| Project/Area Number |
14078212
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Nagoya University |
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Principal Investigator |
KITAMURA Masato Nagoya University, Research Center for Materials Science, Professor, 物質化学国際研究センター, 教授 (50169885)
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| Project Period (FY) |
2002 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥24,400,000 (Direct Cost: ¥24,400,000)
Fiscal Year 2005: ¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 2004: ¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 2003: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2002: ¥6,000,000 (Direct Cost: ¥6,000,000)
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| Keywords | Mechanism / BINAP / Ruthenium / Asymmetric hydrogenation / Leuckart-Wallach reaction / Allyl ether synthesis / Allyl ether cleavage / Williamson's ether synthesis / 二官能性触媒 / 分子触媒反応 / アリルエーテル / アリル炭酸エステル / 触媒的脱保護 / キナルジン酸 / 無添加 / ルテニウム錯体 / BINAP-Ru錯体 / 副鏡像異性体 / 重水素標識 / 同位体導入型式 / エナンチオ選択性 / アレニウスの式 / BINAP-Rh錯体 / 分子機構 / α-アミノ酸誘導体 / モノヒドリド-不飽和機構 / 触媒サイクル / 鏡像面選択機構 / 不斉触媒設計 |
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| Research Abstract |
Asymmetric hydrogenation of a-(acylamino)acrylic esters with Ru(CH_3COO)_2 [(S)-binap] (BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) has been revealed to proceed via monohydride-unsaturate mechanism. The enantioselectivity that is opposite to the (S)-BINANP-Rh case has been interpreted in terms of stereo-complementary models of the enamide/metal chelate complexes. The detailed analysis of the isotopomer ratios has proved that the major S and minor R enantiomers are produced via the same mechanism involving diastereomeric intermediates. With (Z)-3-phenyl-2-butenoic acid, however, the minor enantiomer is formed mostly by mechanisms that differ from the major one. The observed enantioselectivity has generally been interpreted to result from competing diastereomorphic catalytic cycles caused by a single chiral catalyst; however, this supposition has not been substantiated. Our study calls into question such a generalized treatment. Furthermore, in this research project, we have found two new catalyses 1. Cp^*Rh(III)-catalyzed Leuckart-Wallach (LW)-type reductive amination of ketones and 2. catalytic allyl ether cleavage and formation using [CpRu(CH_3CN)_3]PF_6 and 2-pyridinecarboxylic acid derivatives. Both process are very clean and operational simple. In particular, the new salt waste-free allyl ether synthesis has overcome the long-pending problems in Williamson's ether synthesis.
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