Tungsten‐Catalyzed Direct N‐Alkylation of Anilines with Alcohols

Abstract The implementation of non‐noble metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of non‐noble metal catalysts. Herein, we report a tungsten‐catalyzed N ‐alkylation reaction of anilines with primary alcohols via BH/HA. This phosphine‐free W(phen)(CO) 4 (phen=1,10‐phenthroline) system was demonstrated as a practical and easily accessible in‐situ catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.