Updated on 2022/05/25

写真a

 
KANOMATA, Nobuhiro
 
Affiliation
Faculty of Science and Engineering, School of Advanced Science and Engineering
Job title
Professor

Concurrent Post

  • Affiliated organization   Global Education Center

  • Faculty of Science and Engineering   Graduate School of Advanced Science and Engineering

Research Institute

  • 2020
    -
    2022

    理工学術院総合研究所   兼任研究員

Education

  • 1987.04
    -
    1990.03

    Waseda University   Graduate School of Science and Engineering   Major in Applied Chemistry  

    Doctoral Program

  • 1985.04
    -
    1987.03

    Waseda University   Graduate School of Science and Engineering   Major in Applied Chemistry  

    Master’s Program

  • 1981.04
    -
    1985.03

    Waseda University   School of Science and Engineering   Department of Chemistry  

Degree

  • 1990.02   早稲田大学   工学博士

  • Waseda University   Dr. of Eng.

Research Experience

  • 2007.04
    -
    Now

    Waseda University   Faculty of Science and Engineering / Department of Chemistry and Biochemistry, School of Advanced Science and Engineering   Professor

  • 2005.04
    -
    2007.03

    Waseda University   Faculty of Science and Engineering / Department of Chemistry, School of Science and Engineering   Professor

  • 2004.04
    -
    2006.03

    RIKEN Institute   Collaborative Researcher

  • 2003.04
    -
    2005.03

    National Institute of Informatics   Collaborative Researcher

  • 1999.04
    -
    2005.03

    Meiji University   School of Science and Technology   Associate Professor

  • 1999.04
    -
    2004.03

    RIKEN Institute   Visiting Researcher

  • 1998.10
    -
    2001.09

    JST   PRESTO Researcher

  • 1998.10
    -
    1999.03

    RIKEN Institute

  • 1997.10
    -
    1998.09

    RIKEN Institute   Cooperative Researcher

  • 1994.10
    -
    1997.09

    RIKEN Institute   Special Postdoctoral Researcher

  • 1992.04
    -
    1994.04

    The University of Chicago   Department of Chemistry   Postdoctral Fellow

  • 1990.04
    -
    1992.03

    Waseda University   School of Science and Engineering   Research Associate

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Professional Memberships

  • 2002
    -
    Now

    Catalysis Society of Japan

  • 2001
    -
    Now

    The Pharmaceutical Society of Japan

  • 1990
    -
    Now

    American Chemical Society

  • 1986
    -
    Now

    Society of Synthetic Organic Chemistry, Japan

  • 1985.01
    -
    Now

    Chemical Society of Japan

  •  
     
     

    International Society of Heterocyclic Chemistry

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Research Areas

  • Structural organic chemistry and physical organic chemistry

  • Bioorganic chemistry

  • Synthetic organic chemistry

Research Interests

  • CO2-absorbing agent

  • Direct Air Capture

  • nitrogen heteroaromatic

  • small natural product

  • biomimetic molecule

  • cyclophane

  • planar chiral catalyst

▼display all

Papers

  • Asymmetric synthesis of (−)-dehydro-exo-brevicomin with a photoisomerisation–intramolecular acetalisation sequence

    Shun Hirasawa, Tsuyoshi Masuda, Ken Mukai, Yusuke Miyoshi, Nobuhiro Kanomata

    Organic & Biomolecular Chemistry   19 ( 31 ) 6897 - 6903  2021.07  [Refereed]

    Authorship:Last author, Corresponding author

    DOI

  • Biomimetic systems involving sequential redox reactions in glycolysis – the sulfur effect

    Narihito Ogawa, Sei Furukawa, Yuya Kosugi, Takayuki Takazawa, Nobuhiro Kanomata

    Chemical Communications   56 ( 85 ) 12917 - 12920  2020  [Refereed]

    Authorship:Last author, Corresponding author

     View Summary

    Magnesium hemithioacetates were used as model cysteine compounds to mimic natural hemithioacetals, and their biomimetic oxidation reactions using a model NAD+ compounds were investigated.

    DOI

  • Elucidation of Racemization Process of Azaspirene Skeleton in Neutral Aqueous Media

    Shun Hirasawa, Ken Mukai, Shinnosuke Sakai, Shinnosuke Wakamori, Takahiro Hasegawa, Kazunori Souma, Nobuhiro Kanomata, Narihito Ogawa, Mamoru Aizawa, Makoto Emoto

    The Journal of Organic Chemistry   83 ( 23 ) 14457 - 14464  2018.12  [Refereed]  [International journal]

    Authorship:Corresponding author

     View Summary

    Azaspirene and related congeners, which possess various biological activities, have a unique spirocyclic core structure. However, there are few studies on the chemical properties of (−)-azaspirene, despite the fact that it may provide important insights into unveiling the biosynthetic pathway. Here, we report a nine-step chemical synthesis of an azaspirene analogue with a new finding that the natural (−)-azaspirene skeleton easily racemizes in neutral aqueous media.

    DOI

  • Azaspirene Analogs Inhibit the Growth of Human Uterine Carcinosarcoma In Vitro and In Vivo

    Makoto Emoto, Kyoko Yano, Batsuren Choijamts, Shinnosuke Sakai, Shun Hirasawa, Shinnosuke Wakamori, Mamoru Aizawa, Kazuki Nabeshima, Katsuro Tachibana, Nobuhiro Kanomata

    ANTICANCER RESEARCH   35 ( 5 ) 2739 - 2746  2015.05  [Refereed]

     View Summary

    Uterine carcinosarcoma is a highly aggressive gynecological neoplasm that responds poorly to conventional chemotherapy and radiotherapy. Recent studies have shown high angiogenic activities of this tumor, hence anti-angiogenic approaches are expected to provide new treatment strategies for this tumor. In previous work, azaspirene was isolated from Neosartorya sp. fungi, and in vitro anti-angiogenic activities were shown. In the present study, the anti-angiogenic effects of azaspirene analogs, synthetic molecules with a shorter ethyl group replacing a hexadienyl side-chain of the natural compound, were assessed in vitro using human umbilical vein endothelial cells (HUVECs) co-cultured with FU-MMT-3 human uterine carcinosarcoma cells. The anti-tumor and anti-angiogenic effects of these analogs were also evaluated in vivo using FU-MMT-3 xenografted tumors in nude mice. The azaspirene analogs inhibited the tube formation of HUVECs induced by FU-MMT-3 cells in vitro and significantly suppressed tumor growth in vivo compared to the untreated group (control). A significant reduction of the microvessel density in tumors was observed, in comparison to the control. No apparent toxicity, including body loss, was observed in any mice treated in this study. These azaspirene analogs may be effective against uterine carcinosarcoma, possibly acting via potent antiangiogenic effects.

  • Remote steric effects of C-2-symmetric planar-chiral terpyridine ligands on copper-catalyzed asymmetric cyclopropanation reactions

    Nanako Mugishima, Nobuhiro Kanomata, Norihiko Akutsu, Hironobu Kubota

    TETRAHEDRON LETTERS   56 ( 14 ) 1898 - 1903  2015.04  [Refereed]

    Authorship:Corresponding author

     View Summary

    A series of enantioselective cyclopropanation reactions of substituted alkenes with diazoacetates was investigated in the presence of Cu(OTf)(2) with C-2-symmetric planar-chiral bridged 2,2':6',2 ''-terpyridines. Planar-chiral terpyridine-copper complexes exhibited moderate diastereomeric excesses with good enantioselectivities of cis-cyclopropane products in catalytic asymmetric cyclopropanation reactions of various styrene derivatives with ethyl diazoacetate. A remote steric effect was found to enhance enantioselectivity for the cyclopropanation induced by a sterically demanding substituent beyond the ansa-bridge of pyridinophane ligands on the other side of the reaction site as a relay of steric influences through flexible cyclophane bridges. (C) 2015 Elsevier Ltd. All rights reserved.

    DOI

  • Planar-to-Planar Chirality Transfer in the Excited State. Enantiodifferentiating Photoisomerization of Cyclooctenes Sensitized by Planar-Chiral Paracyclophane

    Ryo Maeda, Takehiko Wada, Tadashi Mori, Shigeyuki Kono, Nobuhiro Kanomata, Yoshihisa Inoue

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   133 ( 27 ) 10379 - 10381  2011.07  [Refereed]

    Authorship:Corresponding author

     View Summary

    Photochemical planar-to-planar chirality transfer was effected by using (R)-[10] paracyclophane-12-carboxylates as a planar-chiral sensitizer and (Z)-cyclooctene and (Z,Z)-1,5-cyclooctadiene as prochiral substrates to give a planar-chiral (E)and (E,Z)-isomer in up to 44% and 87% enantiomeric excess, respectively, the latter of which being the highest ever reported for a sensitized photochirogenic reaction.

    DOI

  • Enantioselective Cyclopropanation Reactions with Planar-Chiral Pyridinium Ylides: A Substituent Effect and a Remote Steric Effect

    Nobuhiro Kanomata, Ryo Sakaguchi, Kazuki Sekine, Satomi Yamashita, Hiroko Tanaka

    ADVANCED SYNTHESIS & CATALYSIS   352 ( 17 ) 2966 - 2978  2010.11  [Refereed]

    Authorship:Lead author, Corresponding author

     View Summary

    Novel planar-chiral pyridinium ylides were designed, and generated in situ from the corresponding pyridinium salts with triethylamine. Ylides with a common parapyridinophane skeleton reacted efficiently with electron-deficient dicyanoalkenes, or malononitriles, to produce optically active cyclopropane derivatives with high enantioselectivity (up to 99% ee). Remote steric effects were observed on the enantioselectivities, where the R(2) groups of the pyridinophane core resulted in higher ee values of the products. Density function theory (DFT) calculations are in good agreement with our experimental results: the energetically favored transition state leads to the major stereoisomer, namely the trans-cyclopropane products.

