2000 Fiscal Year Final Research Report Summary
Highly Efficient Synthesis of Useful Chiral Synthon by a Catalytic Asymmetric Acylation
| Project/Area Number |
11640598
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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., Faculty of Science, Associate Professor, 理学部, 助教授 (90185687)
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| Project Period (FY) |
1999 – 2000
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| Keywords | catalytic asymmetric acylation / chiral 1, 2-diamine / benzoyl chloride / mero-diol / racemic alcohol / choral synthon / asymmetrization / kinetic resolution |
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| Research Abstract |
Recently, much attention has been focused on the non-enzymatic 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 catalytic amount of chiral 1, 2-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 established that a chiral 1, 2-diamine derived from (S)-proline could function as a highly efficient catalyst for the catalytic asymmetrization of meso-1, 2-diols. Catalytic asymmetric acylation of cis-2-cyclopentene-1, 4-diol 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 excellent enantioselectivity. Thus obtained 4-benzoyloxy-2-cyclopenten-1-ol was readily converted to (R)-4-benzoyloxy-2-cyclopenten-1-one, a chiral building block for various prostaglandins, by the treatment of pyridinium dichromate (PDC). Catalytic asymmetric acylation of meso-1, 3-diols has been also successfully performed with achiral benzoyl chloride in the presence of only 0.5 mol% of chiral 1, 2-diamine derived from (S)-proline, combined with 1.5 equivalent of triethylamine. This highly efficient asymmetric acylation of alcohols afforded various useful chiral building blocks.
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