Mechanistic Study of Domino Rearrangement-Promoted Meta C-H Activation in 2-Methyl--methoxyaniline via Cu(NHC): Motivation and Selectivity.

Here we report a detailed theoretical study of the mechanism of Cu-catalyzed domino rearrangement of 2-methyl--methoxyaniline with a deep understanding of the unique motivation and selectivity of these migrations. We find that the Cu catalyst accelerates the [1,3]-methoxy migration to the methyl-bound position of umpolung phenyl. The following domino transfer prefers methyl [1,2]-migration, and the rate-determining step for the whole reaction is the transfer of a proton from the phenyl ring to amine to finish the catalytic cycle.