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The Furan Shuffling Hypothesis: A Biogenetic Proposal for Eremophilane Sesquiterpenoids
Author(s) -
Lardon Nicolas,
Liffert Raphael,
Linden Anthony,
Gademann Karl
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201901898
Subject(s) - stereochemistry , furan , chemistry , carvone , sesquiterpene , enantioselective synthesis , shuffling , mathematics , organic chemistry , limonene , catalysis , statistics , chromatography , essential oil
Based on the structural similarities of the recently isolated eremophilane‐type sesquiterpenoids microsphaeropsisin B and C and the iso ‐eremophilane periconianone C, a revised biogenetic hypothesis for C8–C11‐connected iso ‐eremophilanes is presented and corroborated by strong experimental evidence. The first enantioselective total syntheses of microsphaeropsisin B and C were achieved starting from a known intermediate, whose synthesis was elaborated previously in the total synthesis of periconianone A, and in a total of 15 steps starting from γ‐hydroxy carvone. Mild reaction conditions for the subsequent α‐ketol rearrangement not only resulted in the herein proposed conversion of microsphaeropsisin B into periconianone C, but also in the conversion of microsphaeropsisin C into 4‐ epi ‐periconianone C.