A wide range of halogenated bicyclo[1.1.1]pentanes are accessed by functional group tolerant radical ring-opening of tricyclo[1.1.1.01,3]pentane, using triethylborane as initiator.

A computationally guided development of the first efficient protocol to trifluoromethylthiolate aryl and vinyl Csp2–O bonds is presented, showcasing important reactivity requirements for the introduction of potentially reactive functional groups under homogeneous Ni-catalysis.

A unified framework that explains the reactivity of [1.1.1]propellane through electron delocalization.