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Title: Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

Abstract

Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1598824
Report Number(s):
PNNL-SA-129112
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie International Edition
Additional Journal Information:
Journal Volume: 130; Journal Issue: 14
Country of Publication:
United States
Language:
English
Subject:
aryl ether, hydrogenation, palladium, methanolysis, selective cleavage

Citation Formats

Wang, Meng, Gutierrez-Tinoco, Oliver Y., Camaioni, Donald M., and Lercher, Johannes A. Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds. United States: N. p., 2018. Web. doi:10.1002/ange.201709445.
Wang, Meng, Gutierrez-Tinoco, Oliver Y., Camaioni, Donald M., & Lercher, Johannes A. Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds. United States. doi:10.1002/ange.201709445.
Wang, Meng, Gutierrez-Tinoco, Oliver Y., Camaioni, Donald M., and Lercher, Johannes A. Mon . "Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds". United States. doi:10.1002/ange.201709445.
@article{osti_1598824,
title = {Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds},
author = {Wang, Meng and Gutierrez-Tinoco, Oliver Y. and Camaioni, Donald M. and Lercher, Johannes A.},
abstractNote = {Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.},
doi = {10.1002/ange.201709445},
journal = {Angewandte Chemie International Edition},
number = 14,
volume = 130,
place = {United States},
year = {2018},
month = {3}
}

Works referenced in this record:

Cellulosic Biofuels--Got Gasoline?
journal, August 2009


The Path Forward for Biofuels and Biomaterials
journal, January 2006

  • Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H.
  • Science, Vol. 311, Issue 5760, p. 484-489
  • DOI: 10.1126/science.1114736

The Biofuels Landscape Through the Lens of Industrial Chemistry
journal, August 2009


Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis
journal, June 2016

  • Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.
  • Angewandte Chemie International Edition, Vol. 55, Issue 29
  • DOI: 10.1002/anie.201510351

Wege zur Verwertung von Lignin: Fortschritte in der Biotechnik, der Bioraffination und der Katalyse
journal, June 2016

  • Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.
  • Angewandte Chemie, Vol. 128, Issue 29
  • DOI: 10.1002/ange.201510351

Catalytic Biorefining of Plant Biomass to Non-Pyrolytic Lignin Bio-Oil and Carbohydrates through Hydrogen Transfer Reactions
journal, June 2014

  • Ferrini, Paola; Rinaldi, Roberto
  • Angewandte Chemie International Edition, Vol. 53, Issue 33
  • DOI: 10.1002/anie.201403747

Catalytic Biorefining of Plant Biomass to Non-Pyrolytic Lignin Bio-Oil and Carbohydrates through Hydrogen Transfer Reactions
journal, June 2014


Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids
journal, April 2014

  • Barta, Katalin; Ford, Peter C.
  • Accounts of Chemical Research, Vol. 47, Issue 5, p. 1503-1512
  • DOI: 10.1021/ar4002894

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006

  • Huber, George W.; Iborra, Sara; Corma, Avelino
  • Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098
  • DOI: 10.1021/cr068360d

Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
journal, October 2015


Catalytic Conversion of Biomass: Challenges and Issues
journal, September 2008


Design of solid catalysts for the conversion of biomass
journal, January 2009

  • Rinaldi, Roberto; Schüth, Ferdi
  • Energy & Environmental Science, Vol. 2, Issue 6
  • DOI: 10.1039/b902668a

The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010

  • Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
  • Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
  • DOI: 10.1021/cr900354u

Selective, Nickel-Catalyzed Hydrogenolysis of Aryl Ethers
journal, April 2011


Biomass conversion: Lignin up for break-down
journal, December 2014

  • Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.
  • Nature Chemistry, Vol. 6, Issue 12, p. 1035-1036
  • DOI: 10.1038/nchem.2120

Rhodium-mediated hydrogenolysis/hydrolysis of the aryl ether bond in supercritical carbon dioxide/water: an experimental and theoretical approach
journal, January 2015

  • Chatterjee, Maya; Chatterjee, Abhijit; Ishizaka, Takayuki
  • Catalysis Science & Technology, Vol. 5, Issue 3
  • DOI: 10.1039/C4CY01417K

C-C or C-O Bond Cleavage in a Phenolic Lignin Model Compound: Selectivity Depends on Vanadium Catalyst
journal, January 2012

