Crimmin, MRMRCrimminChen, WWChenHooper, TNTNHooperWhite, AJOAJOWhite2017-10-162018-08-302017-08-30Angewandte Chemie, 2017, 129 (41), pp.12861-128651521-3757http://hdl.handle.net/10044/1/51850Through 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.This is the peer reviewed version of the following article: W. Chen, T. N. Hooper, J. Ng, A. J. P. White, M. R. Crimmin, Angew. Chem. 2017, 129, 12861, which has been published in final form at https://dx.doi.org/10.1002/ange.201706378.  This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.03 Chemical SciencesOrganic ChemistryJournal Articlehttps://www.dx.doi.org/10.1002/ange.201706378UF090149655474677367