1993 Fiscal Year Final Research Report Summary
Enantioselective Synthetic Reactions using Chiral Lithium Amide Bases
| Project/Area Number |
03403023
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
Chemical pharmacy
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| Research Institution | University of Tokyo |
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Principal Investigator |
KOGA Kenji Faculty of Pharmaceutical Sciences profassor, 薬学部, 教授 (10012600)
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| Co-Investigator(Kenkyū-buntansha) |
NAKAJIMA Makoto University of Tokyo, Faculty of Pharmaceutical Sciences assistant, 薬学部, 助手 (50207792)
KAWASAKI Hisashi University of Tokyo, Faculty of Pharmaceutical Sciences assistant, 薬学部, 助手 (10186083)
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| Project Period (FY) |
1991 – 1993
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| Keywords | Asymmetric deprotonation / Asymmetricalkylation / Chiral lithium amide / Asymmetric protonation / Asymmetric catalytic reaction / Enantioselective reaction / Ligand exchange / Multinuclear NMR |
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| Research Abstract |
Studies using deuterated cyclohexanone derivatives determined the protons that are selectively deprotonated in the asymmetric deprotonation reactions
The stereochemistry of the asymmetric alpha-alkylation of cyclic ketones was clarified on the basis of the reactions with 4-substituted cyclohexanones
Asymmetric protonation of achiral enolates was achieved, based on which the method to convert racemic ketones into optically active ones was established. Studiesusing deuterated compounds clarified that this protonation proceeded through protonation of chiral amines
The solution structures of three chiral lithium amides were determined by ^6Li and ^<15>N-NMR spectroscopy, and their crystal structures were determined by X-ray analysis. The solution structure (agregation state) was able to be controlled by strong external ligands. The relationship between these results and the actual reactions was clarified.
The asymmetric deprotonation reactions described above were extended to catalytic asymmetric reactions, the mechanism of which was proposed
Catalytic asymmetric alkylation was successfully achieved with high efficiency. The mechanistic study is in progress.
Asymmetric aldol and Darzens reactions using chiral bases were achieved
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Research Products
(12 results)
