Enantioselective Desymmetrization Triggered by Iminium-Enamine Activation: Access to Complex Cyclohepta[b]indoles.

The expeditious construction of complex molecules having multiple stereocentres is highly desirable in organic chemistry. In the present communication, we report the development of an organocatalytic asymmetric desymmetrization of prochiral enal-tethered cyclohexadienones via the C3-selective Friedel-Crafts alkylation of indoles triggered by LUMO-lowering iminium activation/HOMO-raising enamine activation. The reaction provides access to bicyclic enones, which further undergo acid-mediated intramolecular annulation from C2-position to afford highly strained cyclohepta[b]indoles with five contiguous stereocentres and three new C-C bonds in excellent enantioselectivity and diastereoselectivity.