NHC Catalysis for Umpolung Pyridinium Alkylation via Deoxy-Breslow Intermediates

Umpolung N-heterocyclic carbene (NHC) catalysis of non-aldehyde substrates offers new pathways for C-C bond formation, but has proven challenging to develop in terms of viable substrate classes. Here, we demonstrate that pyridinium ions can undergo NHC addition and subsequent intramolecular C-C bond formation through a deoxy-Breslow intermediate. The alkylation demonstrates, for the first time, that deoxy-Breslow intermediates are viable for catalytic umpolung of areniums.

Automated summary

This study demonstrates that pyridinium ions can undergo NHC addition and intramolecular C-C bond formation through a deoxy-Breslow intermediate, presenting a new pathway for catalytic reactions of non-aldehyde substrates.