Rapid synthesis of 2-substituted bicyclo[1.1.1]pentanes. (A) Examples of the BCP framework in pharmaceutical compounds. Relative number of patents containing 1,3- and 1,2-disubstituted BCPs. (B) One-pot C–H functionalization to access a key disubstituted BCP intermediate with orthogonal functional handles. Functionalization of this intermediate is done via photoredox catalysis to access diverse 1,2-disubstituted BCPs. (C) Photoredox catalysis enables diversification of a common 1,2,3-trisubstituted BCP intermediate to 2-aminated, 2-arylated, difunctionalized, and trifunctionalized BCPs.