Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, Shanghai Key Laboratory of New Drug Design, and State Key Laboratory of Bioengineering Reactor, School of Pharmacy, East China University of Science and Technology, Shanghai 200237, P. R. China.
Key Laboratory for Advanced Materials and Joint International Research Laboratory for Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
Org Lett. 2022 Mar 4;24(8):1700-1705. doi: 10.1021/acs.orglett.2c00334. Epub 2022 Feb 21.
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 nitrile has been rarely used as a pro-electrophilic reagent. Computational investigations confirmed the transient existence of a highly electrophilic keteniminium intermediate.
本文开发了一种简单高效的方法来制备具有挑战性的α-芳基伯酰胺。该无金属偶联过程由三氟甲磺酸（TfOH）促进的α-硅基腈的亲电活化引发，生成偕亚胺离子物种，然后通过[3,3]-σ重排与芳基亚砜反应得到目标产物。据我们所知，α-硅基腈很少被用作亲电试剂。计算研究证实了高亲电性的偕亚胺离子中间体的瞬时存在。
