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Design, Synthesis, and Biological Activity of Small Organic Molecules for Environmental Stress Response

DOI： 10.5059/yukigoseikyokaishi.81.733

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

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

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

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

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

Abstract

Antimicrobial resistance is a never‐ending challenge, which should be considered seriously, especially when using unprescribed “over‐the‐counter” drugs. The synthesis and investigation of novel biologically active substances is among the directions to overcome this problem. Hence, 18 novel 5,6‐dihydrotetrazolo[1,5‐c]quinazolines were synthesized, their identity, purity, and structure were elucidated by elemental analysis, IR, LC‐MS, ¹Н, and ¹³C NMR spectra. According to the computational estimation, 15 substances were found to be of toxicity Class V, two of Class IV, and only one of Class II. The in vitro serial dilution method of antimicrobial screening against Escherichia coli, Staphylococcus aureus, Klebsiella aerogenes, Pseudomonas aeruginosa, and Candida albicans determined b3, c1, c6, and c10 as the “lead‐compounds” for further modifications to increase the level of activity. Substance b3 demonstrated antibacterial activity that can be related to the calculated high affinity toward all studied proteins: 50S ribosomal protein L19 (PDB ID: 6WQN), sterol 14‐alpha demethylase (PDB ID: 5TZ1), and ras‐related protein Rab‐9A (PDB ID: 1WMS). The structure–activity and structure–target affinity relationships are discussed. The targets for further investigations and the anatomical therapeutic chemical codes of drug similarity are predicted.

DOI： 10.1002/ardp.202300029

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

Stable and Unstable Concentration Oscillations Induced by Temperature Oscillations on Reversible Nonequilibrium Chemical Reactions of Helicene Oligomers
Temperature oscillations can affect behaviors of living things. In this article, we describe the effect of triangle temperature oscillations on reversible nonequilibrium chemical reactions detected as concentration oscillations. When amplification through self-catalytic reactions is involved in the chemical reactions, concentration oscillations exhibit diverse nonequilibrium phenomena, which include equilibrium intersecting, equilibrium noncontact, and equilibrium sliding. Both stable and unstable concentration oscillations occur, during which repeated cycles provide the same and different concentration oscillations, respectively. Concentration oscillations are classified according to their waveforms in concentration/time profiles, the shapes of hysteresis curves in concentration/temperature profiles, the nature of self-catalytic reactions, and their relationships with equilibrium. An unstable concentration oscillation may be transformed into a stable concentration oscillation, which is described on the basis of the classifications. Experimental examples are shown using reversible association and dissociation reactions of helicene oligomers.

DOI： 10.3390/ijms24010693

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Journal of Translational Autoimmunity  

Selective Induction of Thymic Stromal Lymphopoietin Expression by Novel Nitrogen-Containing Steroid Compounds in PAM-212 Cells

DOI： 10.1016/j.jtauto.2022.100186

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Authorship：Last author   Publishing type：Research paper (scientific journal)  

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Language：English   Publisher：American Chemical Society (ACS)  

A rhodium-catalyzed insertion of sulfur into unprotected peptide disulfides in aqueous solvents has been developed, which yields mixtures of trisulfides and tetrasulfides. This method can be applied to peptides containing amino acids such as Gly, Phe, Tyr, Ser, Met, Asp, Gln, and Lys and provides polysulfides with various amino acid residues without being affected by functional groups. A reaction can be conducted on a gram scale. Vasopressin can also be converted into its corresponding polysulfides.

CiNii Research

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

A rhodium-catalyzed insertion of sulfur into unprotected peptide disulfides in aqueous solvents has been developed, which yields mixtures of trisulfides and tetrasulfides. This method can be applied to peptides containing amino acids such as Gly, Phe, Tyr, Ser, Met, Asp, Gln, and Lys and provides polysulfides with various amino acid residues without being affected by functional groups. A reaction can be conducted on a gram scale. Vasopressin can also be converted into its corresponding polysulfides.

DOI： 10.1021/acs.orglett.2c03257

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DOI： DOI: 10.1021/acs.orglett.2c03257

Repository Public URL： https://hdl.handle.net/2324/7183558

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Informa UK Limited  

Hydrogen sulfide, hydropersulfides, and hydropolysulfides have been revealed to play important physiological roles such as cell signaling and protection against oxidative stress, but the underlying mechanisms and dynamics of action remain elusive. It is generally accepted that these species act by two-electron redox mechanisms, while the involvement of one-electron redox chemistry has received less attention. In this study, the radical-scavenging activity of hydrogen persulfide, hydrogen polysulfides (HSnH n = 2–4), and diallyl- or dialkyl-sulfides (RSnR, n = 1–4) was measured. Furthermore, their antioxidant effects against free radical-mediated human plasma lipid peroxidation were assessed by measuring lipid hydroperoxides. It was found that disodium disulfide, trisulfide, and tetrasulfide acted as potent peroxyl radical scavengers, the rate constant for scavenging peroxyl radical being 3.5 × 105, 4.0 × 105, and 6.0 × 105 M−1 s−1 in PBS pH 7.4 at 37 °C respectively and that they inhibited plasma lipid peroxidation efficiently, the efficacy is increased with the catenation number. Disodium tetrasulfide was 1.5 times as reactive as Trolox toward peroxyl radical and inhibited plasma lipid peroxidation more efficiently than ascorbate and Trolox. On the other hand, diallyl- and dialkyl-sulfides did not exert significant radical-scavenging activity, nor did they inhibit lipid peroxidation efficiently, except for diallyl tetrasulfide, which suppressed plasma lipid peroxidation, despite less significantly than disodium tetrasulfide. Collectively, this study shows that hydrogen persulfide and hydrogen polysulfides act as potent radical-scavenging antioxidants and that, in addition to two-electron redox mechanisms, one electron redox reaction may also play important role in the in vivo defense against deleterious oxidative stress.

DOI： 10.1080/10715762.2023.2165918

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

The method of rhodium-catalyzed insertion reaction of perfluoroarenes between unprotected peptide cystine disulfides is developed. The method is applicable to peptides containing amino acids such as Ser, Asn, Asp, and Lys without affecting hydroxy, primary amine, carboxylic acid, and amide groups. The reaction does not require a base and proceeds under acidic, neutral, and basic conditions. No free thiols are detected, and the reaction is considered to proceed via rhodium thiolates. A crossover experiment shows minimal scrambling of organothio groups.

DOI： 10.1002/ajoc.202200340

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DOI： DOI:10.5939/sjws.220014

Authorship：Lead author,　Corresponding author  

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Language：Japanese   Publisher：The Society of Japanese Women Scientists  

<p>Organic compounds containing heteroatoms in the third row of the periodic table, particularly sulfur and phosphorous, are widely used in pharmaceuticals and biostimulants. It is essential to develop novel efficient synthetic methods for heavy-heteroatom organic compounds containing sulfur and phosphorous atoms. Compared with oxygen and nitrogen atoms, which are second-row heteroatoms, sulfur and phosphorous atoms are larger, polarizable, and oxidizable. Thus, these heavy-heteroatom organic compounds can interact well with biomacromolecules and exhibit diverse biological functions. In this work, a novel method of synthesizing heavy-heteroatom organic compounds using transition-metal catalysts was developed. The reactions use inexpensive sulfur reagents and are reversible and energy-saving without the need to use bases. This transition-metal-catalyst method can be carried out in a homogeneous system in water, and provides chemically modified peptides and proteins. Synthetic compounds for biostimulants and pharmaceuticals have been developed using designed unsymmetric bis (heteroaryl) HetAr–X–HetAr’ compounds, which have flexible and rigid HetAr groups containing sulfur and phosphorus atoms capable of interacting with biomacromolecules, and exhibit various biological activities.</p>

DOI： 10.5939/sjws.220014

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Rhodium-Catalyzed Synthesis of Unsymmetric Di(heteroaryl)ureas Involving an Equilibrium Shift
Unsymmetric di(heteroaryl)ureas such as HetAr1-NHCONH-HetAr2 are efficiently synthesized from two symmetric ureas, HetAr1-NHCONH-HetAr1 and HetAr2-NHCONH-HetAr2, by rhodium-catalyzed exchange reactions. The equilibrium in some of the reactions can be shifted to the formation of unsymmetric ureas by the aggregation of the dimers formed by inter- and intramolecular hydrogen bonding.

