The tricyclic azepino[1,2-a]indole acetates 7, readily accessible by visible-light-driven catalytic photooxygenation of cyclohepta[b]indoles 1, are convenient precursors to novel and uncommon cyclic C,N-diacyliminium ions 3. We report here the first Lewis acid-catalyzed C-C bond forming reactions of these species with TMSCN and silyl enol ethers as nucleophiles and utilizing TIPSOTf as well as Sc(OTf)3 as catalysts. Employing Sc(OTf)3/pybox complexes as a chiral catalyst system, regio- and enantioselective asymmetric alkylations with silyl enol ethers were achieved.