Gold(I)-Catalyzed Synthesis of Highly Substituted 1,4-Dicarbonyl Derivatives via Sulfonium [3,3]-Sigmatropic Rearrangement.
Gold(I)-Catalyzed Synthesis of Highly Substituted 1,4-Dicarbonyl Derivatives via Sulfonium [3,3]-Sigmatropic Rearrangement.
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金 (I) 催化通过锍 [3,3]-Sigmatropic 重排合成高度取代的 1,4-二羰基衍生物。
DOI：
10.1021/acs.orglett.0c04023
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发表时间：
2020
期刊：
影响因子：
5.2
通讯作者：
A. Voituriez
中科院分区：
文献类型：
--
作者：
Weiping Zhou;A. Voituriez
开发了一种高效和直接的金催化方法，用于从商业上可获得或容易获得的炔烃和乙烯基亚砜底物合成2-取代4-氧代-4-芳基丁醛衍生物。将该方法扩展到使用1-环烯基亚硫醚，可以方便地合成五元环、六元环和七元环环烷基基-1-酮主链。随后，在许多活性药物成分中发现的四氢环烷基[b]吡咯衍生物被以良好的产率分离出来。机理研究表明，在此过程中，一个硫中间体发生了[3，3]-Sigmatroy重排。
An efficient and straightforward gold-catalyzed protocol for the synthesis of 2-substituted 4-oxo-4-arylbutanal derivatives from commercially available or easily accessible alkynes and vinylsulfoxide substrates has been developed. Extension of the methodology to the use of 1-cycloalkenyl sulfoxides allowed the facile synthesis of five-, six-, and seven-membered-ring cycloalkyl-1-one backbone. Subsequently, the tetrahydrocycloalkyl[b]pyrrole derivatives, which are found in many active pharmaceutical ingredients, were isolated in good yields. Mechanistic investigation highlighted a [3,3]-sigmatropic rearrangement of a sulfonium intermediate in this process.