Generation of vinyl cations by solvolysis reactions. A lesser known genre of carbenium ions

Abstract

Generation of Vinyl Cations by Solvolysis ReactionsA lesser known genre of carbenium ions Among the reactive intermediates in organic chemistry, carbenium ions are the most important and extensively studied (1). Although they were discovered shortly after 1900 (2), carbenium ions have been well recognized only

Stable Carbocations. 198. Formation of Allyl Cations via Protonation of Alkynes in Magic Acid Solution. Evidence for 1,2-Hydrogen and Alkyl Shifts in the Intermediate Vinyl Cations

“…During the last ten years, however, extensive studies on the solvolysis of vinyl derivatives, the plurality of which have been a-phenyl substituted, have provided indirect evidence for the intermediacy of vinyl cations. 5 Recently, the reaction of -aryl vinyl fluorides with SbFs has been reported to yield vinyl cations as stable species in low nucleophilic media by both Hanack63 and Masamune.6b Discrepancies of results and the question of whether real vinyl cations were indeed observed, however, remain to be resolved.…”

The reaction of cis- and trans-1,2-dianisyl-2-phenylvinyl-2-13C bromides with acetic acid and silver acetate

“…[Traduit par le journal] There is considerable interest in vinyl cations and a nuniber of reviews on the subject are available (1)(2)(3)(4). Recently in this laboratory, ' T-labeling coupled with cmr analysis was used to nieasure the extents of degenerate rearrangenients arising froni 1,2-aryl shifts in triarylvinyl cations (5,6).…”