Intermolecular Redox-Neutral Amine C-H Functionalization Induced by the Strong Boron Lewis Acid B(C6 F5 )3 in the Frustrated Lewis Pair Regime.

N,N-Dimethylmesitylamine undergoes an intermolecular redox-neutral C-H activation/C-C coupling process upon treatment with dimethyl acetylenedicarboxylate and the strong boron Lewis acid B(C6 F5 )3 . Similarly, N,N-dimethylmesitylamine reacts with two molar equivalents of ethyl acrylate to give the respective unsaturated coupling product with H2 transfer to the acrylic ester to form the ethyl propionate/B(C6 F5 )3 adduct. N,N-Dimethylmesitylamine also undergoes a C-H activation at the benzylic ortho sp3 -carbon atom with dihydrogen formation upon treatment with Piers' borane [HB(C6 F5 )2 ]. The last two reactions of N,N-dimethylmesitylamine were analyzed by DFT calculations.