Synthesis of the natural product descurainolide and cyclic peptides from lignin-derived aromatics
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Alternative sources of potential feedstock chemicals are of increasing importance as the availability of oil decreases. The biopolymer lignin is viewed as a source of useful mono-aromatic compounds as exemplified by the industrial scale production of vanillin from this biomass. Alternative lignin-derived aromatics are available in pure form but to date examples of the use of these types of compounds are rare. Here we address this issue by reporting the conversion of an aromatic keto-alcohol to the anti- and syn-isomers of Descurainolide A. The key step involves a rhodium-catalyzed allylic substitution reaction. Enantioenriched allylic alcohols were generated via an isothiourea-catalyzed kinetic resolution enabling access to both the (2R,3R) and (2S,3S) enantiomers of anti-Descurainolide A. In addition we show that the ligninderived keto-alcohols can be converted into unnatural amino acid derivatives of tyrosine. Finally, these amino acids were incorporated into cyclic peptide scaffolds through the use of both chemical and an enzyme-mediated macrocylisation.
Ojo , O S , Nardone , B , Musolino , S F , Neal , A , Wilson , L , Lebl , T , Slawin , A M Z , Cordes , D B , Taylor , J E , Naismith , J H , Smith , A D & Westwood , N J 2018 , ' Synthesis of the natural product descurainolide and cyclic peptides from lignin-derived aromatics ' , Organic & Biomolecular Chemistry , vol. 16 , no. 2 , pp. 266-273 . https://doi.org/10.1039/C7OB02697H
Organic & Biomolecular Chemistry
© 2017 the Authors. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/ 10.1039/C7OB02697H
DescriptionThe authors acknowledge the EPSRC UK National Mass Spectrometry Facility at Swansea University for mass spectrometry analysis. Financial support from: the Engineering and Physical Sciences Research Council (grant EP/J018139/1, EP/K00445X/1 (NJW, ADS, OSO), the doctoral training grant (ARN) and the CRITICAT Centre for Doctoral Training [Ph.D. studentship to SFM; Grant code: EP/L016419/1]), the Leverhulme Trust (JET), European Research Council (ERC-2013-ADG (JHN))
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