Abstract: | Through serendipitous discovery, a palladium bis(phosphine) complex was identified as a catalyst for the selective transformation of sp2C?F and sp2C?H bonds of fluoroarenes and heteroarenes to sp2C?Al bonds (19 examples, 1 mol % Pd loading). The carbon–fluorine bond functionalization reaction is highly selective for the formation of organoaluminium products in preference to hydrodefluorination products (selectivity=4.4:1 to 27:1). Evidence is presented for a tandem catalytic process in which hydrodefluorination is followed by sp2C?H alumination. |