Fig. 1: Synthesis of α-chiral bicyclo[1.1.1]pentanes.
From: Direct catalytic asymmetric synthesis of α-chiral bicyclo[1.1.1]pentanes
a Examples of bicyclo[1.1.1]pentanes (BCPs) in pharmaceutical research. The near-ubiquitous precursor is [1.1.1]propellane (1). b Current approaches to α-chiral bicyclo[1.1.1]pentanes typically require the use of chemical resolution, or stoichiometric chiral auxiliaries/reagents. c Catalytic asymmetric synthesis of α-chiral BCPs is possible through insertion of α-diazoesters into BCP bridgehead C–H bonds, or iridium-catalyzed allylic substitution by BCP-zinc complexes formed from ring-opening of 1 with Grignard reagents under thermal conditions. d This work: design of a multicatalytic asymmetric radical addition to [1.1.1]propellane to directly access α-chiral BCPs, where the stereocenter and BCP are formed simultaneously on ring opening of 1.
