We herein report the first example of an electrochemical approach in promoting gold-catalyzed oxidative coupling of terminal alkynes.

Internal and terminal alkynes react with phosphanylalumanes, i. e., P-Al single-bond species, through heating but without any additional additives.

Molecules 30 and 33 are synthesized from 1,3,5-triethynyladamantane by a series of Sonogashira coupling reactions involving terminal alkynes and aryl iodides.

Terminal alkynes will react selectively over internal alkynes in all cases examined including both aryl and alkenyl complexes.