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
posted on 2013-09-06, 00:00authored byGeorgia Velegraki, Manolis Stratakis
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 (Fe3+) 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).