title: Stereoselective tandem ring opening of imidazoles with electron-deficient acetylenes and water: synthesis of functionalized (Z,Z)-1,4-diaza-2,5-dienes.
abstract: 1-Substituted imidazoles undergo exceptionally facile stereoselective ring opening under the influence of electron-deficient acetylenes and water (equimolar ratio of the reactants) in MeCN at 45-60 °C without any catalysts to afford functionalized (Z,Z)-1,4-diaza-2,5-dienes, (Z,Z)-propenylaminoethenylformamides, in up to 80% yields. The reaction is rationalized to proceed in a tandem manner via zwitterionic vinyl carbanions formed by nucleophilic addition of imidazole to the triple bond. The carbanionic center is then quenched with water followed by the rearrangement of the intermediate 2-hydroxy-3-alkenylimidazolines.
authors.affiliation: A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation. boris_trofimov@irioch.irk.ru
authors.forename: Boris A
authors.initials: BA
authors.lastname: Trofimov
authors.forename: Ludmila V
authors.initials: LV
authors.lastname: Andriyankova
authors.forename: Lina P
authors.initials: LP
authors.lastname: Nikitina
authors.forename: Kseniya V
authors.initials: KV
authors.lastname: Belyaeva
authors.forename: Anastasia G
authors.initials: AG
authors.lastname: Mal'kina
authors.forename: Lubov N
authors.initials: LN
authors.lastname: Sobenina
authors.forename: Andrei V
authors.initials: AV
authors.lastname: Afonin
authors.forename: Igor A
authors.initials: IA
authors.lastname: Ushakov
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D001372:Aza Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D004583:Electrons; D007093:Imidazoles / Q000737:chemistry*; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000480:Alkynes; D001372:Aza Compounds; D007093:Imidazoles; D014867:Water