Multifold C-C Coupling and Unorthodox Cyclization Catalysis for Selective Synthesis of Indolotriarylmethanes, Indolocarbazoles, and Their Analogues: A Control Experiment Study.

Abstract

The selective construction of medicinally and synthetically important indole-based unsymmetrical triarylmethanes using indoles and aldehydes is challenging because the significant nucleophilicity of indole leads to C-C coupling with an azafulvene intermediate to build up the alternative bis(indolyl)methane products, which may be useful synthons. A new, straightforward, ligand-free CuII catalytic strategy for easy syntheses of unsymmetrical indolotriarylmethanes and new bisindolylbenzoyl analogues is established through the dual C-C coupling of an assembly of three reaction partners comprising aldehydes, indoles, and arylboronic acids. More importantly, this approach is exploited for multifold C-C coupling cyclization reactions with C-C cleavage using symmetrical bisindolylbenzoylmethanes in the presence of an organic base and aerial molecular oxygen as a stoichiometric oxidant. In contrast to the formation of a simple cyclocondensation product indolocarbazole, it undergoes unprecedented selective pseudo-four-component tandem oxidative cyclization with fragmentation from a 1,3-dicarbonyl compound to produce valuable fused 5,7-dihydroindolo[2,3-b]carbazoles through the functionalization of two indole C(sp2)-H and one C(sp3)-H bond of the active methylene residue. For a better understanding of the new reactions, we have studied various competition experiments and ESI-MS and 3D Mid-IR-ATR spectral analyses of the ongoing reactions. The predicted DFT transition state model is also in agreement with the experimental results.