LiCl-Mediated Preparation of Functionalized Benzylic Indium(III) Halides and Highly Chemoselective Palladium-Catalyzed Cross-Coupling in a Protic Cosolvent

Sensitive functional groups such as COR, CHO, or CH₂OH can be present in benzylic indium reagents prepared by the direct insertion of indium in the presence of LiCl. These reagents undergo palladium-catalyzed cross-coupling reactions in the presence of a protic cosolvent after activation with iPrMgCl·LiCl (see scheme). Remarkable chemoselectivities are achieved by using various electrophiles containing NH or OH groups.