The implementation of earth-abundant 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 earth-abuandant metal catalysts. Herein,
we report a tungsten-catalyzed <i>N</i>-alkylation reaction of amines with
primary alcohols via BH/HA. This phosphine-free W(phen)(CO)<sub>4</sub>
(phen=1,10-phenthroline) system was
demonstrated as a practical and easily accessible <i>in-situ</i> 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.
Tungsten-Catalyzed Direct N-Alkylation of Amines with Alcohols
