Diastereoselective Transfer of Tri(di)fluoroacetylsilanes-Derived Carbenes to Alkenes

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.

Automated summary

In this study, a novel visible-light-induced transition-metal-free cyclopropanation reaction of alkenes was reported. The reaction exhibited high selectivity and was suitable for various alkene substrates, demonstrating its synthetic potential in gram-scale reactions and late-stage functionalization.