Photochemical Approach to the Cyclohepta[b]indole Scaffold by Annulative Two-Carbon Ring-Expansion

We report on the implementation of the concept of a photochemically elicited two-carbon homologation of a pi-donor-pi-acceptor substituted chromophore by triple-bond insertion. Implementing a phenyl connector between the slide-in module and the chromophore enabled the synthesis of cylohepta[b]indole-type building blocks by a metal-free annulative one-pot two-carbon ring expansion of the five-membered chromophore. Post-irradiative structural elaboration provided founding members of the indolo[2,3-d]tropone family of compounds. Control experiments in combination with computational chemistry on this multibond reorganization process founded the basis for a mechanistic hypothesis.