2001 Fiscal Year Final Research Report Summary
Practical Synthesis of Chiral Building Blocks by Highly Efficient Catalytic Asymmetric Acylation
| Project/Area Number |
12554021
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 展開研究 |
|---|
| Research Field |
Organic chemistry
|
|---|
| Research Institution | IBARAKI UNIVERSITY |
|---|
Principal Investigator |
ORIYAMA Takeshi IBARAKI Univ., Fac. of Sci., Professor, 理学部, 助教授 (90185687)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
YAMASAKI Noritsugu DAICEL Chemical Industries, ltd., Research Associate, 筑波研究所・精密合成グループ, 主任研究員
|
|---|
| Project Period (FY) |
2000 – 2001
|
| Keywords | chiral building block / practical synthesis / chiral 1,2-diamine / benzoyl chloride / triethylamine / kinetic resolution / asymmetrization / catalytic asymmetric acylation |
|---|
| Research Abstract |
Recently, much attention has been focused on the non-enzymatic asymmetric acylation of racemic alcohols and meso-diols. We have already demonstrated asymmetric acylation of racemic secondary alcohols and meso-l,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- l , 2-diols. Catalytic asymmetric acylation of cw-2-cyclopentene- l ,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-l-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 in the presence of only 0.5 mol% of chiral 1,2-diamine, combined with 1.5 equivalents of triethylamine. Catalytic kinetic resolution of racemic primary alcohols has been also performed with substituted benzoyl chloride in the presence of only 0.3 mol% of chiral 1,2-diamine derived from (S)-proline. This highly efficient asymmetric acylation of alcohols afforded various useful chiral building blocks.
|
Research Products
(12 results)
