In this chapter the metal-catalyzed cross-coupling reactions of indium organometallics are reviewed. First, the various methods for the preparation of organoindium (transmetalation, direct insertion and indation of alkynes) are described and their structure are analyzed. Then, the reactivity in metal-catalyzed reactions is reviewed according to an organization based on the metal catalyst. The main section is the cross-coupling reaction under palladium catalysis which includes a general introduction, synthetic scope analysis, versatility and applications of the different indium organometallics and the reactive organic electrophiles (aryl, alkenyl, alkyl halides, triflates and others). Finally, other metal-catalyzed cross-coupling reactions are included along with general conclusions.
Overall, indium organometallics are shown as useful reagents for cross-coupling reactions with a variety of organic electrophiles. Their main features are the readily transmetalation to different transition metal complexes (palladium, nickel, rhodium, copper or iron) to transfer the organic groups attached to indium, and the high versatility and chemoselectivity as well.