    DOI

  • Synthesis of planar-chiral bridged bipyridines and terpyridines by metal-mediated coupling reactions of pyridinophanes

    Nobuhiro Kanomata, Jun Suzuki, Hironobu Kubota, Kiichiro Nishimura, Terumichi Enomoto

    TETRAHEDRON LETTERS   50 ( 23 ) 2740 - 2743  2009.06  [Refereed]

    Authorship:Lead author, Corresponding author

     View Summary

    We have accomplished efficient synthesis of planar-chiral bridged 2,2'-bipyridine (S)-6, C(2)-symmetric bipyridinophane (S,S)-7, bridged 2,2':6',2 ''-terpyridines (S)-11, and C(2)-symmetric terpyridine (S,S)-12 by metal-mediated biaryl cross-coupling or homo-coupling reactions of the corresponding 6-halo[10](2,5)pyridinophanes. Stille-type and Negishi cross-coupling reactions are particularly useful for the syntheses of 6, 11, and 12. On the other hand, nickel-mediated homo-coupling reaction worked best for achieving the synthesis of structurally unique bipyridinophane 7. (C) 2009 Elsevier Ltd. All rights reserved.

    DOI

  • Synchronized stereocontrol of planar chirality by crystallization-induced asymmetric transformation

    Nobuhiro Kanomata, Gou Mishima, Jun Onozato

    TETRAHEDRON LETTERS   50 ( 4 ) 409 - 412  2009.01  [Refereed]

    Authorship:Lead author, Corresponding author

     View Summary

    Synchronized stereocontrol of two planar-chiral units was accomplished by using crystallization-induced asymmetric transformation (CIAT) of cyclophane-type bridged bisnicotinate derivatives 5b and 7. After screening Various linkers, (S)-2-amino-1-butanol and (S)-tert-leucinol were found to be the most effective for CIAT of the corresponding bridged bisnicotinate 5b and 7, respectively, whose diastereomeric ratio finally reached 97% and 88%. respectively. (c) 2008 Elsevier Ltd. All rights reserved.

    DOI

  • Synthesis of bridged nicotinates having [n](2,5)pyridinophane skeletons (n=8-14)

    N Kanomata, S Yamada, T Ohhama, A Fusano, Y Ochiai, J Oikawa, M Yamaguchi, F Sudo

    TETRAHEDRON   62 ( 17 ) 4128 - 4138  2006.04  [Refereed]

    Authorship:Lead author, Corresponding author

     View Summary

    Synthesis of various bridged nicotinates 6 having [n](2,5)pyridinophane skeletons (n=8-14) was accomplished by the unique pyridine-fori-nation reaction of methyl propiolate with a series of formyl-substituted (vinylimino)phosphoranes 5, which were prepared from the corresponding cycloalkanones 1 via Vilsmeier-Haack formylation giving chloro-substituted cycloalkenals 2, their thermal and photochemical transformation to formyl azirines 4, and the following ring-opening reactions with triphenylphosphine. The HPLC analysis of [11](2,5)pyridinophane derivatives, (S-p,S)-14 and (R-p,S)-14, showed that these diastereomers rapidly epimerize themselves at room temperature and that their planar-chirality was thermodynamically less stable as compared to the corresponding [11](2,5)cyclophane systems. (c) 2006 Elsevier Ltd. All rights reserved.

    DOI

  • Synthesis of planar-chiral paracyclophanes via samarium(II)-catalyzed intramolecular pinacol coupling

    T Ueda, N Kanomata, H Machida

    ORGANIC LETTERS   7 ( 12 ) 2365 - 2368  2005.06  [Refereed]

    Authorship:Corresponding author

     View Summary

    A series of [n]paracyclophanediols (n = 8-12) was synthesized by samarium-catalyzed pinacol coupling for their ansa-bridge formation. Enantiomerically pure [n]paracyclophane esters were derived from the diols in a several steps via chiral resolution (for n = 10) or via crystallization-induced asymmetric transformation (for n = 11) by using amino alcohol auxiliaries and their selective cleavages.

    DOI

  • Studies on syntheses and functional properties of structurally unique nitrogen aromatics

    Nobuhiro Kanomata

    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN   61 ( 4 ) 352 - 359  2003.04  [Refereed]  [Invited]

    Authorship:Lead author, Last author, Corresponding author

     View Summary

    Nitrogen aromatics always remain updated synthetic targets as functional or bioconjugate molecules from the aspects of unique reactivity of their nitrogen atom incorporated. We have been studying structurally unique nitrogen aromatics prepared by the reaction of (vinylimino)phosphoranes and demonstrated their synthetic application to coenzyme analogs reacting in highly enantioselective and regioselective manner in some biomimetic systems and stereoselective transformation of their planar-chiral molecules. In this article, we review our research works including the latest results regarding design, syntheses and biomimetic asymmetric reactions of bridged NADH analogs and their stereocontrol of planar chirality via crystallization-induced asymmetric rope-skipping transformation, namely stereocontrol of molecular jump-rope.

    DOI

  • Adsorption-Induced Asymmetric Transformation of Planar-Chiral Pyridinophanes

    Nobuhiro Kanomata, Jun Oikawa

    Tetrahedron Letters   44 ( 18 ) 3625 - 3628  2003.04

    Authorship:Lead author, Corresponding author

  • A simple method removing 2-oxazolidinone and 2-hydroxyethylamine auxiliaries in methoxide-carbonate systems for synthesis of planar-chiral nicotinate

    N Kanomata, S Maruyama, K Tomono, S Anada

    TETRAHEDRON LETTERS   44 ( 18 ) 3599 - 3603  2003.04  [Refereed]

    Authorship:Lead author, Corresponding author

     View Summary

    A facile and practical removal of 2-oxazolidinone and 2-hydroxyethylamine auxiliaries was accomplished by treating the corresponding N-acyl-2-oxazolidin one and N-(2-hydroxyethyl)amide derivatives in simple methoxide-carbonate systems. The presence of excess DMC (dimethyl carbonate) accelerates the N-acyl bond cleavage for those substrates under mild reaction conditions, and the present method was found to be useful especially for the synthesis of planar-chiral nicotinate. (C) 2003 Elsevier Science Ltd. All rights reserved.

    DOI

  • Stereocontrol of Molecular Jump-rope: Crystallization-induced Asymmetric Transformation of Planar-chiral Cyclophanes

    Nobuhiro Kanomata, Yoshiharu Ochiai

    Tetrahedron Letters   42 ( 6 ) 1045 - 1048  2001.02  [Refereed]

    Authorship:Lead author, Corresponding author

  • Biomimetic Oxidation and Asymmetric Reduction with Coenzyme NAD Analogs.

    Nobuhiro KANOMATA

    Journal of Synthetic Organic Chemistry, Japan   57 ( 6 ) 512 - 522  1999.06  [Refereed]

    Authorship:Lead author, Last author, Corresponding author

     View Summary

    Coenzyme NAD+/NADH, a major cofactor of dehydrogenases, functions as an autorecycling redox agent in biological systems, which is exemplified by enantioselective reduction of pyruvate to L-lactate and oxidation of glyceraldehyde-3-phosphate to 1, 3-bisphosphoglycerate as is observed in anaerobic glycolysis. This article reviews biomimetic asymmetric reduction and oxidation in NAD+/NADH model systems. The first part outlines highly enantioselective reduction of benzoylformate, a lactate analog, with representative NADH model compounds mimicking biological reduction in lactate dehydrogenase. In this section, the well-developed model reactions are grouped based on the types of NADH models ; one having a chiral center at the C-4 position of its 1, 4-dihydronicotinoyl ring and the other good for recycling use. The latter half describes the detailed history on the less developed biomimetic oxidation with NAD+ model compounds. This section classifies the model reactions based on the types of model substrates to summarize the oxidation of alcohols, aldehydes, and formates into aldehydes (or ketones), carboxylates, and carbon dioxide, respectively, with regioselective formation of the corresponding NADH model compounds as analogous reactions in alcohol-, glyceraldehyde-3-phosphate-, and formate dehydrogenases

    DOI

  • Novel pyridine-formation reactions of 2-(phosphoranylideneamino)acrylaldehydes with acetylenic esters. Synthesis of 2-mono- and 2,5-disubstituted nicotinates

    N Kanomata, T Nakata

    HETEROCYCLES   48 ( 12 ) 2551 - 2558  1998.12  [Refereed]

    Authorship:Lead author, Corresponding author

     View Summary

    Preparation of 2-(phosphoranylideneamino)acrylaldehydes, novel formyl-substituted (vinylimino)phosphoranes, was accomplished by the reaction of formyl-2H-azirines with triphenylphosphine. Their novel pyridine-formation reactions with acetylenic esters achieved the preferential formation of 2-mono- and 2,5-disubstituted nicotinate derivatives.

