Thermolysis of isomigrastatin and its congeners via [3,3]-sigmatropic rearrangement: a new route to the synthesis of migrastatin and its analogues.
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]
Ju
Jianhua
J
Division of Pharmaceutical Sciences, University of Wisconsin National Cooperative Drug Discovery Group, University of Wisconsin-Madison, Madison, WI 53705, USA.
Lim
Si-Kyu
SK
Jiang
Hui
H
Seo
Jeong-Woo
JW
Her
Yeng
Y
Shen
Ben
B
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
D007783:Lactones; D018942:Macrolides; D010881:Piperidones; C455261:isomigrastatin; C418199:migrastatin