Indium(iii) as π-acid catalyst for the electrophilic activation of carbon-carbon unsaturated systems

This review focuses on the utilization of indium(iii) as π-acid for the activation of C-C unsaturated bonds in organic synthesis. In addition to its well-known σ-coordination with carbonyl derivatives, indium(iii) undergoes efficient π-coordination with unsaturated systems to trigger nucleophilic addition. Accordingly, indium(iii) halides and salts (InX3, X = Cl, Br, I, OTf, ONf, NTf2) have been reported as useful catalysts for a broad range of carbon-carbon and carbon-heteroatom bond formation reactions, including hydrofunctionalization (hydroarylation, hydroamination, hydroalkoxylation, and hydrothiolation), enyne cycloisomerization, and related reactions. In these reactions the counterion has a significant effect on the catalytic activity, and the development of novel In(iii) complexes and the generation of highly electrophilic cationic indium(iii) species has increased its synthetic applications as a π-acid catalyst.