  • Biomimetic Oxidation of Aldehyde with NAD+ Models: Glycolysis-Type Hydrogen Transfer in an NAD+/NADH Model System

    Nobuhiro Kanomata, Masayuki Suzuki, Mamiko Yoshida, Tadashi Nakata

    Angewandte Chemie, International Edition   37 ( 10 ) 1410 - 1412  1998.05  [Refereed]

    Authorship:Lead author, Corresponding author

  • 補酵素の不斉還元機能を模倣する.-架橋型NADHモデルの設計・合成と不斉還元反応

    鹿又宣弘

    化学と工業   51 ( 2 ) 183 - 186  1998.02

    Authorship:Lead author, Last author, Corresponding author

  • Synthesis and chemistry of 1,3,5,7-tetranitrocubane including measurement of its acidity, formation of o-nitro anions, and the first preparations of pentanitrocubane and hexanitrocubane

    KA Lukin, JC Li, PE Eaton, N Kanomata, J Hain, E Punzalan, R Gilardi

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   119 ( 41 ) 9591 - 9602  1997.10  [Refereed]

     View Summary

    Nitro groups on alternate corners of cubane enhance the acidity of cubyl hydrogen (pK(a) similar to 21) and provide sufficient activation for ready anion formation. The sodium salt of 1,3,5,7-tetranitrocubane reacts easily with electrophiles and leads thereby to yet more highly substituted cubanes, like carbomethoxy- and (trimethylsilyl)tetranitrocubane. Anions from these species are also easily formed and are useful for further substitution on the cubane nucleus. Dinitrogen tetraoxide reacts with the anion of tetranitrocubane to give 1,2,3,5,7-pentanitrocubane, the first cubane to contain vicinal nitro groups. The reaction probably involves oxidation of the anion to the corresponding radical. Similarly, the anion of pentanitrocubane is used to prepare 1,2,3,4,5,7-hexanitrocubane, the most highly nitrated cubane made to date. Single-crystal X-ray structural information is given for both penta- and hexanitrocubane.

  • Highly Enantioselective Reduction with Novel, Bridged NADH Models

    Nobuhiro Kanomata, Tadashi Nakata

    Angewandte Chemie, International Edition in English   36 ( 11 ) 1207 - 1211  1997.06  [Refereed]

    Authorship:Lead author, Corresponding author

  • Syntheses and properties of 5-substituted [n](2,4)pyridinophanes, model compounds of NAD(P)

    Tadayoshi Oikawa, Nobuhiro Kanomata, Masaru Tada

    The Journal of Organic Chemistry   58 ( 8 ) 2046 - 2051  1993.04  [Refereed]

    DOI

  • Nucleophilic Radical Substitution of Polychloroazines

    Masaru Tada, Nobuhiro Kanomata, Mamoru Igarashi

    HETEROCYCLES   36 ( 5 ) 1127 - 1127  1993  [Refereed]

     View Summary

    Polychloroazines (1-6) are susceptible to homolytic chlorine substitution by alkyl radicals. In general, the chlorine at the ortho-position to the ring nitrogen is readily replaced by an alkyl radical like adamantyl and tert-butyl. However, the chlorine at the C2-position of pyrimidine did not show any sign of the radical substitution. The reactivity decreases in the order of adamantyl, tert-butyl, and isopropyl radicals.

    DOI

  • On the reaction of (vinylimino)phosphorane and related compounds. 22. Syntheses and structural studies of methanocycloundeca[b]pyrrole ring systems

    Nobuhiro Kanomata, Kenichi Kamae, Yukio Iino, Makoto Nitta

    The Journal of Organic Chemistry   57 ( 20 ) 5313 - 5318  1992.09  [Refereed]

    Authorship:Lead author

    DOI

  • On the reaction of (vinylimino)phosphoranes and related compounds. 20. Syntheses and properties of methanocyclodeca[b]pyridine ring systems

    Nobuhiro Kanomata, Hiroyuki Kawaji, Makoto Nitta

    The Journal of Organic Chemistry   57 ( 2 ) 618 - 625  1992.01  [Refereed]

    Authorship:Lead author

    DOI

  • Alkylation of pyridine‐3,5‐dicarboxamide and pyridine‐3,5‐dicarbonitriles by radical substitution

    Nobuhiro Kanomata, Hisashi Nagahara, Masaru Tada

    Journal of Heterocyclic Chemistry   29 ( 6 ) 1567 - 1571  1992  [Refereed]

    Authorship:Lead author

     View Summary

    Structural modification of NAD(P) model compounds, N,N,N',N'‐tetramethylpyridine‐3,5‐dicarboxamide (1), pyridine‐3,5‐dicarbonitrile (2), and 4‐methylpyridine‐3,5‐dicarbonitrile (3), have been explored by the reaction with alkyl radicals such as the 1‐adamantyl, tert‐butyl, and isopropyl radicals. The alkyl substitutions of compounds 1, 2, and 3 with the 1‐adamantyl and the tert‐butyl radical gave both 2‐mono and 2,6‐disubstitution products, whereas the reaction of compound 2 with the isopropyl radical gave 2‐mono 6c, 2,4‐di 7c, 2,6‐di 8c, and 2,4,6‐trisubstitution 9c products. Copyright © 1992 Journal of Heterocyclic Chemistry

    DOI

  • On the reaction of (vinylimino)phosphoranes and related compounds synthesis and properties of novel 1,6-methanocyclodeca[b]cyclohepta[d]pyrrole

    Makoto Nitta, Hiroyuki Kawaji, Nobuhiro Kanomata

    Tetrahedron Letters   33 ( 2 ) 251 - 254  1992.01  [Refereed]

    Authorship:Last author

     View Summary

    The title compound was synthesized by thermal reaction of 3-phosphoranyldeneamino-1,6-methano[10]annulene with 2-cholortropone in a single step. The examination of 1H NMR spectrum revealed that there is little contribution of peripheral 18-π electron conjugation, but it is rather composed of 1-azaaxulene and methano[10]annulene moieties.

    DOI

  • Synthesis and spectroscopic properties of 1-azamkthanocyclopentacycloundecene ring systems

    Makoto Nitta, Nobuhiro Kanomata, Masaru Tada

    Tetrahedron Letters   31 ( 9 ) 1291 - 1294  1990.01  [Refereed]

     View Summary

    Novel 1-aza-6,11- and 1-aza-4,9-methnocyclopentacycloundecene ring systems were synthesized by the reaction of 3,8-methano[11]annulenone with N-(1-phenylvinylimino)triphenylphosphorane followed by dehydrogenation. These compounds are diatropic as 14pielectron vinylogues of 1-azaazulene.

    DOI

  • The reactions of N-vinyliminophosphoranes. Part 14. A short new synthesis of [n](2,4)pyridinophane ring system (n= 9–6): static and dynamic structural studies of [7]- and [6](2,4)pyridinophanes

    Nobuhiro Kanomata, Makoto Nitta

    J. Chem. Soc., Perkin Trans. 1   ( 4 ) 1119 - 1126  1990  [Refereed]

    Authorship:Lead author

     View Summary

    A short new synthesis of the [n](2,4)pyridinophane ring system (n= 9–6) consists of allowing N-vinyl- and N-(1-phenylvinyl)iminophosphoranes to react with cyclic α,β-unsaturated ketones. Structural studies of the compounds prepared were based on spectroscopic measurements and MNDO calculations. The 1H and 13C NMR spectra at various temperatures showed dynamic behaviour for the oligomethylene chains of [7]- and [6]-(2,4)pyridinophane derivatives (8c,d). The energy barriers ΔGc‡ of the bridge flipping are 12–13 kcal mol–1(Tc, 20 °C) for (8c) and 21–22 kcal mol–1 kcal mol–1(Tc, 150° C) for (8d). The lower-energy process of the oligomethylene chain in (8d) is the pseudorotation with Ea= 10.3 ± 0.2 kcal mol–1, ΔH‡= 9.8 ± 0.2 kcal mol–1, and ΔS‡=–4.8 cal mol–1 deg–1. Two stable conformations of the hexamethylene bridge of (8d) were unambiguously determined by low-temperature NMR. The strain of the [n](2,4)pyridinophane ring system was found to increase as the chain length becomes shorter. Remarkable deformation of the pyridine rings of (8c,d) was suggested by the geometrical optimization by MNDO calculation and the red shift of the UV spectrum.

    DOI

  • On the Reaction ofN-Vinyliminophosphoranes with 2,4,6-Cyclooctatrienone. Intermediate Formation of 8-Azabicyclo[5.3.1]undeca-2,4,7,9-tetraene Ring System

    Makoto Nitta, Nobuhiro Kanomata

    Bulletin of the Chemical Society of Japan   62 ( 7 ) 2401 - 2403  1989.07  [Refereed]

    Authorship:Last author

     View Summary

    The reaction of N-(1-phenylvinyl)iminotriphenylphosphorane and of N-(1,3,5-cycloheptatrienyl)iminotributylphosphorane with 2,4,6-cyclooctatrienone gave an intermediacy of 8-azabicyclo[5.3.1]undeca-2,4,7,9-tetraene derivatives, which underwent an intramolecular Diels–Alder reaction to construct a tetracyclic ring system.

    DOI

  • Synthesis and structural studies of [n](2,4)pyridinophane ring system

    Nobuhiro Kanomata, Makoto Nitta

    Tetrahedron Letters   29 ( 46 ) 5957 - 5960  1988.01  [Refereed]

    Authorship:Lead author

     View Summary

    The facile synthesis of [n](2,4)pyridinophane ring system (n = 9–6) was accomplished by the reaction of N-(1-phenylvinyl)iminophosphorane with cyclic α, β-unsaturated ketones. The chain flipping was studied by 1H NMR spectra at various temperatures.

    The facile synthesis of [n](2,4)pyridinophane ring system (n = 9-6) was accomplished by the reaction of N-(1- phenylvinyl)iminophosphorane with cyclic α,β-unsaturated ketones.

