Palladium-Catalyzed Carbon-Fluorine and Carbon-Hydrogen Bond Alumination of Fluoroarenes and Heteroarenes.

Through serendipitous discovery, a palladium bis(phosphine) complex was identified as a catalyst for the selective transformation of sp2 C-F and sp2 C-H bonds of fluoroarenes and heteroarenes to sp2 C-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 sp2 C-H alumination.