| Project/Area Number |
09640705
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | IBARAKI UNIVERSITY |
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Principal Investigator |
ORIYAMA Takeshi IBARAKI Univ.Fac.of Sci.Associate Professor, 理学部, 助教授 (90185687)
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| Project Period (FY) |
1997 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1998: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1997: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Keywords | meso-diol / chiral diamine / benzoyl chloride / racemic secondary alcohol / triethylamine / asymmetrization / kinetic resolution / catalytic asymmetric acylation / 対称-1,2-ジオール / 光学活性ジアミン |
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| Research Abstract |
Recently, much attention has been focused on the nonenzymatic asymmetric acylation of racemic secondary alcohols and meso-diols. We have also demonstrated asymmetric acylation of racemic secondary alcohols and meso-1,2-diols by the reaction with achiral benzoyl halide in the presence of a chiral diamine derived from (S)-proline. Some papers which are based on the catalytic asymmetric acylation of alcohols with achiral acylating agents have emerged successively in recent years. However, neither methodology has been developed to such a level as to find widespread use in organic synthesis.
We establish that a chiral diamine derived from (S)-proline can function as a highly efficient catalyst for the catalytic asymmetrization of meso-1 , 2-diols. Catalytic asymmetric acylation of mesa-1,2-diols has been successfully performed by the reaction with benzoyl chloride in the presence of 0.5 mol% of chiral diamine combined with a stoichiometric amount of triethylamine to give the corresponding monobenzoate with good to excellent enantioselectivities. Catalytic asymmetric acylation of racemic secondary alcohols has been also successfully performed with achiral benzoyl chloride in the presence of only 0.3 moL% of chiral diamine derived from (S)-proline, combined with 0.5 equivalent of triethylamine.
Reactions of alcohols with benzoyl chloride in the presence of TMEDA at -78 ﾟC resulted in very fast acylation to afford the corresponding benzoates in excellent yields.
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