    DOI

  • Preparation, 1,3-Dipolar Cycloaddition, and Thermal and Photochemical Reactions of 3,5-exo- and 3,5-endo-7-Methylene-4-azatetracyclo[4.2.1.0.2,803,5]nona-9-ones

    Nobuhiro Kanomata, Tadashi Kobayashi, Takashi Uetake, Shuji Okada, Makoto Nitta

    Bulletin of the Chemical Society of Japan   60 ( 2 ) 683 - 687  1987.02  [Refereed]

    Authorship:Lead author

     View Summary

    The 1,3-Dipolar cycloaddition of phenyl azide with 1,3,5-trimethyl-6-methylenetricyclo[3.2.1.02,7]oct-3-en-8-one occurred onto the endocyclic double bond to give the exo- and endo-adducts (7 and 8) in a similar ratio. Upon photoirradiation, 7 and 8 eliminated a nitrogen molecule to give 3,5-exo- and 3,5-endo-1,3,6-trimethyl-7-methylene-4-azatetracyclo[4.2.1.0.2,803,5]nona-9-ones (9 and 10) in good yields. The 1,3-Dipolar cycloaddition of 2,4,6-trimethylbenzonitrile oxide with 9 and 10 occurred onto the exocyclic double bond to give two stereoisomers in each case. The stereoselectivity of the reactions is discussed on the basis of the stereoelectronic factor of the aziridine ring. The thermal reaction of 9 and 10 as well as photoirradiation of 9 caused a simple C–N bond cleavage of the aziridine ring. However, photoirradiation of 10 or its dimethyl analogue caused an unusual skeletal rearrangement resulting in the formation of 9-methylene-6-phenyl-6-azatricyclo[3.3.1.02,8]nona-3-en-7-one ring system. Mechanistic pathways of the rearrangement were postulated.

    DOI

  • Synthesis and Properties of Norcaradiene-Cycloheptatriene System Fused with Isoxazole Ring

    Makoto Nitta, Nobuhiro Kanomata, Kensuke Takahashi, Yutaka Takakura, Katsuhiro Saito

    HETEROCYCLES   26 ( 12 ) 3105 - 3105  1987  [Refereed]

     View Summary

    Novel norcaradiene-cycloheptatriene systems fused with arylisoxazoles were synthesized and their temperature dependent 1H nmr spectra were studied. while the fusion of isoxazole ring much shifted the norcaradiene-cycloheptatriene equilibrium to the side of norcaradiene form, the rapid isomerizations of the norcaradienes with their enantiomers were observed and their δG‡c values were obtained.

    DOI

  • The Synthesis and Properties of 3-Arylcyclohepta[d]isoxazolylium Ions

    Makoto Nitta, Nobuhiro Kanomata

    Chemistry Letters   15 ( 11 ) 1925 - 1928  1986.11  [Refereed]

    Authorship:Last author

     View Summary

    3-Arylcyclohepta[d]isoxazolylium tetrafluoroborates were synthesized by the cycloaddition of tricarbonyl(2-5-η-2,4,6-cycloheptatrienone)iron with aromatic nitrile oxides followed by several reactions. The pKR+ values of these ions are less than +1.0 showing that the stability of the tropylium ions is much decreased by the fusion of the isoxazole ring.

    DOI

  • Genetic dissection of pheromone processing reveals main olfactory system-mediated social behaviors in mice

    Tomohiko Matsuo, Tatsuya Hattori, Akari Asaba, Naokazu Inoue, Nobuhiro Kanomata, Takefumi Kikusui, Reiko Kobayakawa, Ko Kobayakawa

    PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA   112 ( 3 ) E311 - E320  2015.01  [Refereed]

     View Summary

    Most mammals have two major olfactory subsystems: the main olfactory system (MOS) and vomeronasal system (VNS). It is now widely accepted that the range of pheromones that control social behaviors are processed by both the VNS and the MOS. However, the functional contributions of each subsystem in social behavior remain unclear. To genetically dissociate the MOS and VNS functions, we established two conditional knockout mouse lines that led to either loss-of-function in the entire MOS or in the dorsal MOS. Mice with whole-MOS loss-of-function displayed severe defects in active sniffing and poor survival through the neonatal period. In contrast, when loss-of-function was confined to the dorsal MOB, sniffing behavior, pheromone recognition, and VNS activity were maintained. However, defects in a wide spectrum of social behaviors were observed: attraction to female urine and the accompanying ultrasonic vocalizations, chemoinvestigatory preference, aggression, maternal behaviors, and risk-assessment behaviors in response to an alarm pheromone. Functional dissociation of pheromone detection and pheromonal induction of behaviors showed the anterior olfactory nucleus (AON)-regulated social behaviors downstream from the MOS. Lesion analysis and neural activation mapping showed pheromonal activation in multiple amygdaloid and hypothalamic nuclei, important regions for the expression of social behavior, was dependent on MOS and AON functions. Identification of the MOS-AON-mediated pheromone pathway may provide insights into pheromone signaling in animals that do not possess a functional VNS, including humans.

    DOI

  • Synthesis and Structural Revision of Phomopsin B, a Novel Polyketide Carrying a 10-Membered Cyclic-Ether Ring

    Yuko Izuchi, Hiroyuki Koshino, Yayoi Hongo, Nobuhiro Kanomata, Shunya Takahashi

    ORGANIC LETTERS   13 ( 13 ) 3360 - 3363  2011.07  [Refereed]

     View Summary

    Total synthesis of the proposed structure 2 for phomopsin B was achieved by using an intramolecular olefin metathesis as a key step. The spectral data, however, did not match with those of the natural product reported. Re-examination of the reported NMR data led to the structural revision of phomopsin B to known dothiorelone A 18. The R configuration of dothiorelone A was determined by total synthesis through a cross-metathesis with a chiral olefin 19.

    DOI

  • Formal total synthesis of aspergillide A

    Yuko Izuchi, Nobuhiro Kanomata, Hiroyuki Koshino, Yayoi Hongo, Tadashi Nakata, Shunya Takahashi

    Tetrahedron: Asymmetry   22 ( 2 ) 246 - 251  2011.01  [Refereed]

     View Summary

    The formal total synthesis of aspergillide A 1 is described. The cross-metathesis of enone 6 with 6-hepten-2-ol derivative 5 provided E-olefin 15 corresponding to the C4–C14 backbone of 1. The CBS asymmetric reduction of 15 gave allyl alcohol 16, which was transformed into β-alkoxyacrylate 4 which had a formyl group. SmI2-induced reductive cyclization of 4 gave a 2,6-syn-2,3-trans THP derivative 3 in good yield. After methoxymethylation of 3, the resulting compound 19 was submitted to desilylation and hydrolysis, to afford Fuwa’s key intermediate 2 for the total synthesis of 1.

    DOI

  • Novel chemoembolization using calcium-phosphate ceramic microsphere incorporating TNP-470, an anti-angiogenic agent

    Makoto Emoto, Yasuko Naganuma, Batsuren Choijamts, Toshiki Ohno, Hajime Yoshihisa, Nobuhiko Kanomata, Tatsuhiko Kawarabayashi, Mamoru Aizawa

    CANCER SCIENCE   101 ( 4 ) 984 - 990  2010.04  [Refereed]

     View Summary

    The purpose of the present study was to develop a new method of chemoembolization to improve the therapeutic effectiveness and safety profile of cancer treatment. A chemoembolization approach was designed for human solid tumors using resorbable calcium-phosphate ceramic microspheres loaded with an agent anti-angiogenic to tumor vasculature in vivo. The human uterine sarcoma cell line FU-MMT-3 was used in this study because this tumor is aggressive and also exhibits a poor response to radiotherapy or any chemotherapy currently used. The calcium-phosphate ceramic microspheres loaded with TNP-470, an antiangiogenic agent, were injected into FU-MMT-3 xenografts in nude mice three times per week for 8 weeks. The treatment using TNP-470-loaded microspheres suppressed tumor growth, compared to treatment with TNP-470 alone, microspheres alone, and the control. The mean tumor weight after treatment using TNP-470-loaded microspheres was significantly lower than that after treatment with microspheres alone. These ceramic microspheres were remarkably embolized in tumor microvessels as well as in the feeding arteries and a significant reduction of intratumoral vascularity was also demonstrated following treatment with TNP-470-loaded microspheres. Severe loss of body weight was not observed in any mice treated with the TNP-470-loaded microspheres, compared to treatment with TNP-470 alone. These results suggest that targeting tumor vasculature in human uterine sarcoma using calcium-phosphate microspheres might be more effective and safer than the treatment that employs anti-angiogenic agent alone. This new chemoembolization method incorporating an anti-angiogenic agent may contribute to the effective treatment of locally advanced or recurrent solid tumors. (Cancer Sci 2010; 101: 984-990)

    DOI

  • Anti-tumorigenesis of hollow calcium-phosphate microsphere loaded with anti-angiogenic agent

    M. Aizawa, T. Ohno, N. Kanomata, K. Yano, M. Emoto

    BIOCERAMICS, VOL 20, PTS 1 AND 2   361-363   1215 - +  2008  [Refereed]

     View Summary

    We have successfully synthesized hollow biphasic calcium -phosphate microspheres consisting of the P-tricalcium phosphate (beta-Ca-3(PO4)(2); beta-TCP) and calcium-deficient hydroxyapatite (DAp) using an ultrasonic spray-pyrolysis technique. The resulting hollow biphasic microspheres have been applied as a carrier of a drug delivery system (DDS) for medical treatment of cancers. An anti-angiogenic agent, TNP-470 (Takeda), was used as one of drug models. We have performed biological evaluations in vitro and in vivo using the biodegradable calcium-phosphate microsphere loaded with TNP-470. The results of in vitro and in vivo testing indicate that the microspheres loaded with TNP-470 inhibit i) the proliferation of FU-MMT-3 cells as a tumor model and ii) the enlargement of tumor sizes as a model of nude mice injected with FU-MMT-3 cells. The biological evaluations demonstrate that the present microspheres loaded with TNP-470 have an excellent anti-tumorigenesis effect.

