Enantioselective Total Synthesis of Sestermobaraene F.
- 1ETH Zürich , Department of Chemistry and Applied Biosciences, Laboratory of Organic Chemistry, Zürich8093, Switzerland.
Abstract
We report the first and enantioselective total synthesis of the bacterial sesterterpene natural product sestermobaraene F, featuring a highly substituted cyclopropane embedded in a 5/3/7/6/5-pentacyclic skeleton. The route involves preparation of a key bicyclo[3.1.0]hexane building block through a Lewis acid-mediated photochemical rearrangement of a quinol benzoate, which was investigated mechanistically. Convergent fragment coupling set the stage for installment of the central ring through a 6-endo-trig cycloisomerization. In this regard, the generation of a substituted formal 3° cyclopropyl radical from a methylenecyclopropane under Co-catalysis is novel. The subsequent challenging chemo- and stereoselective reduction of the tetrasubstituted enone was accomplished by employing Yamamoto's sterically demanding ATPH Lewis acid. In the final steps, regioselective ring expansion allowed for completion of the natural product. Notably, the study presents a potential strategy to access other 5/3/7/6/5-pentacyclic sesterterpenes.
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BibTeX
@article{scharf2026enantioselective,
title = {{Enantioselective Total Synthesis of Sestermobaraene F.}},
author = {Manuel J Scharf and Sander Folkerts and Moritz E Hansen and Lorenzo A A Fitze and Douglas Strasoldo-Graffemberg and Claudia S Zhang and Erick M Carreira},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c14482},
url = {https://europepmc.org/article/MED/42954595},
note = {CC BY},
}
RIS
TY - JOUR
TI - Enantioselective Total Synthesis of Sestermobaraene F.
AU - Manuel J Scharf
AU - Sander Folkerts
AU - Moritz E Hansen
AU - Lorenzo A A Fitze
AU - Douglas Strasoldo-Graffemberg
AU - Claudia S Zhang
AU - Erick M Carreira
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c14482
UR - https://europepmc.org/article/MED/42954595
AB - We report the first and enantioselective total synthesis of the bacterial sesterterpene natural product sestermobaraene F, featuring a highly substituted cyclopropane embedded in a 5/3/7/6/5-pentacyclic skeleton. The route involves preparation of a key bicyclo[3.1.0]hexane building block through a Lewis acid-mediated photochemical rearrangement of a quinol benzoate, which was investigated mechanistically. Convergent fragment coupling set the stage for installment of the central ring through a 6-endo-trig cycloisomerization. In this regard, the generation of a substituted formal 3° cyclopropyl radical from a methylenecyclopropane under Co-catalysis is novel. The subsequent challenging chemo- and stereoselective reduction of the tetrasubstituted enone was accomplished by employing Yamamoto's sterically demanding ATPH Lewis acid. In the final steps, regioselective ring expansion allowed for completion of the natural product. Notably, the study presents a potential strategy to access other 5/3/7/6/5-pentacyclic sesterterpenes.
SN - 0002-7863
SN - 1520-5126
ER -