2004 Fiscal Year Final Research Report Summary
Reductive Asymmetric Cross Pinacol Coupling Utilizing Planar Chiral Transition Metal Complexes
| Project/Area Number |
14340201
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Osaka Prefecture University |
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Principal Investigator |
UEMURA Motokazu Osaka Prefecture University, Faculty of Integrated Arts & Sciences, Professor, 総合科学部, 教授 (90047241)
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| Co-Investigator(Kenkyū-buntansha) |
KAMIKAWA Ken Osaka Prefecture University, Faculty of Integrated Arts & Sciences, Assistant Professor, 総合科学部, 助手 (40316021)
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| Project Period (FY) |
2002 – 2004
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| Keywords | diol / diamine / β-amino alcohol / cross pinacol coupling |
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| Research Abstract |
Enantiomerically pure β-diols, diamines, and amino alcohols have found widespread use as chiral ligands or auxiliaries as asymmetric reactions, and are also important in key synthetic intermediates for biologically active natural products. While optically pure b-diols have been conveniently prepared by catalytic aymetric dihydroxylation of the olefins with high optical purity, the generally accepted method for the preparation of chiral diamines involvesan optical resolution of racemic compounds with certain chiral carboxylic acids. A reductive coupling of carbonyl or imine compounds, homo-pinacol coupling, is the most direct method for the preparation of b-diols or diamine. Although this reaction can be achieved in high yield by lanthanoid metals or low valent transition metals, highly diastereoselective formation of b-diols or diamines is problematic under conventional reductive coupling. We have succeeded that samarium idode-mediated cross-coupling of N-tosyl ferrocenylideneamine with planar chiral ferrocenecarboxaldehydes or benzaldehyde chromium complexes gave diastereoselectively the corresponding anti-β-amino alcohols by coupling with planar chiral arylaldehydes. Dynamic kinetic resolution of a configurationally equilibrated reactive species generated from achiral N-tosyl ferrocenilideneamine and benzylideneamine by reduction with samarium iodide was observed in the cross-coupling with planar chiral arylaldehydes giving both antipodes of β-amino alcohols depending on thee planar chirality. The obtained anti-β-amino with the ferrocene ring was utilized as a ligand for catalytic asymmetric reduction of acetophenone.
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Research Products
(25 results)
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[Journal Article] Stereoselective Allylation Reactions Utilizing Optically Active Dinucular α,β-Unsaturated Fischer Carbene Complexes with Planar Chirality of (Arene)chromium Complexes2004
Author(s)
Kamikawa, K., Tachibana, A., Shimizu, Y., Uchida, K., Furusho, M., Uemura, M
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Journal Title
Description
「研究成果報告書概要(和文)」より
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[Journal Article] Stereoselective Synthesis of Atropisomeric Korupensamines A and B Utilizing Planar Chiral Arene Chromium Complex2004
Author(s)
Watanabe, T., Tanaka, Y., Shoda, R., Sakamoto R., Kamikawa, K., Uemura, M.
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Journal Title
Description
「研究成果報告書概要(和文)」より
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[Journal Article] Stereoselective Allylation Reactions Utilizing Optically Active Dinucular a,b-Unsaturated Fischer Carbene Complexes with Planar Chirality of (Arene)chromium Complexes2004
Author(s)
Kamikawa, K., Tachibana, A., Shimizu, Y., Uchida, K., Furusho, M., Uemura, M
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Journal Title
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Planar Chiral (η^6-Arene) Ruthenium Cp Complex in Organic Synthesis : Diastereoselective Complexation of Arene Compounds with Benzylic Alcohol and Its Synthetic Application to Chiral Biaryls2003
Author(s)
Kamikawa, K., Norimura, K., Furusyo, M., Uno, T., Sato, Y., Konoo, A., Bringmann, G., Uemura, M.
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Journal Title
Organometallics 22
Pages: 9
Description
「研究成果報告書概要(和文)」より
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[Journal Article] Planar Chiral (h^6-Arene) Ruthenium Cp Complex in Organic Synthsis : Diastereoselective Complexation of Arene Compounds with Benzylic Alcohol and Its Synthetic Application to Chiral Biaryls2003
Author(s)
Kamikawa, K., Norimura, K., Furusyo, M., Uno, T., Sato, Y., Konoo, A., Bringmann, G., Uemura, M.
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Journal Title
Organomeallics. 22
Pages: 3
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Stereoselective Synthesis of Atropisomeric Korupensamines A and B Utilizing Planar Chiral Arene Chromium Complex2003
Author(s)
Watanabe, T., Tanaka, Y., Shoda, R., Sakamoto, R., Kamikawa, K., Uemura, M
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Journal Title
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] The Lactone Concept-a Novel Approach to the Metal=Assisted Atropselective Construction of Axially Chiral Biaryl System2002
Author(s)
Bringmann, G., Breuning, M., Pfeifer, R.-M., Schenk, W.A., Kamikawa, K., Uemura, M.
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Journal Title
J.Organomet.Chem. 661
Pages: 17
Description
「研究成果報告書概要(和文)」より
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[Journal Article] The Lactone Concept-a Novel Approach to the Metal=Assisted Atropselective Construction of Axially Chiral Biaryl System2002
Author(s)
Bringmann, G., Breuning, M., Pfeifer, R.-M., Schenk, W.A., Kamikawa.K, Uemura, M.
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Journal Title
J.Organomet.Chem. 661
Pages: 17
Description
「研究成果報告書概要(欧文)」より
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