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

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journal contribution
posted on 16.11.2020, 19:03 by Yu-Qi Fang, Li Dang
Here we report a detailed theoretical study of the mechanism of Cu+-catalyzed domino rearrangement of 2-methyl-N-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 ortho 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.