| 1. |
Keita Shichijo, Hisashi Shimakoshi, Green Molecular Transformation in Dual Catalysis: Photoredox Activation of Vitamin B12 Using Heterogeneous Photocatalyst, ChemPlusChem, 2024.03, This concept focuses on dual-catalysis using metal complexes and heterogeneous photocatalysts. Vitamin B12 derivatives are sophisticated metal complexes that facilitate enzymatic reactions in the biological systems. The B12 enzymes inspired reactions catalytically proceed in dual-catalyst systems of B12 derivatives and heterogeneous photocatalysts, such as titanium oxide (TiO2) and metal-organic frameworks (MOFs), under light irradiation. The cobalt ions in vitamin B12 derivatives are effectively reduced by photoexcited photocatalysts, producing low-valent Co(I) species. The photoinduced nucleophilic Co(I) species react with an alkyl halide to form an organometallic complex with a Co-C bond. The Co-C bond dissociates during photolysis to generate alkyl radicals. Based on this mechanism, dual-catalysis effectively promotes various light-driven organic syntheses and light-driven dehalogenation reactions of toxic alkyl halides. The concepts of the dual-catalyst system and recent progress in this field are discussed in this concept.. |
| 2. |
Kaito Sasaki, Keita Shichijo, Mamoru Fujitsuka, Hisashi Shimakoshi, Visible Light-Driven Borylation of Aryl Halides by B12 Derivative Based on Dual Photoredox Strategy, Journal of Porphyrins and Phthalocyanines, 10.1142/S108842462350081, 27, 7, 1270-1277, 2023.03, Reductive dehalogenation of an aryl halide (Ar-X) subsequent coupling with bis(pinacolato)diboron (B2pin2) to form an arylboronate (Ar-Bpin) by the photo-excited B12 complex of the CoI oxidation state with an iridium photosensitizer (PS), [Ir(dtbbpy)(ppy)2]PF6, under anaerobic conditions was reported. The robust B12 complex and iridium PS provided the highest turnover numbers of over 3,800 for the borylation reaction at room temperature. The CoI state of the B12 complex was formed via the reductive quenching pathway of [Ir(dtbbpy)(ppy)2]PF6 by visible light irradiation in the presence of N, N-diisopropylethylamine (i-Pr2NEt) as a sacrificial reductant which was confirmed by a photoluminescence lifetime analysis. A sub-pico second time-resolved spectroscopic analysis showed that the electron transfer from the excited CoI state of the B12 complex (*CoI) to the Ar-X occurred in the order of the rate constants for electron transfer (k”eT), Ar-I > Ar-Br > Ar-Cl. Based on the mechanistic studies, dual excitation of PS and the B12 complex is involved in the catalytic reaction and single electron transfer (SET) from *CoI to Ar-X could provide the aryl radical by fragmentation of the Ar-X radical anion. The aryl radical should react with the radical trapping reagent, B2pin2, to form the Ar-Bpin product. . |
| 3. |
K. Shichijo, Y. Kametani, Y. Shiota, K. Yoshizawa, M. Fujitsuka, H. Shimakoshi, Effect of Macrocycles on the Photochemical and Electrochemical Properties of Cobalt-Dehydrocorrin Complex: Formation and Investigation of Co(I) Species., Inorg. Chem., 62, 11785-11795, 2023.09, Co(II)-Pyrocobester (P-Co(II)), a dehydrocorrin complex, was semisynthesized from vitamin B12 (cyanocobalamin), and its photochemical and electrochemical properties were investigated and compared to those of the cobseter (C-Co(II)), the cobalt corrin complex. The UV-vis absorptions of P-Co(II) in CH2Cl2, ascribed to the π-π* transition, were red-shifted compared to those of C-Co(II) due to the π-expansion of the macrocycle in the pyrocobester. The reversible redox couple of P-Co(II) was observed at E1/2 = –0.30 V vs. Ag/AgCl in CH3CN, which was assigned to the Co(II)/Co(I) redox couple by UV-vis, ESR and molecular orbital analysis. This redox couple was positively shifted by 0.28 V compared to that of C-Co(II). This is caused by the high electronegativity of the dehydrocorrin macrocycle, which was estimated by DFT calculations for the free base ligands. The reactivity of the Co(I)-pyrocobester (P-Co(I)) was evaluated by the reaction with methyl iodide in CV and UV-vis to form a photo-sensitive Co(III)-CH3 complex (P Co(III)-CH3). The properties of the excited state of P-Co(I), *Co(I), were also investigated by femtosecond transient absorption (TA) spectroscopy. The lifetime of *Co(I) was estimated to be 29 ps from the kinetic trace at 587 nm. The lifetime of *Co(I) became shorter in the presence of Ar-X, such as iodobenzonitrile (1a), bromobenzonitrile (1b), and chlorobenzonitrile (1c), and the rate constants of electron transfer (ET) between the *Co(I) and Ar-X were determined to be 2.9 × 1011 M–1s–1, 4.9 × 1010 M–1s–1, and 1.0 × 1010 M–1s–1 for 1a, 1b, and 1c, respectively. . |
| 4. |
Keita Shichijo, Hisashi Shimakoshi, Visible light-driven photocatalytic benzoyl azides formation from
benzotrichlorides using rhodium ion modified TiO2, Journal of Photochemistry and Photobiology, 14, 100170-100178, 2023.01, Visible light-driven benzoyl azides formation catalyzed by a rhodium ion modified TiO2 (Rh3+/TiO2) is reported.
