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Published November 9, 2022 | v2
Journal Article Open

Asymmetric Total Synthesis of Havellockate

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.

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.

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Additional details

Created:
November 20, 2023
Modified:
November 20, 2023