  • Hanson, Susan K.; Wu, Ruilian; Silks, Louis A. “Pete”
  • Angewandte Chemie International Edition, Vol. 51, Issue 14, p. 3410-3413
  • DOI: 10.1002/anie.201107020

CC or CO Bond Cleavage in a Phenolic Lignin Model Compound: Selectivity Depends on Vanadium Catalyst
journal, January 2012

  • Hanson, Susan K.; Wu, Ruilian; Silks, Louis A. “Pete”
  • Angewandte Chemie, Vol. 124, Issue 14
  • DOI: 10.1002/ange.201107020

Chemo- and Regioselective Hydrogenolysis of Diaryl Ether C−O Bonds by a Robust Heterogeneous Ni/C Catalyst: Applications to the Cleavage of Complex Lignin-Related Fragments
journal, December 2015

  • Gao, Fang; Webb, Jonathan D.; Hartwig, John F.
  • Angewandte Chemie International Edition, Vol. 55, Issue 4
  • DOI: 10.1002/anie.201509133

One-Pot Catalytic Conversion of Cellulose and of Woody Biomass Solids to Liquid Fuels
journal, September 2011

  • Matson, Theodore D.; Barta, Katalin; Iretskii, Alexei V.
  • Journal of the American Chemical Society, Vol. 133, Issue 35, p. 14090-14097
  • DOI: 10.1021/ja205436c

Enhancing Aromatic Production from Reductive Lignin Disassembly: in Situ O-Methylation of Phenolic Intermediates
journal, September 2016


Palladium-Catalyzed Hydrolytic Cleavage of Aromatic C−O Bonds
journal, January 2017

  • Wang, Meng; Shi, Hui; Camaioni, Donald M.
  • Angewandte Chemie International Edition, Vol. 56, Issue 8
  • DOI: 10.1002/anie.201611076

Palladium-Catalyzed Hydrolytic Cleavage of Aromatic C−O Bonds
journal, January 2017


Synthesis of ketones from biomass-derived feedstock
journal, January 2017

  • Meng, Qinglei; Hou, Minqiang; Liu, Huizhen
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14190

Homogeneous Metal Salt Catalysis in Organic Reactions. I. The Preparation of Vinyl Ethers by Vinyl Transetherification
journal, June 1957

  • Watanabe, Warren H.; Conlon, Lawrence E.
  • Journal of the American Chemical Society, Vol. 79, Issue 11
  • DOI: 10.1021/ja01568a044

Hydrogenation and cleavage of the C-O bonds in the lignin model compound phenethyl phenyl ether over a nickel-based catalyst
journal, April 2013


Titanium Nitride-Nickel Nanocomposite as Heterogeneous Catalyst for the Hydrogenolysis of Aryl Ethers
journal, January 2014

  • Molinari, Valerio; Giordano, Cristina; Antonietti, Markus
  • Journal of the American Chemical Society, Vol. 136, Issue 5, p. 1758-1761
  • DOI: 10.1021/ja4119412

Highly selective hydrogenation of arenes using nanostructured ruthenium catalysts modified with a carbon–nitrogen matrix
journal, April 2016

  • Cui, Xinjiang; Surkus, Annette-Enrica; Junge, Kathrin
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11326

A Series of NiM (M = Ru, Rh, and Pd) Bimetallic Catalysts for Effective Lignin Hydrogenolysis in Water
journal, April 2014

  • Zhang, Jiaguang; Teo, Jason; Chen, Xi
  • ACS Catalysis, Vol. 4, Issue 5
  • DOI: 10.1021/cs401199f

Nucleophilic Substitution in Aromatic Ethers. II. Kinetics of the Methanolysis of 2,4-Dinitrodiphenyl Ethers
journal, September 1949

  • Ogata, Yoshiro.; Okano, Masaya.
  • Journal of the American Chemical Society, Vol. 71, Issue 9
  • DOI: 10.1021/ja01177a078

Notes- Ketal versus Hemiketal Formation for Cyclohexanone and Methanol
journal, August 1960

  • Kubler, Donald; Sweeney, L.
  • The Journal of Organic Chemistry, Vol. 25, Issue 8
  • DOI: 10.1021/jo01078a606