The Rh3+/TiO2 was prepared as a visible light responsive photocatalyst by a simple procedure from TiO2 and
RhCl3･3H2O. The Rh3+/TiO2 exhibited a broaden visible light absorption from 400 nm to 600 nm. Benzoyl azide
formation from a benzotrichloride and a trimethylsilyl azide (TMS-N3) was performed catalyzed by the Rh3+/
TiO2 under visible light irradiation (λ ≥ 420 nm) in air at room temperature. In this reaction, the benzotrichloride
was effectively reduced by the single electron transfer (SET) from the Rh3+/TiO2, and the benzoyl azide
was produced in 71% yield via the reaction between the benzoyl chloride and TMS-N3. In addition, several
benzotrichloride derivatives were applied to this reaction and the corresponding benzoyl azide derivatives were
formed in up to 71% yield. A kinetic analysis was also performed on these reactions, and it was suggested that the
SET is the rate determining step in this reaction.. |
| 5. |
J. Cheng, Y. Shiota, M. Yamasaki, K. Izukawa, Y. Tachi, K. Yoshizawa, H. Shimakoshi, Mechanistic Study for the Reaction of B12 Complexes with m-Chloroperbenzoic Acid in Catalytic
Alkane Oxidations
, Inorg. Chem., 61, 9710-9724, 2022.09, The oxidation of alkanes with m-chloroperbenzoic acid (mCPBA) catalyzed by the B12 derivative, heptamethyl cobyrinate, was investigated under several conditions. During the oxidation of cyclohexane, heptamethyl cobyrinate works as a catalyst to form cyclohexanol and cyclohexanone at a 0.67 alcohol to ketone ratio (A/K) under aerobic conditions in 1hr. The reaction rate shows a first-order dependence on the [catalyst] and [mCPBA] while independent of [cyclohexane]; Vobs = k2[catalyst][mCPBA]. The kinetic deuterium isotope effect (KIE) was determined to be 1.86, suggesting that substrate hydrogen atom abstraction (HAA) is not dominantly involved in the rate-determining step. By the reaction of mCPBA and heptamethyl cobyrinate at low temperature, the corresponding cobalt (III) acylperoxido complex was formed which was identified by UV-vis, IR, ESR, and ESI-MS. A theoretical study suggested the homolysis of the O-O bond in the acylperoxido complex to form Co(III)-oxyl (Co-O•) and the m-chlorobenzoyloxyl radical. Radical trapping experiments using N-tert-butyl-α-phenylnitrone (PBN) and CCl3Br, product analysis of various alkane oxidations, and computer analysis of the free energy for radical abstraction from cyclohexane by Co(III)-oxyl suggested that both Co(III)-oxyl and m-chlorobenzoyloxyl radical could act as hydrogen-atom transfer (HAT) reactants for the cyclohexane oxidation.. |
| 6. |
J. Cheng, H. Matsumoto, K. Shichijo, Y. Miura, H. Shimakoshi, Effect of Catalyst Support in B12-Based Heterogeneous Catalysts for Catalytic Alkane Oxidations., Bull. Chem. Soc. Jpn., 95, 1250-1252, 2022.05, Heterogeneous catalysts composed of the vitamin B12 derivative with a polymer or mesoporous silica were synthesized and characterized. These two types of catalysts were used in alkane oxidation reactions with the mCPBA oxidant, and an improved catalytic efficiency was obtained by the polymer supported B12 catalyst with a monolith structure compared to that of the monomeric B12 catalyst. The catalytic effects were also evaluated in several alkane substrates and the polymer supported B12 catalyst showed a better performance in all reactions compared to the silica-supported B12 catalyst.. |
| 7. |
