1,3-Dipolar cycloadditions of diphenyldiazomethane to thioketones: Rate measurements disclose thiones to be superdipolarophiles
作者： Rolf Huisgen , Elke Langhals
DOI: 10.1002/HC.20262
关键词:
摘要: 1,3-Dipolar cycloadditions of diphenyldiazomethane to thioketones afford 2,5-dihydro-1,3,4-thiadiazoles 8, which rapidly lose N2. The liberated thiocarbonyl ylides 10 furnish thiiranes 9 by electrocyclic ring closure. rate constants, measured spectrophotometry (DMF, 40°C) for 16 cycloaliphatic and aromatic one cyclic trithiocarbonate, stretch over five powers with fluorene-9-thione at the top 2,2,5,5-tetramethylcyclopentanethione bottom. Electron-releasing substituents decrease cycloaddition thiobenzophenone; thus, ambiphilic reacts as nucleophilic partner electrophilic thioketone. influence size on reactivity cycloalkanethiones, are sterically hindered two gem-dimethyl groups, will be discussed. Compared electron-deficient CC bonds, thiones superdipolarophiles. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:433–442, 2006; Published online in InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20262
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