Copper Catalyzed Alcohol Oxidation and Cleavage of β-O-4 Lignin Model Systems: From Development to Mechanistic Examination

H. Eemil P. Salonen, Carsten P.A. Mecke, Miika I. Karjomaa, Pekka M. Joensuu, Ari M.P. Koskinen*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

2 Citations (Scopus)
27 Downloads (Pure)

Abstract

Lignin, an abundant natural polymer with high aromaticity, is a potential source of renewable chemicals and fuels among other biomaterials. Herein, a study on copper catalyzed alcohol oxidation and cleavage of lignin β-O-4 model substrates is reported. The potential of CuX/BiPy/TEMPO(/additive) systems (X=halide or triflate, BiPy=2,2’-bipyridine; TEMPO=2,2,6,6-tetramethylpiperidine-N-oxyl) was explored and the optimized protocol was studied with several type of model compounds. Mechanistic studies elucidated two types of cascade reactions: Both involve a cleavage of Cα–Cβ bond, which is most likely activated by 1) primary alcohol oxidation in β-O-4 glycerolaryl ethers resulting in retro-aldol cleavage and 2) Cβ–H oxidation after secondary alcohol oxidation in β-O-4 ethanolaryl ethers leading to oxidative radical cleavage. The first process affords aromatic aldehydes while the latter delivers aryl acids.

Original languageEnglish
Pages (from-to)12446-12454
Number of pages9
JournalChemistrySelect
Volume3
Issue number44
DOIs
Publication statusPublished - 30 Nov 2018
MoE publication typeA1 Journal article-refereed

Keywords

  • biomass conversion
  • catalysis
  • copper
  • lignin
  • oxidation

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