DOI： 10.1021/acs.orglett.1c03485

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

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

Language：Others  

Unstable and Stable Thermal Hysteresis Under Thermal Triangle Waves

Language：Others  

Rhodium-Catalyzed Oxidation of Unprotected Peptide Thiols to Disulfides with Oxygen in Water

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

DOI： 10.3390/molecules25163595

Language：Others  

Transition-Metal-Catalyzed Synthesis of Organophosphorus Compounds Involving P-P Bond Cleavage

Language：Others  

Rhodium-catalyzed phosphorylation reaction of water-soluble disulfides using hypodiphosphoric acid tetraalky esters in water

Language：Others  

Language：Others  

Reversible Formation of Self-assembly Gels Containing Giant Vesicles in Trifluoromethylbenzene Using Oxymethylenehelicene Oligomers with Terminal C16 Alkyl Groups

Language：Others  

Language：Others  

Optically active iodohelicene derivatives exhibit histamine N-methyl transferase inhibitory activity.

DOI： 10.1038/s41429-018-0118-z

Language：Others  

Acid-catalyzed synthesis of condensed polycyclic diaryl ethers from arenols

Language：Others  

Rhodium-Catalyzed Synthesis of Organosulfur Compounds using Sulfur

Language：Others  

Rhodium-catalyzed synthesis of unsymmetric di(heteroaryl) compounds via heteroaryl exchange reactions

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

Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex

Language：Others  

Rhodium-Catalyzed Synthesis of Dialkyl(Heteroaryl)Phosphine Sulfides by Phosphinylation of Heteroaryl Sulfides

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

Catalytic method for the synthesis of C-N-linked BI(HETEROARYL)S using heteroaryl ethers and N -Benzoyl heteroarenes
C-N-linked bi(heteroaryl)s are synthesized by a rhodium-catalyzed N-heteroarylation reaction of N-benzoyl heteroarenes including azoles/azolones, pyridones, cyclic ureas, and cyclic imides using heteroaryl aryl ethers. The reaction involves the covalent bond-exchange reaction of N-CO and HetAr-O bonds without using metal bases and exhibits a broad applicability, giving diverse C-N-linked bi(heteroaryl)s containing five- and six-membered heteroarenes. The N-heteroarylation of N-H azoles/azolones and pyridone proceeds at higher reaction temperatures.

DOI： 10.1021/acs.orglett.8b00245

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

Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP)5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP)5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.

DOI： 10.1021/acs.orglett.7b03825

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

Synthesis of Unsymmetric HetAr-X-HetAr' Compounds by Rhodium-Catalyzed Heteroaryl Exchange Reactions
Unsymmetric HetAr-X-HetAr' compounds have flexible and chiral structures, and are expected to exhibit various biological activities by interacting with proteins and nucleic acids. Unsymmetric HetAr-X-HetAr' compounds were efficiently synthesized by rhodium-catalyzed heteroaryl exchange reactions, which involved equilibrium control by judicious design of organic heteroaryl reagents. By using this method, unsymmetric HetAr-O-HetAr', HetAr-S-HetAr', and HetAr-CH2-HetAr' compounds as well as HetAr-F compounds were obtained from heteroaryl aryl ethers and various heteroaryl reagents. The rhodium-catalyzed synthesis has a broad applicability, which gives novel unsymmetric HetAr-X-HetAr' compounds containing five- and six-membered heteroarenes.

DOI： 10.3987/REV-17-869

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

Rhodium-Catalyzed Synthesis of Unsymmetric Di(heteroaryl) Ethers Using Heteroaryl Exchange Reaction
Unsymmetric di(heteroaryl) ethers were synthesized by the rhodium-catalyzed heteroaryl exchange reaction of heteroaryl aryl ethers and heteroaryl esters at equilibrium. Diverse unsymmetric di(heteroaryl) ethers containing five-and six-membered heteroarenes were obtained. Di(heteroaryl) ethers can be synthesized starting from diaryl ethers, because heteroaryl aryl ethers are obtained by the heteroaryl exchange reaction of diaryl ethers.

DOI： 10.1055/s-0036-1588801

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

Chemical braking exhibited by ethynylhelicene (M)-nonamer in solution: Competitive reaction system of self-catalysis to form double-helix and approach towards equilibrium to form random-coil
Chemical braking occurs in a dilute solution during a structural change of ethynylhelicene (M)-nonamer from the metastable double-helix state to the random-coil state, being at equilibrium, where the reaction is initially rapid and then substantially retard. The chemical braking is derived from the competitive chemical reaction system in dilute solution: An energetically uphill self-catalytic reaction to form double-helix and the downhill reaction to form the random-coil. (C) 2017 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2017.03.083

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

Rhodium-Catalyzed Synthesis of Unsymmetric Di(heteroaryl) Sulfides Using Heteroaryl Ethers and S-Heteroaryl Thioesters via Heteroarylthio Exchange
Unsymmetric di(heteroaryl) sulfides were synthesized by a rhodium-catalyzed heteroarylthio exchange reaction of heteroaryl aryl ethers and S-(heteroaryl) thioesters. The reaction has broad applicability, giving diverse unsymmetric di(heteroaryl) sulfides containing five- and six-membered heteroarenes. No base is required in this reaction, which has been developed by the judicious design of organic substrates.

DOI： 10.1021/acs.joc.6b02585

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

Rhodium-catalyzed P-P bond exchange reaction of diphosphine disulfides
A rhodium-catalyzed exchange reaction of diphosphine disulfides, a diphosphine oxide, and a diphosphine is developed. Various symmetric diphosphine disulfides containing alkyl and phenyl groups are exchanged, giving equilibrium mixtures, from which unsymmetric diphosphine disulfides are readily separated by silica gel chromatography. The resulting unsymmetric diphosphine disulfide is regio-selectively added to an aldehyde.

DOI： 10.1039/c6cc07302f

Language：English  

Chemical reactions involving noncovalent bond formation are discussed with regard to the equilibrium and nonequilibrium states: An equilibrium-to-equilibirum chemical reaction involves change of equilibrium states by changing the environment; a nonequilibrium-to-equilibrium reaction involves change of metastable state to equilibrium. Complex nature of the chemical reactions, especially in the latter, is shown in terms of the multiple-path nature in the microscopic molecular structure changes and macroscopic concentration changes. Irreversible and reversible nonequilibrium-to-equilibrium chemical reactions are also compared in terms of the multiple-path. Helicene oligomers, which reversibly form double-helix and random-coil by temperature changes, are discussed with regard to the reversible nonequilibrium-to-equilibrium chemical reaction with self-catalysis, where notable chemical phenomena appear under nonequilibrium conditions.

DOI： 10.1246/bcsj.20160133

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

Synthesis of Symmetrical and Unsymmetrical 1,4-Dithiins by Rhodium-Catalyzed Sulfur Addition Reaction to Alkynes
A convenient synthetic method for 1,4-dithiins was developed using sulfur and alkynes. A rhodium complex catalyzes the addition reaction of sulfur with cyclic alkynes giving the corresponding symmetrical 1,4-dithiines under reflux conditions in 2-butanone. Unsymmetrical 1,4-dithiins are synthesized by the reaction of sulfur with dialkyl acetylenedicarboxylates in the presence of cyclic alkynes or vinyl ethers.

DOI： 10.1055/s-0035-1561452

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

Rhodium-Catalyzed Transformation of Heteroaryl Aryl Ethers to Heteroaryl Fluorides
A rhodium complex catalyzed the conversion of the C-O bond of heteroaryl aryl ethers to the C-F bond. The reaction of (4-chloro-phenylthio)pentafluorobenzene with heteroaryl aryl ethers provided heteroaryl fluorides and heteroaryl (4-chlorophenylthio)tetrafluorophenyl ethers; this involved the cleavage of a single heteroaryl C-O bond under equilibrium conditions. The reaction of heteroaryl aryl ethers with 2-fluorobenzothiazole in which two heteroaryl and aryl C-O bonds were cleaved provided heteroaryl fluorides and aryl fluorides. The reactions were applicable to five-membered and six-membered heteroaryl aryl ethers and also to diaryl ethers possessing one or two electron-withdrawing groups.

DOI： 10.1039/c6cc05400e

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

A palladium complex derived from Pd-2(dba)(3) and tris(2,4,6-trimethoxyphenyl)phosphine catalyzes the addition reaction of thioesters to norbornenes, giving trans-2-acyl -3-organothionorbornanes. The transadducts are predominantly obtained with the acyl group at the endo-position and the organothio group at the exo-position. Aroyl and heteroaroyl thioesters as well as alkanoyl thioesters were reacted, including S-(4-tolyl) phenylthioglyoxylate and methyl 2-(4-tolylthio)-2-oxo-acetate. (C) 2015 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2015.05.042

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

Chiral silica (P)-nanoparticles grafted with (P)-helicene recognize the molecular structure of a chiral diol disulfide in the presence of monool disulfide and dibutyl disulfide. The (P)-nanoparticles selectively adsorb the diol disulfide, aggregate, and precipitate from solution. Under rhodium-catalyzed equilibrium among three disulfides, the diol disulfide is removed from solution by precipitation, which induces an equilibrium shift in the solution. By conducting the precipitation experiment twice, we obtained the dial disulfide in 37&#37; yield from a statistical 1:2:1 equilibrium mixture of three disulfides. The method is applied to a racemic monool disulfide, and an optically active dial disulfide is obtained via kinetic resolution and equilibrium shift. (C) 2015 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2015.05.106

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

Synthesis of thiiranes by rhodium-catalyzed sulfur addition reaction to reactive alkenes
A rhodium complex derived from RhH(PPh3)(4), dppe, and 4-ethynyltoluene catalyzes the addition reaction of sulfur to norbornenes giving the corresponding thiiranes under acetone reflux conditions. The rhodium complex effectively transfers a sulfur atom to the double bond from sulfur, and exo-adducts are obtained. The reaction is also applicable to (E)-cyclooctene and cyclic allenes. The ring-opening reaction of the thiiranes with lithium aluminium hydride gives the corresponding thiols.

