Solventless Catalytic C–H and C–X Functionalization Without Ball Milling

A low-cost, operationally simple approach to seven different solventless Rh-, Ru-, Ir- and Pd-catalyzed C–H and C–X functionalizations, as well as the synthesis of difficult-to-make rhodacyclic complexes, is presented. The method uses open air grinding and heating, is reproducible, gives competitive yields compared with automated ball milling protocols, and can be extended to the late-stage modification of various bioactive compounds.