The Critical Role of Reductive Steps in the Nickel-Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds

Meng Wang, Yuntao Zhao, Donghai Mei, R. Morris Bullock, Oliver Y. Gutiérrez, Donald M. Camaioni, Johannes A. Lercher

Research output: Contribution to journalArticle

Abstract

The hydrogenolysis of the aromatic C−O bond in aryl ethers catalyzed by Ni was studied in decalin and water. Observations of a significant kinetic isotope effect (kH/kD=5.7) for the reactions of diphenyl ether under H2 and D2 atmosphere and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is involved in the rate-limiting step. All kinetic evidence points to the fact that H addition occurs concerted with C−O bond scission. DFT calculations also suggest a route consistent with these observations involving hydrogen atom addition to the ipso position of the phenyl ring concerted with C−O scission. Hydrogenolysis initiated by H addition in water is more selective (ca. 75 %) than reactions in decalin (ca. 30 %).

Original languageEnglish
JournalAngewandte Chemie - International Edition
DOIs
Publication statusAccepted/In press - Jan 1 2019

Fingerprint

Hydrogenolysis
Carbon Monoxide
Nickel
Ether
Hydrolysis
Ethers
Hydrogen
Kinetics
Chemical potential
Discrete Fourier transforms
Isotopes
Water
Atoms
decalin

Keywords

  • catalysis
  • C−O bond cleavage
  • hydrogenolysis
  • nickel
  • reaction mechanisms

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

The Critical Role of Reductive Steps in the Nickel-Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds. / Wang, Meng; Zhao, Yuntao; Mei, Donghai; Bullock, R. Morris; Gutiérrez, Oliver Y.; Camaioni, Donald M.; Lercher, Johannes A.

In: Angewandte Chemie - International Edition, 01.01.2019.

Research output: Contribution to journalArticle

Wang, Meng ; Zhao, Yuntao ; Mei, Donghai ; Bullock, R. Morris ; Gutiérrez, Oliver Y. ; Camaioni, Donald M. ; Lercher, Johannes A. / The Critical Role of Reductive Steps in the Nickel-Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds. In: Angewandte Chemie - International Edition. 2019.
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AU - Gutiérrez, Oliver Y.

AU - Camaioni, Donald M.

AU - Lercher, Johannes A.

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