Fang Yu-Qi, Dang Li
Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063, P. R. China.
Org Lett. 2020 Dec 4;22(23):9178-9183. doi: 10.1021/acs.orglett.0c03004. Epub 2020 Nov 16.
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.
在此，我们报告了对铜催化的2-甲基-甲氧基苯胺多米诺重排机理的详细理论研究，深入理解了这些迁移的独特动机和选择性。我们发现铜催化剂加速了[1,3]-甲氧基向umpolung苯基甲基连接位置的迁移。随后的多米诺转移更倾向于甲基[1,2]-迁移，整个反应的速率决定步骤是质子从苯环转移到胺以完成催化循环。
