Copper-mediated conversion of complex ethers to esters: enabling biopolymer depolymerisation under mild conditions

Ganyuan Xiao; James Montgomery; Christopher S. Lancefield; Isabella Panovic; Nicholas J. Westwood

doi:10.1002/chem.202000088

Copper-mediated conversion of complex ethers to esters: enabling biopolymer depolymerisation under mild conditions

Ganyuan Xiao, James Montgomery, Christopher S. Lancefield, Isabella Panovic, Nicholas J. Westwood^*

^*Corresponding author for this work

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

Abstract

Selective processing of the β-O-4 unit in lignin is essential for the efficient depolymerisation of this biopolymer and therefore its successful integration into a biorefinery set-up. An approach is described in which this unit is modified to incorporate a carboxylic ester with the goal of enabling the use of mild depolymerisation conditions. Inspired by preliminary results using a Cu/TEMPO/O₂ system, a protocol was developed that gave the desired β-O-4-containing ester in high yield using certain dimeric model compounds. The optimised reaction conditions were then applied to an oligomeric lignin model system. Extensive 2D NMR analysis demonstrated that analogous chemistry could be achieved with the oligomeric substrate. Mild depolymerisation of the ester-containing oligomer delivered the expected aryl acid monomer.

Original language	English
Pages (from-to)	12397-12402
Number of pages	7
Journal	Chemistry - A European Journal
Volume	26
Issue number	54
Early online date	3 Sept 2020
DOIs	https://doi.org/10.1002/chem.202000088
Publication status	Published - 25 Sept 2020

Keywords

Biomass
Lignin
Mild depolymerization
TEMPO oxidation
Copper

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10.1002/chem.202000088Licence: CC BY

Xiao-2020-Copper-mediated-conversion-CEJ-CC
Copyright © 2020 The Authors. Published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 1.62 MBLicence: CC BY

Unravelling the chemistry: Unravelling the chemistry that drives lignocellulose degradation in nature
Lancefield, C. S. (PI)
The Leverhulme Trust
1/09/18 → 31/08/21
Project: Fellowship
CRITICAT CDT: Critical Resource Catalysis - CRITICAT
Smith, A. D. (PI), Nolan, S. P. (CoI) & Westwood, N. J. (CoI)
EPSRC
1/05/14 → 31/10/22
Project: Standard

Copper-mediated conversion of complex ethers to esters: enabling biopolymer depolymerisation under mild conditions (dataset)
Westwood, N. J. (Creator), Xiao, G. (Creator), Montgomery, J. (Creator), Lancefield, C. S. (Creator) & Panovic, I. (Creator), Figshare, 2020
DOI: 10.6084/m9.figshare.12795062
Dataset

Cite this

@article{691d05dc8a7f4ad488ed97d38ffa3718,

title = "Copper-mediated conversion of complex ethers to esters: enabling biopolymer depolymerisation under mild conditions",

abstract = "Selective processing of the β-O-4 unit in lignin is essential for the efficient depolymerisation of this biopolymer and therefore its successful integration into a biorefinery set-up. An approach is described in which this unit is modified to incorporate a carboxylic ester with the goal of enabling the use of mild depolymerisation conditions. Inspired by preliminary results using a Cu/TEMPO/O2 system, a protocol was developed that gave the desired β-O-4-containing ester in high yield using certain dimeric model compounds. The optimised reaction conditions were then applied to an oligomeric lignin model system. Extensive 2D NMR analysis demonstrated that analogous chemistry could be achieved with the oligomeric substrate. Mild depolymerisation of the ester-containing oligomer delivered the expected aryl acid monomer.",

keywords = "Biomass, Lignin, Mild depolymerization, TEMPO oxidation, Copper",

author = "Ganyuan Xiao and James Montgomery and Lancefield, {Christopher S.} and Isabella Panovic and Westwood, {Nicholas J.}",

note = "Authors acknowledge the China Scholarship Council (G.X. studentship), the University of St Andrews (G.X. and J.R.D.M. studentships) and the EPSRC-funded CRITICAT Centre for Doctoral Training (studentship to I.P.; EP/L016419/1) for PhD funding. C.S.L. thanks the Leverhulme Trust Early Career Fellowship (ECF-2018-480) and the University of St Andrews.",

year = "2020",

month = sep,

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doi = "10.1002/chem.202000088",

language = "English",

volume = "26",

pages = "12397--12402",

journal = "Chemistry - A European Journal",

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publisher = "John Wiley & Sons, Ltd",

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TY - JOUR

T1 - Copper-mediated conversion of complex ethers to esters

T2 - enabling biopolymer depolymerisation under mild conditions

AU - Xiao, Ganyuan

AU - Montgomery, James

AU - Lancefield, Christopher S.

AU - Panovic, Isabella

AU - Westwood, Nicholas J.

N1 - Authors acknowledge the China Scholarship Council (G.X. studentship), the University of St Andrews (G.X. and J.R.D.M. studentships) and the EPSRC-funded CRITICAT Centre for Doctoral Training (studentship to I.P.; EP/L016419/1) for PhD funding. C.S.L. thanks the Leverhulme Trust Early Career Fellowship (ECF-2018-480) and the University of St Andrews.

PY - 2020/9/25

Y1 - 2020/9/25

N2 - Selective processing of the β-O-4 unit in lignin is essential for the efficient depolymerisation of this biopolymer and therefore its successful integration into a biorefinery set-up. An approach is described in which this unit is modified to incorporate a carboxylic ester with the goal of enabling the use of mild depolymerisation conditions. Inspired by preliminary results using a Cu/TEMPO/O2 system, a protocol was developed that gave the desired β-O-4-containing ester in high yield using certain dimeric model compounds. The optimised reaction conditions were then applied to an oligomeric lignin model system. Extensive 2D NMR analysis demonstrated that analogous chemistry could be achieved with the oligomeric substrate. Mild depolymerisation of the ester-containing oligomer delivered the expected aryl acid monomer.

AB - Selective processing of the β-O-4 unit in lignin is essential for the efficient depolymerisation of this biopolymer and therefore its successful integration into a biorefinery set-up. An approach is described in which this unit is modified to incorporate a carboxylic ester with the goal of enabling the use of mild depolymerisation conditions. Inspired by preliminary results using a Cu/TEMPO/O2 system, a protocol was developed that gave the desired β-O-4-containing ester in high yield using certain dimeric model compounds. The optimised reaction conditions were then applied to an oligomeric lignin model system. Extensive 2D NMR analysis demonstrated that analogous chemistry could be achieved with the oligomeric substrate. Mild depolymerisation of the ester-containing oligomer delivered the expected aryl acid monomer.

KW - Biomass

KW - Lignin

KW - Mild depolymerization

KW - TEMPO oxidation

KW - Copper

U2 - 10.1002/chem.202000088

DO - 10.1002/chem.202000088

M3 - Article

SN - 1521-3765

VL - 26

SP - 12397

EP - 12402

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 54

ER -

Copper-mediated conversion of complex ethers to esters: enabling biopolymer depolymerisation under mild conditions

Abstract

Keywords

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Projects

Unravelling the chemistry: Unravelling the chemistry that drives lignocellulose degradation in nature

CRITICAT CDT: Critical Resource Catalysis - CRITICAT

Datasets

Copper-mediated conversion of complex ethers to esters: enabling biopolymer depolymerisation under mild conditions (dataset)

Cite this