1995 Fiscal Year Final Research Report Summary
Chiral Recognition and Stereoselective Catalysis of Chiral Footprint Cavities.
Project/Area Number |
06680560
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Research Category |
Grant-in-Aid for General Scientific Research (C)
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Allocation Type | Single-year Grants |
Research Field |
Bioorganic chemistry
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Research Institution | Nara Women's University |
Principal Investigator |
MORIHARA Kensaku Nara Women's Univ., Department of Chem., Professor, 理学部, 教授 (90029950)
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Project Period (FY) |
1994 – 1995
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Keywords | Molecular Imprinting / Footprint Cavities / Chiral Recognition / Autocatalysis / Asymmetric Amplification |
Research Abstract |
This research project concerned the "footprint catalysis" study ; it was aimed its application to (1) enantioselective catalysis and (2) autocatalytic assymetric amplification. The footprint catalysis means an artificial catalytic antibody study, that is, a method for tailor-made catalyst design based on specific catalytic action of footprint cavities imprinted on a silica gel surface by the author's molecular imprinting with a proper template. Results : (1) The chirally imprinted footprint cavities using L-proline-hydantoin template showed highly enantioselective catalytic activities in nucleophilic cleavage of hydantoin rings of L-proline-, 5-methyl, and 5-phenyl-hydantoins. The cavities transformed L-isomers nearly 20 times effectively than D-isomers. An unique mechanism was proposed for these high enantioselectivities based on asymmetric face recognition of hydantoin rings. (2) Footprint cavities imprinted with meso- (Z-Ala) _2NH catalized transacylation of LL,DD,and racemic isomers of (Z-Ala)_2O,respectively. In the catalysis, Z-L-alaninate, and Z-D-alaninate, one of the reaction product, stereoselectively showed competitive inhibition. It implied that cavities imprinted with meso- (Z-Ala) _2NH stereoselectively catalize meso- (Z-Ala) _2O under the presence of 2-D-alaninate to proceed transacylation of Z-D-alaninate, the latter of which promote the stereo-selective catalysis. Thus a potential autocatalytic asymmetric amplification was kinetically suggested to occur by the feed back mechanism.
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