs for carbon–hydrogen bond transformations.

CiNii Research

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Journal of Organic Chemistry  

We successfully developed a decatungstate-catalyzed benzylic C(sp3)-H alkylation of sulfonanilides by utilizing the hydrogen bond between the sulfonamide group of the substrates and decatungstate photocatalysts. Using this catalytic system, site-selective C(sp3)-H alkylation was achieved at the benzylic position near the sulfonamide group.

DOI： 10.1021/acs.joc.5c00027

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Repository Public URL： https://hdl.handle.net/2324/7347378

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Organic Letters  

This study demonstrates the rhodium-catalyzed divergent synthesis of 5-, 5,6-, and 8-membered silacyclic compounds, such as benzosilole, silolosiline, and disilocine, from (2-hydrosilylaryl)acetylenes. To achieve high product selectivity, intra- and intermolecular reactions are controlled by tuning the mono- and bidentate phosphine ligands on the rhodium catalyst precursor. Deuterium labeling experiments and computational studies reveal that the annulation reaction proceeds via hydride transfer to the alkyne moiety.

DOI： 10.1021/acs.orglett.4c04694

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Language：Japanese   Publisher：The Society of Synthetic Organic Chemistry, Japan  

<p>The control of site-selectivity is important to obtain the desired products efficiently in synthetic organic chemistry. Because there are many C-H bonds with similar reactivities in organic molecules, it was difficult to promote site-selective C-H transformations without using directing groups. In this award article, I describe new strategies to control site-selectivity in C-H transformations using noncovalent interactions, such as hydrogen bond, Lewis acid-base interaction and electrostatic interaction, between the catalyst and the substrate. As a result, highly site-selective C-H transformations have been achieved. By using Lewis acid-base interaction between the substrate and reagent, <i>ortho</i>-selective C(sp²)-H borylation and silylation were achieved. In addition, site-selective C(sp²)-H trifluoromethylation was developed by inclusion of the aromatic substrate into cyclodextrin by supramolecular interaction.</p>

DOI： 10.5059/yukigoseikyokaishi.82.954

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Language：English   Publisher：Journal of Computational Chemistry  

The regioselective radical C-H trifluoromethylation of aromatic compounds have been shown to proceed in good yield and high regioselectivity when cyclodextrin (CD) is present. Yet, the reaction mechanism and the role of CD during the reaction have remained obscure. To this end, here we performed density functional theory (DFT) calculations to the conformations obtained by semiempirical quantum mechanical molecular dynamics calculations to reveal the reaction mechanism and the role of CD in controlling regioselectivity. The results show that metal salt increases the yield but do not affect the regioselectivity, which we further confirmed by an experiment. In contrast, multiple CD-substrate complex conformations and reaction pathways were obtained, and CD was shown to contribute to improving the regioselectivity by stabilizing the intermediate state via encapsulation. The present study indicates that CDs can increase the regioselectivity by stabilizing the intermediate and product states while only marginally affecting the transition state.

DOI： 10.1002/jcc.27430

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Chemistry - A European Journal  

We have developed a gold-catalyzed cascade reaction of aryldiynes bearing a hydrosilyl group to afford a variety of unexplored 5H-benzo[b]indeno[2,1-d]silines. The reaction system is applicable to the synthesis of bidirectionally π-extended silacycles from tetra(alkynyl)aryl compounds. Computational studies suggest that 5H-benzo[b]indeno[2,1-d]silines are formed via the insertion of a vinyl carbocation intermediate into the Si-H bond.

DOI： 10.1002/chem.202403163

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Authorship：Last author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Chemical Communications  

We synthesized a cyclic molecule from diarylalkynes and Meldrum's acid derivatives as the methylenation reagent via double Friedel-Crafts reaction. Single-crystal X-ray structure analysis confirmed the twisted structure of the molecule. We also investigated their physical properties and homoconjugation by UV-Vis, photoluminescence, DFT and TD-DFT calculations.

DOI： 10.1039/d4cc00890a

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Repository Public URL： https://hdl.handle.net/2324/7344076

Language：English   Publisher：Royal Society of Chemistry (RSC)  

We synthesized a cyclic molecule from diarylalkynes and Meldrum's acid derivatives as the methylenation reagent via double Friedel–Crafts reaction. Single-crystal X-ray structure analysis confirmed the twisted structure of the molecule. We also investigated their physical properties and homoconjugation by UV-Vis, photoluminescence, DFT and TD-DFT calculations.

CiNii Research

Authorship：Last author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Organic Letters  

We synthesized cyclic π-conjugated molecules by double Friedel−Crafts reaction of amino group-substituted 1,2-bis(2-phenylethynyl)benzene with Meldrum’s acid derivative. The structures of the cyclic π-conjugated molecules were determined by single-crystal X-ray structure analysis. The oxidation of the dimethylamino group-substituted π-conjugated molecule with NOBF4 gave a closed-shell dication that is stable at >210 °C. The monoradical cation of the di(4-methoxyphenyl)amino group-substituted π-conjugated molecule is stable in dichloromethane solution (half-life of nearly 15 days) and shows near-infrared absorption.

DOI： 10.1021/acs.orglett.4c02001

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Repository Public URL： https://hdl.handle.net/2324/7344075

Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

Boronic acid synthesis primarily involves the introduction of boronyl groups. However, an alternative route that involves the functionalization of boronic acids has not received much attention. This study describes the catalytic C(sp3)-H alkylation of ortho-tolylboronic acids utilizing the interaction between a free boronyl group [−B(OH)2] and a decatungstate photocatalyst [W10O32]4-. The boronyl groups of the alkylated products could be converted without isolation of the alkylated product.

DOI： 10.1021/acs.orglett.4c01043

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Repository Public URL： https://hdl.handle.net/2324/7344072

Language：English   Publisher：American Chemical Society (ACS)  

Boronic acid synthesis primarily involves the introduction of boronyl groups. However, an alternative route that involves the functionalization of boronic acids has not received much attention. This study describes the catalytic C(sp^3)–H alkylation of ortho-tolylboronic acids utilizing the interaction between a free boronyl group [−B(OH)_2] and a decatungstate photocatalyst [W_<10>O_<32>]^<4–>. The boronyl groups of the alkylated products could be converted without isolation of the alkylated product.

CiNii Research

Publishing type：Research paper (scientific journal)   Publisher：ACS Catalysis  

We report carbamoylarylation of alkenes using N-aryl oxamic acid derivatives under visible-light irradiation. Reactions of alkenes with carbamoyl radicals generated using N-aryl oxamic acid derivatives to afford Giese-type products or 3,4-dihydroquinolin-2(1H)-ones via ortho-radical addition to an aryl amide moiety have been previously reported. However, this study reveals that the introduction of a removable bulky group onto the nitrogen atom of N-aryl oxamic acids facilitates the radical addition of carbamoyl radicals to alkenes, resulting in 1,4-aryl migration via C(aryl)-N bond cleavage, thus affording arylpropanamides. Various alkenes, such as acrylic acid and styrene derivatives, are successfully applied to the synthesis of a variety of arylpropanamide derivatives, including 1,4-dicarbonyl amides, forming two C-C bonds.

DOI： 10.1021/acscatal.4c00523

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DOI： acscatal.4c00523

Other Link： https://pubs.acs.org/doi/10.1021/acscatal.4c00523

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

Abstract

The 5‐ammonium‐4,4‐dimethylvaleryl (Amv) group was generated by conversion of acryloyl group through decatungstate‐catalyzed addition of C(sp³)−H bond of i‐BuNH₂⋅HCl under the irradiation of UV light (365 nm or 405 nm). Treatment of Amv‐protected alcohols and anilines with aqueous Na₂CO₃ promoted the efficient deprotection of Amv. This is a unique method for the efficient removal of acryloyl groups from phenols, alcohols, and anilines. The selective removal of acryloyl groups through Amv in the presence of another acetyl or benzoyl group was demonstrated. The base‐triggered intramolecular cyclization of Amv was monitored by the release of a fluorescent molecule, and it was found that cyclization by Na₂CO₃ was very rapid (within 1 min) and that some weak bases such as 2,6‐lutidine are sufficient to promote cyclization.

DOI： 10.1002/ejoc.202301015

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Other Link： https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202301015

Language：English   Publisher：Chemical Record  

Site-selective C−H transformations are important to obtain desired compounds as single products in a highly efficient manner. However, it is generally difficult to achieve such transformations because organic substrates contain many C−H bonds with similar reactivities. Therefore, the development of practical and efficient methods for controlling site selectivity is highly desirable. The most frequently used strategy is “directing group method”. Although this method is highly effective and promotes site-selective reactions, it has several limitations. Our group recently reported other methods to achieve site-selective C−H transformations using non-covalent interactions between a substrate and a reagent or a catalyst and a substrate (non-covalent method). In this personal account, the background of site-selective C−H transformations, our reaction design to achieve site-selective C−H transformations, and recently reported reactions are explained.

DOI： 10.1002/tcr.202300149

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Language：English   Publisher：Chemical Record  

Fluorinated functional groups, including trifluoromethyl group, play important roles in the development of drugs, agrochemicals, and organic functional materials. Therefore, the development of highly effective and practical reactions to introduce fluorinated functional groups into (hetero)aromatic compounds is highly desirable. We have achieved several regioselective C−H trifluoromethylation and related reactions by electrophilic and nucleophilic activation of six-membered heteroaromatic compounds and steric protection of aromatic compounds. These reactions proceed in good to excellent yields, even on a gram scale, with high functional group tolerance, and are applicable to the regioselective trifluoromethylation of drug molecules. In this personal account, the background of the introduction reactions of fluorinated functional groups, our reaction designs to achieve regioselective C−H trifluoromethylation and the related reactions of (hetero)aromatic compounds are explained.

DOI： 10.1002/tcr.202300003

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Advanced Synthesis and Catalysis  

We developed a site-selective intermolecular C(sp3)−H alkylation of saccharides with electron-deficient alkenes using photocatalysis by anthraquinone and tetrabutylammonium decatungstate (TBADT). The main reaction site of anthraquinone-catalyzed C(sp3)−H alkylation is determined by the weakness of the C−H bond. The reaction site can be switched by changing the photocatalyst to TBADT, and the site-selectivity is controlled by the steric hindrance between the bulkier TBADT photocatalyst and the substituents of the saccharides. The reaction is compatible with several electron-deficient alkenes and saccharides, and provides C-saccharides in good yields. Furthermore, the monoalkylated product was obtained in excellent yield, even on the gram scale, under TBADT photocatalysis. Applicability was demonstrated by site-selective C(sp3)−H alkylation of glycosyl derivatives. The reactions proceed via a site-selective hydrogen atom transfer between the photocatalyst and saccharide, and the generated carbon radical reacts with an electron-deficient alkene to give alkylated products.

