Synthesis of the Marine Alkaloid Cylindricine C and Serendipitous Synthesis of Its 2,13-Di-epi Stereoisomer
Date
2023-09-18
Journal Title
Journal ISSN
Volume Title
Publisher
American Chemical Society
Abstract
A new approach to the marine alkaloid cylindricine C afforded its previously unreported (±)-2,13-di-epi stereoisomer as the major product along with a minor amount of the racemic parent alkaloid. Key steps included a stereoselective dianion alkylation of a monoester of 1,2-cyclohexanedicarboxylic acid and an annulation based on the tandem conjugate addition of a primary amine to an acetylenic sulfone, followed by intramolecular acylation of the resulting sulfone-stabilized carbanion. The cis-azadecalin moiety thus formed, comprising the cyclohexane A-ring and enaminone B-ring of the products, was further elaborated by the selenenyl chloride-induced cyclofunctionalization of a pendant butenyl substituent with the enaminone moiety, followed by a seleno-Pummerer reaction. Desulfonylation and enaminone reduction afforded the final products. Molecular modeling and X-ray crystallography provided further insight into these processes.
Description
Supplementary materials associated with this article are available:
Back, Thomas, 2023, "Synthesis of the Marine Alkaloid Cylindricine C and Serendipitous Synthesis of its 2,13-Di-epi Stereoisomer", https://doi.org/10.5683/SP3/YLTS4G, Borealis, V1
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © 2023 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi-org/10.1021/acs.joc.3c01467