    DOI

  • N含有シクロファンの面不斉を立体制御する手法の開発

    鹿又宣弘

    ファインケミカル   32 ( 19 ) 5 - 13  2003.11

    Authorship:Lead author, Last author, Corresponding author

  • Bridge Flipping Data from Dynamic 1H-NMR Spectra of 2,6-Dimethyl-[9](3,5)-Pyridophane and its Pyrylium and N-Methylpyridinium Analogs

    Alexandru T. Balaban, Teodor-Silviu Balaban, Makoto Nitta, Nobuhiro Kanomata

    Bulletin des Sociétés Chimiques Belges   101 ( 12 ) 1047 - 1051  1992  [Refereed]

    Authorship:Last author

     View Summary

    Dynamic 1H‐NMR spectra between room temperature and −90 °C for the title compounds indicate that the flipping of the nonamethylene bridge is slowed down on cooling (ΔGc‡ = 9.8 kcal/mol for the 2/8 methylene groups in the pyridinophane with coalescence temperature Tc = −58 °C) but the pseudorotation persists even at −90 °C. The bridge flipping is somewhat easier in the N‐methylpyridinium (ΔGc‡ = 9.7 kcal/mol, Tc = −63 °C) and in the pyrylophanium perchlorates (ΔGc‡ = 8.9 kcal/mol, Tc = −78 °C).

    DOI

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Books and Other Publications

  • 理工系のための一般化学

    柴田, 高範, 石原, 浩二, 井村, 考平, 鹿又, 宣弘, 寺田, 泰比古, 中井, 浩巳, 中尾, 洋一, 中田, 正久, 古川, 行夫, 山口, 正

    東京化学同人  2021.01 ISBN: 9784807909940

  • Chemistry, The Central Science

    ( Part: Joint translator)

    2015.12 ISBN: 9784621300107

  • Chemistry, The Central Science

    上野 圭司, 荻野 和子, 鵜沼 英郎, 鹿又 宣弘( Part: Joint translator)

    2015.12 ISBN: 9784621300114

  • 有機化学

    清水, 功雄, 只野, 金一

    オーム社  2011.11 ISBN: 9784274211034

  • 合成有機化学 : 反応機構によるアプローチ

    Parashar, Rakesh Kumar, 柴田, 高範, 小笠原, 正道, 鹿又, 宣弘, 斎藤, 慎一(化学), 庄司, 満

    東京化学同人  2011.03 ISBN: 9784807907373

Misc

  • Structure, dynamism, and enantioselectivity of planar-chiral pyridines for ylide-catalyzed asymmetric cyclopropanation of malononitriles

    Nobuhiro Kanomata, Kazuya Nakagawa, Yosuke Fujiyasu, Yusuke Miyashita

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   248  2014.08

    Research paper, summary (international conference)  

  • Synthesis of novel C-2-symmetric planar-chiral bispyridinophanes and their applications to asymmetric catalysis

    Satoko Yasuda, Narihito Ogawa, Nobuhiro Kanomata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   244  2012.08

    Research paper, summary (international conference)  

  • Synthesis of the ruthenium complexes of planar- chiral 2,2 ':6 ',2 ''-terpyridine and their catalytic asymmetric transfer hydrogenation reactions

    Kyohei Kotani, Nobuhiro Kanomata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   244  2012.08

    Research paper, summary (international conference)  

  • Synthesis of the ruthenium complexes of planar-chiral 2,2 ':6 ',2 ''-terpyridine and their catalytic asymmetric transfer hydrogenation reactions

    Kyohei Kotani, Nobuhiro Kanomata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   244  2012.08

    Research paper, summary (international conference)  

  • わくわくする化学のこころ(化学教育 徒然草)

    鹿又 宣弘

    化学と教育   60 ( 7 )  2012.07

    CiNii

  • ORGN 418-Efficient synthesis of C2-symmetric planar-chiral bipyridines and their asymmetric cyclopropanation reactions

    Kiichiro Nishimura, Nobuhiro Kanomata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   236  2008.08

    Research paper, summary (international conference)  

  • ORGN 20-Remote steric effect on enantioselective cyclopropanation reactions with planar-chiral pyridinophanes

    Nobuhiro Kanomata, Ryo Sakaguchi, Kazuki Kimura, Hironobu Kubota, Kazuki Sekine

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   235  2008.04

    Research paper, summary (international conference)  

  • ORGN 576-Synthesis of planar-chiral bridged bipyridines and terpyridines

    Nobuhiro Kanomata, Jun Suzuki, Hironobu Kubota

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   232  2006.09

    Research paper, summary (international conference)  

  • Stereocontrol of planar-chiral paracyclophanes by using adsorption-induced asymmetric transformation.

    N Kanomata, H Machida, J Oikawa

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   228   U144 - U144  2004.08

    Research paper, summary (international conference)  

  • NADH

    Nobuhiro Kanomata

    Journal of Synthetic Organic Chemistry, Japan   61 ( 4 ) 370 - 370  2003.04  [Invited]

    Authorship:Lead author, Last author

    Article, review, commentary, editorial, etc. (scientific journal)  

    DOI

  • Novel synthetic method for paracyclophanes by samarium iodide-catalyzed intramolecular pinacol coupling.

    N Kanomata, T Ueda

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   224   U238 - U238  2002.08

    Research paper, summary (international conference)  

  • Stereocontrol of planar-chiral pyridinophanes.

    N Kanomata, S Anada, M Yamaguchi, Y Ochiai

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   222   U65 - U65  2001.08

    Research paper, summary (international conference)  

  • Biomimetic redox reactions of anaerobic glycolysis in NAD(+)/NADH model system.

    N Kanomata, M Suzuki, M Yoshida, T Nakata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   216   U371 - U371  1998.08

    Research paper, summary (international conference)  

  • Design, synthesis, and asymmetric reduction of bridged NADH models having parapyridinophane structure

    N Kanomata, T Nakata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   213   443 - ORGN  1997.04

    Research paper, summary (international conference)  

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Industrial Property Rights

  • 置換ピペラジン化合物及び酸性ガス用の吸収剤、吸収液

    鹿又 宣弘, 由渕 武

    Patent

Awards

  • Incentive Award in Synthetic Organic Chemistry, Japan

    2002.02  

  • Banyu Award in Synthetic Organic Chemistry, Japan

    1997.02  

Research Projects

  • 燃焼排ガスからの二酸化炭素回収システムに適した二酸化炭素吸収材に係る新規薬剤の開発

    川崎重工業株式会社 

    Project Year :

    2020.04
    -
    2022.03
     

  • 低濃度二酸化炭素回収システムによる炭素循環モデル構築実証

    環境省  二酸化炭素の資源化を通じた炭素循環社会モデル構築促進事業

    Project Year :

    2019.08
    -
    2022.03
     

  • 光異性化を鍵反応とする性フェロモン(-)-デヒドロ-exo-ブレビコミンの高効率不斉全合成研究

    三菱マテリアル  三菱マテリアル-早大理工包括協定にともなう2019年度研究助成

    Project Year :

    2019.07
    -
    2020.02
     

  • 二酸化炭素吸収性能を有する新規アミンの合成と機能評価

    株式会社IHI 

    Project Year :

    2009.04
    -
    2019.03
     

  • 次世代省エネルギー型CO2回収技術の実用化開発

    新エネルギー・産業技術総合開発機構(NEDO)  戦略的省エネルギー技術革新プログラム

    Project Year :

    2015.04
    -
    2018.03
     

  • Development of novel fused planar-chiral catalysts and their asymmetric catalysis based on the concept of dynamism control

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Challenging Exploratory Research

    Project Year :

    2015.04
    -
    2017.03
     

    KANOMATA Nobuhiro

     View Summary

    We have designed and synthesized novel planar-chiral parapyridinophane catalysts of the 2nd generation, whose ansa-bridges are tethered to a part of their pyridine rings to freeze their characteristic rope-skipping racemization even at higher temperatures. Pyridinophane catalysts fused with six membered ring effected highly enantioselective ylide-mediated cyclopropanation reactions to afford optically active trans-cyclopropanes exclusively with excellent enantiomeric excesses. For pyridinophane catalysts fused with five membered ring, their catalytic abilities were improved remarkably by introducing remote steric effect: incorporation of large substituents on such pyridine catalysts exerted a significant increase of enantioselectivity close to the level of the catalyst fused with six membered ring. Consequently, we have developed successfully novel fused pyridinophane catalysts with higher planar-chiral stability to achieve high level of asymmetric induction as organocatalysts.