DOI： 10.1002/adsc.202300329

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Other Link： https://onlinelibrary.wiley.com/doi/10.1002/adsc.202300329

Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Organic Letters  

The decatungstate photocatalyst [W10O32]4-efficiently promoted the C(sp3)-H alkylation of the trifluoroacetic acid salt of valine methyl ester (H-Val-OMe·TFA) with electron-deficient alkenes under UV irradiation. The electrostatic interaction between the cationic ammonium group (+NH3) of the main chain and anionic [W10O32]4-played an important role in this reaction. The influence of various protected amino acids in the C(sp3)-H alkylation was investigated as the model reaction for the alkylation of Val-containing peptides. The introduction of an alkyne moiety into Val through this alkylation was successful, and successive copper-catalyzed azide-alkyne cycloaddition (CuAAC) was demonstrated. The C(sp3)-H bond of a Val residue located at the second from the N-terminus was also successfully converted. C(sp3)-H alkylation of oligopeptides containing two Val residues selectively proceeded proximally to the N-terminus.

DOI： 10.1021/acs.orglett.3c01154

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PubMed

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Organic Letters  

We developed the visible-light-induced hydrodesulfurization of alkyl aryl thioethers via the reductive cleavage of the C(aryl)-S bond using 1-hydroxypyrene as a Brønsted acid-reductant bifunctional photocatalyst. The hydrodesulfurization reaction proceeded under simple reaction conditions (1-hydroxypyrene and Et3N in THF under purple LED illumination); this reaction did not require chemicals commonly used for hydrodesulfurization, such as hydrosilanes, transition metal catalysts, and/or stoichiometric amounts of metal reagents. Detailed mechanistic studies based on control experiments, spectroscopic measurements, and computational studies revealed that the cleavage of the C(aryl)-S bond and the formation of the C(aryl)-H bond proceeded via the formation of the ion pair between the radical anion of alkyl aryl thioether and Et3N+H, resulting in the generation of a sulfur radical. In addition, the 1-hydroxypyrene catalyst was regenerated via hydrogen atom transfer (HAT) from Et3N.

DOI： 10.1021/acs.orglett.3c01061

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Organic Letters  

The first example of the 3-position-selective C(sp2)-H trifluoromethylation of pyridine rings was established. 3-Position-selective trifluoromethylation was achieved by the nucleophilic activation of pyridine and quinoline derivatives through hydrosilylation and successive electrophilic trifluoromethylation of the enamine intermediate. This reaction was applicable to perfluoroalkylation at the 3 position of the pyridine rings and late-stage trifluoromethylation of a bioactive molecule. Mechanistic studies indicated that the reaction proceeds via the formation of N-silyl enamine and trifluoromethylated enamine intermediates.

DOI： 10.1021/acs.orglett.2c03327

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Other Link： https://pubs.acs.org/doi/10.1021/acs.orglett.2c03327

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Novel triarylmethanols and triarylmethyl cations with diphenylamino groups were designed and synthesized. The triarylmethyl cations exhibited near-infrared (NIR) emission in toluene solution, solid film state, and polystyrene (PS) film. The emission intensities of the triarylmethyl cations were strongest in the PS film. The relative quantum yield of the PS film increased as the number of diphenylamino groups increased. In addition, triarylmethanols exhibit dual emission in their aggregated state owing to the intermolecular interactions between triphenyl amine moieties and/or hydroxy groups. These findings are interesting because NIR and dual emissions are not observed in the dimethylamino group-substituted triarylmethyl cation, which is referred to as the "malachite green," and the corresponding triarylmethanol, respectively.

DOI： 10.1002/ejoc.202200873

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Other Link： https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202200873

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

We have developed the divergent deaminative borylation and hydrodeamination of primary aromatic amines using bis(pinacolato)diboron. These transformations can be switched by the reaction conditions. Mechanistic and computational studies have suggested that the cleavage of the C–N bond and the formation of C–B bond are unlikely to involve free aryl radical intermediates. However, hydrodeamination is shown to proceed via hydrogen atom transfer between the corresponding aryl radical and an ethereal solvent.

DOI： 10.1021/acs.orglett.2c01663

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Other Link： https://pubs.acs.org/doi/10.1021/acs.orglett.2c01663

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Angewandte Chemie - International Edition  

New ligands for the iridium-catalyzed C(sp3)−H borylation of aliphatic compounds were established. In sharp contrast to 6-methyl-2,2′-bipyridine and 6-isobutyl-2,2′-bipyridine, 2,2′-bipyridine and 1,10-phenanthroline derivatives bearing a hydrosilylmethyl group (which would give a thermally stable NNSi pincer complex) served as suitable ligands for the reaction. Among them, a phenanthroline-based NNSi pincer ligand was shown to be an excellent ligand, and various aliphatic compounds were efficiently converted to the corresponding borylated products using the Ir/NNSi pincer catalyst system. The NNSi pincer ligand showed unique selectivity and enabled the iridium-catalyzed C(sp3)−H borylation using pinacolborane [H−B(pin)] instead of B2(pin)2. The formation of an iridium complex bearing a quinoline-based NNSi pincer ligand from [IrCl(cod)]2 was observed, and the catalytic activity of the complex was demonstrated.

DOI： 10.1002/anie.202202327

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Other Link： https://onlinelibrary.wiley.com/doi/10.1002/anie.202202327

Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：The Society of Synthetic Organic Chemistry, Japan  

<p>Regiocontrol is very important to obtain the desired products efficiently in synthetic organic chemistry. Because there are many C-H bonds with similar reactivities in organic molecules, it was difficult to promote regioselective C-H transformations without using directing groups. In this account, I describe a new strategy to control regioselectivities in C-H transformations using noncovalent interactions, such as hydrogen bond and Lewis acid-base interaction, between the catalyst and the substrate. As a result, highly regioselective C-H transformations have been achieved. By using the catalytic system, the rate of the C-H transformation was accelerated and the yield of the product was improved dramatically. In addition, the substrate and functional group specificities were expressed.</p>

DOI： 10.5059/yukigoseikyokaishi.80.421

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：GEORG THIEME VERLAG KG  

Pyrene is one of the most attractive polycyclic aromatic hydrocarbons (PAHs) in photochemistry. Based on their redox properties, pyrenes have potential as photosensitizers. In this review, we summarize recent developments in pyrene-catalyzed photoinduced organic reactions occurring via energy transfer or single-electron transfer based on the excited state of the pyrene.

DOI： 10.1055/a-1739-4793

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Other Link： https://www.thieme-connect.com/products/ejournals/abstract/10.1055/a-1739-4793

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Organic Letters  

A palladium(II)-catalyzed enantioselective arylation of unbiased secondary C(sp3)-H bonds was developed. The enantioselectivity was controlled by the combination of a pyridyl or isoquinolinyl directing group and an amino acid, N-Boc-2-pentyl proline. A variety of 2-propyl azaaryls and biaryl iodides were employed to provide arylated products in moderate to good yields (up to 82%) with high enantioselectivities (up to 93:7 er). This reaction is a rare example of an amino-acid-enabled enantioselective acyclic methylene C(sp3)-H arylation. Furthermore, the reaction proceeded with high enantioselectivity even on a gram scale, and the product was transformed to a 5,6,7,8-tetrahydroisoquinoline bioactive molecule. Kinetic isotope effect (KIE) experiments indicated that C-H activation is the rate-determining step for the enantioselective C(sp3)-H arylation.

DOI： 10.1021/acs.orglett.1c04215

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PubMed

Language：English   Publishing type：Research paper (scientific journal)   Publisher：ACS Catalysis  

Site-selective C(sp3)-H alkylation of 2-methylanilinium salts via radical intermediates was developed. The anionic decatungstate photocatalyst ([W10O32]4-) interacts with the ammonium group of the substrate through electrostatic interaction and selectively abstracts a hydrogen atom from the proximal benzylic carbon atom under UV irradiation. A variety of 2-methylanilinium salts reacted with electron-deficient alkenes. The alkylated product was successfully converted into an aryl iodide via cleavage of the C-N bond and a tetrahydrobenzoazepinone derivative by intramolecular cyclization. Mechanistic studies clearly show the existence of the interactions between [W10O32]4- and the ammonium group.

DOI： 10.1021/acscatal.2c00278

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

A new synthetic method for preparing fluorenes from amino group-containing biaryls and Meldrum's acid derivatives was developed. The reaction proceeded without a catalyst and loss of functional groups. The corresponding six- and seven-membered cyclic products were obtained using biaryl ether and ortho-terphenyl as substrates, respectively.

DOI： 10.1039/d1cc06212c

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DOI： 10.1039/D1CC02326H

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DOI： 10.1021/acs.orglett.1c01503

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DOI： 10.1021/acs.orglett.1c01259

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DOI： 10.3762/bjoc.17.74

Other Link： https://www.beilstein-journals.org/bjoc/articles/17/74

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DOI： 10.1246/cl.200939

Other Link： https://www.journal.csj.jp/doi/full/10.1246/cl.200939

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DOI： 10.1039/d1ob00326g

Other Link： https://pubs.rsc.org/en/Content/ArticleLanding/2021/OB/D1OB00326G#!divAbstract

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.joc.0c01038

Other Link： https://pubs.acs.org/doi/10.1021/acs.joc.0c01038

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DOI： 10.1002/adsc.202000306

Other Link： https://onlinelibrary.wiley.com/doi/full/10.1002/adsc.202000306

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DOI： 10.1021/acs.orglett.0c00946

Other Link： https://pubs.acs.org/doi/10.1021/acs.orglett.0c00946

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DOI： 10.1039/D0OB00484G

Other Link： https://pubs.rsc.org/en/content/articlelanding/2020/ob/d0ob00484g#!divAbstract

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.3762/bjoc.16.39

Other Link： https://www.beilstein-journals.org/bjoc/articles/16/39

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DOI： 10.1021/jacs.9b113497

Other Link： https://pubs.acs.org/doi/10.1021/jacs.9b11349

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DOI： 10.1021/acs.joc.9b02267

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DOI： 10.1039/c9cc07692a

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DOI： 10.1021/acs.orglett.9b01474

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DOI： 10.1248/cpb.c18-00586

Language：English   Publishing type：Research paper (scientific journal)  

The meta-selective introduction of functional groups into aromatic substrates was successfully achieved by hydrogen-bond-controlled meta-selective C-H borylation and successive conversion of the boryl group to other functional groups. By this method a wide range of functional groups could be introduced without isolation of the borylated intermediates. The desired meta-functionalized aromatic products were obtained in a one-pot manner even on a gram scale. Regioselective synthesis of multisubstituted aromatic compounds was also achieved.

