title: Synthesis of polyketide stereoarrays enabled by a traceless oxonia-Cope rearrangement.
abstract: Polyketide antibiotics bearing skipped polyols represent a synthetic challenge. A SiCl4-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.
authors.affiliation: CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai 200032 (China) http://honggroup.sioc.ac.cn.
authors.forename: Lin
authors.initials: L
authors.lastname: Yang
authors.forename: Guoli
authors.initials: G
authors.lastname: He
authors.forename: Ruifeng
authors.initials: R
authors.lastname: Yin
authors.forename: Lili
authors.initials: L
authors.lastname: Zhu
authors.forename: Xiaoxia
authors.initials: X
authors.lastname: Wang
authors.forename: Ran
authors.initials: R
authors.lastname: Hong
mesh_terms: D061065:Polyketides / Q000138:chemical synthesis*; D066244:Proton Magnetic Resonance Spectroscopy; D013237:Stereoisomerism
chemical_list: D061065:Polyketides
keywords: allenes; diastereoselectivity; polyketides; rearrangement; synthetic methods