Acceptorless dehydrogenation of amines and alcohols using simple ruthenium chloride

A highly efficient, economic and environmental friendly catalyst system has been developed for the dehydrogenation of alcohols and amines using simple RuCl3 center dot nH(2)O and N-benzylhexamethylenetetramine. The in situ catalyst system efficiently oxidized the primary and secondary amines and secondary alcohols into nitrile, imine and ketone products, respectively in moderate to excellent yields. The developed catalyst system was also found to be efficient for the dehydrogenation of N-heterocyles. A detailed mechanism study revealed the first example of N-benzylhexamethylenetetramine (HMTA-Bz) being simultaneously acting as base, reducing agent and hydride source to generate the [Ru(II)(H)(2)] species as the active catalyst. The mechanism studies also revealed both the alcohol and amine oxidation involves dehydrogenative pathway with the evolution of hydrogen as the only by-product. The developed catalyst system also provides possible platform for the release of hydrogen from liquid organic hydrogen carriers (LOHCs). (C) 2020 Elsevier Inc. All rights reserved.