Solvent-Mediated Enantioselective Rauhut-Currier Cyclization via Iminium and Enamine Activation.

In this work, we have developed an unconventional and highly enantioselective solvent-promoted Rauhut-Currier cyclization of enal-tethered cyclohexadienone by exploiting the reactivity of a simple Jørgensen-Hayashi catalyst through the merging of iminium and enamine activation. This asymmetric desymmetrization reaction has broad substrate scope in good yields with high to excellent enantioselectivity. DFT calculations suggest that the elimination of the alkoxy group is the rate-limiting step and that it proceeds through proton abstraction by solvent instead of a direct 1,3-proton shift.