Miyaura Borylation and One‐Pot Two‐Step Homocoupling of Aryl Chlorides and Bromides under Solvent‐Free Conditions

Abstract Solvent‐free protocols for Miyaura borylation and the one‐pot, two‐step homocoupling of aryl halides are reported for the first time. Bis(dibenzylideneacetone)palladium(0) [Pd(dba) 2 ] is an optimal source of palladium for Miyaura borylation, while for one‐pot two‐step homocoupling palladium(II) acetate [Pd(OAc) 2 ] gives highest yields. Aryl bromides are coupled most efficiently using the DPEphos ligand. Chlorides are coupled using XPhos. The developed protocols are robust, versatile and easily reproducible on a large scale. magnified image