DOI： 10.1021/acs.orglett.9b00030

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.orglett.9b00030

Other Link： https://pubs.acs.org/doi/10.1021/acs.orglett.9b00030

Language：English   Publishing type：Research paper (scientific journal)  

We developed a palladium-catalyzed C–H N-heteroarylation of N-protected-2,5-disubstituted imidazoles at the C4-position using N-heteroaryl halides as a coupling partner. Intensive reaction condition screening led us to identify fluo-rinated bathophenanthroline 7 as the optimum ligand for the palladium catalyst. This reaction will enhance lead optimization of drug candidates by facilitating the synthesis of hetero-biaryl compounds containing an imidazole ring.

DOI： 10.1248/cpb.c18-00586

Language：English   Publishing type：Research paper (scientific journal)  

A procedure yielding pure 2-(1-methylnonyl)phenol (1) as a colorless oil is presented. An oven-dried Schlenk flask with a Teflon-coated magnetic stir bar and a reflux condenser with a three-way stopcock is primarily used as paraphernalia. A discussion on ortho-monoalkylated phenol derivatives as important bioactive compounds and functional materials concludes the chapter.

DOI： 10.1002/0471264229.os094.20

Language：English   Publishing type：Research paper (scientific journal)  

Toxic aggregation of amyloid peptide and protein is intimately related to a number of human diseases, including Alzheimer's disease (AD). Here, we developed biocompatible photooxygenation catalyst 9, which can selectively oxygenate and degrade the pathogenic aggregation of AD-related amyloid-β peptide (Aβ) under near-infrared (NIR) light irradiation. On the basis of the structure of a fluorescent Aβ probe, CRANAD-2, a bromine atom was introduced to increase the production of singlet oxygen for photooxygenation. The use of julolidine and perfluoroalkylborate moieties as electron-donor and -acceptor components, respectively, markedly enhanced the photocatalytic activity and reduced phototoxicity. Photooxygenation of aggregated Aβ by 9 under NIR irradiation in the presence of cells attenuated the cytotoxicity of Aβ. The tissue permeability of NIR enabled catalytic photooxygenation of aggregated Aβ under the mouse skin. Moreover, injection of the catalyst to the AD-model mouse brain along with NIR light irradiation led to a significant decrease in the intact Aβ level in the brain. An artificial chemical catalysis that can selectively transform toxic aggregates of peptides and proteins to non-toxic species under physiologic conditions would find therapeutic applications to treat currently- incurable amyloid diseases. Because peptide and protein aggregation generally depends on intermolecular hydrophobic interactions, covalent installation of hydrophilic oxygen atoms from aerobic oxygen to a peptide or protein (i.e., oxygenation) would decrease the aggregative property. Here, we report a biocompatible photooxygenation catalyst that can selectively oxygenate and degrade the pathogenic aggregation of the peptide responsible for Alzheimer's disease (AD) under near-infrared light irradiation. The detoxicating chemical catalysis targeting aggregated amyloid-β peptide proceeded in the AD-model mouse brain. The results obtained in this study are an important step toward using artificial catalysis as a potential therapeutic strategy against amyloid diseases. A biocompatible photooxygenation catalyst that can selectively oxygenate and degrade the pathogenic aggregation of Alzheimer's disease (AD)-related amyloid-β peptide (Aβ) under near-infrared light irradiation has been developed. The catalyst oxygenates Aβ embedded under the skin of a living mouse and diminishes the intact Aβ level in an AD-model mouse brain. The new catalyst is potentially applicable for the treatment of peripheral amyloid diseases and AD.

DOI： 10.1016/j.chempr.2018.02.008

Language：English   Publishing type：Research paper (scientific journal)  

We developed 2-position-selective, direct C-H trifluoromethylation, pentafluoroethylation, and heptafluoropropylation of quinoline derivatives. Regioselective transformation was achieved without derivatization of the quinolines. The reaction proceeded at room temperature with high functional group tolerance, even in gram scale. Notably, the reaction was applicable to substrates containing a functional group sensitive to oxidation and a drug molecule.

DOI： 10.1021/acs.orglett.8b00339

Language：English   Publishing type：Research paper (scientific journal)  

A combination of simple π-conjugated molecules bearing a lone pair on heteroatom(s) and activators afforded new solidstate fluorescent materials. A solid-state red-emitting material that exhibits aggregation-induced emission was also synthesized by the present method.

DOI： 10.1246/cl.180735

Language：English   Publishing type：Research paper (scientific journal)  

A combination of simple π-conjugated molecules bearing a lone pair on heteroatom(s) and activators afforded new solidstate fluorescent materials. A solid-state red-emitting material that exhibits aggregation-induced emission was also synthesized by the present method.

DOI： 10.1246/cl.180735

Language：English   Publishing type：Research paper (scientific journal)  

This personal account summarizes our recent progress in the development of C-H transformations. We achieved ortho -selective C-H borylations and silylations by using Lewis acid-base interaction between two substrates and we achieved meta - and ortho -selective C-H borylations by using hydrogen bonding or Lewis acid-base interaction between a hydrogen donor or Lewis acid unit of a ligand and a functional group of a substrate. Regioselective C-H trifluoromethylations and related reactions of six-membered heteroaromatic compounds were realized at their 2- and 4-positions and at their benzylic positions. In addition, we developed C-H transformations directed towards the synthesis of organic functional materials, such as highly soluble polyimides or π-conjugated molecules containing either heteroatom(s) or a Lewis acid-base interaction. 1 Introduction 2 Regioselective C-H Transformations Controlled by Noncovalent Bond Interactions 2.1 Regioselective C-H Transformations Controlled by Lewis Acid-Base Interaction between Two Substrates 2.2 Regioselective C-H Transformation Controlled by Hydrogen Bonding between Ligand and Substrate 2.3 Regioselective C-H Transformations Controlled by Lewis Acid-Base Interactions between Ligands and Substrates 3 Trifluoromethylation and Related Transformations of Six-Membered Heteroaromatic Compounds 3.1 2-Position-Selective C-H Trifluoromethylation of Six-Membered Heteroaromatic Compounds 3.2 4-Position-Selective C-H Trifluoromethylation of Six-Membered Heteroaromatic Compounds 3.3 Benzyl Position-Selective C-H Trifluoromethylation of Six-Membered Heteroaromatic Compounds 4 C-H Transformations Leading to the Synthesis of Organic Functional Materials 4.1 Heteroatom-Containing π-Conjugated Molecules 4.2 π-Conjugated Molecules Containing a Lewis Acid-Base Interaction 4.3 Soluble Polyimide Derivatives 5 Conclusions.

DOI： 10.1055/s-0037-1610531

Language：English   Publishing type：Research paper (scientific journal)  

An iridium-catalyzed ortho-selective C-H borylation of phenol and aniline derivatives has been successfully developed. Iridium/bipyridine-catalyzed C-H borylation generally occurred at the meta- and para-positions of aromatic substrates. Introduction of an electron-withdrawing substituent on the bipyridine-type ligand and a methylthiomethyl group on the hydroxy and amino groups of the phenol and aniline substrates, however, dramatically altered the regioselectivity, affording exclusively ortho-borylated products. The reaction proceeded in good to excellent yields with good functional group tolerance. C-H borylation was applied to the synthesis of a calcium receptor modulator.

DOI： 10.1021/acs.orglett.7b02936

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.orglett.7b01423

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.orglett.7b00923

Language：English   Publishing type：Research paper (scientific journal)  

The rhenium-catalyzed synthesis of 1,3-diiminoisoindolines and their related compounds from aromatic or heteroaromatic imidates and carbodiimides are reported via C-H bond activation. This reaction is the first example of a transition-metal-catalyzed insertion of carbodiimides into an aromatic or heteroaromatic C-H bond and a novel method for synthesizing 1,3-diiminoisoindolines and their related compounds. Unsymmetrical 1,3-diiminoisoindolines were easily obtained using this method. The reaction proceeded in good to excellent yield using a variety of substrates.

DOI： 10.1021/acs.orglett.6b01012

Language：English   Publishing type：Research paper (scientific journal)  

Mechanistic insight into the construction of quaternary silicon chiral centers by rhodium-catalyzed synthesis of spiro-9-silabifluorenes through dehydrogenative silylation is reported. The C₂-symmetric bisphosphine ligand, BINAP, was effective in controlling enantioselectivity, and axially chiral spiro-9-silabifluorenes were obtained in excellent yields with high enantiomeric excess. Monitoring of the reaction revealed the presence of a monohydrosilane intermediate as a mixture of two constitutional isomers. The reaction proceeded through two consecutive dehydrogenative silylations, and the absolute configuration was determined in the first silylative cyclization. Competitive reactions with electron-rich and electron-deficient dihydrosilanes indicated that the rate of silylative cyclization increased with decreasing electron density on the silicon atom of the starting dihydrosilane. Further investigation disclosed a rare interconversion between the two constitutional isomers of the monohydrosilane intermediate with retention of the absolute configuration. Silicon-centered chirality: A combination of [{RhCl(cod)}₂] (cod=1,5-cyclooctadiene) and chiral bisphosphine ligand, (R)-BINAP, catalyzes the asymmetric induction of axial chirality through two consecutive dehydrogenative silylations of unactivated C(sp²)-H bonds (see scheme). A mechanistic investigation revealed that the absolute configuration is determined in the first dehydrogenative silylation, and this reaction may involve a rare example of C-Si bond cleavage with retention of the silicon-centered chirality.

DOI： 10.1002/chem.201504718

Language：English   Publishing type：Research paper (scientific journal)  

We developed a copper-catalyzed 5-position-selective C-H trifluoromethylation of 8-aminoquinoline derivatives. The reaction proceeded with high functional group tolerance under mild conditions. In the case of quinolines with an amide, carbamate, urea, or sulfonamide group at the 8-position of quinoline moieties, a radical scavenger experiment indicated that the reaction proceeded via a radical pathway. The protecting group of an 8-amidoquinoline derivative could be removed by hydrolysis. On the other hand, the trifluoromethylation of 8-aminoquinolines was also promoted by other Lewis acids as well as a copper catalyst and proceeded even in the presence of a radical scavenger. These results indicated that the trifluoromethylation of 8-aminoquinolines proceeded via a Friedel-Crafts-type reaction. Interestingly, the copper salt works as either a catalyst for the formation of a CF₃ radical or a Lewis acid to promote a Friedel-Crafts-type reaction, depending on the substrate.

DOI： 10.1039/c6ob01325b

Language：English   Publishing type：Research paper (scientific journal)  

This personal account summarizes our recent progress in the development of C-H transformations. We achieved ortho -selective C-H borylation and silylation using Lewis acid-base interaction between two substrates, and meta -selective C-H borylation using hydrogen bonding between a hydrogen donor unit of a ligand and a substrate functional group. Regioselective C-H trifluoromethylation and related reactions of 6-membered heteroaromatic compounds were realized at the 2-, 4-, and benzylic-positions of the heteroaromatic rings. In addition, we developed C-H transformations directed towards the synthesis of organic functional materials, such as highly soluble polyimides and π-conjugated molecules containing either heteroatom(s) or a Lewis acid-base interaction.