  • Research on development of efficient chirality alternation methods under thermodynamic conditions

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Challenging Exploratory Research

    Project Year :

    2012.04
    -
    2014.03
     

    NOBUHIRO Kanomata, OGAWA Narihito

     View Summary

    We have investigated isomerization properties of [14]parapyridinophane derivatives and demonstrated that crystallization-induced and adsorption-induced asymmetric transformations are efficient protocols to prefer the opposite sense of stereochemistry in planar-chiral [14]parapyridinophane derivatives, respectively. We have also found that azaspirene analog having its characteristic spiro skeleton readily undergoes racemization in neutral aqueous media and that efficient resolution was achieved by using an appropriate chiral auxiliary to resolve the analog by the following acidic hydrolysis of each diastereoisomer to afford highly enantio-enriched azaspirene analog in excellent yields without a loss of their enantiomeric excesses. The sequential transformation to enantiomerically pure analog and its recycling process to its racemic body achieved an efficient synthetic route to an optically active analog of azaspirene.

  • 生物学・化学・情報科学融合のための戦略的先進理工学研究基盤の形成

    文部科学省  私立大学戦略的研究基盤形成支援事業

    Project Year :

    2009.04
    -
    2014.03
     

  • Stereocontrol with planar-chiral pyridines by using structually unique properties of their ansa-bridges

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C)

    Project Year :

    2007
    -
    2008
     

    KANOMATA Nobuhiro

  • グラブリジン新規合成ルートの開発研究

    Project Year :

    2004.04
    -
    2005.03
     

  • Synthetic studies on novel catalysts incorporating multi planar-chiral units

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (B)

    Project Year :

    2002
    -
    2005
     

    KANOMATA Nobuhiro

     View Summary

    This project aimed the new development of efficient synthetic methodologies to provide novel planar-chiral molecules and design/synthesis of multi planar-chiral molecules as novel phase transfer catalysts.
    We have accomplished novel samarium-mediated intramolecular pinacol coupling for synthesis of a series of cyclophanediols in up to 64% yield which were transformed to planar-chiral[n] paracyclophanes(8-12). We have also developed stereocontrol of planar-chiral[11] paracyclophanes by using crystallization-induced asymmetric transformation. Synthesis of a series of[n] parapyridinophanes was also developed by the reaction of(vinylimino) phosphorane intermediates.
    These planar-chiral pyridinophane and cyclophane molecules were transformed to multi planar-chiral ammonium salts and their asymmetric alkylation reactions were investigated as asymmetric phase transfer catalysis. Moderate enantioselectivity was observed with up to 75% ee for benzylation of a glycin derivative. We have thoroughly examined the catalytic activities of the pyridinophane and the cyclophane catalysts and the former showed the better enantioselectivities for asymmetric alkylation reactions.

  • An Efficient Method of Removing Chiral 2-Oxazolidinone Auxiliaries in a Methoxide-Carbonate System. Its Optimization and Synthetic Application

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C)

    Project Year :

    2000
    -
    2001
     

    KANOMATA Nobuhiro

     View Summary

    We have accomplished the efficient N-acyl bond cleavage of both N-acyl-2-oxazolidinone and N-(2-hydroxyethyl)amide based on the reaction with NaOMe in the presence of excess dimethyl carbonate to accomplish a clean removal of those chiral auxiliaries. These reactions generally proceed under mild conditions to give the corresponding methyl esters in high yields. The N-acyl bond cleavage described here are especially useful for sterically demanding molecules with quaternary carbons neighboring exocyclic or carbamoyl carbonyl of N-acyl-2-oxazolidinones or N-(2-hydroxyethyl)amides and for thermodynamically less stable molecules such as atropisomeric compounds with planar, axial, or herical chirality, which face a risk of isomerization at higher temperatures.

  • 新しい酸化還元補酵素モデル化合物の合成とその機能性に関する研究

    日本学術振興会  科学研究費助成事業 奨励研究(A)

    Project Year :

    1995
     
     
     

    鹿又 宣弘

     View Summary

    本研究は特異な構造を有する新規なNAD^+モデル化合物を構築し、その補酵素機能を追求することを目的として研究を行った。本年度中に得られた成果は以下の通りである。
    1新規なニコチン酸エステル合成法の開発。NAD^+モデル化合物の前駆体であるニコチン酸エステル誘導体の合成研究として、ビニルイミノホスホラン構造を有するホスホラニリデンアミノエナ-ルとアセチレン誘導体との反応による新規なピリジン環形成反応について検討した。ホスホラニリデンアミノエナ-ル誘導体の合成法としてアジリン誘導体とホスフィンの反応による新たなビニルイミノホスホラン合成法を開発した。これらのホスホラニリデンアミノエナ-ル誘導体と活性アセチレンとの反応により新たなピリジン環形成反応が進行し、種々のニコチン酸エステル誘導体を良好な収率で与えることを見いだした。
    2パラピリジノファン骨格を有するNAD^+モデル化合物の合成。補酵素の行う不斉還元反応のモデル化を効率的に行う上でパラピリジノファン構造を有する架橋ニコチン酸アミド誘導体が有用なモデル化合物であると考え、その合成法を検討した。合成法として前述のニコチン酸エステル合成法を応用した。ビニルイミノホスホラン構造を有する2-ホスオラニリデンアミノシクロドデセン-1-カルボキシアルデヒドと活性アセチレンとの反応を検討したところ期待したニコチン酸エステル誘導体を与える反応が進行し、新規なパラピリジノファン骨格を有する架橋ニコチン酸エステル誘導体が得られることを見出した。また、架橋ニコチン酸エステル誘導体からアミド化、N-アルキル化を経てパラピリジノファン骨格を有する新規な架橋NAD^+モデル化合物の合成を行った。今後はこれらの化合物を用いた不斉還元反応を行い、補酵素反応の有機化学的モデル化を検討する。

  • 含窒素架橋芳香族化合の合成と性質に関する研究

    日本学術振興会  科学研究費助成事業 奨励研究(A)

    Project Year :

    1991
     
     
     

    鹿又 宣弘

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Specific Research

  • 純液体アミンを用いる高効率二酸化炭素吸収・放散システムの構築と機能評価

    2021  

     View Summary

    地球温暖化対策の一つに発電所等由来の排気ガスからCO2を分離・回収する二酸化炭素貯留回収技術(CCS)がある.我々はアミンを純液体として用いることでエネルギー効率の高いCO2回収系を構築できると考え,研究に着手した.市販原料より合成した4種のジエチレントリアミン誘導体と参照物質であるジエタノールアミン(DEA) を用い,純液体としてのCO2吸収・放散性能評価を行なったところ,アミン1 mol 当たりのCO2吸収率はDEAより最大で2倍優れた値を示した.さらにCO2放散率はDEAをはるかに凌駕して約90%に達し,これらの純液体アミンがCO2回収の繰り返し利用に適した分子であることを明らかとした.

  • D2対称[10][10]パラピラジノファンの合成と機能創製

    2021  

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     我々はこれまでに根岸カップリングとGlaserカップリングを鍵反応とした[10]パラピラジノファン類の合成を報告している.本研究では,X線結晶構造解析により(+)-[10]パラピラジノファンの絶対立体配置をSと決定するとともに,2本目の架橋鎖を導入することでD2対称性を有する(S)-[10][10]パラピラジノファンを合成することに成功した.また,(S)-[10]-および(S)-[10][10]-パラピラジノファンから誘導されたN,N’-ジオキシド触媒を用い,ベンズアルデヒドに対する触媒的不斉アリル化反応を行ったところ,付加体であるホモアリルアルコールが最大66% eeで得られた.これらの結果から,パラピラジノファンのN,N’-ジオキシドが不斉触媒として有用であることを明らかにした.

  • フッ素により活性化された面不斉相間移動触媒の創製と機能評価

    2020  

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    我々はこれまでに,様々な面不斉ピリジノファン相間移動触媒について研究を行ってきた.今回,ピリジノファン上に4-フルオロフェニル基,および3,5-ジフルオロフェニル基を導入した触媒(S,S)-2,3を合成し,これらの不斉誘起能を検証する目的で研究を行った.触媒 (S,S)-2,3 をそれぞれ 1 mol% 存在下,グリシン誘導体の不斉ベンジル化を行ったところ, 前者は75% eeで,また後者は95% eeで(S)-フェニルアラニン誘導体を与えた.これらの結果から,(S,S)-3が極めて高い不斉誘起能を有する触媒であること,フッ素の導入位置が高い不斉誘起能を有する触媒設計において極めて重要であることを明らかとした.

  • 有機アミン分子を用いる高効率二酸化炭素吸収・放散システムの構築と機能評価

    2020  

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    本研究では再利用可能な燃焼排ガス用のアミン開発を目的として新たにアミン化合物A〜Eを設計・合成し,純液体としてのCO2吸収・放散性能の評価を行うことで,熱効率のよい高機能性アミンのスクリーニングを行った.合成アミンA〜Eと参照アミンDEAに模擬排気ガスを流し,CO2吸収量を測定した結果,アミンA, BではCO2捕捉率が単位質量当りでDEAと同程度の値を示し,物質量当りでは,A〜EいずれもDEAの1.5-2倍程度のCO2を吸収した.また,放散率は90%以上と極めて高い値であった.これらの結果より,今回開発したアミン化合物A〜EはCO2の吸収・放散の点で再利用に適した実用性に耐えうる燃焼排ガス用アミンであることを実証した.

  • 新たな擬面不斉ピリジンの設計・合成と不斉触媒機能評価

    2019   菊池惇人, 宮下裕輔

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    10炭素の架橋鎖を有する面不斉ピリジノファンは不斉触媒として高い立体選択性を発揮するものの,反応中にラセミ化が起こることが課題であった.本研究では高い熱安定性を付与した新たな縮環擬面不斉ピリジンを設計し,シクロプロパン化における触媒機能を検証した.その結果,ピリジン窒素近傍にヒドロキシ基を導入した触媒が最大95% eeで所望のトランスシクロプロパンを与え,高エナンチオ選択的かつ高ジアステレオ選択的に反応することを見いだした.本反応は触媒の擬面不斉部位に立体特異的であり,ヒドロキシ基を除去すると不斉収率が大きく低下することから,高い不斉誘起能の発現にヒドロキシ基の導入が極めて有用であり,優れた不斉触媒として機能することが示された.

