| 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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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥14,600,000 (Direct Cost: ¥14,600,000)
Fiscal Year 2004: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2003: ¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2002: ¥7,100,000 (Direct Cost: ¥7,100,000)
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| Keywords | diol / diamine / β-amino alcohol / cross pinacol coupling / 1,2-アミノアルコール / クロスピナコールカップリング / 面不斉 / 不斉補助基 / ピナコール反応 / クロスカップリング / アミノアルコール |
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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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