DOI： 10.5059/yukigoseikyokaishi.74.1058

Language：English   Publishing type：Research paper (scientific journal)  

A manganese- and borane-mediated synthesis of isobenzofuranones from esters and oxiranes is developed. The reaction proceeded at aromatic, heteroaromatic, and olefinic C-H bonds with high functional group tolerance. This is the first example of a manganese-catalyzed C-H transformation using an oxygen-directing group. Triphenylborane played an important role in this reaction to cooperatively promote the annulation reaction. Kinetic isotope effect experiments revealed that C-H bond activation of the aromatic rings was the rate-determining step.

DOI： 10.1021/acs.orglett.5b03474

Language：English   Publishing type：Research paper (scientific journal)  

In this review, transition-metal-catalyzed or -mediated C-H transformations leading to the synthesis of organic functional materials, such as oligomers, polymers, and π-conjugated molecules, are summarized. 1 Introduction 2 Oligomers and Polymers 2.1 Synthesis of Oligomers and Polymers 2.2 Chemical Modification of Polymers 3 π-Conjugated Molecules 3.1 Indenes and Fluorenes 3.2 Acenes 3.3 Triphenylenes 3.4 Chemical Modification of Perylene Diimides 3.5 Nanographenes 3.6 Condensed Polycyclic π-Conjugated Molecules with Five-Membered Heteroaromatic Rings 3.7 π-Conjugated Molecules with Nitrogen-Containing Six-Membered Heteroaromatics 3.8 Porphyrins 3.9 Miscellaneous (π-Conjugated Molecules) 4 Miscellaneous (Excluding Polymers and π-Conjugated Molecules) 5 Outlook and Conclusions.

DOI： 10.1055/s-0035-1560346

Language：English   Publishing type：Research paper (scientific journal)  

The current work describes the marked rate of acceleration caused by phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp³)-H bonds. The reactivity was affected by the steric and electronic nature of the phosphine ligands. The use of the bulky and electron-rich diphosphine ligand (R)-DTBM-SEGPHOS was highly effective to yield the dehydrogenative silylation products selectively in the presence of a hydrogen acceptor. An appropriate choice of C₂-symmetric chiral diphosphine ligand enables the asymmetric dehydrogenative silylation via the enantioselective desymmetrization of the C(sp³)-H bond. The unprecedented catalytic germylation of C(sp³)-H bonds with dehydrogenation was also examined with the combination of the rhodium complex and a wide bite angle diphosphine ligand to provide the corresponding 2,3-dihydrobenzo[b]germoles in good yield.

DOI： 10.1021/acs.joc.5b00920

Language：English   Publishing type：Research paper (scientific journal)  

Synthesis of heteroatom-containing ladder-type π-conjugated molecules was successfully achieved via a palladium-catalyzed intramolecular oxidative C-H/C-H cross-coupling reaction. This reaction provides a variety of π-conjugated molecules bearing heteroatoms, such as nitrogen, oxygen, phosphorus, and sulfur atoms, and a carbonyl group. The π-conjugated molecules were synthesized efficiently, even in gram scale, and larger π-conjugated molecules were also obtained by a double C-H/C-H cross-coupling reaction and successive oxidative cycloaromatization.

DOI： 10.1002/chem.201501116

Language：English   Publishing type：Research paper (scientific journal)  

We describe the development of an intermolecular unactivated C(sp³)-H bond functionalization towards the direct synthesis of tertiary carbamates. The transformation proceeded using a readily available, abundant first-row transition metal catalyst (copper), and isocyanates as the source of the amide moiety. This is a novel strategy for direct transformation of a variety of unactivated hydrocarbon feedstocks to N-alkyl-N-aryl and N,N-dialkyl carbamates without pre-functionalization or installation of a directing group. The reaction had a broad substrate scope with 3° > 2° > 1° site selectivity. The reaction proceeded even on a gram scale, and a corresponding free amine was directly obtained when the reaction was performed at high temperature. Kinetic studies suggested that radical-mediated C(sp³)-H bond cleavage was the rate-determining step.

DOI： 10.1039/c5sc00238a

Language：English   Publishing type：Research paper (scientific journal)  

We successfully developed rhodium-catalysed synthesis of multi-substituted silylindenes from 2 equivalents of aryl alkynes and 1 equivalent of hydrosilanes in moderate to good yields via C-H bond activation for the first time. The silyl groups of the obtained silylindenes could be converted to several other functional groups.

DOI： 10.1039/c5cc01569c

Language：English   Publishing type：Research paper (scientific journal)  

We successfully developed an iridium-catalyzed ortho-selective C-H silylation of aromatic compounds. The reaction exhibited a wide substrate scope, and a variety of π-conjugated molecules were synthesized in good to excellent yields, even in gram scale. Several silyl groups could also be introduced into the products. The experimental results indicated that the regioselectivity could be controlled by a Lewis acid-base interaction between the Lewis acidic silicon atoms of fluorinated hydrosilanes and the Lewis basic nitrogen atoms of aromatic compounds.

DOI： 10.1021/acs.orglett.5b00529

Language：English   Publishing type：Research paper (scientific journal)  

Rhenium-catalysed C(sp³)-H bond borylation in the absence of any oxidant, hydrogen acceptor, or external ligand, with the generation of H₂ as the sole byproduct is described. The transformation, which represents a rare example of rhenium-catalysed C(sp³)-H bond functionalisation, features high atom efficiency and simple reaction conditions. This journal is

DOI： 10.1039/c4cc09508a

Language：English   Publishing type：Research paper (scientific journal)  

A copper-mediated terminal position-selective C-(sp³)-H acetoxylation using a bidentate directing group and AgOAc as an oxidant was achieved. This reaction has high functional group tolerance and is not affected by steric hindrance. The reaction proceeds in excellent yield, even in gram scale, and the directing group can be removed after the reaction. Aromatic C(sp²)-H acetoxylation also proceeded under similar reaction conditions.

DOI： 10.1021/ol5022542

Language：English   Publishing type：Research paper (scientific journal)  

Acylated buckyferrocene and ruthenocene, Fe(η⁵-C ₆₀Me₅)(η⁵-C₅H₄COR) (R = Me, Ph, and CHCHPh) and Ru(η⁵-C₆₀Me ₅)(η⁵-C₅H₄COR) (R = Me and Ph), were obtained by Friedel-Crafts acylation of the parent buckymetallocenes with the corresponding acid chlorides and aluminum chloride in carbon disulfide at ambient temperature. The electron withdrawing and sterically hindered nature of the acyl groups were revealed by X-ray crystallography, infrared spectroscopy and electrochemical measurements. The possibility of further derivatizing the acylated products was illustrated by the conversion of the acetyl buckyruthenocene into the corresponding hydroxy and acetoxy compounds Ru(η⁵-C₆₀Me₅)(η⁵-C ₅H₄CH(OH)Me) and Ru(η⁵-C ₆₀Me₅)(η⁵-C₅H ₄CH(OAc)Me). This journal is

DOI： 10.1039/c3dt52002a

Language：English   Publishing type：Research paper (scientific journal)  

We achieved intra- and intermolecular C(sp³)-H alkoxylation of benzylic positions of heteroaromatic compounds using CuBr_n (n = 1, 2)/5,6-dimethylphenanthroline (or 4,7-dimethoxyphenanthroline) and ( ^tBuO)₂ as a catalyst and an oxidant, respectively. The reaction proceeded at both terminal and internal benzylic positions of the alkyl groups. The intramolecular alkoxylation was performed on a gram scale. This journal is

DOI： 10.1039/c4ob00215f

Language：English   Publishing type：Research paper (scientific journal)  

A palladium-catalyzed regioselective activation of C(sp²)-H and C(sp³)-H bonds of benzamides and carboxamides, followed by coupling with disilanes to afford organosilanes in moderate to high yields, with the aid of 8-aminoquinoline as a directing group, is reported. Catalytic C(sp ²)-H germanylation of benzamides also proceeds under the same palladium catalysis. The reaction tolerates a wide variety of functional groups and is scalable without yield reduction. The bidentate directing group is readily removed and recovered by the reaction with a hydrazine, with concominant generation of an acyl hydrazide.

DOI： 10.1021/ol500519y

Language：English   Publishing type：Research paper (scientific journal)  

We have successfully achieved the molybdenum hexacarbonyl [Mo(CO) ₆] mediated desulfurization of thiols and disulfides. In this reaction, the sulfhydryl (SH) mercapto groups of aryl, benzyl, primary and secondary alkyl thiols, and S-S single bonds of disulfides can be removed. This reaction has high functional group tolerance and is not affected by steric hindrance. The results of the reactions in acetone-d ₆ suggest that the sources of hydrogen in the thiol and disulfide desulfurizations are the hydrogen atom(s) of a sulfhydryl group and acetone (solvent), respectively, and that the desulfurization proceeds via the formation of an organomolybdenum species.

DOI： 10.1055/s-0034-1378315

Language：English   Publishing type：Research paper (scientific journal)  

Pyridine N-oxide-BF₂CF₃ and-BF₂C ₂F₅ complexes and their derivatives were synthesized. Most of the complexes show fluorescence both in solution and in the solid state. By expanding the π-conjugated skeleton, the color of the fluorescence could be changed dramatically. A fluorophore with a high solvent dependency could also be produced. Since such compounds can be synthesized on a gram scale in high yield, and are stable to oxygen, water, and heat, the complexes hold great potential as organic functional materials. Too complex for simple answers: Complexes of pyridine N-oxide with BF₂CF₃ and BF ₂C₂F₅, and their derivatives were synthesized. Most of the complexes fluoresce, both in solution and in the solid state. By expanding the π-conjugated skeleton, the color of the fluorescence could be changed dramatically. Owing to their properties such complexes hold potential as organic functional materials.

DOI： 10.1002/asia.201301688

Language：English   Publishing type：Research paper (scientific journal)  

Copper-catalyzed synthesis of benzo[d]isothiazol-3(2H)-ones and N-acyl-benzothiazetidine by intramolecular dehydrogenative cyclization is described. In this reaction, a new nitrogen-sulfur (N-S) bond is formed by N-H/S-H coupling. The present reaction has high functional group tolerance and gives products in gram scale. This method promotes double cyclization, allowing for synthesis of a drug intermediate.

DOI： 10.1021/jo401056g

Language：English   Publishing type：Research paper (scientific journal)  

Rhenium and manganese-catalyzed regioselective insertion of unsaturated molecules into aromatic and olefinic C-H bonds have been achieved. In some cases, successive intramolecular nucleophilic cyclization proceeded. We have also succeeded in regioselective insertion of alkynes into a non-strained C-C single bond of 1,3-dicarbonyl compounds using a rhenium or manganese catalyst. In addition, we have succeeded in regio-and stereo-defined cycloaddition reactions. By using a rhodium or palladium catalyst, we have achieved direct and efficient carbon-heteroatom bond formations via C-H bond activation.