DOI： 10.1039/c5cc01570g

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

RhH(PPh3)(4) and 1,3-bis(dicyclohexyl)phosphinopropane (dcypp) catalyze the 2-methylthiolation of oxazoles and thiazoles using 2-(methylthio)thiazole as a thiolating reagent. The methylthio transfer reaction is under equilibrium, and various 2-methylthiolated thiazoles and oxazoles were obtained in moderate to good yields by removing thiazole under refluxing o-dichlorobenzene.

DOI： 10.3987/COM-14-S(K)59

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

A palladium-catalyzed addition reaction of aroyl/heteroaroyl acid anhydrides to norbornenes
A palladium complex derived from Pd-2(dba)(3) and dppp catalyzes the addition reaction of aroyl/heteroaroyl acid anhydrides to norbornenes, giving 2-aroyl/heteroaroyl-3-aroyloxy/heteroaroyloxy-bicyclo[2,2,1]-heptanes. The C-O bond of acid anhydride is cleaved, and the aroyl/heteroaroyl and aroyloxy/heteroaroyloxy groups are added to alkenes. trans-Adducts are selectively obtained with the endo-benzoyl group and exo-benzoyloxy group.

DOI： 10.1039/c4cc07759h

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

A catalyst changes the course of a reaction without affecting the relative thermodynamic stability of substrates and products, and a catalytic reaction must be exergonic in order to obtain high yields of the product and to attain reasonable reaction rates. In the case that the desired reaction is in equilibrium or is endergonic, devices for making products thermodynamically more stable than substrates are needed. In this review, the transition-metal-catalyzed synthesis of organosulfides using a substitution reaction is summarized, where metal inorganic and organic co-substrate/co-product methods are used in developing exergonic reactions. (C) 2014 Published by Elsevier Ltd.

DOI： 10.1016/j.tetlet.2014.04.081

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

RhH(PPh3)4 and 1,2-bis(diphenylphosphino)benzene (dppBz) catalyze the aryl exchange reaction of polyfluorinated diaryl sulfides. By employing these catalysts, unsymmetrical polyfluorinated diaryl sulfides are synthesized by the reaction of symmetrical polyfluorinated diaryl sulfides and substituted pentafluorobenzenes in the presence of triisopropylsilane. © 2013 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2013.06.021

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A complex of [RhH(PPh3)4] and 1,2-bis(diphenylphosphino)benzene (dppBz) catalyzes the syntheses and reactions of N-acylphthalimides. N-Acylphthalimides were synthesized by the imidation of thioesters or acid fluorides by N-(organothio)phthalimides. CN bond cleavage in N-acylphthalimides was also catalyzed by the same rhodium complex. Thioesters and N-(phosphinoyl)phthalimides were obtained from reactions with phosphinothioates
acid fluorides and N-(tetrafluoroaryl)phthalimides were obtained from reactions with substituted pentafluorobenzenes. © 2013 WILEY-VCH Verlag GmbH &amp
Co. KGaA, Weinheim.

DOI： 10.1002/ajoc.201300094

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

RhH(PPh3)4 and 1,2-bis(diphenylphosphino)benzene (dppBz) catalyzed the oxidative coupling reaction of aryl benzyl ketones giving 2,3-diaryl-1,4-diketones in high yields. 3,3-Dimethyl-1-methylthio-2-butanone was used as the oxidizing reagent, which was converted to 3,3-dimethyl-2- butanone and dimethyl disulfide. Rhodium enolates were catalytically formed from ketones, which underwent oxidative coupling using an organosulfur reagent. © 2013 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2012.12.107

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In the presence of catalytic amounts of RhH(PPh3)(4) and 1,2-bis(diphenylphosphino)ethane (dppe), ketones reacted with o-difluorobenzenes giving benzofurans in high yields. The alpha-arylation of ketones and furan cyclization proceeded without using a base. Benzofuran cyclization was applied to substituted pentafluorobenzenes to give 6-substituted-4,5,7-trifluorobenzofuranes.

DOI： 10.3987/COM-12-S(N)57

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

Substituted pentafluorobenzenes react with sulfur to give bis(4-substituted 2,3,5,6-tetrafluorophenyl) sulfides in the presence of RhH(PPh3)(4), 1,2-bis(diphenylphosphino)benzene (dppBz), and tributylsilane. The reaction proceeds efficiently between room temperature and 80 degrees C. A comparative study of the reactivities of an organic trisulfide and a tetrasulfide showed notable substrate specificity. Di-tert-butyl tetrasulfide reacted with reactive aryl monofluorides and substituted pentafluorobenzenes. Di-tert-butyl trisulfide reacted with aryl monofluorides. The reactivity was explained on the basis of the difference in S-S bond energy.

DOI： 10.1021/ol302497m

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

In the presence of catalytic amounts of RhH(PPh3)(4) and 1,2-bis(diphenylphosphino)ethane (dppe), 1-nitroalkanes reacted with a diaryl disulfide giving 1-arylthio-1-nitroalkanes in air. The equilibrium to form thermodynamically disfavored products was shifted by the rhodium-catalyzed oxidation of thiols to disulfides and water. The thiolation reaction of cyclic nitroalkanes proceeded in high yields provided that suitable diaryl disulfides were employed depending on the substrate: di(p-chlorophenyl) disulfide was used for the thiolation reaction of 1-nitroalkanes, 1-nitrocyclopentane and 1-nitrocycloheptane with acidic alpha-protons (pK(a) 16 and 17); di(p-methoxyphenyl) disulfide for 1-nitrocyclobutane and 1-nitrocyclohexane with less acidic alpha-protons (pK(a) ca. 18). Related reactivities were observed in the thiolation reactions of malonate and 1,2-diphenylethanone. (C) 2012 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2012.07.132

Language：Japanese  

A catalyst is a substance that changes the course of reactions without affecting the relative stability of substrates and products. The development of an efficient catalyst, which decreases the activation energy of a reaction, results in equilibrium when the relative thermodynamic stabilities of the substrates and products are close. I found that a transition-metal complex could be used as a catalyst in the synthesis and transformation of organosulfur and organophosphorus compounds, and a variety of rhodium-catalyzed reactions involving cleavage of heteroatom bonds such as C-H, C-S, C-F, S-S, P-P bonds were developed. Such single bond metathesis reactions are often under equilibrium. The control of such equilibrium to provide the desired products with high efficiency has recently become a subject of interest. I developed an equilibrium control method using co-substrates. I also developed another method, that uses thermodynamically intermediate compounds to shift equilibrium. This method using a combination of transition-metal catalysis and equilibrium control can be generally used for the synthesis of organoheteroatom compounds.

DOI： 10.5059/yukigoseikyokaishi.70.809

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

In the presence of catalytic amounts of RhH(CO)(PPh3)(3) and 1,2-bis(diphenylphosphino)benzene (dppBz), acyl groups were transferred between benzyl ketones and thioesters/aryl esters. The rhodium complex catalyzed the cleavage of ketone CO-C bonds and intermolecular rearrangement giving unsymmetric ketones. The acyl-transfer reaction also occurred with 1-(p-chloropheny1)-3-(p-cyanophenyl)propane-2-one giving unsymmetric ketones.

DOI： 10.1021/ol3017148

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

A rhodium complex catalyzed the reaction of aryl methyl ethers and thioesters giving the corresponding aryl esters and methyl sulfides. S-(p-Chlorophenyl) p-(dimethylamino)benzothioate was used for the reaction of methyl aryl ethers with electron-withdrawing groups, and an S-(p-tolyl) derivative was used for those with electron-donating groups. Polymethoxybenzenes were converted to the esters in a regioselective manner.