Keita Shichijo, Midori Watanabe, Yoshio Hisaeda, Hisashi Shimakoshi, Development of Visible Light-Driven Hybrid Catalysts Composed of Earth Abundant Metal Ions Modified TiO2 and B12 Complex, Bull. Chem. Soc. Jpn., 2022.05, The development of highly-functional visible light-driven hybrid catalysts (B12-Mn+/TiO2) prepared from B12 complexes (B12) derived from natural vitamin B12, earth-abundant metal ions (Mn+), and titanium oxide (TiO2) was reported. The metal ions, such as Cu2+, Ni2+, Fe2+, Zn2+, Mn2+, Al3+, and Mg2+, were modified on the surface of TiO2 (2.4×10-5 − 9.9×10-5 mol/g) to obtain the effective response to visible light, and the B12 complex was also loaded (6.2×10-6 − 1.1×10-5 mol/g) to produce a highly-functional hybrid catalyst. Amide formations from dichlorodiphenyltrichloroethane (DDT) catalyzed by the B12-Mn+/TiO2 proceeded in up to 89% yields in the presence of triethylamine (NEt3) under visible light irradiation (λ≧420 nm) in air at room temperature. These hybrid catalysts were able to be classified into two groups based on these reactivities, and it was found that the B12-Mg2+/TiO2 showed the most effective catalytic activities of all the prepared samples. The B12-Mg2+/TiO2 also catalyzed the syntheses of fine chemicals, such as N,N-diethyl-3-methylbenzeamide (DEET), and N,N-diethylcyanoformamide, from the corresponding trichloromethyl compounds (FG-CCl3) with about 80% yields.. |
| 8. |
Moniruzzaman, Mohammad; Yano, Yoshio; Ono, Toshikazu; Hisaeda, Yoshio; Shimakoshi, Hisashi, Aerobic Electrochemical Transformations of DDT to Oxygen-Incorporated Products Catalyzed by a B-12 Derivative, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 10.1246/bcsj.20210316, 94, 11, 2784-2791, 2021.11. |
| 9. |
Moniruzzaman, Mohammad; Yano, Yoshio; Ono, Toshikazu; Imamura, Kenji; Shiota, Yoshihito; Yoshizawa, Kazunari; Hisaeda, Yoshio; Shimakoshi, Hisashi, Electrochemical Synthesis of Cyanoformamides from Trichloroacetonitrile and Secondary Amines Mediated by the B-12 Derivative, JOURNAL OF ORGANIC CHEMISTRY, 10.1021/acs.joc.1c00837, 86, 22, 16134-16143, 2021.11. |
| 10. |
Hisashi Shimakoshi, Yoshio Hisaeda, Bioinspired Electrolysis for Green Molecular Transformations of Organic Halides Catalyzed by B12 Complex, The Chemical Record, 2021.05, Naturally-occurring B12-dependent enzymes catalyze various molecular transformations that are of particular interest from the viewpoint of biological chemistry as well as synthetic organic chemistry. Inspired by the unique property of the B12-dependent enzymes, various catalytic reactions have been developed using its model complex. Among the B12 model complexes, heptamethyl cobyrinate, synthesized from natural vitamin B12, is highly soluble in various organic solvents and a redox active cobalt complex with an excellent catalysis in electroorganic synthesis. The electrochemical dechlorination of pollutant organic chlorides, such as DDT, was effectively catalyzed by the B12 complex. Modification of the electrode surface by the sol-gel method to immobilize the B12 complex was also developed. The B12 modified electrodes were effective for the dehalogenation of organic halides with high turnover numbers based on the immobilized B12 complex. Electrolysis of an organic halide catalyzed by the B12 complex provided dechlorinated products under anaerobic conditions, while the electrolysis under aerobic conditions afforded oxygen incorporated products, such as an ester and amide along with dechlorination. Benzotrichloride was transformed into ethylbenzoate or N,N-diethylbenzamide in the presence of ethanol or diethylamine, respectively. This amide formation was further expanded to a unique paired electrolysis. Electrochemical reductions of an alkene and alkyne were also catalyzed by the B12 complex. A cobalt-hydrogen complex should be formed as a bioinspired intermediate. Using the B12 complex, light-assisted electrosynthesis was also developed to save the applied energy.. |
| 11. |