DOI： 10.5059/yukigoseikyokaishi.71.425

Language：English   Publishing type：Research paper (scientific journal)  

By the reaction of amines with alkylborane reagents in the presence of a catalytic amount of copper(II) acetate Cu(OAc)₂ and di-tert-butyl peroxide, a cross-coupling reaction proceeded and alkylated amines were obtained in good to excellent yields. Phenols are also applicable for this reaction, and the corresponding alkyl aryl ethers were produced.

DOI： 10.1021/ol400323z

Language：English   Publishing type：Research paper (scientific journal)  

We achieved copper-catalyzed intramolecular and intermolecular alkoxylation of azoles. This reaction is a rare example of transition-metal-catalyzed C-H alkoxylation of heteroaromatic compounds. In addition, the alkoxylation reaction proceeded well even in gram scale. In most intermolecular alkoxylations, the use of an excess amount of alcohols (in some cases, alcohols are used as a solvent) is indispensable to efficiently promote the alkoxylation reaction, but this alkoxylation reaction proceeded using only 1 equiv of alcohols.

DOI： 10.1021/ol303533z

Language：English   Publishing type：Research paper (scientific journal)  

The treatment of a variety of hydrosilanes, each incorporating a benzylic C(sp³)-H bond, with a rhodium catalyst resulted in intramolecular dehydrogenative silylation. This silylation reaction was found to occur at typically unreactive C(sp³)-H bonds located at terminal positions on alkyl chains. Interestingly, the rhodium catalyst also promoted regioselective silylation at a site internal to an alkyl chain.

DOI： 10.1021/ol303353m

Language：English   Publishing type：Research paper (scientific journal)  

A new phosphine oxide with a chiral phosphine center was synthesized from a bis(biphenyl)phosphine oxide by dehydrogenative intramolecular cyclization via P-H and C-H bond activation under palladium catalysis. The absolute configuration of one enantiomer of the phosphine oxide was determined by single crystal X-ray structure analysis. By reducing the phosphine oxide, the corresponding phosphine, which also has a chiral center, was produced. The phosphine compounds could be optically resolved by chiral HPLC column chromatography.

DOI： 10.3987/COM-12-12595

Language：English   Publishing type：Research paper (scientific journal)  

The reaction of α-thioketones and alkynes in the presence of a rhenium catalyst, [HRe(CO)₄]_n, gave γ-thio-α, β-unsaturated ketones in excellent yields. The alkynes were inserted into the carbon-sulfur bond of the α-thioketones, and isomerization of a double bond provided the products with high regio- and stereoselectivities. This reaction also proceeded in an intramolecular fashion.

DOI： 10.1021/ol302810u

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/jo3021506

Language：English   Publishing type：Research paper (scientific journal)  

Rhenium-or manganese-catalyzed transformations based on the cleavage of inactive bonds, such as carbonhydrogen and carboncarbon bonds are discussed. Such transformations are recognized as key methods to realize efficient and powerful reactions. We also reveal novel regio- and/or stereodefined cycloaddition reactions using a rhenium or manganese catalyst. Most of the catalytic activities are typical of rhenium and manganese carbonyl complexes.

DOI： 10.1246/bcsj.20120015

Language：English   Publishing type：Research paper (scientific journal)  

A new method is described for the regioselective synthesis of multisubstituted pyridine derivatives. Treatment of N-acetyl β-enamino ketones with alkynes in the presence of the rhenium catalyst, Re ₂(CO) ₁₀, gives multisubstituted pyridines regioselectively. In this reaction, the N-acetyl moieties are important for the selective formation of the multisubstituted pyridines. This reaction proceeds via insertion of alkynes into a carbon-carbon single bond of β-enamino ketones, intramolecular nucleophilic cyclization, and elimination of acetic acid.

DOI： 10.1021/ol301273j

Language：English   Publishing type：Research paper (scientific journal)  

We have succeeded in the allylation of aromatic and olefinic C-H bonds of benzoic and acrylic acids using a rhenium catalyst, Re₂(CO) ₁₀. In this reaction, isomerization of the introduced allyl group to the 1-propenyl group did not occur.

DOI： 10.1039/c1cc12359a

Language：English   Publishing type：Research paper (scientific journal)  

The rhenium-catalyzed synthesis of cyclopentenone derivatives via double aldol condensation and successive Nazarov reaction is described. The cyclopentenones were converted to the corresponding cyclopentadienes using organolithium reagents. Cyclopentadienes with four different substituents could be synthesized by stepwise double aldol condensation using a ketone and two types of aldehydes, followed by treatment with an organolithium reagent.

DOI： 10.1055/s-0030-1260324

Language：English   Publishing type：Research paper (scientific journal)  

Polycyclic aromatic compounds can be synthesized from 2-benzylic- or 2-allylbenzaldehydes using a catalytic amount of In(III) or Re(I) complexes. By using this method, polycyclic aza-aromatic compounds can also be prepared efficiently. In these reactions, only water is formed as a side product.

DOI： 10.1021/jo200861s

Language：English   Publishing type：Research paper (scientific journal)  

Dibenzophosphole oxides were obtained from secondary hydrophosphine oxides with a biphenyl group by dehydrogenation via phosphine-hydrogen and carbon-hydrogen bond cleavage in the presence of a catalytic amount of palladium(II) acetate, Pd(OAc) ₂. By using this reaction, a ladder-type dibenzophosphole oxide could also be synthesized by double intramolecular dehydrogenative cyclization.

DOI： 10.1021/jo201030j

Language：English   Publishing type：Research paper (scientific journal)  

Rhenium-catalyzed synthesis of naphthalene-substituted aryl bromides or iodides via C-H bond activation, and its use for palladium-catalyzed cross-coupling reactions with tetraethynylporphyrin are described. A series of novel meso-substituted tetraalkynylporphyrins with naphthalene moieties were obtained.

DOI： 10.1055/s-0030-1261199

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of β-keto sulfones with terminal alkynes gave unsaturated δ-keto sulfones in good to excellent yields under rhenium catalysis. In this reaction, the insertion of the alkynes into the nonstrained carbon-carbon single bond between the α- and β-positions of the β-keto sulfones proceeded smoothly, and (Z)-isomers were produced with high regio- and stereoselectivities.

DOI： 10.1021/ol2008507

Language：English   Publishing type：Research paper (scientific journal)  

Rhenium carbonyl complex-catalyzed synthetic organic reactions are discussed. Kusama and Narasaka reported that a rhenium complex, ReBr(CO) ₅, which catalytically promotes Friedel-Crafts acylation. Kusama, Iwasawa, and co-workers reported that the rhenium complex ReCl(CO)₅ catalyzes tandem cyclization of ω-ω-acetylenic dienol silyl ethers. Farona and Greenlee reported that a mixture of catalytic amounts of ReX(CO) ₅ (X = Cl or Br) and EtAlCl₂ promotes olefin metathesis of terminal and internal olefins. The rhenium catalyst is found to promote C-H bond activation followed by insertion of an acrylate, intramolecular nucleophilic cyclization, and finally the elimination of aniline to give the cyclopentadiene derivative, which then complexes to the metal. Fuchikami and co-workers reported the reduction of carboxylic acids to alcohols by dihydrogen.

DOI： 10.1021/cr100241u

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of aromatic aldimines with terminal alkenes in the presence of a rhenium catalyst, [HRe(CO)₄]_n, gives 2-alkenylbenzylamines in good to excellent yields. This reaction proceeds via the insertion of the alkene into a C-H bond at the ortho-position of the imino group of the aromatic aldimine followed by sequential β-hydride elimination from the formed alkyl rhenium intermediate and then by hydrogenation of the imino group of the aldimine.

DOI： 10.1016/j.jorganchem.2010.09.064

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of tertiary amines with diazoacetate in the presence of a catalytic amount of an iron salt, FeCl₃, in ethanol gave glycine derivatives. In this reaction, a carbon-nitrogen single bond of the amine was cleaved.

DOI： 10.1039/c0cc03781h

Language：English   Publishing type：Research paper (scientific journal)  

Formal C(sp²)-H and C(sp³)-H cross-coupling reactions were carried out by iridium-catalyzed transfer dehydrogenation of primary alcohols and sequential manganese-catalyzed insertion of the formed aldehydes into a carbon-hydrogen bond of aromatic or olefinic compounds.

DOI： 10.1055/s-0030-1259040

Language：English   Publishing type：Research paper (scientific journal)  

The synthesis of unsymmetric functionalized pentacenes from 1,4-anthraquinones and functionalized isobenzofurans, which were prepared by transformation via C-H bond activation, was successfully accomplished. Examples of the synthesis of pentacenes with functional groups at the 5-position are still rare. These obtained functionalized pentacenes are highly soluble in hexane, toluene, and THF.

DOI： 10.1021/ol102349r

Language：English   Publishing type：Research paper (scientific journal)  

Figure Presented. Aminoindane derivatives were synthesized diastereoselectively by the treatment of aromatic imines with allenes in the presence of a catalytic amount of a rhenium complex, [HRe(CO)₄] _n. The allenes inserted into the aromatic C-H bonds.

DOI： 10.1021/ol101627x

Language：English   Publishing type：Research paper (scientific journal)  

We have succeeded in formal regioselective functionalization of alkanes by iridium-catalyzed dehydrogenation, hydrozirconation of the resulting alkenes, and electrophilic reaction of the generated alkylzirconium intermediate.

DOI： 10.1039/c0cc00243g

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of malonates without a substituent at the active methylene moiety with terminal alkynes gave salicylates regioselectively. In contrast, when malonates bearing a substituent at the active methylene moiety were used, cyclic β-keto esters were generated regioselectively. Treatment of the formed cyclic β-keto esters with In(OTf)
₃
gave phenol derivatives via decarboxylation.

DOI： 10.1246/cl.2010.894

Language：English   Publishing type：Research paper (scientific journal)  

A rhenium complex, [ReBr(CO)₃(thf)]₂, catalyzed insertion of terminal alkynes into a C-H bond of active methylene sites of 1,3-dicarbonyl compounds. When a catalytic amount of isocyanide or molecular sieves was added to the reaction mixture, the reaction course changed markedly, and insertion of alkynes into a C-C single bond between α- and β-positions of cyclic and acyclic β-keto esters occurred. The formed acyclic δ-keto esters could be converted to 2-pyranones, which were applied to the synthesis of multisubstituted aromatic compounds via the Diels-Alder reaction and successive elimination of carbon dioxide. In the case of the rhenium-catalyzed reactions between terminal alkynes and β-keto esters without substituent at the α-position, tetrasubstituted benzenes were produced regioselectively by two-to-one reaction of the components. The yields of tetrasubstituted benzenes were improved by using a manganese catalyst.