DOI： 10.1021/ol2033724

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

Rhodium/phosphine complexes catalyze equilibrium acyl transfer reactions between acid fluorides, aryl esters, acylphosphine sulfides, and thioesters. The use of appropriate co-substrates to accept heteroatom groups shifted the equilibrium to desired products. Acylphosphine sulfides and aryl esters were converted to acid fluorides using benzoylpentafluorobenzene as the fluoride donor, and the fluorination reaction of thioesters employed (4-tolylthio)pentafluorobenzene. Acid fluorides were converted into acylphosphine sulfides and thioesters using diphosphine disulfides and disulfides/triphenylphosphine, respectively. Aryl esters were obtained from acid fluorides and phenols in the presence of triphenylsilane. Aryl esters, acylphosphine sulfides, and thioesters were also interconverted in the presence of rhodium complexes. These rhodium-catalyzed acyl transfer reactions proceeded under neutral conditions without using acid or base. The involvement of acyl rhodium intermediates in these reactions was suggested by the carbothiolation reaction of thioesters and alkynes. (C) 2011 Published by Elsevier Ltd.

DOI： 10.1016/j.tet.2011.07.031

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

In the presence of catalytic amounts of RhH(PPh3)(4), 1, 2-bis(diphenylphosphino)ethane (dppe), and dimethyl disulfide, cyclic and acyclic alpha-phenyl ketones reacted with p-cyano-alpha-methylthioacetophenone giving alpha-methylthio-alpha-phenylketones. The activated catalyst containing dimethyl disulfide was effective for the alpha-methylthiolation reaction of these less reactive substrates. (C) 2010 Wiley Periodicals, Inc. Heteroatom Chem 22:18-23, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20650

DOI： 10.1002/hc.20650

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

Chlorination of the corresponding ketones with phenylphosphonic dichloride (PhPOCl2) provided ethyl 6(4)-chloro-2-methyl-4(6)-phenyl-1,4(6)dihydropyrimidine-5-carboxylate in good yield. The cross-coupling reactions of organoboronic acids or triethylborane with 1-tert-butyl 5-ethyl 4-chloro-2-methyl-6-phenyl-1,6-dihydropyrimidine-1,5-dicarboxylate synthesized by regiospecific alkoxycarbonylation of the chlorinated dihydropyrimidine afforded 1,4(3,4)-dihydropyrimidines having a variety of functional groups at position-6(4) in good to excellent yields.

DOI： 10.3987/COM-11-12244

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

A rhodium-catalyzed method for the synthesis of organophosphorus compounds directly from organosulfur compounds was developed. In the presence of RhH(PPh3)(4) and depe, the reaction of 1-alkylthioalkynes with tetraethyldiphosphine disulfide gave 1-alkynylphosphine sulfides. The same complex catalyzed the reaction of thioesters giving acylphosphine sulfides. (C) 2011 Published by Elsevier Ltd.

DOI： 10.1016/j.tetlet.2011.02.112

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

In the presence of catalytic amounts of RhH(PPh3)(4) and 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-benzothiazoles, 1,3-benzoxazoles, and benzothiophene reacted with alpha-(phenylthio)isobutyrophenone giving 2-phenylthio derivatives. Reactive monocyclic heteroaromatics, 1-methyl-1,2,3,4-tetrazole and 2-cyanothiophene were also converted into the 5-phenylthio derivatives. The use of an appropriate phenylthio transfer reagent is crucial for the efficient catalyzed conversion of heteroaromatic C-H bonds into C-S bonds. (C) 2011 Published by Elsevier Ltd.

DOI： 10.1016/j.tetlet.2011.02.077

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

In the presence of catalytic amounts of RhH(PPh(3))(4), 1,2-bis(diphenylphosphino)ethane (dppe), and dimethyl disulfide, ketones without alpha-activating groups were alpha-methylthiolated with 1,2-diphenyl-2methylthio-1-ethanone giving alpha-methylthio ketones. The reaction of unsymmetrical ketones proceeded at the more substituted carbons. The initial formation of kinetic alpha-methylthiolated products followed by their rearrangement to thermodynamic products was observed in the reaction of alpha-phenyl ketones. Aldehydes, phenylacetate, and phenylacetonitrile were also alpha-methylthiolated under these conditions. (C) 2011 Published by Elsevier Ltd.

DOI： 10.1016/j.tet.2011.01.071

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

A rhodium complex derived from RhH(PPh(3))(4) and Me(2)PhP catalyzed the carbothiolation reaction of 1-alkylthio-1-alkynes and 1,4-diaryl-1,3-butadiynes giving (Z)-4-alkylthio-4-aryl-3-arylethynyl-3-buten-1-ynes. Terminal alkynes such as 1-decyne and (t-butylthio)acetylene underwent the carbothiolation reaction using a RhH(PPh(3))(4)-dppb catalyst. The reactions proceeded via cis-addition with C-C bond formation at the less hindered acetylene carbon. (C) 2011 Published by Elsevier Ltd.

DOI： 10.1016/j.tetlet.2010.12.065

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

A rhodium complex catalyzed the equilibrium acyl transfer reaction between acid fluorides and thioesters. In the presence of fluoride or thiolate acceptors, the reaction could be shifted to either product. RhH(PPh3)(4)-dppe catalyzed the reaction of acid fluorides and diorgano disulfides in the presence of triphenylphosphine giving thioesters, which was accompanied by triphenylphosphine difluoride. The same complex catalyzed the reaction of aryl thioesters and hexafluorobenzene giving acid fluorides, which was accompanied by 1,4-di(arylthio)-2,3,5,6-tetrafluorobenzenes. (C) 2010 Published by Elsevier Ltd.

DOI： 10.1016/j.tetlet.2010.09.009

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

Rhodium-Catalyzed Organothio Exchange Reaction of alpha-Organothioketones with Disulfides
RhH(PPh3)(4) and 1,2-bis(diphenylphosphino)ethane (dppe) catalyzed the organothio exchange reaction of alpha-organothioketones and organic disulfides. The reaction was affected by the structure of the substrate: alpha-phenylthio and alpha-alkylthio aryl ketones reacted effectively with diaryl and dialkyl disulfides; alpha-phenylthio dialkyl ketones reacted with diaryl disulfides but not with dialkyl disulfides; diaryl disulfides with electron-donating p-substituents were more reactive than those with electron-withdrawing p-substituents.

DOI： 10.1248/cpb.58.1349

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

Transition metal complexes catalyzed the dialkylphosphinothioation reaction of alcohols and phenols with tetraalkyldiphosphine disulfides in high yields. Phenols were reacted in the presence of RhH(PPh(3))(4) and 1,2-bis(dimethylphosphino)ethane under THF reflux, and alcohols with Pd(OAc)(2) and 1,2-bis(diphenylphosphino)benzene under chlorobenzene reflux. Primary alcohols reacted faster than secondary alcohols under these conditions, and protected tyrosine and serine were phosphinothioated with minimal racemization. Tetraphenyldiphosphine dioxide also underwent the P-O bond formation reaction. (C) 2010 Published by Elsevier Ltd.

DOI： 10.1016/j.tetlet.2010.07.040

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

A rhodium complex catalyzed the reaction of acid fluorides and tetraethyldiphosphine disulfide giving acylphosphine sulfides. Aromatic acid fluorides with electron donating p-groups reacted smoothly giving the products in high yields. Aliphatic acid fluorides with secondary and tertiary a-carbons were also converted to alkanoylphosphine sulfides, whereas the reaction of a substrate with an a-methylene carbon was accompanied by enol ester formation. (C) 2010 Published by Elsevier Ltd.

DOI： 10.1016/j.tetlet.2010.07.038

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

A rhodium complex Rh(2)(OAc)(4) catalyzed the reaction of nitrobenzenes and diphenylphosphine oxide HP(=O)Ph(2) giving o-(diphenylphosphinoyloxy)anilines predominantly, which were accompanied by small amounts of the p-isomers. Nitorobenzenes possessing a bulky o-substituent, particularly o-(t-butyl)nitrobenzenes, underwent the reaction in high yields. The reaction is considered to involve the reductive formation of O-phosphinoyl-N-arylhydroxyamines from nitrobenzenes, and o-phosphinoyloxylation by the rearrangement. (C) 2010 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2010.04.029

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

RhCl3 catalyzed the alkylthio exchange reaction of insulin and dithiodiglycolic acid in water under homogeneous conditions. Insulin was rapidly consumed, and mono- and bis-exchanged insulin were formed along with the disulfide exchanged A and B chain. The disulfide bond at the A7/B7 was initially exchanged, which was followed by the A6/A11 and A20/B19 disulfides.

DOI： 10.3987/COM-09-S(S)110

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

In the presence of RhH(PPh(3))(4) and 1,2-bis(diphenylphosplino)ethane, tetramethyldiphosphine disulfide and aldehydes were added producing [1-(dimethylthiophosphosphinoyloxy)alkyl]dimethylphosphine sulfides in high yields. Acetophenones with electron-withdrawing P-groups also yielded 1,2-adducts. (C) 2009 published by Elsevier Ltd.