Mohammad Moniruzzaman, Yoshio Yano, Toshikazu Ono, Yoshio Hisaeda, Hisashi Shimakoshi, Electrochemical approach to trifluoroacetamide synthesis from 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) catalyzed by B12 complex, Journal of Porphyrins and Phthalocyanines, https://doi.org/10.1142/S1088424621500292, 2021.01, One-pot synthetic approach to produce trifluoroacetamide has been developed using an electrochemical method with the B12 complex as a catalyst under mild conditions, in air, at room temperature. Thirty examples of trifluoroacetamide were synthesized from 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) in moderate to good yields. This user-friendly strategy is compatible with a broad range of trifluoroacetamide syntheses.. |
| 12. |
Zhongli Luo, Kenji Imamura, Yoshihito Shiota, Kazunari Yoshizawa, Yoshio Hisaeda, Hisashi Shimakoshi, One-Pot Synthesis of Tertiary Amides from Organic Trichlorides through Oxygen Atom Incorporation from Air by Convergent Paired Electrolysis, J. Org. Chem., https://doi.org/10.1021/acs.joc.1c00161, 86, 5983-5990, 2021.04, A convergent paired electrolysis catalyzed by a B12 complex for the
one-pot synthesis of a tertiary amide from organic trichlorides (R-CCl3) has been
developed. Various readily available organic trichlorides, such as benzotrichloride
and its derivatives, chloroform, dichlorodiphenyltrichloroethane (DDT), trichloro-2,2,2-trifluoroethane (CFC-113a), and trichloroacetonitrile (CNCCl3), were converted to amides in the presence of tertiary amines through oxygen incorporation from air at room temperature. The amide formation mechanism in the paired electrolysis, which was mediated by a cobalt complex, was proposed.. |
| 13. |
Shimakoshi, Hisashi; Shichijo, Keita; Tominaga, Shiori; Hisaeda, Yoshio; Fujitsuka, Mamoru; Majima, Tetsuro, Catalytic Dehalogenation of Aryl Halides via Excited State Electron Transfer from the Co(I) State of B-12 Complex, CHEMISTRY LETTERS, 10.1246/cl.200241, 49, 7, 820-822, 2020.07, Catalytic Dehalogenation of Aryl Halides via Excited State Electron Transfer from the Co(I) State of B12 Complex. |
| 14. |
Anai, Yuki; Shichijo, Keita; Fujitsuka, Mamoru; Hisaeda, Yoshio; Shimakoshi, Hisashi, Synthesis of a B-12-BODIPY dyad for B(12-)inspired photochemical transformations of a trichloromethylated organic compound, CHEMICAL COMMUNICATIONS, 10.1039/d0cc04274a, 56, 80, 11945-11948, 2020.10, The B12 complex-BODIPY dyad was synthesized by peripheral modification of the cobalamin derivative. The photophysical properties of the dyad were investigated by UV-vis, PL, and transient absorption spectroscopies. The visible light-driven dechlorination reaction of the trichlorinated organic compound, DDT, was reported. The dyad showed an efficient catalysis for the dechlorination under N2 with turnover numbers of over 220 for the reaction. The one-pot syntheses of an ester and amide from DDT and benzotrichloride were also achieved using the dyad in air.. |
| 15. |
Keita Shichijo, Mamoru Fujitsuka, Yoshio Hisaeda, Hisashi Shimakoshi, Visible light-driven photocatalytic duet reaction catalyzed by the B-12-rhodium-titanium oxide hybrid catalyst, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 10.1016/j.jorganchem.2019.121058, 907, 121058, 2020.02. |
| 16. |
Hisashi Shimakoshi, Yoshio Hisaeda, Electrochemistry and catalytic properties of vitamin B12 derivatives in nonaqueous media, Current Opinion in Electrochemistry, https:// doi.org/ 10.1016/ j.coelec.2017.12.001, 8, 24-30, 2017.12, Electroorganic synthesis mediated by vitamin B12 derivatives has been developed in nonaqueous media. Especially, amphiphilic heptamethyl cobyrinate with a high solubility in various organic solvents was used in various kinds of electroorganic syntheses based on enzymatic function. Electrolysis of an organic halide catalyzed by the B12 model complex provided dechlorinated products under anaerobic conditions, while the electrolysis under aerobic conditions afforded oxidized products such as an ester and amide with dechlorination. Electrochemical reductions of an alkene and alkyne were also catalyzed by the B12 model complex at less negative applied potentials than those of the alkene and alkyne reductions. A bioinspired intermediate, expected as a cobalt-hydrogen complex, should be formed and catalyze the reaction.. |
