Ligand-Controlled Ruthenium-Catalyzed Borrowing-Hydrogen and Interrupted-Borrowing-Hydrogen Methodologies: Functionalization of Ketones Using Methanol as a C1 Source.

Abstract

Herein we report simple, highly efficient, and phosphine-free N,C-Ru and N,N-Ru catalysts for ligand-controlled borrowing-hydrogen (BH) and interrupted-borrowing-hydrogen (I-BH) methods, respectively. This protocol has been employed on a variety of ketones using MeOH as a green, sustainable, and alternative C1 source to form a C-C bond through the BH and I-BH methods. Reasonably good substrate scope, functional group tolerance, and good-to-excellent yields at 70 °C are the added highlights of these methodologies. Controlled experiments reveal that an in situ formed formaldehyde is one of the crucial elements in this ligand-controlled selective protocol, which upon reaction with a ketone generates an enone as an intermediate. This enone in the presence of the N,C-Ru catalyst and N,N-Ru catalyst through the BH and I-BH pathways yields methylated ketones and 1,5-diketones, respectively.