ChemInform Abstract: Enantioselective Rhodium(I) Donor Carbenoid-Mediated Cascade Triggered by a Base-Free Decomposition of Arylsulfonyl Hydrazones

The reaction of diyne arylsulfonyl hydrazone substrates under rhodium(I)/BINAP catalysis gives access to sulfonated azacyclic frameworks in a highly enantioselective manner. This new cascade process considerably increases the molecular complexity by generating two C-C bonds, one C-S bond, and one C-H bond. Theoretical calculations, competitive experiments, and deuterium labeling have jointly been used to propose a mechanism that accounts for the reaction. The mechanism involves the formation of vinyl rhodium carbenoids, hydride migratory insertion, and intermolecular stereoselective nucleophilic attack. The last two steps are the key to the stereoselectivity of the process.