DOI： 10.1016/j.tetlet.2009.03.135

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

Rhodium-Catalyzed Methylthio Transfer Reaction between Ketone α-Positions: Reversible Single-Bond Metathesis of C-S and C-H Bonds
In the presence of a catalytic amount of RhH(PPh(3))(4) and 1,2-bis(diphenylposphino)ethane (dppe), alpha-phenylthio ketones were methylthiolated with p-cyano-alpha-methylthioacetophenone giving alpha-phenylthio-alpha-methylthioketones. The methylthio transfer reaction between the ketone alpha-positions was reversible and at equilibrium, and the methylthio group was transferred in preference to the phenylthio group. The reaction of tertiary alkyl methylthiomethyl ketones proceeded in high yields; the reaction of diastereomeric 4-(tert-butyl)-2-phenylthiocyclohexanones gave an axial 2-methylthiolated product.

DOI： 10.1021/ol802619e

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

In the presence of RhH(PPh(3))(4), the reaction of 1,2-alkadienes, tetramethyldiphosphine disulfide, and camphorsulfonic acid gave (E)-2-dimethylthiophosphinoyl-2-alkenes. The reaction involved the P-P cleavage and the transfer of the thiophosphinoyl group to 1,2-alkadienes with concomitant formation of thiophosphinic anhydride. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.10.075

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

In the presence of a catalytic amount of RhH(PPh(3))(4) and 1,2-bis (diphenylphosphino)benzene, an aromatic fluoride, an organic disulfide (0.5 equiv), and triphenylphosphine (0.5 equiv) reacted in refluxing chlorobenzene to give an aryl sulfide in high yield. Since triphenylphosphine trapped fluoride atoms forming phosphine difluoride, both organothio groups of the disulfide reacted effectively, and the fluoride substituent reacted more readily than the chloride and bromide. The reaction of hexafluorobenzene and a diaryl disulfide gave 1,4-diarylthio-2,3,5,6-tetrafluorobenzene, 1,2,4,5-tetraarylthio-3,6-difluorobenzene, and hexaarylthiobenzene in a stepwise manner; pentafluorobenzene gave 1-arthio-2,3,5,6-tetrafluorobenzene; 1,2,3,4-tetrafluorobenzene gave 1,2-diarylthio-3,6-difluorobenzene; and 1,2,4,5-tetrafluorobenzene gave 1,4-diarylthio-2-5-difluorobenzene. The polyarylthiolation reaction of polyfluorobenzenes exhibited a strong tendency to form 1,4-difiuorobenzenes.

DOI： 10.1021/ja8049996

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

Rhodium complexes are efficient catalysts for the synthesis of organosulfur compounds. They catalyze the addition reaction of organosulfur groups to unsaturated compounds, the substitution of C-H with organosulfur groups, and single-bond metathesis reactions. They cleave S-S bonds and transfer the organosulfur groups to various organic and inorganic molecules, including alkynes, allenes, disulfides, sulfur, isonitriles, imines, diphosphines, thiophosphinites, hydrogen, 1-alkylthio-1-alkynes, thioesters, and allyl sulfides.

DOI： 10.1351/pac200880050993

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

The Wilkinson complex RhCl(PPh(3))(3) catalyzes equilibrating alkylthio exchange reaction of thioesters with disulfides. The treatment of a thioester and a dialkyl disulfide in refluxing diethyl ketone in the presence of RhCl(PPh(3))(3) (2.5 mol &#37;) for 1.5 h gave an alkylthio exchanged thioester. The reaction of S-methyl ester was conducted shifting the equilibrium by removing volatile dimethyl disulfide. (c) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.01.109

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

A rhodium complex catalyzes two types of single bond metathesis reactions of two CS bonds depending on the added ligand: CS/CS to CS/CS metathesis and CS/CS to CC/SS metathesis. In the presence of a catalytic amount of RhH(PPh(3))(4) and 1,1 '-bis(diphenylphosphino)ferrocene (dppf), two 1-alkylthioalkynes exchange alkylthio groups to give equilibrium mixtures of four 1-alkylthioalkynes. When tris(p-methoxyphenyl)phosphine or diphenylmethylphosphine is used, 1,3-butadiynes are obtained. (c) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.01.040

Language：Others  

Transition-Metal-Catalyzed Synthesis of Organophosphorous and Organosulfur Compounds

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

A rhodium complex RhH(PPh3)(4) catalyzes the C-P bond forming reaction of 1-alkynes and tetrapbenylbiphosphine in the presence of 2,4-dimethylnitro benzene giving 1-alkynylphosphines and its oxides. (c) 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2006.04.158

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

RhCl3 catalyzed the alkylthio exchange reaction of hydrophilic disulfides in water under homogeneous conditions, and equilibrium was attained in several hours. The reaction was applied to the exchange Of unprotected glutathione disulfide. The reaction of dimethyl disulfide and hydrophilic distilfides under heterogeneous conditions also proceeded effectively. The mechanism turned out to be dependent on the water solubility of the substrates: The reaction of bis(3-hydroxypropyl) disulfide took place in the dimethyl disulfide phase, whereas the reaction of bis(6-aminohexyl) disulfide dihydrochloride proceeded in the water phase. (c) 2005 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jorganchem.2005.11.049

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

DOI： 10.1021/ja055775s

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

DOI： 10.1021/ja0527121

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

RhH(PPh3)(4) catalyzes reduction of disulfides to thiols by hydrogen and RhH(PPh3)(4)/1,4-bis(diphenylphosphino)butane (dppb) catalyzes oxidation of thiols to disulfides by oxygen. (c) 2005 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2005.06.169

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

Alkyl and aryl dithiophosphinates were synthesized by the reaction of disulfides with biphosphine disulfides in the presence of RhH(PPh3)(4) and 1,2-diphenylphosphinoethane (dppe). The catalyst also promoted synthesis of thiophosphinates and selenothiophosphinates from disulfides and diselenides. (c) 2005 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2005.06.109

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

RhH(PPh3)(4) and cis-1,2-bis(diphenylphosphino)ethylene (dppv) catalyze the exchange of sulfur atoms between sulfur and organic polysulfides. The exchange of dialkyl trisuffides with sulfur proceeds at a high efficiency within 5 min at room temperature yielding a mixture of organic polysulfides. (c) 2005 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2005.05.024

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

Rhodium complexes RhH(PPh3)(4) and Rh(acac)(CH2=CH2)(2) catalyze sulfuration of isonitrile with sulfur giving isothiocyanates in high yields. The metal-catalyzed reaction is rapid in refluxing acetone, and completes within 3 h in most cases. The reaction exhibits induction period, which disappeared by preheating sulfur in refluxing acetone for 1.5 h. Use of several organic polysulfides in this transformation was examined in order to compare the reactivity. (C) 2005 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2005.01.069

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

GaCl3 catalyzes alpha-ethynylation reaction of silyl enol ethers with triethylsilylated chloroethyne at 130 degreesC. (C) 2003 Elsevier B.V. All rights reserved.

DOI： 10.1016/S0022-328X(03)00456-X

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

Rhodium complex RhH(PPh3)(4) and 1,1'-bis(diphenylphosphino)ferrocene catalyze the regio- and stereoselective additions of diaryl disulfides and diaryl diselenides to 1-alkynes giving (Z)-1-arylseleno-2-arylthio-1-alkenes. The catalyst promotes the addition reaction of dibutyl disulfide and dibutyl diselenide to 1-octyne with a similar selectivity giving (Z)-1-butylseleno-2-butylthio-1-octene but with a lower catalytic activity. The same product is obtained with a higher yield, when excess dibutyl disulfide is used against dibutyl diselenide in the presence of RhH(PPh3)(4) and 1,4-diphenylphosphinobutane.

DOI： 10.1021/jo034990t

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

DOI： 10.1021/ja035221u

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

Reaction of dialkyl disulfides or diselenides with allenes is catalyzed by a rhodium-phosphine complex and trifluoromethanesulfonic acid giving (E)-2-alkylthio(seleno)-1,3-dienes and (E)-2-alkylthio(seleno)-2-alkenes. Unlike the reaction of alkynes, the reaction of allene is accompanied by hydride transfer.

DOI： 10.1002/adsc.200303010

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

In the presence of GaCl3, silyl enol ethers are sequentially ethynylated at the a-carbon atom with chlorotrimethylsilyl-ethyne giving (alpha-enynylated, (alpha-endiynylated and alpha-entriynylated ketones.

DOI： 10.1246/cl.2003.298

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

DOI： 10.1021/ja026108r

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

In the presence of GaCl3, silyl enol ethers are ethynylated at the alpha-carbon atom with chlorotrimethylsilylethyne. This reaction can provide alpha-ethynylated aryl ketones possessing acidic alpha-protons without isomerization to conjugated allenyl ketones.

