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, Ronald M.; Gutierrez-Tinoco, Oliver Y.; Camaioni, Donald M.; Lercher, Johannes A.

doi:10.1002/ange.201909551

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

Journal Article · Mon Jan 20 04:00:00 EST 2020 · Angewandte Chemie International Edition

DOI:https://doi.org/10.1002/ange.201909551· OSTI ID:1614997

^[1]; Zhao, Yuntao ^[2]; ^[3]; ^[1]; ^[1]; ^[1]; ^[1]

BATTELLE (PACIFIC NW LAB)
UNIVERSITY PROGRAMS
TIANJIN UNIVERSITY

Hydrogenolysis of the aromatic C-O bond in aryl ethers is catalyzed by Ni in decalin or water at 150 °C. Observations of a significant kinetic isotope effect (kH/kD = 5.7) for the reactions of diphenyl ether under H2 and D2 and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is the rate-limiting step rather than C-O scission. Hydrogen addition occurs on the metal before C-O bond scission. DFT calculations indicate that hydrogen atom addition to the ortho position followed by C-O scission is energetically more feasible than C-O scission followed by H addition to either phenoxyl or phenyl moieties. Hydrogenolysis initiated via H addition in water is more selective (~75 %) compared to reactions in decalin (~30 %). The high selectivity for hydrogenolysis is attributed to stabilization of polar transition state by water as a polar solvent.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1614997

Report Number(s):: PNNL-SA-144365

Journal Information:: Angewandte Chemie International Edition, Journal Name: Angewandte Chemie International Edition Journal Issue: 4 Vol. 59

Country of Publication:: United States

Language:: English

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