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Development of a catalytic enantioselective synthesis of the guanacastepene and heptemerone tricyclic core

Harned, Andrew M. and Stoltz, Brian M. (2019) Development of a catalytic enantioselective synthesis of the guanacastepene and heptemerone tricyclic core. Tetrahedron, 75 (24). pp. 3166-3177. ISSN 0040-4020. PMCID PMC6959853. https://resolver.caltech.edu/CaltechAUTHORS:20190227-085618755

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Abstract

For nearly two decades, synthetic chemists have been fascinated by the structural complexity and synthetic challenges afforded by the guanacastepene and heptemerone diterpenoids. Numerous synthetic approaches to these compounds have been reported, but to date the application of enantioselective catalysis to this problem has not been realized. Herein we report an enantioselective synthesis of an advanced intermediate corresponding to the tricyclic core common to the guanacastepenes and heptemerones. Highlights of this work include sequential Pd-catalyzed decarboxylative allylic alkylation reactions to generate the two all carbon quaternary stereocenters, the use of ring-closing metathesis to close the A ring in the presence of a distal allyl sidechain, and a regio- and diastereoselective oxidation of a trienol ether to introduce oxygenation on the A ring.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1016/j.tet.2019.02.053DOIArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/pmc6959853/PubMed CentralArticle
ORCID:
AuthorORCID
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2019 Published by Elsevier Ltd. Received 12 January 2019, Revised 20 February 2019, Accepted 22 February 2019, Available online 27 February 2019. This paper is dedicated to Professor Ryan A. Shenvi on receipt of the Tetrahedron Young Investigator Award. We thank the NIH-NIGMS (R01GM080269 and postdoctoral fellowship F32GM073332 to A.M.H.), Amgen, the Gordon and Betty Moore Foundation, and Caltech for financial support.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
NIH Postdoctoral FellowshipF32GM073332
AmgenUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
CaltechUNSPECIFIED
Subject Keywords:Allylic alkylation; Pd catalysis; Olefin metathesis; Stereoselectivity; Natural products
Issue or Number:24
PubMed Central ID:PMC6959853
Record Number:CaltechAUTHORS:20190227-085618755
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20190227-085618755
Official Citation:Andrew M. Harned, Brian M. Stoltz, Development of a catalytic enantioselective synthesis of the guanacastepene and heptemerone tricyclic core, Tetrahedron, Volume 75, Issue 24, 2019, Pages 3166-3177, ISSN 0040-4020, https://doi.org/10.1016/j.tet.2019.02.053. (http://www.sciencedirect.com/science/article/pii/S0040402019302133)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:93289
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:27 Feb 2019 17:04
Last Modified:10 Apr 2020 19:41

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