  • 高活性面不斉テルピリジン高分子触媒の設計と不斉反応への応用

    2018  

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    我々は市販のMerrifield樹脂に対して面不斉テルピリジンを固定化することで,表面のみに均一な状態で配位部位を有する高分子テルピリジンの合成と不斉反応への応用を目的として研究を行った.低分子面不斉テルピリジンに対し4’位選択的にボロン酸エステルを導入し,鈴木宮浦カップリングによりリンカーを導入後Merrifield樹脂に固定化し,所望の高分子テルピリジン配位子を合成した.この高分子配位子を用いて銅触媒存在下,ジアゾ酢酸エチルとスチレンによる不斉シクロプロパン化を行ったところ,6:4のジアステレオ選択性でtrans-シクロプロパン誘導体が得られ,触媒として10回程度のTONを示すことが明らかとなった. 

  • 光学活性ピラジノファンの創製とその不斉立体制御法の開発

    2017  

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    ピラジノファンはC2対称面不斉分子としてその動的挙動や不斉誘起能に興味がもたれるものの,合成例は皆無であった.我々はGlaserカップリングを鍵反応とする[10]パラピラジノファンの合成を検討した結果,前駆体である末端ジアルキンを酢酸銅とビピリジン存在下に分子内環化させることで,パラピラジノファンジインが良好な収率で得られることを見いだし,これらを還元して所望の[10]パラピラジノファンとそのメチルエステル誘導体の初の合成を達成した.[10]パラピラジノファンの面不斉反転における速度論解析を行った結果,類似のピリジノファンよりもラセミ化速度がかなり遅く,両者の活性化エントロピー項の違いが異性化速度の支配要因であることを明らかとした.

  • ダイナミズム制御を設計指針とする新規面不斉反応場の創出と触媒機能

    2014  

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     熱安定性を向上させた面不斉ピリジノファン触媒として,5および6員環縮環構造を有する新たな面不斉触媒を設計・合成し,不斉シクロプロパン化反応を検討した.その結果,剛直な5員環縮環触媒,より柔軟な6員環縮環触媒を用いたシクロプロパン化反応において,トランス生成物をそれぞれ67%ee ,90%ee で与えることを見いだした.特に後者の面不斉ピリジン触媒は僅かに1炭素の違いにより前者の不斉誘起能を大きく凌駕し,柔軟な架橋鎖を有する非縮環触媒の不斉誘起能(94% ee)に迫る不斉触媒機能を発揮した.以上の結果より,自由度の高いピリジノファン架橋鎖の動的挙動が高エナンチオ選択性の発現に極めて重要な役割を果たしていることが示された.

  • 面不斉有機リン触媒の設計・合成とその触媒機能創製

    2014  

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    面不斉を持つ有機化合物は新しい不斉素子として注目されているものの,面不斉固有の機能を発揮する実用的物質の開発例は極めて少ない.本研究では,シクロファンを不斉源として有する面不斉ホスホニウム有機触媒を合成し,相間移動触媒の反応条件におけるベンジル化反応について検討した.水酸化セシウム存在下,グリシン誘導体のベンジル化を行ったところ,高収率でフェニルアラニン誘導体を与えることが明らかとなったが,得られた生成物についての光学活性は確認できなかった.この結果から,面不斉部位を1つ導入したホスホニウム触媒はベンジル化の触媒機能は保持するものの,不斉触媒としての機能は持たないことが示された.

  • 面不斉ホスホニウム有機触媒の設計・合成とその触媒機能

    2013   小川熟人

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    面不斉を持つ有機化合物は新しい不斉素子として注目されており,ここ数年の間に急速に研究が進んできが,面不斉固有の機能を発揮する実用的物質の開発例は極めて少ないのが現状である.本研究では,面不斉シクロファンを複数集合させた「ホスホニウム有機触媒」を創製し,この全く新しいタイプの新規不斉有機触媒の機能発現と有機合成化学への応用を研究目的として研究に着手した.特に,面不斉素子として単環性シクロファンを用い,面不斉有機触媒として提案する①不斉相間移動触媒および②不斉リンイリド触媒の創製と機能創出について検討を行った.我々がこれまでに開発した面不斉シクロファン合成法に従い,アンサ鎖としてデカメチレン鎖を有する光学活性ベンジルアルコールから対応するクロロ体およびブロモ体を合成し,三塩化リンとの反応で3つのシクロファンユニットを持つ面不斉ホスフィンの合成を検討した.しかしながら,種々の反応条件を用いて検討を加えたものの,目的とするホスフィン誘導体は得られなかった.そこで,ベンジルブロミドをモデル基質とし,ヨウ素を活性化剤としてに用いた条件で,THF溶媒中60℃にて反応を行ったところ,所望の反応が進行し,3級ホスフィンであるトリベンジルホスフィン,および4級ホスホニウム塩であるテトラベンジルホスホニウムの生成を質量分析により確認した.そこで,反応溶媒をエーテルに代え,100mgスケールにて同様の反応を行ったところ,4級ホスホニウムのモデル化合物であるテトラベンジルホスホニウムブロミドを17%の収率で単離することに成功した.そこで,シクロファン構造を有する面不斉ベンジルブロミドを基質として三塩化リンと反応を行ったところ,低収率ではあるが,目的化合物である面不斉4級ホスホニウム塩の生成を初めて確認することに成功した.現在これらの反応条件の最適化を検討中である.一方,不斉リンイリド触媒の反応研究として,トリフェニルホスフィンとハロ酢酸エステルから誘導される4級ホスホニウムをモデル触媒として用い,種々塩基存在下に電子不足アルケンであるマロノニトリルとの反応を行ったが,この系では期待した触媒活性を示さず,目的とするシクロプロパン化合物は得られなかった.このことから,二つ目の目的としたリンイリド触媒による不斉シクロプロパン化反応の開発は困難であると判断し,面不斉触媒による同様の検討は中断することとした.以上の結果より,本研究では研究目的の一つである面不斉シクロファンを4つ導入した4級ホスホニウム塩の生成を初めて確認することに成功した.今後は本触媒の効率良い合成法の検討を行うとともに,触媒機能の有無について検討する予定である.

  • C<sub>2</sub>対称面不斉ピリジン配位子の合成と不斉反応への応用

    2011   小川熟人

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    本研究では,シクロファン構造を有する面不斉ピリジンを新しい不斉有機分子,不斉配位子の有力候補と捉え,これまでにない“C2対称面不斉ピリジン配位子の合成と不斉反応への応用”を目指すことを研究目的として研究を行った.はじめに,面不斉に由来する光学活性ピリジノファンを2個組み込んだ新たなC2対称二座配位子として,新規な面不斉ジピリジルイミンと面不斉ジピリジルエーテルの合成を検討した.ブロモピリジノファン誘導体に対し,ナトリウムアミド存在下にBuchwald-Hartwigクロスカップリングを行うことで面不斉ジピリジルイミンを,カリウムtert-ブトキシドを用いたクロスカップリング反応により面不斉ジピリジルエーテルを合成した.このうち新たに合成した面不斉ジピリジルイミンでは,1つのピリジノファン部位がアミノピリジンとピリジンイミンの平衡混合物として存在すること,ならびにその存在比に温度依存性が認められることを見いだした.これらの新規配位子を不斉触媒配位子とする触媒反応について検討を行った.銅触媒を用い,ジアゾ酢酸エステルとスチレンによる触媒的不斉シクロプロパン化を行ったところ,面不斉ジピリジルイミン,面不斉ジピリジルエーテルはいずれも 2-5 mol% の触媒量でシクロプロパン化が進行し,光学活性シクロプロパン体を与えた.特に面不斉ジピリジルイミンを用いた場合,収率74%でシクロプロパン体を与え,トランス体が29% ee, シス体は48% eeであった.従来の面不斉ビピリジンでは面不斉ピリジノファンのピリジン環部分が直結した構造であったため,系中で発生する金属錯体の安定性に問題があったが,今回アミンおよびエーテルとして窒素原子および酸素原子を挟むことで,金属錯体の安定性が向上し,より高い触媒活性が得られたものと考えられる.今後アミン窒素原子上に置換基を導入することで電子的および立体的に触媒活性を制御し,不斉収率の向上に向けて研究を継続する予定である.

