title: Synthesis and characterization of beta-haloalkenyl-lambda3-bromanes: stereoselective Markovnikov addition of difluoro(aryl)-lambda3-bromane to terminal acetylenes.
abstract: Reported here for the first time are the synthesis, isolation, and characterization of hypervalent beta-haloalkenyl-lambda3-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-lambda3-bromane activated by BF3-i-Pr2O resulted in fluoro-lambda3-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-beta-fluoroalkenyl-lambda3-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino lambda3-bromanation-chlorine shift-fluorination or lambda3-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-beta-chloroalkenyl-lambda3-bromanes stereoselectively in high yields. The beta-chloroalkenyl-lambda3-bromanes contain three kinds of halogen atoms, F, Cl, and Br, in the molecule.
authors.affiliation: Faculty of Pharmaceutical Sciences, University of Tokushima, 1-78 Shomachi, Tokushima 770-8505, Japan. mochiai@ph.tokushima-u.ac.jp
authors.forename: Masahito
authors.initials: M
authors.lastname: Ochiai
authors.forename: Yoshio
authors.initials: Y
authors.lastname: Nishi
authors.forename: Takeshi
authors.initials: T
authors.lastname: Mori
authors.forename: Norihiro
authors.initials: N
authors.lastname: Tada
authors.forename: Takashi
authors.initials: T
authors.lastname: Suefuji
authors.forename: Hermann J
authors.initials: HJ
authors.lastname: Frohn