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KINETIC RESOLUTION OF sec-ALCOHOLS WITH TWISTED AMIDES

仲醇与扭曲酰胺的动力学解析

基本信息

批准号：
08640755
负责人：
YAMADA Shinji
金额：
$ 1.34万
依托单位：
OCHANOMIZU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640755/
关键词：
twisted amides asymmetric acylation kinetic resolution hydroxy group ester sec-alcohol diol amide ヒドロキシル基

项目摘要

1. Synthesis of chiral twisted amides4-alkyl-3-pivaloyl-1,3-thiazolidine-2-thiones possessing twisted amide bonds were synthesized. The structure and geometry were confirmed by 13C NMR and IR spectroscopies.2. Kinetic resolution of recemic sec-alcoholsThe twisted amides were used for the enantioselective acylation of sec-alcohols under neutral conditions. Acylations of the sec-alcohols with an amide having t-Bu group at 4-position gave the corresponding esters in 50-84% ee with (S) configuration. When methyl magnesium bromide was used as a base, the configuration of the products werereversed.3. Desymmetrization of meso-diolsEnantioselective monoacylation of meso-diols with (S)-4-t-butyl-1,3-thiazolidine-2-thione were performed to give monoesters in high yields. Very high enantioselectivity (90%ee) was obtained for cis-1,4-dihydroxytetraline. The stereochemistry at the carbon attached to the pivaloyloxy group is (S) configuration.4. Relationships between 13C-15N coupling constants and twist anglesA series of twisted amides enliched to 99% with 15N was synthesized via several steps from commercially available [15N] glycine and [15N] leucine. The C-N coupling constants were measured using 13C NMR spectroscopy. It was found that as the twist angle increase, the 1JC (O), N value decreases. This result suggests that the 13C-15N coupling constant is a useful parameter for the study of amide bond twisting.

1.合成了一种具有扭曲酰胺键的4-烷基-3-特戊酰基-1，3-四氢噻唑-2-硫酮。通过13 C NMR和IR光谱对其结构和几何构型进行了表征.外消旋仲醇的动力学拆分在中性条件下，用扭体酰胺对仲醇进行了不对称酰化反应。仲醇与4-位带有叔丁基的酰胺酰化反应，得到相应的酯，其ee值为50-84%，为（S）构型。当以甲基溴化镁为碱时，产物的构型发生了逆转.内消旋二醇的去对称化研究了内消旋二醇与（S）-4-叔丁基-1，3-噻唑烷-2-酮的对映选择性单酰化反应，高产率地得到了内消旋二醇单酯。顺式-1，4-二羟基四氢萘的对映选择性高达90%ee。与新戊酰氧基连接的碳上的立体化学是（S）构型。以[15 N]甘氨酸和[15 N]亮氨酸为原料，经多步反应合成了一系列15 N含量高达99%的扭体酰胺。使用13 C NMR光谱测量C-N偶合常数。结果表明，随着扭转角的增大，1 JC（O），N值减小。这一结果表明，13 C-15 N耦合常数是一个有用的参数，研究酰胺键扭曲。