Ciaran Lahive

  • University of St Andrews
  • School of Chemistry
  • Purdie Building North Haugh
  • St Andrews KY16 9ST
  • United Kingdom

 

My SuBiCat publications:

 

2016  Advanced Model Compounds for Understanding Acid-Catalyzed Lignin Depolymerization: Identification of Renewable Aromatics and a Lignin-Derived Solvent

Ciaran W. Lahive, Peter J. Deuss, Christopher S. Lancefield, Zhuohua Sun, David B. Cordes, Claire M. Young, Fanny Tran, Alexandra M. Z. Slawin, Johannes G. de Vries, Paul C. J. Kamer, Nicholas J. Westwood, and Katalin Barta, J. Am. Chem. Soc. 2016, 138(28), 8900–8911

The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges to methodology development. Ideally, new methods should be tested on model compounds that are complex enough to mirror the structural diversity in lignin but still of sufficiently low molecular weight to enable facile analysis. In this contribution, we present a new class of advanced (β-O-4)-(β-5) dilinkage models that are highly realistic representations of a lignin fragment. Together with selected β-O-4, β-5, and β–β structures, these compounds provide a detailed understanding of the reactivity of various types of lignin linkages in acid catalysis in conjunction with stabilization of reactive intermediates using ethylene glycol. The use of these new models has allowed for identification of novel reaction pathways and intermediates and led to the characterization of new dimeric products in subsequent lignin depolymerization studies. The excellent correlation between model and lignin experiments highlights the relevance of this new class of model compounds for broader use in catalysis studies. Only by understanding the reactivity of the linkages in lignin at this level of detail can fully optimized lignin depolymerization strategies be developed.

 

2016  Metal Triflates for the Production of Aromatics from Lignin

Peter J. Deuss, Ciaran W. Lahive, Christopher S. Lancefield, Nicholas J. Westwood, Paul C. J. Kamer, Katalin Barta, Johannes G. de Vries, ChemSusChem 2016, 9, 1–9

The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields under mild reaction conditions. The methodology relies on the use of catalytic amounts of easy-to-handle metal triflates (M(OTf)x). Initially, we evaluated the reactivity of a broad range of metal triflates using simple lignin model compounds. More advanced lignin model compounds were also used to study the reactivity of different lignin linkages. The product aromatic monomers were either phenolic C2-acetals obtained by stabilization of the aldehyde cleavage products by reaction with ethylene glycol or methyl aromatics obtained by catalytic decarbonylation. Notably, when the method was ultimately tested on lignin, especially Fe(OTf)3 proved very effective and the phenolic C2-acetal products were obtained in an excellent, 19.3±3.2 wt % yield.

My SuBiCat poster presentations:

 

Synthesis and use of advanced lignin β-5 model compounds

Renewable Chemicals from Lignin conference, London, UK, November 2014

 

E-mail: cwl6@st-andrews.ac.uk

Direct phone: +44 (0)1334 4614048/14017