| 17. |
Hui Tian, Hisashi Shimakoshi, Sinheui Kim, Gyurim Park, Youngmin You, Yoshio Hisaeda, Photocatalytic Function of B12 Complex with Cyclometalated Iridium(III) Complex as Photosensitizer under Visible Light Irradiation, Dalton Transaction, 10.1039/c7dt03742b, 47, 675-683, 2017.12, A visible light induced three-component catalytic system with the cobalamin derivative (B12) as a catalyst, the cyclometalated iridium(III) complex (Irdfppy, Irppy, Irpbt and [Ir{dF(CF3)ppy}2(dtbpy)]PF6 as a photosensitizer and triethanolamine as an electron source under N2 was developed. This catalytic system showed a much higher catalytic efficiency than the previous catalytic system using [Ru(bpy)3]Cl2 as the photosensitizer for the dechlorination reaction of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT). Noteworthy is the fact that the remarkable high turnover number (over ten thousand) based on B12, which ranks at the top among the reported studies, was obtained when Irdfppy was used as a photosensitizer. This photocatalytic system was also successfully applied to the B12 enzyme-mimic reaction, i.e., the 1,2-migration of the phenyl group of 2-bromomethyl-2-phenylmalonate. The plausible reaction mechanism was proposed, which involved two quenching pathways, an oxidative quenching pathway and a reductive quenching pathway, to be responsible for the initial electron transfer of the excited-state photosensitizers during the DDT dechlorination reaction. Transient photoluminescence experiments revealed that oxidative quenching of the photosensitizer dominated over the reductive quenching pathway.. |
| 18. |
Hui Tian, Hisashi Shimakoshi, Kenji Imamura, Yoshihito Shiota, Kazunari Yoshizawa, and Yoshio Hisaeda, Photocatalytic alkene reduction by B12-TiO2 hybrid catalyst coupled with C-F bond cleavage for gem-difluoroolefin synthesis, Chemical Communication, 10.1039/c7cc04377e, 53, 9478-9481, 2017.07, Photocatalytic synstheses of gem-difluoroolefins were performed using the B12-TiO2 hybrid catalyst during C=C bond reduction of α-trifluoromethyl styrenes with C-F bond cleavage at room temperature under nitrogen. The gem-difluoroolefins were used as synthetic precursors for fluorinated cyclopropanes.. |
| 19. |
Shimakoshi Hisashi, Yoshio Hisaeda, Hybrid Catalyst for Light-Driven Green Molecular Transformations, ChemPlusChem, 10.1002/cplu.201600303, 82, 18-29, 2016.10, This review is focused on the development of a hybrid catalyst composed of photosensitizers and a metal complex, especially B12 derivatives. The semiconductor-metal complex composites become an effective photocatalyst for molecular transformations due to the synergistic effect by both components. As a design of the B12 complex for the hybridization with TiO2, cobyrinic acid having seven carboxyric groups derived from naturally-occurring B12 was a simple and straightforward compound, which stably immobilized on the TiO2. By using the hybrid catalysts, light driven B12-dependent enzymes mimic reactions, such as the dechlorination of organic halide pollutants, and the radical mediated isomerization reactions catalytically proceeded. In addition to the enzyme mimic reaction, bioinspired reactions were also developed with the hybrid catalyst. The B12-TiO2 hybrid catalyst was used for the hydrogen evolution or alkenes reduction by UV light irradiation, and the cobalt-hydrogen complex (Co-H complex) was considered as a putative intermediate of the reactions. The multidisciplinary concept for the design of a hybrid catalyst is described in this review.. |
| 20. |
