Dearomative Migratory Rearrangement of 2-Oxypyridines Enabled by α-Imino Rhodium Carbene.

The unprecedented dearomative migratory rearrangement reactions of 2-oxypyridines with N-sulfonyl-1,2,3-triazoles have been developed under rhodium catalysis, providing a reliable and efficient protocol for accessing N-substituted 2-pyridones. These two distinct rearrangements feature the controllable 1,4-migration of a carbonate group from O-to-C as well as the O-to-N 1,6-migration of an acyl group via α-imino rhodium carbene transfer. Moreover, the reaction of pyridotriazoles with 2-oxypyridines delivers the 1,4-migration products in high efficiency.