Organocatalytic C-F Bond Activation with Alanes

Hydrodefluorination reactions (HDF) of per- and polyfluorinated olefins and arenes by cheap aluminum alkyl hydrides in non-coordinating solvents can be catalyzed by O and N donors. TONs with respect to the organocatalysts of up to 87 have been observed. Depending on substrate and concentration, high selectivities can be achieved. For the prototypical hexafluoropropene, however, low selectivities are observed (E/Z approximate to 2). DFT studies show that the preferred HDF mechanism for this substrate in the presence of donor solvents proceeds from the dimer Me4Al2(mu-H)(2)center dot THF by nucleophilic vinylic substitution (SNV)-like transition states with low selectivity and without formation of an intermediate, not via hydrometallation or sigma-bond metathesis. In the absence of donor solvents, hydrometallation is preferred but this is associated with inaccessibly high activation barriers at low temperatures. Donor solvents activate the aluminum hydride bond, lower the barrier for HDF significantly, and switch the product preference from Z to E. The exact nature of the donor has only a minimal influence on the selectivity at low concentrations, as the donor is located far away from the active center in the transition states. The mechanism changes at higher donor concentrations and proceeds from Me2AlH center dot THF via SNV and formation of a stable intermediate, from which elimination is unselective, which results in a loss of selectivity.