DOI： 10.1351/PAC-CON-09-09-21

Language：English   Publishing type：Research paper (scientific journal)  

By heating aryl aldehydes with catalytic amounts of a rhenium complex, ReBr(CO)₅, and N-phenylacetamide in toluene, indenone derivatives are obtained in good to excellent yields. This reaction proceeds via (1) the formation of an isobenzofuran derivative by the insertion of an aldehyde into the C-H bond of another aldehyde (C-H bond activation) and successive intramolecular nucleophilic cyclization, (2) nucleophilic addition of the formed isobenzofuran derivative to the third aldehyde, (3) isomerization, and (4) intramolecular aldol condensation.

DOI： 10.1021/ol100947p

Language：English   Publishing type：Research paper (scientific journal)  

Esterification reactions from cyclic 1,3-diketones and alcohols are carried out in the presence of several Lewis acids. In particular, indium(III) triflate, In(OTf)₃, iron(III) triflate, Fe-(OTf)₃, copper(II) triflate, Cu(OTf)₂, and silver(I) triflate, AgOTf, show high catalytic activities. These reactions proceed through the carbon-carbon bond cleavage by a retro-aldol reaction and were found to be highly regioselective even in the presence of other functional groups. This type of reaction can also be applied to the preparation of the keto esters during the synthesis of seratrodast, which is an antiasthmatic and eicosanoid antagonist.

DOI： 10.1002/asia.200900553

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) We have succeeded in the development of three approaches to the synthesis of aromatic compounds from 1,3-dicarbonyl compounds and alkynes. The first approach is a manganese-catalyzed [2+2+2] cycloaddition between 1,3-dicarbonyl compounds, which have no substituents at the active methylene moiety, and terminal alkynes. This reaction proceeds with high regioselectivity when aryl acetylenes are employed as the alkyne component. The second approach is a rhenium- or manganese-catalyzed formal [2+1+2+1] cycloaddition between β-keto esters and two kinds of alkynes. In this reaction, the aromatic compounds are obtained by the following reaction sequence: (1) insertion of the first alkyne into a carbon-carbon single bond of a β-keto ester, (2) formation of 2-pyranones via intramolecular cyclization with the elimination of ethanol, and (3) Diels-Alder reaction between the formed 2-pyranone and the second alkyne. This reaction provides multisubstituted aromatic compounds in a regioselective manner. The third approach is a rheniumcatalyzed formal [2+2+1+1] cycloaddition reaction from two 1,3-diketones and one alkyne. In this reaction, the aromatic skeleton is constructed from three carbons of the first 1,3-diketone, two carbons of the alkyne, and one carbon of the second 1,3-diketone.

DOI： 10.1021/jo902072q

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of β-enamino esters with terminal allenes in the presence of a catalytic amount of a rhenium complex, [ReBr(CO)₃(thf)] ₂, gave α-alkenylated β-imino or β-enamino esters. In this reaction, a new carbon-carbon bond is formed between the active methylene moiety of the β-enamino esters and the -carbon of the terminal allenes.

DOI： 10.1055/s-0029-1218281

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of alkynes with cyclic and acyclic 1,3-dicarbonyl compounds in the presence of a catalytic amount of a rhenium or manganese complex gives ring-expanded and carbon-chain extension products, respectively. In these reactions, alkynes insert into a non-strained carbon-carbon single bond of 1,3-dicarbonyl compounds. The ring-expansion reaction is also promoted by the addition of 4-Å molecular sieves instead of a catalytic amount of an isocyanide.

DOI： 10.1002/asia.200900137

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of cyclic βKeto esters with terminal alkynes in the presence of a catalytic amount of a rhenium complex, [ReBr(CO)₃(thf)] ₂, gave bicyclo[3.3.1]nonene derivatives. The reaction conditions and yields of the bicyclo[3.3.1]nonenes were improved by the sequential use of tetrabutylammonium fluoride (TBAF) after the rhenium-catalyzed reactions.

DOI： 10.1021/ol900772h

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of olefins bearing a directing group with α,β- unsaturated carbonyl compounds, alkynes, or aldehydes in the presence of a catalytic amount of a rhenium complex, [ReBr(CO)₃(thf)]₂ gave γ,δ-unsaturated carbonyl compounds, dienes, and allyl silyl ethers, respectively. This reaction proceeds via C-H bond activation, insertion of unsaturated molecules into the formed rhenium-carbon bond, and then reductive elimination (or transmetalation in the case of aldehydes).

DOI： 10.1021/ol900962v

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) Treatment of β-keto esters with terminal acetylenes in the presence of a catalytic amount of a manganese complex, MnBr(CO) ₅, and molecular sieves, gave multisubstituted aromatic compounds in good to excellent yields. This reaction employs [2 + 2 + 2] cycloaddition of β-keto esters and 2 equiv of terminal acetylenes with dehydration. In the case of a 1,3-diketone, the corresponding acetophenone derivative and its deacylated compound can be synthesized selectively.

DOI： 10.1021/ol800969h

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) A reaction between a β-keto ester and an acetylene in the presence of a rhenium complex, [ReBr(CO)₃(thf)] ₂, as a catalyst, provided a 2-pyranone derivative in excellent yield via retro-aldol reaction (C-C single bond cleavage). By adding an acetylene-bearing ester group(s) after the formation of 2-pyranones, an aromatization reaction proceeded and multisubstituted aromatic compounds were obtained in good to excellent yields.

DOI： 10.1021/ol801226t

Language：English   Publishing type：Research paper (scientific journal)  

Rhenium- and manganese-catalyzed reactions between β-keto esters and acetylenes, followed by treatment with tetrabutylammonium fluoride, gave 2-pyranone derivatives regioselectively.

DOI： 10.1039/b814694b

Language：English   Publishing type：Research paper (scientific journal)  

A rhenium complex, [ReBr(CO)₃(thf)]₂, catalyzes the insertion of α, β-unsaturated carbonyl compounds into a C-H bond of aromatic compounds having nitrogen-containing directing groups. In this reaction, Re₂(CO)₁₀ can also be used as a catalyst. When imines are employed as the aromatic substrates, sequential cyclization proceeds and indene derivatives are obtained in good to excellent yields. This reactivity is in contrast to those of ruthenium and rhodium complexes, which are usually used as catalysts in the insertion reactions of unsaturated molecules into a C-H bond. Investigations on the reaction mechanism indicate that the rhenium catalyst promotes C-H bond activation of aromatic compounds, the insertion of α, β-unsaturated carbonyl compounds into a Re-C bond, and intramolecular nucleophilic cyclization followed by reductive elimination and the elimination of an amine.

DOI： 10.1246/bcsj.81.1393

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of 2-propynyl alcohols with several nucleophiles in the presence of a catalytic amount of a rhenium complex, [ReBr(CO)₃(thf)] ₂, gave coupling products via dehydration. In these reactions, C-C, C-O, and C-S bonds can be constructed under mild conditions.

DOI： 10.1246/cl.2008.878

Language：English   Publishing type：Research paper (scientific journal)  

Hydantoin derivatives were obtained by the reactions of terminal alkynes with isocyanates in the presence of a catalytic amount of a manganese complex, MnBr(CO)₅. This reaction also proceeded using a rhenium complex, Re₂(CO)₁₀, or an iron complex, Fe(CO)₅, as a catalyst.

DOI： 10.1246/cl.2008.740

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K(C₆₀R₅) (1, R = Me, Ph) was generated by deprotonation of C₆₀R₅H (2) and allowed to react with N-fluoropyridinium triflate and N-chloro- and N-bromosuccinimide in benzene at 25°C for 10 min to obtain halogenated fullerenes C₆₀R ₅X (3a: R = Me, X = F; 3b: R = Me, X = Cl; 3c: R = Me, X = Br; 4a: R = Ph, X = F; 4b: R = Ph, X = Cl, 4c: R = Ph, X = Br) in good yield. The pentamethyl[60]fullerene halides are useful for the synthesis of a variety of η⁵-fullerene metal complexes. The reaction of the fullerene bromide 3c with the low-valent transition metal complexes Na[Re(CO) ₄], Fe(CO)₅, Ru₃(CO)₁₂, and Na[Co(CO)₄] gave Re(η⁵-C₆₀Me ₅)(CO)₃ (5), Fe(η⁵-C₆₀Me ₅)Br(CO)₂ (6), Ru(η⁵-C₆₀Me ₅)Br(CO)₂ (7), and Co(η⁵-C ₆₀Me₅)(CO)₂ (8), respectively. The structures of halide 3c and rhenium complex 5 were determined by X-ray crystallography. Electrochemical measurements on 3b and 3c were also performed. The iron complex 6 was converted into Fe(η⁵-C₆₀Me₅)Cp (9), Fe(η⁵-C₆₀Me₅)Me(CO)₂ (10), Fe(η⁵-C₆₀Me₅)(CO)₂(CCH) (11), and Fe(η⁵-C₆₀Me₅)(CO)₂(CCPh) (12), by ligand exchange reactions.

DOI： 10.1021/om8001262

Language：English   Publishing type：Research paper (scientific journal)  

With the aid of a directing group, an imine moiety, heteroaromatic compounds add to acetylenes in the presence of a catalytic amount of [ReBr(CO)₃(THF)]₂ at the adjacent position of the directing group regioselectively to give hydroarylation of the acetylenes in good to excellent yields. Similarly, heteroaromatic compounds react with acrylates and isocyanates to give the corresponding hydroarylation products under rhenium catalysis.

DOI： 10.1016/j.tet.2008.01.145

Language：English   Publishing type：Research paper (scientific journal)  

Rhenium complex, [ReBr(CO)₃(thf)]₂-catalyzed reactions between aromatic imines and either acetylenes or α,β- unsaturated carbonyl compounds gave indene derivatives in good to excellent yields. These reactions proceed via C-H bond activation, insertion of acetylenes or α,β-unsaturated carbonyl compounds, intramolecular nucleophilic cyclization, and reductive elimination. Indene derivatives were also obtained from aromatic ketones and α,β-unsaturated carbonyl compounds in the presence of catalytic amounts of the rhenium complex and p-anisidine. Sequential ruthenium-catalyzed hydroamination of aromatic acetylenes with anilines, and rhenium-catalyzed reactions of the formed aromatic ketimines with α,β-unsaturated carbonyl compounds also provided indene derivatives.

DOI： 10.1351/pac200880051149

Language：English   Publishing type：Research paper (scientific journal)  

2,4-Disubstituted quinoline derivatives were obtained from N-aryl-2-propynylamines catalyzed by copper(I) and gold(I) complexes. The quinoline derivatives could also be obtained by the reaction of N-arylaldimines with terminal acetylenes via the formation of N-aryl-2-propynylamines.

