Yizhi Zhang,Gang Zhou,Xingxing Gong,Zhuanzhuan Guo, Xiaotian Qi, Xiao Shen.Diastereoselective Transfer of Tri(di)fluoroacetylsilanes-Derived Carbenes to Alkenes.Angew. Chem. Int. Ed.(沈晓)

        Abstract：

        Stereoselective cyclopropanation reaction of alkenes is usually achieved by metal complexes via singlet-metal-carbene intermediates. However, previous transition-metal-catalyzed cyclopropanation of alkenes with acylsilanes afforded low diastereoselectivity. Herein, we report the first visible-light-induced transition-metal-free cyclopropanation reaction of terminal alkenes with trifluoroacetylsilanes and difluoroacetylsilanes. Both aromatic and aliphatic alkenes as well as electron-deficient alkenes are suitable substrates for the highly cis-selective [2+1] cyclization reaction. A combination of experimental and computational studies identified triplet carbenes as being key intermediates in this transformation. The gram scale reaction and late-stage functionalization demonstrated the synthetic potential of this strategy.

        全文链接请见：

        https://onlinelibrary.wiley.com/doi/10.1002/anie.202202175