title: Modular synthesis of N-vinyl benzotriazoles.
abstract: A modular approach to N1-vinyl benzotriazoles by azide-aryne cycloadditions and Julia-Kocienski reactions is described. Reactions of azidomethyl phenyl-1H-tetrazol-5-yl (PT) sulfide with arynes gave methyl(PT-sulfanyl)-substituted benzotriazoles in 68-89% yields. Oxidation of the sulfides to the sulfones gave the benzotriazole-substituted Julia-Kocienski reagents. Olefination reactions of aldehydes and a ketone with reagents derived from benzyne, 2,3-naphthyne, and 4,5-dimethoxybenzyne precursors proceeded to give various N1-vinyl benzotriazole derivatives. Olefination stereoselectivities are tunable for electron-rich aldehydes, but not for electron-deficient aldehydes and alkanals, where they proceed with good to excellent Z-stereoselectivity.
authors.affiliation: Department of Chemistry, The City College and The City University of New York, 160 Convent Avenue, New York, New York 10031-9198, USA.
authors.forename: Govindra
authors.initials: G
authors.lastname: Singh
authors.forename: Rakesh
authors.initials: R
authors.lastname: Kumar
authors.forename: Jorge
authors.initials: J
authors.lastname: Swett
authors.forename: Barbara
authors.initials: B
authors.lastname: Zajc
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D001386:Azides / Q000737:chemistry; D061565:Cycloaddition Reaction; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D014230:Triazoles / Q000138:chemical synthesis* / Q000737:chemistry; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000447:Aldehydes; D000475:Alkenes; D001386:Azides; C585706:N-vinyl benzotriazole; D014230:Triazoles; D014753:Vinyl Compounds; C012771:benzotriazole
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