DOI： 10.1021/ol026050l

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

Rhodium-catalyzed addition of triphenylphosphine and trifluoromethanesulfonic acid to (E)-1,3-dienes gives (E)-3alkenylphosphonium salts in the anti-Markovnikov mode. The addition reactions to (E)-1,3-dienes proceed more rapidly than those to (Z)-1,3-dienes, which can be utilized to separate pure (Z)1,3-dienes from isomeric mixtures.

DOI： 10.1246/cl.2002.272

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

Silyl enol ethers derived from substituted cyclohexanones are ethenylated with trimethylsilylethyne in the presence of GaCl3. Carbon-carbon bond formation was completed in less than 5 min at room temperature and protodegallation of the organogallium intermediate formed with 6 M sulfuric acid gave beta-enones. The reactions exhibit a bias for the equatorial C-C bond formation, which contrasts the axial stereochemistry of enolate alkylation. The origin of this stereoselectivity is discussed.

DOI： 10.1055/s-2002-19298

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

In the presence of GaCl3, silyl enol ethers derived from either S-alkyl or S-aryl thioesters are ethenylated at the alpha -carbon atom with trimethylsilylethyne in high yields. The reactions of dienolates give alpha,alpha -diethenyl thioesters.

DOI： 10.1246/cl.2001.1080

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

[GRAPHICS]
Addition of dialkyl disulfides to terminal alkynes is catalyzed by a rhodium-phosphine complex and trifluoromethanesulfonic acid giving (Z)-bis(alkylthio)olefins stereoselectively.

DOI： 10.1021/ol015521l

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

[GRAPHICS]
In the presence of GaCl3, silyl enol ethers derived from alpha -substituted beta -ketoesters or malonates are ethenylated at the alpha -carbon atom with trimethylsilylethyne in high yields. Ethenylmalonates can also be synthesized by this method.

DOI： 10.1021/ol015583b

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

[GRAPHICS]
Beckmann rearrangement of oxime is catalyzed by [RhCl(cod)](2), trifluoromethanesulfonic acid, and tris(p-tolyl)phosphine in refluxing dichloroethane, giving the corresponding amide in good yield. Product/acid ratios of 10:20 can be attained in the reaction of benzophenone oximes.

DOI： 10.1021/ol006951z

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

Language：Others  

GaCl3-promoted addition reactions of carbon nucleophiles to alkyne

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

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

Treatment of lithium phenoxide with silylethyne in the presence of GaCl3 gives o-(beta-silylethenyl)phenol in a high yield. The reaction involves carbogallation of phenoxygallium with silylethyne. The reaction of 2,6-disubstituted phenol with one of the substituents being t-butyl group gives ipso-substitution product. Organometallic compounds of gallium and tin, elements which sit diagonally in the periodic table, behave similarly in the carbometallation reaction. (C) 1999 Elsevier Science S.A. All rights reserved.

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

Language：Others  

Novel Aromatic Vinylation Reactions

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

Synthesis of β,β-bis(trimethylstannyl)styrenes by organometal trapping of intermediates in the aromatic vinylation reactions
beta,beta-Bis(trimethylstannyl)styrenes were synthesized by organo-metal trapping of beta,beta-bis(trichlorostannyl)styrenes, which were formed by the reaction of ethyne with phenols or anilines in the presence of SnCl4-Bu3N reagent.

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

Cross-conjugated trienes were synthesized by dimerization of monosubstituted allenes in the presence of a catalyst system consisted of Pd-2(dba)(3), p-nitrophenol, and P(p-Tol)(3).

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

Phenols were vinylated at the ortho-position with ethyne in the presence of SnCl4-Bu3N reagent. The reaction was applicable to phenols possessing either electron-donating or electron-withdrawing groups. 2,6-Divinylphenols were synthesized under modified conditions. A reaction mechanism involving carbostannylation of alkynyltin and phenoxytin was discussed.

DOI： 10.1021/jo980785f

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

N-Alkylanilines and anilines are vinylated at the ortho-position with ethyne in the presence of SnCl4-Bu3N.

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2,6-Divinylation of Phenols with Ethyne

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Rh-Catalyzed Synthesis of Unsymmetric Bicyclic Linked Compounds and Biological Activity

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環境ストレス応答のための生体親和性分子の創生

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触媒的複素環交換反応による多様な非対称複素環化合物の合成と生物活性

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AI技術を活用したバイオスティミュラント候補物質の開発

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生体親和性分子が担う環境ストレス応答医農薬品の創生

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キナバクチンをリード化合物とした抗ABA活性物質の探索

Event date： 2022.9

Language：Japanese  

Country：Other  

無保護ペプチドジスルフィド S-S結合へのロジウム触媒的イオウ挿入反応

Event date： 2022.9

Language：Japanese  

Country：Other  

ヘキサフェニルシクロヘキサアルシンを利用する新規環状アザアルシン誘導体のロジウム触媒合成

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

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Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

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Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

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Event date： 2022.9

Language：Japanese  

Country：Other  

ロジウム触媒を用いる水中均一系ペプチドジスルフィド生成と化学修飾法の開発

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

オンライン

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Event date： 2022.7

Language：Others  

Country：Other  

ロジウム触媒による無保護ペプチドジスルフィドへのアリール基挿入反応

Event date： 2022.7

Language：Others  

Country：Other  

無保護ペプチドジチオールのロジウム触媒的メチレン架橋環化反応の開発

Event date： 2022.7

Language：Others  

Country：Other  

有機ヘテロ元素化合物の遷移金属触媒合成と生物活性

Event date： 2022.7

Language：Others  

Country：Other  

多様な新規環状アザアルシン化合物群のロジウム触媒合成

Event date： 2022.7

Presentation type：Poster presentation  

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Event date： 2022.7

Presentation type：Poster presentation  

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Event date： 2022.7

Presentation type：Oral presentation (invited, special)  

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Event date： 2022.7

Presentation type：Poster presentation  

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Event date： 2022.6

Language：Others  

Country：Other  

Development of novel synthetic organoheteroatom compounds for environmentoal stress response:pharmaceuticals ＆ Biostimulants

Event date： 2022.6

Presentation type：Oral presentation (invited, special)  

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Event date： 2022.6

Language：Others  

Country：Other  

Rhodium-Catalyzed Aryl Insertion Into Unprotected Peptide Disulfides

Event date： 2022.6

Presentation type：Poster presentation  

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Event date： 2022.3

Language：Others  

Country：Other  

Rhodium-Catalyzed synthesis of cyclic azaarsenic derivatives using hexaphenylhexarsane

Event date： 2022.3

Language：Others  

Country：Other  

Rhodium-Catalyzed Oxidation of Unprotected Peptide Thiols to Disulfides with Oxygen in Water

Event date： 2022.3

Language：Others  

Country：Other  

Rhodium-Catalyzed Aryl Insertion Into Unprotected Peptide Disulfides

Event date： 2022.3

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Event date： 2022.3

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Event date： 2022.3

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Event date： 2022.3

Language：Others  

Country：Other  

Event date： 2022.3

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Event date： 2022.2

Language：Others  

Country：Other  

Event date： 2022.2

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Event date： 2021.11

Language：Others  

Country：Other  

Event date： 2021.11

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Event date： 2021.10 - 2021.11

Language：Others  

Country：Other  

Development of novel synthetic organoheteroatom compounds for environmentoal stress response:pharmaceuticals ＆ Biostimulants

Language：Japanese  

Country：Japan  

Ortho-divinylation reaction of phenols with acetylene.

Language：Japanese  

Country：Japan  

2,6 - di- vinylation reaction of phenol using acetylene.

Language：Japanese  

Country：Japan  

Ortho-vinylation reaction of anilines with acetylene.

Language：English  

Country：Japan  

Phenols are 2,6-divinylated by treatment with ethyne at 100 degrees C in chlorobenzene in the presence of SnCl4-Bu3N, the divinylation occurring predominantly to exclusively with phenol, alkylphenols and alkoxyphenols; an appropriate amount of the tin reagent and the correct reaction temperature are essential for the divinylation.

Language：Japanese  

Country：Japan  

Cross-coupling reaction of silylacetylene and silylenolether using gallium chloride.

Language：Japanese  

Country：Japan  

Formation of (.BETA.-stannylvinyl)phenol in the phenol vinylation reaction.

Language：Japanese  

Country：Japan  

Dimerization reaction of allenes promoted by palladium-phenol catalyst.

Language：Japanese  

Country：Japan  

.ALPHA.-Vinylation Reaction of Silyl enol ether.

Language：Japanese  

Country：Japan  

New reactions to combine benzene ring to vynyl group and the periphery.

