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

1 Citation (Scopus)

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
Pages (from-to)1445-1449
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number4
DOIs
Publication statusPublished - Jan 20 2020

Keywords

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

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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