title: Tandem Catalytic Depolymerization of Lignin by Water-Tolerant Lewis Acids and Rhodium Complexes.
abstract: Lignin is an attractive renewable feedstock for aromatic bulk and fine chemicals production, provided that suitable depolymerization procedures are developed. Here, we describe a tandem catalysis strategy for ether linkage cleavage within lignin, involving ether hydrolysis by water-tolerant Lewis acids followed by aldehyde decarbonylation by a Rh complex. In situ decarbonylation of the reactive aldehydes limits loss of monomers by recondensation, a major issue in acid-catalyzed lignin depolymerization. Rate of hydrolysis and decarbonylation were matched using lignin model compounds, allowing the method to be successfully applied to softwood, hardwood, and herbaceous dioxasolv lignins, as well as poplar sawdust, to give the anticipated decarbonylation products and, rather surprisingly, 4-(1-propenyl)phenols. Promisingly, product selectivity can be tuned by variation of the Lewis-acid strength and lignin source.
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Robin
authors.initials: R
authors.lastname: Jastrzebski
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Sandra
authors.initials: S
authors.lastname: Constant
authors.affiliation: School of Chemistry and Biomedical Science Research Complex, University of St. Andrews and EaStCHEM, North Haugh, St. Andrews, Fife, KY16 9ST, United Kingdom.
authors.forename: Christopher S
authors.initials: CS
authors.lastname: Lancefield
authors.affiliation: School of Chemistry and Biomedical Science Research Complex, University of St. Andrews and EaStCHEM, North Haugh, St. Andrews, Fife, KY16 9ST, United Kingdom.
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Westwood
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Bert M
authors.initials: BM
authors.lastname: Weckhuysen
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands. p.c.a.bruijnincx@uu.nl.
authors.forename: Pieter C A
authors.identifier: 0000-0001-8134-0530
authors.initials: PC
authors.lastname: Bruijnincx
mesh_terms: D002384:Catalysis; D058116:Lewis Acids / Q000737:chemistry*; D008031:Lignin / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D058105:Polymerization; D012238:Rhodium / Q000737:chemistry*; D020058:Styrene / Q000737:chemistry; D014867:Water / Q000737:chemistry*
chemical_list: D058116:Lewis Acids; D009942:Organometallic Compounds; D014867:Water; D020058:Styrene; D008031:Lignin; D012238:Rhodium
keywords: biomass; decarbonylation; lewis acid; lignin; tandem catalysis