Language：Japanese  

Country：Japan  

遷移金属触媒を用いたアセチレンへの三級ホスフィンの付加反応

Language：Japanese  

Country：Japan  

触媒量のSnCl₄を用いたフェノールビニル化反応

Language：Japanese  

Country：Japan  

チオエステルシリルエノラートのビニル化反応

Language：English  

Country：Japan  

GaCl3 promotes addition reactions of carbon nucleophiles to a C-C triple bond. Interaction of alkyne with GaCl3 generates a highly reactive electrophile, which aromatic hydrocarbon attacks to give an alkenylated arene. Silylethyne reacts predominantly at the p-position of toluene, while disilylated 1,3-butadiyne exhibits o-selectivity. The behavior of a silylated 1,2-propadiene is intermediate between that of the silylethyne and the disilylated 1,3-butadiyne. In the presence of GaCl3, electrophilic trimerization of silylethyne takes place to give a conjugated hexatriene. In this reaction, silylethyne attacks the GaCl3-activated C-C triple bond. Carbometalation is another interesting addition reaction of an organogallium compound to alkyne. Alkynyldichlorogallium dimerizes in hydrocarbon solvents to give 1,1-dimetallo-1-buten-3-yne. In the presence of GaCl3, silyl enol ether is ethenylated at the alpha -carbon atom with trimethylsilylethyne. Treatment of lithium phenoxide with silylethyne in the presence of GaCl3 gives o-(beta -silylethenyl) phenol. These reactions involve carbogallation of alkynylgallium, gallium enolate, or gallium phenoxide.

Language：Japanese  

Country：Japan  

Novel Reactions of Heteroatom Compounds Using Transition Metal-Sulfonic Acid Catalysts.

Language：Japanese  

Country：Japan  

塩化ガリウムを用いる1,3‐ジカルボニル化合物のビニル化反応

Language：Japanese  

Country：Japan  

ガリウムエノラートの一段階エチニル化反応

Language：Japanese  

Country：Japan  

One-step synthesis of .ALPHA.-ethynyl ketones possessing acidic .ALPHA.-protons.

Language：Japanese  

Country：Japan  

Aromatic Bromination-Rearrangement of Polymethylbenzenes Using GaCl3 Catalyst.

Language：Japanese  

Country：Japan  

One-pot .ALPHA.-Enynylation Reaction of Silyl Enol Ether with Silylethyne Promoted by GaCl3.

Language：Japanese  

Country：Japan  

GaCl3-Promoted Ethenylation of Ester Silyl Enolates with Silylethyne.

Language：Japanese  

Country：Japan  

ロジウム触媒を用いた三級ホスフィンの共役ジエンへの付加反応/(Z)‐1,3‐ジエンの精製法

Language：Japanese  

Country：Japan  

スルホン酸‐ロジウム触媒を用いたアレンへのジスルフィドの付加反応

Language：Japanese  

Country：Japan  

Addition Reaction of Dialkyl Diselenides to Allenes Catalyzed by a Rhodium Complex and Trifluoromethanesulfonic Acid.

Language：Japanese  

Country：Japan  

Transition metal catalyzed addition reaction of tertiary phosphine to alkenes

Language：Japanese  

Country：Japan  

GaCl3 Using.alfa.-Ethenylation Reaction of Ketone

Language：Japanese  

Country：Japan  

Ethynylation reaction of alkylmalonates

Language：Japanese  

Country：Japan  

GaCl3-Catalyzes .ALPHA.-Ethynylation Reaction of Silyl Enol Ether

Language：Japanese  

Country：Japan  

塩化ガリウムを用いるシリルエノールエーテルの一段階エンポリイン化反応

Language：Japanese  

Country：Japan  

Rhodium catalyzed regio- and stereoselective thioselenation of alkynes

Language：Japanese  

Country：Japan  

Addition Reaction of Dialkyl Disulfide to Silylacetylene Catalyzed by Rhodium Complex giving Trialkylthioethylene

Language：Japanese  

Country：Japan  

Rhodium Catalyzed Disulfide Exchange Reaction

Language：Japanese  

Country：Japan  

Addition Reaction of Dialkyl Disulfides to Allenes Catalyzed by a Rhodium Complex and Trifluoromethanesulfonic Acid

Language：Japanese  

Country：Japan  

塩化ガリウムを用いたエノラートの一段階エチニル化反応

Language：Japanese  

Country：Japan  

遷移金属触媒を用いるジスルフィド交換反応

Language：Japanese  

Country：Japan  

遷移金属触媒を用いた3級ホスフィンの1‐アルケンへの付加反応

Language：Japanese  

Country：Japan  

Rhodium Catalyzed Disulfide Exchange Reaction in Water

Language：Japanese  

Country：Japan  

Rhodium Catalyzed Thioester Exchange Reaction with Disulfide

Language：Japanese  

Country：Japan  

Rhodium catalyzed aerobic oxidation of thiol to disulfide

Language：Japanese  

Country：Japan  

Rhodium Catalyzed Disulfide-Trisulfide Exchange Reaction

Language：Japanese  

Country：Japan  

Syntheses and Structures of Stable Carbenes and Organometallic Complex Catalysts.

Language：Japanese  

Country：Japan  

Synthesis of Alkynylsulfides via Rhodium Catalyzed C-H activation of 1-Alkynes

Language：Japanese  

Country：Japan  

RhCl3-Catalyzed Disulfide Exchange Reaction in Water

Language：Japanese  

Country：Japan  

RhCl₃触媒を用いる水中での均一系および不均一系ジスルフィド交換反応

Language：Japanese  

Country：Japan  

ビニルスルフィドとジスルフィドとの触媒的アルキルチオ交換反応

Language：Japanese  

Country：Japan  

アリルスルフィドとジスルフィドとの触媒的アルキルチオ交換反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる芳香族フッ化物のスルフィドへの変換反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるα‐チオケトンのα,α‐ジチオ化置換反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるニトロベンゼンの還元的ホスフィニルオキシ化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるアルキルチオアルキンから1,3‐ジインの生成反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるアルキルチオアルキンのC‐S結合切断再配列反応

Language：Japanese  

Country：Japan  

Transition-metal-catalyzed synthesis of organophosphorous and organosulfur compounds
Organoheteroatom compounds of phosphorous and sulfur are important in relation to the development of biologically active substances and materials. Conventional synthesis in general employed substitution reactions of organohalogen compounds with heteroatom reagents. It was considered that i) the addition reaction to unsaturated compounds; ii) the substitution reaction of C-H bond; iii) single bond metathesis would be more favorable, since the starting materials are readily available, and the reactions are atom-economical. Described here is the use of transition metal catalysis for such syntheses of organosulfur and organophosphorous compounds.

Language：Japanese  

Country：Japan  

塩化ロジウムを用いるインスリンのジスルフィド交換反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるα‐チオケトンのα‐CH/α‐CS結合切断再配列反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるα‐チオケトンのα,α‐ジチオ化置換反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるポリフルオロベンゼンの位置選択的アリールチオ化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる酸フッ化物のチオエステルへの変換反応

Language：Japanese  

Country：Japan  

アルキルチオアルキンと共役ジインのロジウム触媒カルボチオ化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるポリフルオロベンゼンの位置選択的アリールチオ化反応

Language：Japanese  

Country：Japan  

遷移金属触媒を用いる新しい炭素‐リン結合生成反応の開発

Language：Japanese  

Country：Japan  

Rhodium-Catalyzed addition reaction of Biphosphine disulfide to aldehydes

Language：Japanese  

Country：Japan  

Rhodium-catalyzed dimethylthiophosphinylation reaction of hexafluorobenzene

Language：Japanese  

Country：Japan  

Rhodium-Catalyzed Methylthiolation Reaction of Active Methylene Compounds

Language：Japanese  

Country：Japan  

Rhodium-catalyzed C-P bond forming reaction via single bond metathesis of thioalkyne C-S bond and diphosphine P-P bond

Language：Japanese  

Country：Japan  

Rhodium-Catalyzed Phosphinylation Reaction of Acid Fluoride using Diphosphine Disulfide

Language：English  

Country：Japan  

Language：Japanese  

Country：Japan  

Ligand-effect in iron-catalysed Belousov-Zhabotinsky reaction

Language：Japanese  

Country：Japan  

Rhodium-Catalyzed Carbothiolation Reaction of Terminal Alkynes and 1-Alkyl-thioalkynes

Language：Japanese  

Country：Japan  

酸フッ化物を用いる無塩基条件下でのロジウム触媒エステル化反応

Language：Japanese  

Country：Japan  

ロジウム錯体を用いるホスフィノエステルのエノールエステル化反応

Language：Japanese  

Country：Japan  

ロジウム触媒芳香族フッ素置換反応におけるRhH(dppBz)₂錯体の利用とフッ素原子捕捉剤の開発

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるベンジルケトンC‐C結合とチオエステルC‐S結合の切断再配列反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる芳香族メチルエーテル結合切断反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるケトンのα‐メチルチオ化置換反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる芳香族フッ化物のアミノ化反応
The reactivity of organofluorine compounds differs from organochlorine, organobromine, and organoiodine compounds, and development of the substitution reacton of organofluoro compounds can considerably broaden the potential of organic synthesis. Previously, we reported the rhodium-catalyzed arylthiolation reaction of fluorobenzenes with disulfides. The rhodium catalysis method was applied here to the amination reaction of fluorobenzenes with anilines. When anilines and p-nitrofluorobenzene were heat at reflux in chlorobenzene in the presence of RhH(PPh₃)₄ and dppe, triarylamines were obtained. N₂ bubbling improved the yield, which may be due to the removal of hydrogen fluoride (HF) and promotion of product precipitation.

