Formal Asymmetric Catalytic Thiolation witha Bifunctional Catalyst at a Water-Oil Interface: Synthesis of Benzyl Thiols
Formal Asymmetric Catalytic Thiolation witha Bifunctional Catalyst at a Water-Oil Interface: Synthesis of Benzyl Thiols
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DOI：
10.1002/anie.201409894
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发表时间：
2015-04-07
影响因子：
16.6
通讯作者：
Li, Can
中科院分区：
文献类型：
--
作者：
Guo, Wengang;Wu, Bo;Li, Can
采用酸碱双功能方酰胺有机催化剂催化三苯甲基硫醇与原位生成的邻醌甲基化物（o-QMs）的对映选择性共轭加成反应。该转化以高产率（高达99%）和立体选择性（高达97：3 e.r.）进行。以水为溶剂，反应条件温和。该催化体系为光学活性苄硫醇的合成提供了一种新的策略。对照实验表明，o-QM是由方酰胺有机催化剂的叔胺部分产生的，并且水-油两相对于实现高反应性和立体选择性是至关重要的。
The enantioselective conjugated addition of tritylthiol to insitu generated ortho-quinone methides (o-QMs) is catalyzed by an acid-base bifunctional squaramide organocatalyst. The transformation proceeds with high yield (up to 99%) and stereoselectivity (up to 97:3 e.r.) using water as solvent under mild conditions. The catalyst system provides a new strategy for the synthesis of optically active benzyl mercaptans. Control experiments suggested that o-QMs are generated by the tertiary amine moiety of the squaramide organocatalyst and that the water-oil biphase is crucial for achieving high reactivity and stereoselectivity.