Selective mono N-methylation of anilines with methanol catalyzed by rhenium complexes: An experimental and theoretical study

• DOI: 10.1016/j.jcat.2018.08.008
• Publication Date: 2018-09-06T18:16:18Z
• Authors: Duo Wei; Omar Sadek; Vincent Dorcet; Thierry Roisnel; Christophe Darcel; Emmanuel Gras; Eric Clot; Jean-Baptiste Sor...
• Keywords: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry; [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]; [CHIM.CATA]Chemical Sciences/Catalysis; 01 natural sciences; 0104 chemical sciences

Abstract The selective mono-N-methylation of anilines using methanol as an alkylating reagent was achieved with high efficiency under the catalysis of well-defined rhenium complexes bearing tridentate diphosphinoamino ligands and in the presence of a base. The reaction proceeds well for a large scope of anilines (32 examples) with low loadings of both the catalyst (down to 0.5 mol%) and the base (Cs2CO3, down to 5 mol%). The mechanism of the reaction was investigated by DFT (PBE0-D3) calculations.