Nonenzymatic Asymmetric Acylation of meso-Diols

内消旋二醇的非酶促不对称酰化

基本信息

批准号：
09640705
负责人：
ORIYAMA Takeshi
金额：
$ 1.86万
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：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

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.

最近，人们关注的是非酶的非对称不对称酰基化，对外星次醇和中醇的不对称酰化。在存在（S） - proline的手性二胺的情况下，我们还通过与Achiral Benzoyl Halide的反应证明了外星次级醇和Meso-1,2-二醇的不对称酰化。近年来，一些基于醇的催化不对称酰基化的论文已依次出现。然而，这两种方法都没有开发到有机合成中找到宽度的水平。我们确定源自（S） - 磷水的手性二氨基可以用作高效的催化剂，用于催化MESO-1，2-二醇。甲状腺1-二醇的催化不对称不对称酰基生态系统已通过与苯甲酰氯化物的反应成功地进行了手性丁胺的反应，加上0.5 mol％的手性二醇，结合了刻板的三乙胺，三乙胺的含量为良好的单基氮糖，从而使良好的单基氮糖含量获得了良好的enanantioselectioselectioselectioselectioselectioselectioselectioselectioselectioselectioselectioselectioceciotioctiasiostioselectioselectioceciotiaselectioceciotioceionerectioselectioceciotiocecleivies。在仅在（S） - 丙啉（s） - 丙啉素中得出的0.3 mol％的手性二胺的0.3 mol％的催化不对称酰基化也已成功地用苯甲酰氯化物成功地进行，并结合0.5的三乙基氨基氨基胺的含量为0.5等效于三乙基胺的反应。相应的苯甲酸产量优异。