Shimakoshi Hisashi, Zhongli Luo, Yoshio Hisaeda, Electrolysis of Trichloromethylated Organic Compounds under Aerobic Condition Catalyzed by B12 Model Complex for Ester and Amide Formations, Dalton Trans., 10.1039/c6dt00556j, 45, 10173-10180, 2016.04, Electrolysis of benzotrichloride at -0.9 V vs. Ag/AgCl in the presence of B12 model complex, heptamethyl cobyrinate perchlorate (1), in ethanol under aerobic condition using undivided cell equipped with platinum mesh cathode and zinc plate anode produced ethylbenzoate in 56% yield with 92% selectivity. Corresponding esters were obtained when the electrolysis were carried out in various alcohols such as methanol, n-propanol, and i-propanol. Benzoyl chloride was detected by GC-MS during the electrolysis as an intermediate for ester formation. While electrolysis was carried out under anaerobic condition, dechlorinated products, 1,1,2,2-tetrachloro-1,2-diphenylethane and 1,2-dichlorostilibenes (E and Z forms) were obtained instead of ester. ESR spin-trapping experiments using 5,5,-dimethylpyrroline N-oxide (DMPO) revealed that corresponding oxygen-centered radical and carbon-centered radical were steadily generated during the electrolyses under aerobic and anaerobic conditions, respectively. Applications of the aerobic electrolysis to various organic halides such as substituted benzotrichlorides were shown. Furthermore, formation of amides with moderate yields by the aerobic electrolysis of benzotrichloride catalyzed by 1 in the presence of amines in acetonitrile were reported.. |
| 21. |
Shimakoshi Hisashi, Yoshio Hisaeda, Oxygen-Controlled Catalysis by Vitamin B12-TiO2: Formation of Esters and Amides from Trichlorinated Organic Compounds by Photoirradiation, Angew. Chem. Int. Ed., 10.1002/anie.201507782, 54, 15439-15443, 2015.10. |
| 22. |
Shimakoshi Hisashi, Yoko Nagami, Yoshio Hisaeda, Crystal Structure Dependence for Reactivities of B12-TiO2 Hybrid Catalysts with Anatase and Rutile Forms, Rapid Communication in Photoscience/Korea Photoscience Society, 10.5857/RCP.2015.4.1.9, 4, 1, 9-11, 2015.05. |
| 23. |
Shimakoshi Hisashi, Hisaeda Yoshio, A polymerized ionic liquid-supported B12 catalyst with a ruthenium trisbipyridine photosensitizer for photocatalytic dechlorination in ionic liquids, Royal Society of Chemistry, 10.1039/c4dt01360c, 43, 13972-13978, 2014.08, A visible light-driven photocatalyst by immobilizing a B12 complex and a Ru(II) trisbipyridine photosensitizer in a polymerized ionic liquid (PIL) was developed. The synthesized copolymer was characterized by GPC, DLS, and its UV-vis absorption spectra and luminescence spectra. The Ru(II) trisbipyridine photosensitizer in the copolymer showed an enhanced emission compared to that of the monomer in the ionic liquid, 1-butyl-4-methylimidazolium bis(trifluoromethanesulfonly)amide ([C4mim][NTf2]). Formation of the Co(I) species of the B12 complex in the copolymer was confirmed by the UV-vis spectral change in [C4mim][NTf2] containing a sacrificial reductant (triethanolamine) during irradiation with visible light. The copolymer showed a high photocatalytic activity in various ionic liquids for the 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) dechlorination with ~99% conversion after a 2 h visible light irradiation. Furthermore, both the B12 catalyst and the photosensitizer in the polymer were easily recycled for use with the ionic liquid solvent without any loss of catalytic activity.. |
| 24. |
Shimakoshi Hisashi, Hisaeda Yoshio, B12-TiO2 Hybrid Catalyst for Light-Driven Hydrogen Production and Hydrogenation of C-C Multiple Bonds, ChemPlusChem, 10.1002/cplu.201402081, 79, 1250-1253, 2014.06, The B12-TiO2 hybrid catalyst mediated the H2O reduction to form hydrogen under UV light irradiation (1 turnover number per hour). The catalyst also mediated alkene reductions, such as styrene derivatives and alkylacrylates (maximum 100 turnover number per hour), under mild conditions; i.e., room temperature, ordinary pressure, and water or alcohol solvent.. |
