Electrophilic activation of unsaturated systems: Applications to selective organic synthesis

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 electro - philic 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 sulfonyl-allenamides 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. © 2013 IUPAC.