Electrophilic Activation of [1.1.1]Propellane by Silyl-Triflates

Incorporation of a bicyclo[1.1.1]pentyl framework is a sought-after task in recent organic chemistry. Current methods mostly involve radical or nucleophilic pathways. In this study, we describe a general procedure for the synthesis of bridgehead silylbicyclo[1.1.1]pentanes by electrophilic activation. The process works with various nucleophiles, including amines, thiols, carbon, and heterocycles. Silylamines can be desilylated to offer a complementing strategy to synthesize C-H bicyclo[1.1.1]pentanes.