Substituent‐Driven Selective Functionalization of Dibromovinyl‐Aromatics/Heteroaromatics to Give Esters and/or Terminal Alkynes

Interesting room‐temperature transformations of aryl/heteroaryl‐substituted 1,1‐dibromoalkenes have been developed for the generation of esters and terminal alkynes with the aid of sodium alkoxides, which are triggered by the electronic effects of the aryl/heteroaryl ring. The group attached to the aryl ring plays a crucial role in determining the reaction pathway; in general, electron‐withdrawing groups (EWG) direct the reaction to the formation of esters. On the other hand, electron‐donating groups (EDG) on the ring turn the reaction in another direction to produce terminal alkynes.