DOI： 10.1246/cl.2007.1422

Language：English   Publishing type：Research paper (scientific journal)  

Reactions of cyclic amides with unactivated terminal alkynes in the presence of a catalytic amount of a rhenium complex provided (E)-enamides in high regio- and stereoselectivity (E:Z = >99:<1).

DOI： 10.1021/ol702564e

Language：English   Publishing type：Research paper (scientific journal)  

Treatment of norbornenes with internal and terminal acetylenes in the presence of a catalytic amount of [ReBr(CO)₃(thf)]₂ gave cyclobutene derivatives in good to excellent yields.

DOI： 10.1246/cl.2007.1162

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) Isomerization between two isomers of 1,2-disubstituted 3-aminoindenes occurs via the rearrangement of indene frameworks. In contrast to previous rearrangements of indene derivatives, which occur under high-temperature conditions or the irradiation of light, this rearrangement proceeds at room temperature without UV light irradiation. An amino group at the 3-position plays an important role to accelerate the rearrangement under mild conditions.

DOI： 10.1021/jo070537w

Language：English   Publishing type：Research paper (scientific journal)  

A rhenium complex, [ReBr(CO)₃(THF)]₂, catalyzed reactions of aromatic ketimines and aldehydes with dienophiles, followed by dehydration, to give naphthalene derivatives in good to excellent yields. This reaction proceeds via C-H bond activation, insertion of an aldehyde, intramolecular nucleophilic cyclization, reductive elimination, elimination of aniline and Diels-Alder reaction. After dehydration, naphthalene derivatives were formed.

DOI： 10.1016/j.tet.2007.05.083

Language：English   Publishing type：Research paper (scientific journal)  

Regioselective insertion of isocyanates into a C-H bond of heteroaromatic compounds took place using a rhenium catalyst, [ReBr(CO) ₃(thf)] ₂.

DOI： 10.1246/cl.2007.872

Language：English   Publishing type：Research paper (scientific journal)  

A rhenium complex, [ReBr(CO)₃(thf)]₂, catalyzes reactions of aldimines with trimethylsilylacetylene to give propargylamines in excellent yields. The reactions proceed at room temperature under solvent-free conditions.

DOI： 10.1246/cl.2006.1376

Language：English   Publishing type：Research paper (scientific journal)  

Formal [3+2] annulation of arylacetylenes and α,β-unsaturated carbonyl compounds is achieved in a one-pot reaction by successive treatment of the acetylenes with aniline and a catalytic amount of Ru₃(CO) ₁₂ and NH₄PF₆ and C-H bond activation catalyzed by [ReBr(CO)₃(thf)]₂. The result suggests that the second rhenium-catalyzed indene formation is not disturbed by the first catalyst system.

DOI： 10.1021/ol0611292

Language：English   Publishing type：Research paper (scientific journal)  

By the reactions of ketimines bearing a pyridyl or a picolyl group on a nitrogen atom of the imine moiety with tosylisocyanate, 4H-pyrido[1,2-a] pyrimidin-4-one derivatives could be obtained in quantitative yields. In these reactions, tosylisocyanate acts as a carbonyl precursor. The pyridyl or picolyl group is a key functional group because it is not only the constituent structure of the 4H-pyrido[1,2-a]pyrimidin-4-one framework but also the promoter of the formation of a ketene intermediate.

DOI： 10.1039/b516916j

Language：English   Publishing type：Research paper (scientific journal)  

(Chemical Equation Presented) A rhenium complex, [ReBr(CO) ₃(thf)]₂, catalyzed the intermolecular reactions of 1,3-dicarbonyl compounds with terminal acetylenes and gave the corresponding alkenyl derivatives in excellent yields. These reactions could apply to an intramolecular version and gave the corresponding cyclic compounds quantitatively.

DOI： 10.1021/ol0515208

Language：English   Publishing type：Research paper (scientific journal)  

Temperature-dependent ⁵⁷Fe Mössbauer effect spectroscopy has been used to elucidate the metal atom dynamics in three neutral and two cationic bucky ferrocenes. For the three diamagnetic complexes Fe(C ₆₀H₅)Cp (1), Fe(C₆₀Me₅)Cp (2), and Fe(C₆₀Ph₅)Cp (3), the metal atom motion is anisotropic and the temperature dependence of the mean-square amplitude of vibration of the metal atom at a number of temperatures is reported. The Mössbauer lattice temperatures have been determined and compared to the parent ferrocene (6). The synthesis and X-ray crystal structure of 3 have been determined at 153(2) K, and the ¹H and ¹³C NMR spectra have been recorded. The cationic complexes derived from 2 and 3 show spin-lattice relaxation. The relaxation rate appears insensitive to the nearest-neighbor environment of the metal atom in this pair.

DOI： 10.1021/ic050251e

Language：English   Publishing type：Research paper (scientific journal)  

Single crystalline epitaxial films of bucky ferrocene (Fe(C ₆₀(CH₃)₅)C₅H₅), a hybrid molecule of C₆₀ and ferrocene, were grown on MoS₂(0001) substrates. By using reflection high-energy electron diffraction (RHEED) amplified by a microchannel plate (MCP), it was found that the lattice constant of the film decreased from 11.3 ± 0.2 Å at 1-2 monolayer (ML) to 10.2 ± 0.2 Å at 3 ML or thicker. Both of the lattice constants were incommensurate with that of the substrate, which indicates a new type of epitaxial growth. Valence electronic structures of the films at each thickness were measured with ultraviolet photoelectron spectroscopy (UPS) and the energy levels of molecular orbitals were identified in relation to the molecular orientation in the epitaxial film.

Language：English   Publishing type：Research paper (scientific journal)  

The nickel-, palladium-, and platinum-RFC _p complexes η ⁵-RFC _p)(η ³-allylic) (3b, RFC _p = C ₆₀R ₅, R = Me, allylic = methallyl; 4a, R = Ph, allylic = allyl; 4b, R = Ph, allylic = methallyl), Pd(η ⁵- RFC _p)(η ³-allylic) (7a, R = Me, allylic = allyl; 7b, R = Me, allylic = methallyl; 7c, R = Me, allylic = crotyl; 8a, R = Ph, allylic = allyl; 8b, R = Ph, allylic = methallyl; 8c, R = Ph, allylic = crotyl), and Pt(η ⁵-RFC _p)(η ³-methallyl) (9, R = Me; 10, R = Ph), were synthesized by transmetalation between K(RFC _p) (R = Me, Ph) and [Ni(allylic)Br] ₂, [Pd(allylic)Cl] ₂, or [Pt(methallyl)Cl] ₂ in THF at 25 °C for 10 min. The nickel-PhFC _p complexes 4a,b are unusually more stable toward molecular oxygen than the corresponding simple nickel cyclopentadienides and survive in air for many hours at elevated temperature. The crystal structures and the electrochemical properties of the palladium complexes suggest that the unusual stability of the PhFC _p complexes is due to the kinetic stabilization effect of the five Ph groups surrounding the metal atom and the thermodynamic stabilization effect of the electron-withdrawing fullerene moiety, hence suggesting new opportunities for the synthesis of otherwise unstable organometallic compounds.

DOI： 10.1021/om0499153

Language：English   Publishing type：Research paper (scientific journal)  

The Raman spectrum of buckyferrocene (Fe(C₆₀(CH ₃)₅)C₅H₅) changes during laser irradiation at 532 nm. A peak at 1465 cm^-1 decreases and a new peak at 1452 cm^-1 emerges, which resembles the change in the 'pentagonal pinch mode' during the photopolymerization of C₆₀. Photoinduced polymerization is strongly suggested because fragments from the buckyferrocene dimers are observed during the mass spectroscopy of laser desorbed solid samples. The rate constants of the photoinduced change for the powder crystals were determined at various photon intensities, and linearity was observed. The photoinduced change seems to occur extremely fast in densely packed buckyferrocene films fabricated by vacuum deposition.

DOI： 10.1016/j.ssc.2004.07.046

Language：English   Publishing type：Research paper (scientific journal)  

Metathetical coupling of an η⁵-fullerene ruthenium complex Ru(η⁵-C₆₀Me₅)Cl(CO)₂ and sodium cyclopentadienide gives a molecular hybrid of ruthenocene and fullerene, Ru(η⁵-C₆₀Me₅)(η⁵-C ₅H₅) (bucky ruthenocene), the structure of which was determined by spectroscopic and crystallographic analyses. The molecule shows unique reactivity among known ferrocene and ruthenocene compounds.

DOI： 10.1246/cl.2004.68

Language：English   Publishing type：Research paper (scientific journal)  

"Bucky ferrocenes", molecular hybrids of ferrocene and fullerene, have been synthesized in good yield on gram scale by treatment of C₆₀HMe₅ or C₇₀HMe₃ with [FeCp(CO)₂]₂ and their structures studied with physical methods including X-ray crystallography.

DOI： 10.1021/ja026069j

Language：English   Publishing type：Research paper (scientific journal)  

We demonstrate and analyze the epitaxial film formation of a molecular material that cannot be evaporated in vacuum due to thermal decomposition. A solution of the material is sprayed onto single crystalline van der Waals surfaces using a pulse valve under controlled vapor pressure of the solvent. Monolayer epitaxial films are obtained and we propose that the growth is mediated by liquid ultrathin films formed on the surface. Molecular arrangement and electronic structure of C₆₀(CH₃)₅H films are studied by reflection high energy electron diffraction and ultraviolet photoelectron spectroscopy, respectively. The present technique will be useful to study the electronic structure of recently synthesized molecular materials.

DOI： 10.1063/1.1379052

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/ja005564h

Language：English   Publishing type：Research paper (scientific journal)  

Pentamethyl-monohydro[60]fullerene C₆₀Me₅H has been synthesized through five-fold addition of methyleopper reagent to C₆₀. The anion C₆₀Me₅ generated by deprotonation of C₆₀Me₅H forms organometallic complexes with K⁺ and Tl⁺ ions with stronger metal-carbon interaction than that in the corresponding pentaphenylated ligand C₆₀Ph₅ ⁺.

