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

ABSTRACT: The homogeneous transfer hydrogenation of benzonitrile with 2-propanol or 1,4-butanediol produced N-benzylidene benzylamine (BBA, 85% yield) using 5 mol % [Ni(COD)2] as a catalytic precursor and a mixture of Cy2P(CH2)2PCy2 and Cy2P(CH2)2P(O)Cy2 as ancillary ligands, under mild reaction conditions (120 °C, 96 h, tetrahydrofuran). 1,4-Butanediol performed better than 2-propanol 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.

SUBMITTER: Garduno JA

PROVIDER: S-EPMC6641154 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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

Garduño Jorge A JA García Juventino J JJ

ACS omega 20170526 5

The homogeneous transfer hydrogenation of benzonitrile with 2-propanol or 1,4-butanediol produced N-benzylidene benzylamine (BBA, 85% yield) using 5 mol % [Ni(COD)2] as a catalytic precursor and a mixture of Cy2P(CH2)2PCy2 and Cy2P(CH2)2P(O)Cy2 as ancillary ligands, under mild reaction conditions (120 °C, 96 h, tetrahydrofuran). 1,4-Butanediol performed better than 2-propanol as a hydrogen d ...[more]

PMID: 31457582

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