Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary Amines: A Combined Effort

Kenan Tokmic; Bailey J. Jackson; Andrea Salazar; Toby J. Woods; Alison R. Fout

doi:10.1021/jacs.7b07368

Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary Amines: A Combined Effort

Kenan Tokmic, Bailey J. Jackson, Andrea Salazar, Toby J. Woods, Alison R. Fout

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The selective hydrogenation of nitriles to primary amines using a bench-stable cobalt precatalyst under 4 atm of H₂ is reported herein. The catalyst precursor was reduced in situ using NaHBEt₃, and the resulting Lewis acid formed, BEt₃, was found to be integral to the observed catalysis. Mechanistic insights gleaned from para-hydrogen induced polarization (PHIP) transfer NMR studies revealed that the pairwise hydrogenation of nitriles proceeded through a Co(I/III) redox process.

Original language	English (US)
Pages (from-to)	13554-13561
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	139
Issue number	38
DOIs	https://doi.org/10.1021/jacs.7b07368
State	Published - Sep 27 2017

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.7b07368

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title = "Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary Amines: A Combined Effort",

abstract = "The selective hydrogenation of nitriles to primary amines using a bench-stable cobalt precatalyst under 4 atm of H2 is reported herein. The catalyst precursor was reduced in situ using NaHBEt3, and the resulting Lewis acid formed, BEt3, was found to be integral to the observed catalysis. Mechanistic insights gleaned from para-hydrogen induced polarization (PHIP) transfer NMR studies revealed that the pairwise hydrogenation of nitriles proceeded through a Co(I/III) redox process.",

author = "Kenan Tokmic and Jackson, {Bailey J.} and Andrea Salazar and Woods, {Toby J.} and Fout, {Alison R.}",

note = "The authors thank the NSF for financial support with a CAREER award (1351961) to A.R.F. A.R.F. is a Sloan Research Fellow and a Camille Dreyfus Teacher-Scholar. The authors thank Charles R. Markus and Prof. Benjamin J. McCall for use of the p-H2 generator; Charles R. Markus has been supported in part by an NSF award (CHE 12-13811) and a NASA award (NNX13AE62G) to PI Prof. Benjamin J. McCall. Finally, we thank Dr. Lingyang Zhu for help with the PHIP NMR studies.",

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AU - Jackson, Bailey J.

AU - Salazar, Andrea

AU - Woods, Toby J.

AU - Fout, Alison R.

N1 - The authors thank the NSF for financial support with a CAREER award (1351961) to A.R.F. A.R.F. is a Sloan Research Fellow and a Camille Dreyfus Teacher-Scholar. The authors thank Charles R. Markus and Prof. Benjamin J. McCall for use of the p-H2 generator; Charles R. Markus has been supported in part by an NSF award (CHE 12-13811) and a NASA award (NNX13AE62G) to PI Prof. Benjamin J. McCall. Finally, we thank Dr. Lingyang Zhu for help with the PHIP NMR studies.

PY - 2017/9/27

Y1 - 2017/9/27

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AB - The selective hydrogenation of nitriles to primary amines using a bench-stable cobalt precatalyst under 4 atm of H2 is reported herein. The catalyst precursor was reduced in situ using NaHBEt3, and the resulting Lewis acid formed, BEt3, was found to be integral to the observed catalysis. Mechanistic insights gleaned from para-hydrogen induced polarization (PHIP) transfer NMR studies revealed that the pairwise hydrogenation of nitriles proceeded through a Co(I/III) redox process.

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Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary Amines: A Combined Effort

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