title: Thermolysis of isomigrastatin and its congeners via [3,3]-sigmatropic rearrangement: a new route to the synthesis of migrastatin and its analogues.
abstract: Thermolysis of isomigrastatin (1) under neat heating conditions afforded migrastatin (1a). The reaction is proposed to proceed via a concerted [3,3]-sigmatropic rearrangement by which ring expansion is achieved regio- and enantiospecifically. The general applicability of this reaction was demonstrated with six additional isomigrastatin congeners (3-8), providing a new route to the synthesis of migrastatin analogues (3a-8a). [reaction: see text]
authors.affiliation: Division of Pharmaceutical Sciences, University of Wisconsin National Cooperative Drug Discovery Group, University of Wisconsin-Madison, Madison, WI 53705, USA.
authors.forename: Jianhua
authors.initials: J
authors.lastname: Ju
authors.forename: Si-Kyu
authors.initials: SK
authors.lastname: Lim
authors.forename: Hui
authors.initials: H
authors.lastname: Jiang
authors.forename: Jeong-Woo
authors.initials: JW
authors.lastname: Seo
authors.forename: Yeng
authors.initials: Y
authors.lastname: Her
authors.forename: Ben
authors.initials: B
authors.lastname: Shen
mesh_terms: D002851:Chromatography, High Pressure Liquid; D006358:Hot Temperature; D007536:Isomerism; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry*; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D010881:Piperidones / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D007783:Lactones; D018942:Macrolides; D010881:Piperidones; C455261:isomigrastatin; C418199:migrastatin