Carbene-Catalyzed Enantioselective Sulfonylation of Enone Aryl Aldehydes: A New Mode of Breslow Intermediate Oxidation

A carbene-catalyzed sulfonylation reaction between enone aryl aldehydes and sulfonyl chlorides is disclosed. The reaction effectively installs sulfone moieties in a highly enantioselective manner to afford sulfone-containing bicyclic lactones. The sulfonyl chloride behaves both as an oxidant and a nucleophilic substrate (via its reduced form) in this N-heterocyclic carbene (NHC)-catalyzed process. The NHC catalyst provides both activation and stereoselectivity control on a very remote site of enone aryl aldehyde substrates. Water plays an important role in modulating catalyst deactivation and reactivation routes that involve reactions between NHC and sulfonyl chloride. Experimental studies and DFT calculations suggest that an unprecedented intermediate and a new oxidation mode of the NHC-derived Breslow intermediate are involved in the new asymmetric sulfonylation reaction.

Automated summary

A novel carbene-catalyzed sulfonylation reaction between enone aryl aldehydes and sulfonyl chlorides has been disclosed, leading to the efficient installation of sulfone moieties. The NHC catalyst provides activation and stereoselectivity control on a very remote site of the enone aryl aldehyde substrates. Water plays a crucial role in modulating catalyst deactivation and reactivation routes involving reactions between NHC and sulfonyl chloride.