Premium
Reagent Control of [1,2]‐Wagner–Meerwein Shift Chemoselectivity Following the Nazarov Cyclization: Application to the Total Synthesis of Enokipodin B
Author(s) -
Lebœuf David,
Wright Christopher M.,
Frontier Alison J.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201203395
Subject(s) - chemoselectivity , total synthesis , chemistry , reagent , vicinal , ligand (biochemistry) , tandem , combinatorial chemistry , cationic polymerization , stereochemistry , catalysis , organic chemistry , receptor , biochemistry , materials science , composite material
An approach toward the carbon framework of various sesquiterpenes from the herbertane and cuparane families is described, including the concise total synthesis of enokipodin B. The key step is the construction of the vicinal quarternary centers of the skeleton through a tandem Nazarov cyclization/Wagner–Meerwein rearrangement mediated by a copper(II) complex. During this study, it was also found that changing the ligand architecture on the copper(II) promoter improved the chemoselectivity of the cationic rearrangement.