Synthesis of the natural product descurainolide and cyclic peptides from lignin-derived aromatics
MetadataShow full item record
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))
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.
Showing items related by title, author, creator and subject.
Sanz Camacho, Paula; Athukorala Arachchige, Kasun Sankalpa; Slawin, Alexandra Martha Zoya; Green, Timothy F.G.; Yates, Jonathan R.; Dawson, Daniel McLean; Woollins, J Derek; Ashbrook, Sharon Elizabeth (2015-05-20) - Journal articleSolid-state NMR spectra of new P–Se heterocycles based on peri-substituted naphthalene motifs show the presence of unusual J couplings between Se and P. These couplings are between atoms in adjacent molecules and occur ...
Controlling the electromagnetic proximity effect by tuning the mixing between superconducting and ferromagnetic order Stewart, R.; Flokstra, M. G.; Rogers, M.; Satchell, N.; Burnell, G.; Miller, D.; Luetkens, H.; Prokscha, T.; Suter, A.; Morenzoni, E.; Lee, S. L. (2019-07-12) - Journal articleWe present low-energy muon-spin rotation measurements on Cu/Nb/AlOx/Co thin films that probe the newly described electromagnetic (EM) proximity effect. By varying the thickness of the insulating AlOx layer we control the ...
High-resolution solid-state 13C NMR spectroscopy of the paramagnetic metal-organic frameworks, STAM-1 and HKUST-1 Dawson, Daniel M.; Jamieson, Lauren E.; Mohideen, M. Infas H.; McKinlay, Alistair C.; Smellie, Iain A.; Cadou, Romain; Keddie, Neil S.; Morris, Russell E.; Ashbrook, Sharon E. (2012-11) - Journal articleSolid-state C-13 magic-angle spinning (MAS) NMR spectroscopy is used to investigate the structure of the Cu(II)-based metal-organic frameworks (MOFs), HKUST-1 and STAM-1, and the structural changes occurring within these ...