title: Aryl-substituted cyclopropyl acetylenes as sensitive mechanistic probes in the gold-catalyzed hydration of alkynes. Comparison to the Ag(I)-, Hg(II)-, and Fe(III)-catalyzed processes.
abstract: The gold-catalyzed hydration of 2-phenyl- or 2,2-diphenylcyclopropyl acetylene, sensitive probes to trace the formation of vinyl carbocations, provides exclusively the corresponding cyclopropyl methyl ketones. On the other hand, in the Ag(I)- or Fe(III)-catalyzed hydration, a profound vinyl carbocationic character appears in the initially formed metal-alkyne complexes, as judged by the partial (Ag(+)) or exclusive (Fe(3+)) formation of allene-type rearrangement products. These findings provide clear evidence for subtle electronic differences in metal-alkyne complexes, including Au(I or III), Ag(I), Fe(III), and Hg(II).
authors.affiliation: Department of Chemistry, University of Crete, Voutes 71003 Iraklion, Greece.
authors.forename: Georgia
authors.initials: G
authors.lastname: Velegraki
authors.forename: Manolis
authors.initials: M
authors.lastname: Stratakis
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D005290:Ferric Compounds / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D008628:Mercury / Q000737:chemistry*; D015394:Molecular Structure; D012834:Silver / Q000737:chemistry*; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D014867:Water / Q000737:chemistry
chemical_list: D000480:Alkynes; D005290:Ferric Compounds; D014753:Vinyl Compounds; D014867:Water; D012834:Silver; D006046:Gold; D008628:Mercury