| 25. |
Yoshio Hisaeda, 田原圭志朗, Hisashi Shimakoshi, Bioinspired Catalytic Reactions with Vitamin B12 Derivative and Photosensitizers, Pure and Applied Chemistry, 85, 1415-1426, 2013.08. |
| 26. |
M Fujitsuka, Shimakoshi Hisashi, H Tei, M Noda, S Tojo, Hisaeda Yoshio, T Majima, Photoinduced electron transfer in supramolecular donor-acceptor dyads of Zn corrphycene, Physical Chemistry Chemical Physics, 39, 5677-5683, 2013.02. |
| 27. |
Toru Okawara, Abe Masaaki, Shimakoshi Hisashi, Hisaeda Yoshio, A Pd(II)-hydroxyporphycene: Synthesis, characterization, and photoinduced proton-coupled electron transfer, Research on Chemical Intermediates, 39, 161-176, 2013.01. |
| 28. |
Hisashi Shimakoshi, K. Sasaki, Y. Iseki, Yoshio Hisaeda, Synthesis and Photosensitizing Properties of Porphycene with Imidazolium Tag, J. Por. Phthalocyanines, 16, 530-536, 2013.01. |
| 29. |
H. Shimakoshi, L. Li, M. Nishi, Y. Hisaeda, Photosensitizing Catalysis of B12 Complex without Additional Photosensitizer, Chem. Commun., 47, 10921, 2012.05. |
| 30. |
Toru Okawara, Abe Masaaki, Koichi Hashimoto, Shimakoshi Hisashi, Hisaeda Yoshio, Hydrogenation effects in metalloporphycenes: synthesis and redox behavior of Ni(II)-tetra(n-propyl)dihydroporphycene, Chem. Commun., 47, 10921, 2012.05. |
| 31. |
K. Tahara, H. Shimakoshi, A. Tanaka, Y. Hisaeda, Redox Behavior and Electrochemical Catalytic Function of B12-Hyperbranched Polymer, Bull. Chem. Soc. Jpn, 83, 1439-1446, 2011.12. |
| 32. |
K. Tahara, Y. Chen, L. Pan, T. Masuko, H. Shimakoshi, Y. Hisaeda, Electrochemical Catalytic Carbon-Skeleton Rearrangement mediated by Imine/oxime-type B12 Model Complex, Chem. Lett., 40, 177-179, 2011.05. |
| 33. |
H. Shimakoshi, M. Nishi, A. Tanaka, K. Chikama, Y. Hisaeda, Photocatalytic Function of Polymer-Supported B12 Complex with Ruthenium Trisbipyridine Photosensitizer, Chem. Commun., 47, 6548, 2011.05. |
| 34. |
Hisashi Shimakoshi, Makoto Abiru, Keita Kuroiwa, Nobuo Kimizuka, Midori Watanabe Yoshio Hisaeda, Preparation and Reactivity of B12-TiO2 Hybrid Catalyst Immobilized on Glass Plate, Bull. Chem. Soc. Jpn, 83, 170-172, 2011.04. |
| 35. |
Hisashi Shimakoshi, Daisuke Maeda, Yoshio Hisaeda, Supramolecular Assemblies of Crown-substituted Dinickel and Dicobalt Complexes with Guest Cation Binding, Supramolecular Chemistry, 23, 1-2, 131-139, 2011.01. |
| 36. |
S. Izumi, H. Shimakoshi, M. Abe, Y. Hisaeda, Photo-Induced Ring-Expansion Reactions Mediated by B12-TiO2 Hybrid Catalyst B12-Hyperbranched Polymer, Dalton Trans, 39, 3302-3307, 2010.02. |
| 37. |
H. Shimakoshi, M. Abiru, K. Kuroiwa, N. Kimizuka, M. Watanabe, Y. Hisaeda, Preparation and Reactivity of B12-TiO2 Hybrid Catalyst Immobilized on Glass Plate, Bull. Chem. Soc. Jpn, 83, 170-172, 2010.01. |
| 38. |
D. Maeda, H. Shimakoshi, M. Abe, M. Fujitsuka, T. Majima, Y. Hisaeda , Synthesis of a Novel Sn(IV) Porphycene-Ferrocene Triad Linked by Axial Coordination and Solvent Polarity Effect in Photoinduced Charge Separation Process, Inorg. Chem, 49, 2872-2880, 2010.01. |
| 39. |
Hisashi Shimakoshi, Masashi Nishi, Akihiro Tanaka, Katsumi, Chikama, Yoshio Hisaeda, Synthesis and Catalysis of B12-Core-Shell Hyperbranched Polymer, Chemistry Letters, 39, 22-23, 2010.01. |
| 40. |
H. Shimakoshi, M. Abiru, S. Izumi, Y. Hisaeda, Green Molecular Transformation by a B12-TiO2 Hybrid Catalyst as an Alternative to Tributyltin Hydride, Chem. Commun, 6427-6429 , 2009.12. |
| 41. |
H. Shimakoshi, E. Sakumori, K. Kaneko, Y. Hisaeda, B12-TiO2 Hybrid Catalyst for Dehalogenation of Organic Halides, Chem. Lett, 38, 468-469 , 2009.05. |
| 42. |
H. Shimakoshi, K. Shibata, Y. Hisaeda , Molecular Recognition of Redox-Switchable Bis-crown Moieties Assembled on Dicobalt Complex., Inorg. Chem, 48, 1045-1052 , 2009.05. |
| 43. |