  • 面不斉ピリジンの高機能触媒化と不斉反応への応用

    2011  

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    我々はこれまでに様々なピリジノファン骨格を有するピリジニウム塩を合成し,塩基存在下において電子不足アルケンと反応させることで,高エナンチオ選択的にtrans-シクロプロパンが得られることを報告している.さらに,面不斉ピリジンと銅カルベン錯体より系中でピリジニウムイリドを形成し,それを活性種として用いた触媒的不斉シクロプロパン化反応についても達成した.そこで本研究では面不斉ピリジンを有機触媒とする不斉反応系の構築を目的とし,固体塩基存在下,面不斉ピリジンのアルキル化と脱プロトン化によりピリジニウムイリドを系中で発生させ,電子不足アルケンであるベンザロマロノニトリルを基質として触媒的不斉シクロプロパン化反応を検討した.炭酸カリウム存在下,ジクロロエタン溶媒中65℃で反応を行った結果,高エナンチオ選択的にシクロプロパン化反応が進行し,trans-シクロプロパン体が97%収率,91% eeで得られた.また,反応温度を下げて反応を行ったジクロロメタン還流条件においては81%収率,94% eeでtrans-シクロプロパンが得られ,有機触媒である面不斉ピリジノファンの光学純度の低下もほとんど見られなかった.さらに,本触媒反応のエナンチオ選択性における基質一般性について検討した.様々なアリールジシアノアルケンを用いてシクロプロパン化反応を行った結果,いずれの基質においても高エナンチオ選択的に反応が進行し,良好な収率でtrans-シクロプロパンが得られた.特にo-MeOC6H4とo-Tolylを有する基質を用いた際に立体選択性が高く,共に最高96% eeで望みのtrans-シクロプロパン誘導体を与えることを見出した.以上の結果より,以前報告した銅カルベン錯体を用いた触媒的不斉シクロプロパン化反応ではtrans-シクロプロパンの不斉収率が最大で93% ee であったことから,今回新たに構築した有機触媒系による本触媒反応が,極めて有用であることが示された.

  • 様々な長さの架橋鎖を持つ面不斉ピリジンの高度立体制御

    2010  

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    (1) 異性化晶出法を用いる[14](2,5)ピリジノファンの面不斉立体制御 長い炭素架橋鎖を有する[13]-および[14]-(2,5)ピリジノファンの様々な誘導体を合成し,異性化晶出に適合する化合物の探索とその効率的な面不斉立体制御について検討した.その結果,[13](2,5)ピリジノファンでは異性化晶出に適した化合物を確認できなかったが,架橋鎖が一炭素長い[14](2,5)ピリジノファン誘導体1で異性化晶出に適した化合物を見いだし,ピリジン環6位のメチル体,クロロ体,ブロモ体においては86-93% de で面不斉の立体制御が可能であることを明らかにした.また,特にブロモ体の異性化に関する速度論的な解析を行った結果,その面不斉は異性化晶出法が確立している[10](2,5)ピリジノファンとほぼ同程度の安定性を有していることが明らかとなった.さらにキラル補助基の除去が効率的に進行し,面不斉のみを有する (S)-2 の合成に成功した.(2)面不斉テルピリジン触媒の不斉シクロプロパン化における遮蔽効果 長い炭素架橋鎖を有する面不斉ピリジンが不斉反応の立体選択性に与える影響を明らかにする目的で,C14架橋鎖を持つ[14](2,5)ピリジノファン骨格を2箇所に組み込んだC2対称面不斉テルピリジン(Sp,Sp)-TPYの合成を行った.触媒としてCu(OTf)2 存在下,各種オレフィンとジアゾ化合物の不斉シクロプロパン化反応を行ったところ,最大でtrans-1が62%ee,cis-1が74%ee で得られた.相当するC10 架橋鎖型配位子では最大90%ee程度の選択性を示すことから,架橋鎖の自由度が向上することで遮蔽効果の低下を招き,立体選択性が低下したことが示唆される.これらの結果より,面不斉の不斉転写の選択性が遮蔽効果の影響を強く反映していることが明らかとなった.

  • 新規面不斉有機触媒の開発とその不斉反応への応用

    2008  

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    [10](2,5)ピリジノファンの6位に置換基を有する架橋ニコチン酸(A),および [10](3,6)ピリジノファン骨格を有する架橋ピコリン酸(B)を面不斉素子とするキラル四級アンモニウム塩を合成し,相間移動触媒型の不斉アルキル化反応について検討した.これらの反応では,触媒と基質のπスタッキングが有効に機能していることが提案されている.そこで本研究では,基質として用いるグリシンエステル誘導体のベンゾフェノンイミン部位のフェニル基を,より有効なスタッキング機能が期待できるα-ナフチル基で置き換えた新規グリシン誘導体を合成し,このものの立体選択性における影響について検証した.その結果,Aを不斉源とするフェナントレン型の触媒と新規基質との反応では,最大58%eeで(S)-フェニルアラニン誘導体が得られることを見いだした.一方,ピリジンの構造因子が不斉反応に与える影響を評価するため,Aとピリジン窒素の位置が異なるBを組み込んだキラル四級アンモニウム塩を用いて不斉ベンジル化を検討した.結果として,生成物を与える立体選択性が逆転し,(R)-フェニルアラニン誘導体が約30%eeで得られるという対照的な結果を与えた.このことは,反応系内で生じる新規基質のエノラートイオンが従来のフェニル基由来の基質と同様,A,Bそれぞれの不斉源をもつ触媒で異なる面が遮蔽されていることを示唆するものであり,ピリジノファン窒素原子の孤立電子対がエノラートイオンの接近方向を制御している可能性を示唆する結果といえる.しかしながら,α-ナフチル基を有する新規基質では何れの場合も不斉収率は低下しており,当初期待したπスタッキング効果による不斉収率の向上は得られなかった.この原因として,α-ナフチル基の導入により基質のかさ高さが増し,収率が低下すると共に望む立体化学を与える選択性も低下したことが考えられる.

  • 動的遮蔽機能を発揮する面不斉有機触媒の開発とその応用

    2007  

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    本研究では,[10](2,5)ピリジノファンの6位に置換基を有する架橋ニコチン酸(A),および [10](3,6)ピリジノファン骨格を有する架橋ピコリン酸(B)を面不斉素子とする有機触媒反応の開発を行った.特に,AおよびBを不斉源とするキラル四級アンモニウム塩を合成し,相間移動触媒型の不斉アルキル化反応について検討した.その結果,Aを不斉源とするフェナントレン型の触媒では,不斉源であるピリジン環上の置換基を嵩高くすると,不斉ベンジル化のエナンチオ選択性が向上し,最大86%eeで(S)-フェニルアラニン誘導体が得られることを見いだした.一方,ピリジンの構造因子が不斉反応に与える影響を評価するため,Aの異性体であるBを不斉源として有するキラル四級アンモニウム塩を合成してその不斉ベンジル化を検討した.その結果,生成物を与える立体選択性が逆転し,(R)-フェニルアラニン誘導体が約50%eeで得られるという対照的な結果を与えた.このことは,反応系内で生じるエノラートイオンが,A,Bそれぞれの不斉源をもつ触媒で異なる面が遮蔽されていることを示唆するものであり,ピリジノファン窒素原子の孤立電子対がエノラートイオンの接近方向を制御している可能性を強く示唆する結果といえる.

  • 解糖型生体酸化の高度モデル系構築に関する研究

    2005  

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     ニコチンアミドアデニンジヌクレオチド(NAD+)およびその環元体(NADH)は、種々の生化学経路において酸化・不斉還元反応を触媒する重要な補酵素である。これらと同等の機能を有する補酵素モデル化合物を開発し, その反応を生体外でシミュレートすることは、新しい効率的な触媒の開発のためばかりでなく、酵素反応機構の解明を行う上でも, 極めて有意義なアプローチであるが、そのような触媒的な生体模倣反応は未だ報告されていない。また,補酵素NADHの酸化・還元モデル反応のうち,生体酸化モデル系に関するメカニズムは充分解明されてきたとは言い難い。 本研究では,天然酵素反応の生体酸化基質であるシステイン活性型アルデヒドを模倣した含硫黄モデル基質(ヘミチオアセタールモデル基質)を設計・合成し,アルデヒドの生体酸化モデル反応系の構築について検討した。その結果,環状チオラクトール構造を有するヘミチオアセタール誘導体をモデル基質として用いることで,NADモデル補酵素存在下における天然類似の生体酸化型モデル反応が高選択的に進行することを見いだした.さらに,より穏和な条件で反応するモデル反応系の構築を行った.従来は酵素反応条件よりも過剰量のモデル基質,はるかに高温の反応条件を必要とした人工補酵素反応系が,諸条件検討の結果,約2倍の基質を用いる程度で反応が充分進行し,酵素最適温度よりやや高めの50℃でも生体酸化型モデル反応が良好に進行することを突き止めた.また,重水素ラベル実験を通して選択的な水素移動に関する詳細なメカニズムを明らかにした. 本反応は含硫黄モデル基質による効率的なアルデヒド型酸化反応の初めての例であり,本研究の成果は含硫黄モデル基質が人工補酵素系における酸化還元システムの構築に有用であることを示すものである.

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Syllabus

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Committee Memberships

  • 2008
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    日本化学会普及・交流委員会 委員 2008 -

  • 2008
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    日本化学会普及・交流委員会 クイズショーTG主査 2008 -

  • 2008
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    日本化学会普及・交流委員会 化学教育フォーラムTG委員 2008 -

  • 2008
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    日本化学会役員選考委員会 委員 2008年度

  • 2007
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    2008

    日本化学会夢化学小委員会 クイズショーTG主査 2007 - 2008

  • 2006
    -
    2008

    日本化学会夢化学小委員会 幹事会委員 2006 - 2008

  • 2007
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    日本化学会関東支部 代議員 2007 -

  • 2006
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    2007

    日本化学会夢化学小委員会 クイズショーTG委員 2006 - 2007

  • 2006
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    日本化学会会員委員会 委員 2006 -

  • 2003
     
     

    日本化学会関東支部 代議員 2003 - 2003

  • 2002
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    2003

    日本化学会  関東支部幹事

  • 2002
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    2003

    日本化学会関東支部事業企画委員会 委員 2002 - 2003

  • 2002
    -
    2003

    日本化学会関東支部 幹事 2002 - 2003

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