Cyclic Diaryl λ3-Chloranes: Reagents and Their C-C and C-O Couplings with Phenols via Aryne Intermediates

Hypervalent chloranes are a class of rare and poorly explored reagents. Their unique electronic properties confer reactivity that is complementary to that of the common iodanes and emerging bromanes. Highly chemo-and regioselective, metal free, and mild C-C and C-O couplings are reported here. Experimental and computational mechanistic studies elucidate the unprecedented reactivities and selectivities of these systems and the intermediacy of aryne intermediates. The synthetic potential of these transformations is further demonstrated via the post-functionalization of C-C and C-O coupling products obtained from reactions of chloranes with phenols under different conditions.

Automated summary

Hypervalent chloranes are rare and poorly explored reagents that possess unique electronic properties. This study reports highly chemo- and regioselective, metal-free, and mild C-C and C-O couplings using these chloranes. Mechanistic studies reveal the unprecedented reactivities and selectivities of these systems and the involvement of aryne intermediates. The synthetic potential of these transformations is demonstrated through post-functionalization of the coupling products obtained from chloranes and phenols under different conditions.