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Studies towards Simalikalactone D and Quassimarin: Construction of an Advanced Pentacyclic Intermediate
Author(s) -
Shing Tony K. M.,
Zhu Xue Y.,
Yeung Yeung Y.
Publication year - 2003
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.200305158
Subject(s) - regioselectivity , stereochemistry , chirality (physics) , intramolecular force , chemistry , sigmatropic reaction , yield (engineering) , molecule , catalysis , organic chemistry , physics , chiral symmetry breaking , quantum mechanics , nambu–jona lasinio model , quark , thermodynamics
An advanced pentacyclic intermediate, amenable to further elaboration into the target molecules simalikalactone D and quassimarin, has been synthesized from ( S )‐(+)‐carvone in 21 steps and with an overall yield of 12 %. The synthesis is efficient, stereocontrolled, enantiospecific, and chirality productive, creating eight new chiral centres in pentacycle, and should provide opportunities for rapid access to simalikalactone D analogues and other bioactive quassinoids. The reaction sequence involves a regioselective bishydroxylmethylation, a stereocontrolled epoxidation, an epoxymethano‐bridge formation, a 1,3‐sigmatropic rearrangement and an intramolecular Diels–Alder reaction as the key steps.