Direct Catalytic Asymmetric Aldol Reactions of Thioamides: Toward a Stereocontrolled Synthesis of 1,3-Polyols
Direct Catalytic Asymmetric Aldol Reactions of Thioamides: Toward a Stereocontrolled Synthesis of 1,3-Polyols
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DOI：
10.1021/ja909758e
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发表时间：
2009-12-30
影响因子：
15
通讯作者：
Shibasaki, Masakatsu
中科院分区：
文献类型：
--
作者：
Iwata, Mitsutaka;Yazaki, Ryo;Shibasaki, Masakatsu
描述了硫代酰胺与包含(R,R)-Ph-BPE/[Cu(CH3CN)(4)]PF6/LiOAr的软路易斯酸/硬布朗斯台德碱协同催化体系的直接催化不对称羟醛反应。硫代酰胺的高度化学选择性去质子活化允许直接羟醛反应。 α-非支链脂肪醛的反应，容易发生自缩合。硫代酰胺官能团的轻松还原和催化剂控制的第二羟醛反应以高度立体选择性的方式提供1,3-二醇。
A direct catalytic asymmetric aldol reaction of thioamides with a soft Lewis acid/hard Bronsted base cooperative catalytic system comprising (R,R)-Ph-BPE/[Cu(CH3CN)(4)]PF6/LiOAr is described. Highly chemoselective deprotonative activation of thioamides allows for a direct aldol. reaction of alpha-nonbranched aliphatic aldehydes, which are susceptible to self-condensation. Facile reduction of the thioamide functionality and a catalyst-controlled second aldol reaction provides 1,3-diols in a highly stereoselective manner.