title: Domino Friedel-Crafts-type cyclizations of difluoroalkenes promoted by the α-cation-stabilizing effect of fluorine: an efficient method for synthesizing angular PAHs.
abstract: In order to synthesize polycyclic aromatic hydrocarbons with nonlinear arrangements (angular PAHs), acid-promoted domino cyclizations of 1,1-difluoroalk-1-enes and 1,1-difluoroalka-1,3-dienes were studied. 1,1-Difluoroalkenes, each bearing two aryl substituents, were regioselectively protonated with FSO(3)H⋅SbF(5) to generate fluorine-stabilized carbocations, which readily underwent domino Friedel-Crafts-type cyclizations to give carbocycles based on 6/n/m/6 ring systems (n,m=5-7) in good to high yields. Protonation of 1,1-difluoroalka-1,3-dienes took place at their electron-rich methylene (CH(2)) carbon atoms in the presence of milder acids such as camphorsulfonic acid and trifluoromethanesulfonic acid. Domino cyclizations of the resulting fluorine-stabilized allylic carbocations afford carbocycles based on 6/6/6/6 or 6/6/5/6 ring systems in high yields.
authors.affiliation: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571, Japan.
authors.forename: Kohei
authors.initials: K
authors.lastname: Fuchibe
authors.forename: Hideharu
authors.initials: H
authors.lastname: Jyono
authors.forename: Masaki
authors.initials: M
authors.lastname: Fujiwara
authors.forename: Takao
authors.initials: T
authors.lastname: Kudo
authors.forename: Misaki
authors.initials: M
authors.lastname: Yokota
authors.forename: Junji
authors.initials: J
authors.lastname: Ichikawa