通过氟阴离子结合催化实现硅基烯酮缩醛的对映选择性酰化。
Enantioselective acylation of silyl ketene acetals through fluoride anion-binding catalysis.
机构信息
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
出版信息
J Am Chem Soc. 2011 Sep 7;133(35):13872-5. doi: 10.1021/ja205602j. Epub 2011 Aug 10.
Abstract
A highly enantioselective acylation of silyl ketene acetals with acyl fluorides has been developed to generate useful α,α-disubstituted butyrolactone products. This transformation is promoted by a new thiourea catalyst and 4-pyrrolidinopyridine and represents the first example of enantioselective thiourea anion-binding catalysis with fluoride.
摘要
已开发出一种高度对映选择性的硅基烯酮缩醛与酰氟的酰化反应，以生成有用的α,α-二取代丁内酯产物。这种转化由一种新的硫脲催化剂和 4-吡咯吡啶促进，代表了氟阴离子对映选择性硫脲阴离子结合催化的首例实例。
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3
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