Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents

Although the use of catalytic rather than stoichiometric amounts of metal mediator in cross-coupling reactions between organic halides and organometallic counterparts improves significantly the atom economy and waste production, the use of solvents and stoichiometric generation of main-group byproducts (B, Sn and Zn) hamper the 'greenness' and industrial efficiency of these processes. Here we present a highly selective and green Pd-catalysed cross-coupling between organic halides and organolithium reagents proceeding without additional solvents and with short reaction times (10 min). This method bypasses a number of challenges previously encountered in Pd-catalysed cross-coupling with organolithium compounds such as strict exclusion of moisture, dilution and slow addition. Operational ease of this protocol combines the use of industrially viable catalysts loadings (down to 0.1 mol%), scalability of the process (tested up to 120 mmol) and exceptionally favourable environmental impact (E factors in several cases as low as 1).