1994 Fiscal Year Final Research Report Summary
Development of Synthetic Procedure of Physiologically Actlive Substances Using Asymmetric Synthesis Catalyzed by Peptide-Metal Complexes
| Project/Area Number |
05555245
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Science University of Tokyo (1994)
The University of Tokyo (1993) |
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Principal Investigator |
INOUE Shohei Science University of Tokyo, Department of Industrial Chemistry, Professor, 工学部, 教授 (20010762)
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| Project Period (FY) |
1993 – 1994
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| Keywords | Asymmetric Synthesis / Catalyst / Cyanohydrin / Metal Complex / Peptide |
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| Research Abstract |
The present research is concerned with the asymmetric synthesis catalyzed by peptide-metal complexes with a peptide ligand whose amino terminal is modified by a Schiff base carrying a phenolic hydroxyl group. Asymmetric induction takes place by the participation of metal-peptide interaction in the reaction on the metai. Such an unprecedented approach made possible the successful asymmetric hydrocyanation of aldehyde (asymmetric cyanohydrin synthesis) with very high selectivitsy. Although this has not been possible except for enzymatic method, optically active cyanohydrins are very useful as intermediates for the stereoselective synthesis of physiologically active substances. The present method uses readily available amino acid as a catalyst component, and is expected to be practical. Peptide-metal complexes were found also effective for the asymmetric silylcyanation of aldehyde, asymmetric epoxidation of allyl alcohol, and asymmetric alkylation of aldehyde. The mechanism of these asymmetric inductions investigated by NMR studies afforded the guiding principle for the design of effective catalysts. AS an applicaiton of the asymmetric hydrocyanation of aldehyde, asymmetric cyanohydrin synthesis from beta-alkenylaldehyde followed by the highly stereoselective [3,3]sigmatropic chirality transfer was found to provide a facile synthesis of optically active gamma-cyanoallyl alcohol, which is useful as synthetic intermediate for a variety of naturally occurring and physiologically active substances.
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