DOI： 10.1246/cl.2000.270

Event date： 2020.2

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：長崎大学文教キャンパス   Country：Japan  

Event date： 2020.1

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：大阪府立大学中百舌鳥キャンパス   Country：Japan  

Event date： 2020.1

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：NCL Pune   Country：India  

Event date： 2020.1

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：University of Calcutta   Country：India  

Event date： 2019.12

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：東京大学大学院理学系研究科   Country：Japan  

Event date： 2019.11

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：北海道大学   Country：Japan  

Event date： 2019.10

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：広島大学   Country：Japan  

Event date： 2019.7

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：山口大学工学部   Country：Japan  

Event date： 2019.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：シャトレーゼ　ガトーキングダム　サッポロ   Country：Japan  

Event date： 2019.6

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：北海道大学薬学部   Country：Japan  

Event date： 2019.5

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：武蔵野大学   Country：Japan  

Event date： 2019.4

Language：English   Presentation type：Oral presentation (general)  

Venue：東京大学大学院理学系研究科化学専攻   Country：Japan  

Event date： 2019.2

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：富山大学工学部   Country：Japan  

Event date： 2019.1

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：東北大学　理学研究科サイエンスホール   Country：Japan  

Event date： 2018.11

Language：English   Presentation type：Oral presentation (general)  

Venue：Hsinchu, Taiwan   Country：Japan  

Event date： 2018.11

Language：English  

Venue：車山高原、スカイパークホテル   Country：Japan  

We developed an iridium-catalyzed meta-selective C–H borylation of aromatic compounds using a newly designed catalytic system (Graphical Abstract). The bipyridine derived ligand that binds iridium contains a pendant urea moiety. A hydrogen bonding between this urea and a hydrogen-bond acceptor in the substrate places the iridium in close proximity to the meta-C–H bond and thus controls the regioselectivity.
An iridium/bipyridine-catalyzed ortho-selective C-H borylation of aryl sulfides was also developed. High ortho-selectivity was achieved by a Lewis acid-base interaction between a boryl group of the ligand and a sulfur atom of the substrate.
I will also discuss the recent developments based on hydrogen bond-controlled meta-selective C-H borylation.

Event date： 2018.10 - 2018.11

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：マレーシア、ランカウイ島   Country：Japan  

Event date： 2018.10

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：広島大学   Country：Japan  

Event date： 2018.9

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：長崎   Country：Japan  

Event date： 2018.8

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：愛媛大学   Country：Japan  

Event date： 2018.5

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：京都大学理学部セミナーハウス   Country：Japan  

Event date： 2018.3

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：カンボジア、シエムリープ   Country：Cambodia  

Event date： 2018.3

Language：English   Presentation type：Oral presentation (general)  

Venue：カンボジア、シエムリープ   Country：Japan  

Event date： 2017.12

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：東京工業大学大岡山キャンパス   Country：Japan  

Event date： 2017.10

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：広島大学　東広島キャンパス   Country：Japan  

Event date： 2017.9

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：Institute of Chemistry, Chinese Academy of Sciences   Country：China  

Event date： 2017.9

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：Peking University   Country：China  

Event date： 2017.9

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：Tsinghua University   Country：China  

Event date： 2017.8

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：九州大学伊都キャンパス   Country：Japan  

Event date： 2017.6 - 2018.6

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：ベトナム、ホーチミン   Country：Viet Nam  

Event date： 2017.6

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：東ソー（株）東京研究所   Country：Japan  

Event date： 2017.3 - 2018.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：仙台   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学千里山キャンパス   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学千里山キャンパス   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学千里山キャンパス   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学千里山キャンパス   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学千里山キャンパス   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学千里山キャンパス   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学千里山キャンパス   Country：Japan  

Event date： 2024.12

Language：Japanese   Presentation type：Poster presentation  

Venue：早稲田大学国際会議場   Country：Japan  

Event date： 2024.11

Language：Japanese   Presentation type：Poster presentation  

Venue：早稲田大学国際会議場   Country：Japan  

Event date： 2024.11

Language：Japanese   Presentation type：Poster presentation  

Venue：早稲田大学国際会議場   Country：Japan  

Event date： 2024.11

Language：Japanese   Presentation type：Poster presentation  

Venue：早稲田大学国際会議場   Country：Japan  

Event date： 2024.11

Language：Japanese   Presentation type：Poster presentation  

Venue：早稲田大学国際会議場   Country：Japan  

Event date： 2024.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：札幌コンベンションセンター   Country：Japan  

Event date： 2024.6

Language：Japanese   Presentation type：Poster presentation  

Venue：北九州国際会議場   Country：Japan  

Event date： 2024.6

Language：Japanese   Presentation type：Poster presentation  

Venue：北九州国際会議場   Country：Japan  

Event date： 2024.6

Language：Japanese   Presentation type：Poster presentation  

Venue：北九州国際会議場   Country：Japan  

Event date： 2024.6

Language：Japanese   Presentation type：Poster presentation  

Venue：北海道大学   Country：Japan  

Event date： 2024.5

Language：Japanese   Presentation type：Poster presentation  

Venue：九州大学馬出キャンパス   Country：Japan  

Event date： 2024.5

Language：English   Presentation type：Poster presentation  

Venue：Hiroshima   Country：Japan  

Event date： 2024.5

Language：English   Presentation type：Poster presentation  

Venue：Hiroshima   Country：Japan  

Event date： 2024.3

Language：Japanese  

Country：Japan  

Event date： 2024.3

Language：Japanese  

Venue：日本大学 船橋キャンパス   Country：Japan  

Event date： 2024.3

Language：English  

Venue：日本大学 船橋キャンパス   Country：Japan  

Event date： 2024.3

Language：Japanese  

Venue：日本大学 船橋キャンパス   Country：Japan  

Event date： 2024.3

Language：Japanese  

Venue：日本大学 船橋キャンパス   Country：Japan  

Event date： 2023.12

Language：Japanese  

Venue：市民会館おおみや   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：静岡県清水文化会館   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：ラフォーレ那須   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：リゾートホテル　ラフォーレ那須   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：大阪大学、吹田キャンパス   Country：Japan  

Event date： 2023.9

Language：Japanese  

Country：Japan  

Event date： 2023.9

Language：English  

Country：Japan  

Event date： 2023.9

Language：Japanese  

Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2023.8

Language：Japanese  

Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：第59回化学関連支部合同九州大会   Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：第59回化学関連支部合同九州大会   Country：Japan  

Event date： 2023.7

Language：English  

Country：Japan  

Event date： 2023.6

Language：English  

Country：Japan  

Event date： 2023.6

Language：English  

Country：Japan  

Event date： 2023.6

Language：Japanese  

Country：Japan  

Event date： 2023.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2023.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2023.3

Language：English   Presentation type：Oral presentation (general)  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2023.3

Language：English   Presentation type：Oral presentation (general)  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2022.6

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2022.6

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2022.6

Language：Japanese   Presentation type：Symposium, workshop panel (public)  

Venue：九州大学伊都キャンパス椎木講堂   Country：Japan  

Event date： 2022.3

Language：English  

Venue：オンライン   Country：Japan  

Event date： 2022.3

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2022.3

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2022.3

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2022.3

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2022.3

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2022.3

Language：English  

Venue：オンライン   Country：Japan  

Event date： 2022.3

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.11

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.7

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.7

Language：English  

Venue：オンライン   Country：Japan  

Event date： 2021.7

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.7

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.7

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.7

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.6

Language：Japanese  

Venue：九州大学伊都キャンパス椎木講堂＋オンライン   Country：Japan  

Event date： 2021.6

Language：Japanese  

Venue：九州大学伊都キャンパス椎木講堂＋オンライン   Country：Japan  

Event date： 2021.6

Language：Japanese  

Venue：九州大学伊都キャンパス椎木講堂   Country：Japan  

Event date： 2021.5

Language：English  

Venue：Virtual Event   Country：Japan  

Event date： 2021.3

Language：Japanese  

Venue：オンライン   Country：Japan  

Event date： 2021.3

Language：English  

Venue：オンライン   Country：Japan  

Event date： 2020.5

Language：English  

Venue：オンライン   Country：Japan  

Event date： 2020.3

Language：Japanese  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2020.3

Language：Japanese  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2020.3

Language：English  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2020.3

Language：Japanese  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2020.3

Language：Japanese  

Country：Japan  

Event date： 2020.3

Language：Japanese  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2020.3

Language：Japanese  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2020.3

Language：Japanese  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2020.3

Language：Japanese  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2020.3

Language：Japanese  

Venue：東京理科大学野田キャンパス   Country：Japan  

Event date： 2019.11

Language：Japanese  

Venue：北海道大学   Country：Japan  

Event date： 2019.11

Language：English  

Venue：宮崎、フェニックス・シーガイア・リゾート   Country：Japan  

Event date： 2019.9 - 2019.12

Language：Japanese  

Venue：大阪国際交流センター   Country：Japan  

Event date： 2019.9

Language：English  

Venue：首都大学東京南大沢キャンパス   Country：Japan  

Event date： 2019.9

Language：English  

Venue：首都大学東京南大沢キャンパス   Country：Japan  

Event date： 2019.8

Language：Japanese  

Venue：九州大学筑紫キャンパス   Country：Japan  

Event date： 2019.8

Language：Japanese  

Venue：九州大学筑紫キャンパス   Country：Japan  

Event date： 2019.8

Language：Japanese  

Country：Japan  

Event date： 2019.8

Language：Japanese  

Venue：千葉大学西千葉キャンパス   Country：Japan  

Event date： 2019.7

Language：English  

Venue：Heidelberg   Country：Germany  

Event date： 2019.7

Language：English   Presentation type：Symposium, workshop panel (public)  

Venue：北九州国際会議場   Country：Japan  

Event date： 2019.7

Language：Japanese   Presentation type：Symposium, workshop panel (public)  

Venue：北九州国際会議場   Country：Japan  

Event date： 2019.7

Language：English   Presentation type：Symposium, workshop panel (public)  

Venue：北九州国際会議場   Country：Japan  

Event date： 2019.7

Language：Japanese   Presentation type：Symposium, workshop panel (public)  

Venue：北九州国際会議場   Country：Japan  

Event date： 2019.7

Language：Japanese   Presentation type：Symposium, workshop panel (public)  

Venue：北九州国際会議場   Country：Japan  

Event date： 2019.7

Language：English   Presentation type：Symposium, workshop panel (public)  

Venue：北九州国際会議場   Country：Japan  

Event date： 2019.5

Language：Japanese   Presentation type：Symposium, workshop panel (public)  

Venue：東京大学本郷キャンパス   Country：Japan  

Event date： 2019.5

Language：Japanese   Presentation type：Symposium, workshop panel (public)  

Venue：九州大学馬出キャンパス   Country：Japan  

Event date： 2019.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：九州大学馬出キャンパス   Country：Japan  

Event date： 2019.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：千葉、幕張メッセ   Country：Japan  

Event date： 2019.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：千葉、幕張メッセ   Country：Japan  

Event date： 2019.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：甲南大学岡本キャンパス   Country：Japan  

Event date： 2019.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：甲南大学岡本キャンパス   Country：Japan  

Event date： 2019.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：甲南大学岡本キャンパス   Country：Japan  

Event date： 2019.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：甲南大学岡本キャンパス   Country：Japan  

Event date： 2019.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：甲南大学岡本キャンパス   Country：Japan