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Synthesis of Polyketide Stereoarrays Enabled by a Traceless Oxonia‐Cope Rearrangement
Author(s) -
Yang Lin,
He Guoli,
Yin Ruifeng,
Zhu Lili,
Wang Xiaoxia,
Hong Ran
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201407231
Subject(s) - polyketide , oxonium ion , stereoselectivity , chemistry , stereochemistry , aldehyde , combinatorial chemistry , cope rearrangement , ion , biosynthesis , organic chemistry , catalysis , enzyme
Polyketide antibiotics bearing skipped polyols represent a synthetic challenge. A SiCl 4 ‐promoted oxonia‐Cope rearrangement of syn,syn‐2‐vinyl‐1,3‐diols was developed to forge an array of 1,5‐pentenediols, thus providing versatile motifs for the preparation of 1,2,3,5‐stereoarrays in a highly stereoselective manner. Further exploration with Sn(OTf) 2 realized the rearrangement of a cross‐aldehyde which tactically warrants the utility of the current approach to access complex polyketides. The origin of high stereoselectivity is attributed to a chairlike anti‐conformation of the oxonium ion intermediate.