Emiko Sakumori, Kenji Kaneko, Yoshio Hisaeda, B12-TiO2 Hybrid Catalyst for Dehalogenation of Organic Halides, Chemistry Letters, Vol. 38, No. 5, 468-469, 2009, 2009.04. |
| 44. |
Hisashi Shimakoshi, Tatsushi Baba, Yuseuke Iseki, Ayataka Endo, Chihaya Adachi, Midori Watanabe, Yoshio Hisaeda, Photosensitizing properties of the porphycene immobilized in sol-gel derived silica coating films, Tetrahedron Letters, 49, 6198-6201, 2008.07. |
| 45. |
Keishiro Tahara, Hisashi Shimakoshi, Akihiro Tanaka, Yohsio Hisaeda, Synthesis and characterization of vitamin B12-hyperbranched polymer, Tetrahedron Letters, 48, 5065-5068,2007, 2007.07. |
| 46. |
Hisashi Shimakoshi, T. Takemoto, Isao Aritome, Yoshio Hisaeda, Redox-Switchable Molecular Containers Consisting of Dicobalt Complexes, Inorganic Chemistry, 10.1021/ic051482o, 44, 25, 9134-9136, 2005, 44, 9134-9136, 2005.11. |
| 47. |
Hisashi Shimakoshi, Takayuki Kai, Isao Aritome, Yoshio Hisaeda, Syntheses of large-membered macrocycles having multipule hydrogen ｂｏｎｄmoieties, Tetrahedron Letters, 10.1016/S0040-4039(02)02022-1, 43, 46, 8261-8264, 43, 8261-8264, 2003.01. |
| 48. |
Hisahi Shimakoshi, Aki Nakazato, Mami Tokunaga, Kiyofumi Katagiri, Katsuhiko Ariga, Junichi Kikuchi, Yoshio Hisaeda, Hydrophobic vitamin B12 part 18. Preparation of a sol-gel modified electrode trapped with a vitamin B12 derivative and its photoelectrochemical reactivity, Dalton Transactions, 10.1039/b212863b, 11, 2308-2312, 2308-2312, 2003.01. |
| 49. |
Hisashi Shimakoshi, Takeshi Kaieda, Takashi Matsuo, Hideaki, Sato, Yoshio Hisaeda, Syntheses of new water-soluble dicobalt complexes having two cobalt-carbon bonds and their ability for DNA cleavage, Tetrahedron Letters, 10.1016/S0040-4039(03)01252-8, 44, 28, 5197-5199, 44, 5197-5199, 2003.01. |
| 50. |
Hisashi Shimakoshi, Masaomi Koga, Yoshio Hisaeda, Synthesis, characterization, and redox behavior of new dicobalt complexes having monoanionic imine/oxime-type ligands, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.75.1553, 75, 7, 1553-1558, 75, 7, 1553-1558, 2002.07. |
| 51. |
Hisashi Shimakoshi Aki Nakazato, Takashi Hayashi, Yoshimitsu Tachi, Yoshinori Naruta, Yoshio Hisaeda, Electroorganic syntheses of macrocycliclactonesmediated by vitamin B12 model complexes, Journal of Electroanalytical Chemistry, 10.1016/S0022-0728(01)00418-1, 507, 1-2, 170-176, 507, 170-176, 2001.07. |
| 52. |
Hisashi Shimakoshi, Wataru Ninomiya, Yoshio Hisaeda, Reductive coupling of benzyl bromide catalyzed by a novel dicobalt complex having two salen units, Dalton Transaction, 10.1039/b010022f, 13, 1971-1974, 13, 1971-1974, 2001.06. |
| 53. |
Hisashi Shimakoshi, Masaomi Koga, Takashi Hayashi, Yoshimitsu Tachi, Yoshinori Naruta, Yoshio Hisaeda, Formation and cleavage of a dicobalt complex bridged with a pentamethylene group, Chemistry Letters, 10.1246/cl.2001.346, 4, 346-347, 4, 346-347, 2001.04. |
| 54. |
Hisashi Shimakoshi, Akihiro Goto, Yoshimitsu Tachi, Yoshinori Naruta, Yoshio Hisaeda, Synthesis and redox behavior of dialkylated dicobalt complexes having two discrete salen units, Tetrahedron Letters, 10.1016/S0040-4039(01)00040-5, 42, 10, 1949-1951, 42, 1949-1951, 2001.03. |
| 55. |
Masahito Kodera, Hisashi Shimakoshi, Yoshimitsu Tachi, Kou Katayama, Koji Kano, Efficient oxidation of various phenols catalyzed by di-mu-hydroxo-dicopper(II) complexes of a hexapyridine dinucleating ligand, Chemistry Letters, 5, 441-442, 1998.05. |
| 56. |
Masahito Kodera, Hisashi Shimakoshi, Koji Kano, First example of a rigid (mu-oxo-bis-mu-acetato)diiron(III) complex with 1,2-bis[2-di(2-pyridyl)methyl-6-pyridyl]ethane; itsefficient catalysis for functionalization of alkanes, Chemical Communications, 13, 1737-1738, 1996.11. |
| 57. |
Hisashi Shimakoshi, Mami Tokunaga, Keita Kuroiwa, Nobuo Hisaeda, Preparation and electrochemical behavior of hydrophobic vitamin B12 covalently immobilized onto platinum electrode, Chemical Communications, 50-51. |
