Expedient Access to Polyaromatic Biaryls by Unconventional Ag-Catalyzed Cycloaromatization of Alkynylthiophenes and Au-Catalyzed Double C-H Activation.

An unconventional approach for the regioselective synthesis of polyaromatic biaryls via site-selective Ag-catalyzed twofold electrophilic cycloisomerization followed by Au-catalyzed double C-H activation is described. The developed process allows the synthesis of highly decorated biaryls with excellent regioselectivity. As revealed by DFT computations, the reaction represents a rare example of C1-C5 endo - exo and C1-C6 endo - endo cycloaromatization. The formation of the 6-membered ring is predicted to be the fruit of an uncommon SEAr on a vinyl carbocation.