Synthesis of α-Aryl Primary Amides from α-Silyl Nitriles and Aryl Sulfoxides through [3,3]-Sigmatropic Rearrangement
作者:Fan Luo、Hui Zhou、Xiao-Bei Chen、Xue-Jun Liu、Xiao-Dong Chen、Peng-Fei Qian、Xin-Ping Wu、Wei Wang、Shi-Lei Zhang
DOI:10.1021/acs.orglett.2c00334
日期:2022.3.4
A simple and efficient protocol was developed for the preparation of challenging α-aryl primary amides. This metal-free coupling process was triggered by TfOH-promoted electrophilic activation of α-silyl nitrile to generate keteniminium ion species, followed by reaction with aryl sulfoxide through [3,3]-sigmatrophic rearrangement to provide the target product. To the best of our knowledge, α-silyl
开发了一种简单有效的方案来制备具有挑战性的 α-芳基伯酰胺。这种无金属偶联过程是由 TfOH 促进的 α-甲硅烷基腈的亲电活化以产生 keteniminium 离子物质引发的,然后通过 [3,3]-σ 重排与芳基亚砜反应以提供目标产物。据我们所知,α-甲硅烷基腈很少用作亲电子试剂。计算研究证实了高度亲电的酮亚胺中间体的短暂存在。