Preparation of Polyfunctional Organozinc Halides by an InX₃‐ and LiCl‐Catalyzed Zinc Insertion to Aryl and Heteroaryl Iodides and Bromides

A catalytic system consisting of InCl 3 (3 mol %) and LiCl (30 mol %) allows a convenient preparation of polyfunctional arylzinc halides via the insertion of zinc powder to various aryl iodides in THF at 50 °C in up to 95 % yield. The use of a THF/DMPU (1:1) mixture shortens the reaction rates and allows the preparation of keto‐substituted arylzinc reagents. In the presence of In(acac) 3 (3 mol %) and LiCl (150 mol %), the zinc insertion to various aryl and heteroaryl bromides proceeds smoothly (50 °C, 2–18 h). Alkyl bromides are also converted to the corresponding zinc reagents in the presence of In(acac) 3 (10 mol %) and LiCl (150 mol %) in 70–80 % yield.