Forging 1,1′-Bicyclopropenyls by Synergistic Au/Ag Dual-Catalyzed Cyclopropenyl Cross-Coupling
Xiangdong Li, Jérôme Waser
Abstract
1,1'-Bicyclopropenyl is a constitutional isomer of benzene comprising two coupled cyclopropene units with the endocyclic double bonds in conjugation. Due to the intrinsic high strain energy, it remains a long-standing challenge to prepare 1,1'-bicyclopropenyl derivatives, particularly multisubstituted, nonsymmetrical ones, in an efficient and modular manner. Herein a straightforward Au/Ag bimetallic-catalyzed cyclopropenyl cross-coupling has been developed, providing a robust and versatile strategy for the rapid assembly of symmetrical and unsymmetrical 1,1'-bicyclopropenyl derivatives from cyclopropenyl benziodoxoles (CpBXs) and terminal cyclopropenes. Advantages of this strategy include tolerance to a wide range of synthetically useful functional groups, mild reaction conditions, and a simple catalytic system. The obtained 1,1'-bicyclopropenyl derivatives were shown to be valuable synthetic intermediates through selective downstream manipulations.