Language：Japanese  

Country：Japan  

チオエステルによる末端アルキンのロジウム触媒カルボチオ化反応

Language：Japanese  

Country：Japan  

チオアルキンC‐S結合/ジホスフィンP‐P結合の切断再配列反応におけるチオアルキンの置換基効果

Language：Japanese  

Country：Japan  

ジホスフィンジスルフィドを用いるアルコールの触媒的ホスフィニルエステル化反応

Language：Japanese  

Country：Japan  

ケトンとo‐ジフルオロベンゼンを用いるロジウム触媒ベンゾフラン環化反応

Language：Japanese  

Country：Japan  

ケトンとo‐ジフルオロベンゼンを用いるロジウム触媒ベンゾフラン環化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる芳香族フッ化物のアミノ化反応

Language：Japanese  

Country：Japan  

芳香族フッ化物を用いるケトンのロジウム触媒α‐アリール化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる置換ペンタフルオロベンゼンのp‐位チオ化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる複素環化合物のフェニルチオ化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるニトロアルカンの1‐アリールチオ化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる酸フッ化物とチオエステル間の平衡的相互変換

Language：Japanese  

Country：Japan  

ジヒドロピリミジン骨格2位および4(6)位の置換反応

Language：Japanese  

Country：Japan  

N‐スルフェニルアミドと酸フッ化物のロジウム触媒メタセシス反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるケトンおよび複素環化合物の平衡的チオ化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるニトロアルカンの1‐アリールチオ化反応

Language：Japanese  

Country：Japan  

ジヒドロピリミジン骨格2位および4(6)位の置換反応

Language：Japanese  

Country：Japan  

N‐スルフェニルアミドと酸フッ化物のロジウム触媒メタセシス反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる平衡的アシル基転位反応の制御

Language：Japanese  

Country：Japan  

ジヒドロピリミジン骨格2位および4(6)位の置換反応と骨格開裂反応

Language：Japanese  

Country：Japan  

有機イオウ・リン化合物の触媒的平衡制御合成
C-S/C-P bond formation is an essential process for the synthesis of organosulfur and organophosphorus compounds. Recently, we found single-bond metathesis reactions to be useful for such synthesis, and a variety of reactions involving cleavage of heteroatom bonds were developed. Single bond metathesis reactions were often reversible, and therefore the development of the method to control equilibrium turned to be important. We developed an equilibrium control method using co-substrates. Rhodium-catalyzed method can be used for acyl transfer equilibrium between acid fluorides, acylphosphine sulfides, thioesters, and aryl esters. Appropriate co-substrates changed the relative thermodynamic stabilities of substrates and products, and efficiently provided desired products. This method using the combination of a transition metal catalyst and heteroatom acceptors can be generally used for the synthesis of organoheteroatom compounds.

Language：Japanese  

Country：Japan  

芳香族フッ化物を用いる無塩基条件下でのロジウム触媒エーテル化反応

Language：Japanese  

Country：Japan  

置換ペンタフルオロベンゼンによる末端シリルアルキンのロジウム触媒フッ素化反応

Language：Japanese  

Country：Japan  

有機ポリスルフィド/イオウ単体を用いるロジウム触媒芳香族フッ化物のチオ化反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いる複素環化合物の直接チオ化反応

Language：Japanese  

Country：Japan  

ベンジルケトンCC結合とチオエステルCS結合のロジウム触媒的CC/CSメタセシス反応

Language：Japanese  

Country：Japan  

α‐チオケトンとベンジルフェニルケトンのロジウム触媒クロスカップリング反応

Language：Japanese  

Country：Japan  

芳香族メチルエーテルのロジウム触媒切断変換反応

Language：Japanese  

Country：Japan  

有機イオウ化合物とケトンのロジウム触媒C‐C結合形成反応

Language：Japanese  

Country：Japan  

ベンジルフェニルケトンCO‐C結合切断を伴う複素環化合物のロジウム触媒ベンジル化反応

Language：Japanese  

Country：Japan  

ベンジルフェニルケトンCO‐C結合切断を伴う複素環化合物のロジウム触媒ベンジル化反応

Language：Japanese  

Country：Japan  

芳香族C‐S結合切断を伴うロジウム触媒ジアリールスルフィド合成

Language：Japanese  

Country：Japan  

アリール交換を用いるロジウム触媒芳香族スルフィドの合成

Language：Japanese  

Country：Other  

Language：Japanese  

Country：Japan  

芳香族/複素環エーテルから非対称芳香族/複素環スルフィドを合成するロジウム触媒反応

Language：Japanese  

Country：Japan  

ジホスフィンと芳香族スルフィドから芳香族ホスフィンを合成するロジウム触媒反応

Language：Japanese  

Country：Japan  

芳香族/複素環カルボン酸無水物のC‐O単結合切断を伴うノルボルネン誘導体への付加反応

Language：Japanese  

Country：Japan  

芳香族/複素環カルボン酸無水物のC‐O単結合切断を伴うノルボルネン誘導体への付加反応

Language：Japanese  

Country：Japan  

イオウ単体を用いるノルボルネン誘導体へのロジウム触媒イオウ原子付加反応

Language：Japanese  

Country：Japan  

芳香族チオエステルC‐S結合切断を伴うノルボルネン誘導体への付加反応

Language：Japanese  

Country：Japan  

ペンタフェニルシクロペンタホスフィンと芳香族スルフィドのロジウム触媒的切断交換反応

Language：Japanese  

Country：Japan  

シクロアルキンへのロジウム触媒イオウ付加反応を用いる1,4‐ジチインの合成

Language：Japanese  

Country：Japan  

酸無水物とチオエステルのノルボルネン誘導体へのパラジウム触媒的付加反応

Language：English  

Country：Other  

Transition-Metal-Catalyzed Synthesis of Organoheteroatom Compounds

Language：English  

Country：Other  

Rhodium-catalyzed synthesis of organosulfur compounds

Language：English  

Country：Other  

Rhodium-catalyzed synthesis of organosulfur compounds

Language：English  

Country：Other  

Rhodium-catalyzed synthesis of organosulfur compounds

Language：Japanese  

Country：Japan  

置換ペンタフルオロベンゼンをフッ素化剤に用いる芳香族・複素環エーテルのロジウム触媒的フッ素化反応

Language：Japanese  

Country：Japan  

芳香族・複素環エーテルのロジウム触媒的フッ素化反応

Language：Japanese  

Country：Japan  

複素環エーテルから非対称ビス複素環スルフィドを与えるロジウム触媒反応

Language：Japanese  

Country：Japan  

有機フッ素化合物を用いて芳香環・複素環エーテルの二つのエーテル結合をフッ素化するロジウム触媒反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いるジホスフィンジスルフィドP‐P結合交換反応

Language：Japanese  

Country：Japan  

1,4‐ジチインのロジウム触媒的異性化反応とアルキン交換反応

Language：English  

Country：Other  

Rhodium-catalyzed synthesis of di(heteroaryl) HetAr–X–HetAr’ compounds using heteroaryl exchange reactions

Language：Japanese  

Country：Japan  

複素環チオ基交換を伴うロジウム触媒的非対称ビス複素環スルフィドの合成反応

Language：Japanese  

Country：Japan  

ロジウム触媒を用いた1,4‐ジチインの異性化反応とアルキン交換反応

Language：Japanese  

Country：Japan  

複素環スルフィドのホスフィニル化による複素環ジアルキルホスフィン誘導体のロジウム触媒合成

Language：Japanese  

Country：Japan  

複素環エーテルとN‐ベンゾイル複素環化合物のC‐N結合生成によるビス複素環化合物の触媒的合成法の開発

Language：Japanese  

Country：Japan  

ペンタフェニルシクロペンタホスフィンPhP基のジスルフィドへのロジウム触媒挿入反応

Language：Japanese  

Country：Japan  

ジスルフィドのロジウム触媒的チオリン酸エステル化反応

Language：Japanese  

Country：Japan  

ロジウム触媒的複素環交換反応による多様な複素環化合物の合成

Language：English  

Country：Other  

Rhodium-catalyzed Synthesis of Novel Organosulfur Compounds

Language：Japanese  

Language：Japanese  

Language：Japanese  

Language：Japanese  

Language：Japanese  

Language：Japanese  

Language：Japanese