Silylene transfer to carbonyl compounds and subsequent Ireland-Claisen rearrangements to control formation of quaternary carbon stereocenters
Silylene transfer to carbonyl compounds and subsequent Ireland-Claisen rearrangements to control formation of quaternary carbon stereocenters
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DOI：
10.1021/ja042893r
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发表时间：
2005-02-23
影响因子：
15
通讯作者：
Woerpel, KA
中科院分区：
文献类型：
--
作者：
Calad, SA;Woerpel, KA
在本次交流中，我们证明了硅烯转移到羰基化合物为区域和立体选择性烯醇化物的形成提供了一种新方法。在银催化条件下，亚硅基转移到一系列α,β-不饱和酯被证明是形成含有环状甲硅烷基烯酮缩醛官能团的氧杂硅杂环戊烯的通用方法。这些草硅杂环戊烯是有用的合成中间体，可以进行简单且选择性的爱尔兰-克莱森重排和羟醛加成反应，以提供具有多个连续立体中心和季碳中心的产物。
In this communication, we demonstrate that silylene transfer to carbonyl compounds provides a new method for regio- and stereoselective enolate formation. Silylene transfer to a range of α,β-unsaturated esters under silver-catalyzed conditions proved to be a general method for the formation of oxasilacyclopentenes containing a cyclic silyl ketene acetal functionality. These oxasilacyclopentenes are useful synthetic intermediates that can undergo facile and selective Ireland−Claisen rearrangements and aldol addition reactions to provide products with multiple contiguous stereocenters and quaternary carbon centers.