Copper-catalyzed C-H/N-H annulation of enaminones and alkynyl esters for densely substituted pyrrole synthesis

Herein, the copper-catalyzed annulation of enaminones with alkynyl esters for the facile synthesis of different pyrroles with a 2,3,4,5-tetrasubstituted structure has been developed. With Cu(OAc) 2 as the only catalyst, the tunable synthesis of 2-vinyl and 2,3-dicarboxyl-functionalized pyrroles has been achieved by using terminal and internal alkynyl esters, respectively. The synthesis of 2-vinyl pyrroles represents the first example accessing 2-vinyl substituted pyrroles via direct cascade reactions involving vinylation and pyrrole ring formation. The synthesis of 2-vinyl pyrroles has been achieved via copper-catalyzed cascade reactions of enaminones and alkyl propiolates. The synthesis of 2,3-dicarboxylate-functionalized products has been tuned by using internal alkynyl dicarboxylates.