CrossRef enabled

PAC Archives

Archive →

Pure Appl. Chem., 2013, Vol. 85, No. 4, pp. 721-739

Published online 2013-03-13

Electrophilic activation of unsaturated systems: Applications to selective organic synthesis

Samuel Suárez-Pantiga and José M. González*

Departamento de Química Orgánica e Inorgánica and Instituto Universitario de Química Organometálica “Enrique Moles”, Universidad de Oviedo, 33071 Oviedo, Spain

Abstract: Selected examples from previous work on iodonium-triggered approaches for the functionalization of unsaturated systems, which summarize innovative transformations, are presented. This section is mostly focused on C–C bond-forming processes from alkynes that are directly bonded to relevant heteroatoms, such as iodine, silicon, or sulfur. Besides, recent advances related to iodonium-promoted C–H functionalization reactions are briefly outlined. A second section shows representative examples of our current research activity on electrophilic reactions aimed at the activation of unsaturated systems, which now are built upon the potential offered by the so-called carbophilic catalysis. More specifically, a new catalytic cyclopentannulation sequence from N-tosylimines and propargyl tosylates and novel C–H functionalization processes from related tosylates are studied. Likewise, representative examples for the intermolecular Au(I)-catalyzed [2 + 2] cycloaddition reaction of sulfonylallenamides with activated alkenes are given, including the first enantioselective reaction of this type, which is also among the first examples of an intermolecular asymmetric gold-catalyzed reaction. The discussion of the reported iodonium and gold chemistry emphasizes a search for new intermolecular processes, although intramolecular reactions are also pursued and developed.