Asymmetric direct aldol reaction of functionalized ketones catalyzed by amine organocatalysts based on bispidine
Asymmetric direct aldol reaction of functionalized ketones catalyzed by amine organocatalysts based on bispidine
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双吡啶胺类有机催化剂催化官能化酮的不对称直接羟醛反应
DOI：
10.1021/ja800839w
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发表时间：
2008-04-30
影响因子：
15
通讯作者：
Hu, Changwei
中科院分区：
文献类型：
--
作者：
Liu, Jie;Yang, Zhigang;Hu, Changwei
已经设计了含有基于双吡啶和氨基酸的伯-仲胺的有机催化剂来催化官能化酮的不对称直接羟醛缩合反应，所述官能化酮包括α-酮基膦酸酯、α-酮基酯以及作为羟醛缩合反应受体的α，α-二烷氧基酮。以中到高产率（高达97%）和高的对映选择性（高达98%ee）获得了手性叔醇的相应产物。过渡结构的理论研究表明，质子化哌啶是重要的反应性和对映选择性的反应。
Organocatalysts containing primary-secondary amine based on bispidine and amino acid have been designed to catalyze the asymmetric direct aldol reaction of functionalized ketones including alpha-keto phosphonates, alpha-keto esters, as well as alpha,alpha-dialkoxy ketones as aldol reaction acceptors. The corresponding products with chiral tertiary alcohols were obtained in moderate to high yields (up to 97%) and high enantioselectivities (up to 98% ee). A theoretical study of transition structures demonstrated that protonated piperidine was important for the reactivity and enantioselectivity of this reaction.