The impact of macrocycle conformation on the taxadiene-forming carbocation cascade: insight gained from sobralene, a recently discovered verticillene isomer
MetadataShow full item record
AbstractCopyright © 2020 American Chemical Society. DFT calculations on the carbocation intermediates that connect the biosynthetic pathways leading to the sand fly pheromone sobralene and taxadiene have been made. Establishment of the conformation of the macrocyclic carbocation intermediate required to produce the (Z)-C8,C9 alkene bond in sobralene has identified new conformations of the verticillyl carbocation intermediates on the taxadiene biosynthetic pathway. These "sobralene-like" carbocation conformations provide an exothermic pathway to taxadiene and are validated by comparison to closely related structures (X-ray and NMR).
CitationHayes, C. J., Palframan, M. J. and Pattenden, G. (2020) The impact of macrocycle conformation on the taxadiene-forming carbocation cascade: insight gained from sobralene, a recently discovered verticillene isomer, Journal of Organic Chemistry, 85 (6), pp. 4507–4514. DOI: 10.1021/acs.joc.0c00369
PublisherAmerican Chemical Society (ACS)
JournalJournal of Organic Chemistry
PubMed ID32101002 (pubmed)
DescriptionThis is an accepted manuscript of an article published by American Chemical Society in Journal of Organic Chemistry on 26/02/2020, available online: https://doi.org/10.1021/acs.joc.0c00369 The accepted version of the publication may differ from the final published version.
SponsorsThe University of Nottingham
Except where otherwise noted, this item's license is described as https://creativecommons.org/licenses/by-nc-nd/4.0/
- The Impact of Macrocycle Conformation on the Taxadiene-Forming Carbocation Cascade: Insight Gained from Sobralene, a Recently Discovered Verticillene Isomer.
- Authors: Hayes CJ, Palframan MJ, Pattenden G
- Issue date: 2020 Mar 20
- The taxadiene-forming carbocation cascade.
- Authors: Hong YJ, Tantillo DJ
- Issue date: 2011 Nov 16
- Sobralene, a new sex-aggregation pheromone and likely shunt metabolite of the taxadiene synthase cascade, produced by a member of the sand fly Lutzomyia longipalpis species complex.
- Authors: Palframan MJ, Bandi KK, Hamilton JGC, Pattenden G
- Issue date: 2018 May 16
- Studies on taxadiene synthase: interception of the cyclization cascade at the isocembrene stage with GGPP analogues.
- Authors: Chow SY, Williams HJ, Huang Q, Nanda S, Scott AI
- Issue date: 2005 Nov 25