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Asymmetric Total Synthesis of Havellockate

Hafeman, Nicholas J. and Chan, Melinda and Fulton, Tyler J. and Alexy, Eric J. and Loskot, Steven A. and Virgil, Scott C. and Stoltz, Brian M. (2022) Asymmetric Total Synthesis of Havellockate. Journal of the American Chemical Society, 144 (44). pp. 20232-20236. ISSN 0002-7863. doi:10.1021/jacs.2c09583. https://resolver.caltech.edu/CaltechAUTHORS:20221128-494241100.52

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Abstract

The first total synthesis of the furanobutenolide-derived cembranoid diterpenoid havellockate is disclosed. Our convergent strategy employs a Julia–Kocienski olefination to join two enantioenriched fragments to produce a diene that is subsequently used in a propiolic acid esterification/Diels–Alder cascade. This sequence generates the fused carbocyclic core of the natural product in short order. A challenging Zn-mediated Barbier allylation then forges the final C–C bond and also establishes two vicinal stereogenic centers. Finally, a Cu-catalyzed aerobic oxidation facilitates the formation of the β-hydroxybutanolide to complete the total synthesis.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.2c09583DOIArticle
ORCID:
AuthorORCID
Hafeman, Nicholas J.0000-0001-7525-7597
Chan, Melinda0000-0002-2495-0110
Fulton, Tyler J.0000-0002-9343-2456
Alexy, Eric J.0000-0002-2971-9698
Virgil, Scott C.0000-0001-8586-5641
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:This Communication is dedicated to the memory of David A. Evans (1941–2022), a great scientist, educator, mentor, and friend. The authors thank NSF (CHE1800511), NIH (R35GM145239), and the Heritage Medical Research Institute Investigator Program. The authors thank David VanderVelde for NMR assistance and maintenance of the Caltech NMR facility, Dr. Michael Takase and the Caltech XRD facility for XRD assistance, and Dr. Mona Shahgholi for mass spectrometry assistance. The authors thank the Beckman Institute for their support of the Caltech XRD facility as well as the Dow Next Generation Instrument Grant.
Group:Heritage Medical Research Institute
Funders:
Funding AgencyGrant Number
NSFCHE-1800511
NIHR35GM145239
Heritage Medical Research InstituteUNSPECIFIED
Beckman InstituteUNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
Issue or Number:44
DOI:10.1021/jacs.2c09583
Record Number:CaltechAUTHORS:20221128-494241100.52
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20221128-494241100.52
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:118089
Collection:CaltechAUTHORS
Deposited By: Research Services Depository
Deposited On:21 Dec 2022 17:51
Last Modified:21 Dec 2022 17:51

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