Pd(II)-Catalyzed Synthesis of Polycyclic Heteroarenes via an Aminopalladation/C-H Activation/Dealkylation/Decarboxylative Cyclization Cascade.

Abstract

Until now, cascade reactions involving five-membered C,C-palladacycles rely heavily on Pd(0)-catalyzed C-H functionalization of aryl halides initiated by carbopalladation. Herein, we report a novel Pd(II)-catalyzed cascade decarboxylative cyclization of o-alkynylanilines initiated by aminopalladation. In this protocol, o-alkynylanilines undergo sequential anti aminopalladation, C-H activation, and dealkylation to form C,C-palladacycles, which are then trapped by o-bromobenzoic acids or 8-bromo-1-naphthoic acid to produce diverse polycyclic heteroarenes, such as dibenzo[a,c]carbazoles and multiple arene-fused cyclohepta[1,2-b]indoles.