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This Article describes the development of a decarbonylative Pd-catalyzed aryl–fluoroalkyl bond-forming reaction that couples fluoroalkylcarboxylic acid-derived electrophiles [R_FC(O)X] with aryl organometallics (Ar–M′). This reaction was optimized by interrogating the individual steps of the catalytic cycle (oxidative addition, carbonyl de-insertion, transmetalation, and reductive elimination) to identify a compatible pair of coupling partners and an appropriate Pd catalyst. These stoichiometric organometallic studies revealed several critical elements for reaction design. First, uncatalyzed background reactions between R_FC(O)X and Ar–M′ can be avoided by using M′ = boronate ester. Second, carbonyl de-insertion and Ar–R_F reductive elimination are the two slowest steps of the catalytic cycle when R_F = CF₃. Both steps are dramatically accelerated upon changing to R_F = CHF₂. Computational studies reveal that a …