Nickel-Catalyzed Transfer Hydrogenation of Benzonitriles with 2-Propanol and 1,4-Butanediol as the Hydrogen Source

The homogeneous transfer hydrogenation of benzonitrile with 2-propanol or 1,4- butanediol produced Nbenzylidene benzylamine (BBA, 85% yield) using 5 mol % [Ni( COD) 2] as a catalytic precursor and a mixture of Cy2P(CH2)(2)PCy2 and Cy2P(CH2)(2)P(O) Cy-2 as ancillary ligands, under mild reaction conditions (120 circle c, 96 h, tetrahydrofuran). 1,4- Butanediol performed better than 2propanol as a hydrogen donor and yielded.- butyrolactone as the product of transfer dehydrogenation. Selectivity toward dibenzylamine (DBA, 62% yield) was achieved by varying the amount of 1,4- butanediol in the catalytic system. A reaction mechanism was proposed, involving a ligand-assisted O-H bond activation, end-on substrate coordination, and a key dihydrido-Ni(II) intermediate, leading to the in situ formation of primary imines and amines to ultimately yield the secondary imines observed.