Highly Efficient Synthesis of Useful Chiral Synthon by a Catalytic Asymmetric Acylation

通过催化不对称酰化高效合成有用的手性合成子

基本信息

批准号：
11640598
负责人：
ORIYAMA Takeshi
金额：
$ 0.7万
依托单位：
IBARAKI UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

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.

最近，人们关注的是极端二级醇和间醇的非酶不对称酰化。我们还证明了在催化量的手性1，源自（s） - 磷的催化量的手性1，在催化量的手性1中，与苯甲酰卤化物的反应不对称酰基化的二醇不对称酰化。近年来，一些基于醇含醇的催化不对称酰基化的论文已持续出现。但是，这两种方法都没有开发到一个水平以找到在有机合成中广泛使用的水平。我们确定，源自（s） - 磷的手性1，2-二胺可以用作高效催化剂，以促催化MESO的催化不对称。 -1，2-二醇。在0.5摩尔％的手性二氨酸存在下，与苯甲酰氯化物的反应成功地进行了顺式-2-氯苯烯-1、4-二醇的催化不对称酰基化，并与静态量的三乙胺相结合，使得与相应的单基因氮酸盐具有出色。因此，获得的4-苯并氧氧基-2-循环中的1-ol很容易被转换为（R）-4-苯甲酰氧基-2-旋转2-Cyclopenten-1-One，这是一种用于各种前列腺素的手性构建块，通过治疗吡啶素二核酸盐（PDC）（PDC）。在仅在手性1的0.5 mol％的情况下，在苯二酰氯化物中，三二醇的催化不对称酰基化也已成功地进行了苯甲酰氯化物，源自手性的1.5 mol％，源自（S） - 丙烯的2-二胺，合并为1.5二甲基胺。这种高效的酒精不对称酰基化提供了各种有用的手性构件。