An Efficient and Selective Nickel-Catalyzed Direct N-Alkylation of Anilines with Alcohols

Herein, we developed an efficient and selective nickel catalyzed monoalkylation of various primary alcohols with aryl and heteroaryl amines together with diols and amino alcohol derivatives. Notably, the catalytic protocol consisting of an earth-abundant and non precious NiBr2/L1 system enables the transformations in the presence of hydroxyl, alkene, nitrile, and nitro functionalities. As a highlight, we have demonstrated the alkylation of diamine, intramolecular cyclization to N-heterocycles, and functionalization of complex vitamin E, an (+/-)-alpha-tocopherol derivative. Preliminary mechanistic studies revealed the participation of a benzylic C-H bond in the rate -determining step.