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.