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

[Image: see text] 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 Cy(2)P(CH(2))(2)PCy(2) and Cy(2)P(CH(2))(2)P(O)Cy(2) as ancillary ligand...

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Autores principales: Garduño, Jorge A., García, Juventino J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6641154/
https://www.ncbi.nlm.nih.gov/pubmed/31457582
http://dx.doi.org/10.1021/acsomega.7b00545
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author Garduño, Jorge A.
García, Juventino J.
author_facet Garduño, Jorge A.
García, Juventino J.
author_sort Garduño, Jorge A.
collection PubMed
description [Image: see text] 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 Cy(2)P(CH(2))(2)PCy(2) and Cy(2)P(CH(2))(2)P(O)Cy(2) 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 γ-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.
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spelling pubmed-66411542019-08-27 Nickel-Catalyzed Transfer Hydrogenation of Benzonitriles with 2-Propanol and 1,4-Butanediol as the Hydrogen Source Garduño, Jorge A. García, Juventino J. ACS Omega [Image: see text] 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 Cy(2)P(CH(2))(2)PCy(2) and Cy(2)P(CH(2))(2)P(O)Cy(2) 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 γ-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. American Chemical Society 2017-05-26 /pmc/articles/PMC6641154/ /pubmed/31457582 http://dx.doi.org/10.1021/acsomega.7b00545 Text en Copyright © 2017 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Garduño, Jorge A.
García, Juventino J.
Nickel-Catalyzed Transfer Hydrogenation of Benzonitriles with 2-Propanol and 1,4-Butanediol as the Hydrogen Source
title Nickel-Catalyzed Transfer Hydrogenation of Benzonitriles with 2-Propanol and 1,4-Butanediol as the Hydrogen Source
title_full Nickel-Catalyzed Transfer Hydrogenation of Benzonitriles with 2-Propanol and 1,4-Butanediol as the Hydrogen Source
title_fullStr Nickel-Catalyzed Transfer Hydrogenation of Benzonitriles with 2-Propanol and 1,4-Butanediol as the Hydrogen Source
title_full_unstemmed Nickel-Catalyzed Transfer Hydrogenation of Benzonitriles with 2-Propanol and 1,4-Butanediol as the Hydrogen Source
title_short Nickel-Catalyzed Transfer Hydrogenation of Benzonitriles with 2-Propanol and 1,4-Butanediol as the Hydrogen Source
title_sort nickel-catalyzed transfer hydrogenation of benzonitriles with 2-propanol and 1,4-butanediol as the hydrogen source
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6641154/
https://www.ncbi.nlm.nih.gov/pubmed/31457582
http://dx.doi.org/10.1021/acsomega.7b00545
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