The Impact of Macrocycle Conformation on the Taxadiene-Forming Carbocation Cascade: Insight Gained from Sobralene, a Recently Discovered Verticillene Isomer

Hayes, Christopher J.; Palframan, Matthew J.; Pattenden, Gerald

Abstract

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).

Citation

Hayes, C. J., Palframan, M. J., & 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), 4507-4514. https://doi.org/10.1021/acs.joc.0c00369

• Journal Article Type: Article
• Acceptance Date: Feb 26, 2020
• Online Publication Date: Feb 26, 2020
• Publication Date: Mar 20, 2020
• Deposit Date: May 11, 2020
• Publicly Available Date: Feb 27, 2021
• Journal: Journal of Organic Chemistry
• Print ISSN: 0022-3263
• Electronic ISSN: 1520-6904
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 85
• Issue: 6
• Pages: 4507-4514
• DOI: https://doi.org/10.1021/acs.joc.0c00369
• Public URL: https://nottingham-repository.worktribe.com/output/4139512
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.joc.0c00369
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Medicinal Chemistry,copyright© American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.joc.0c00369