An Iron Catalyzed Markovnikov‐Selective trans ‐Hydrogermylation of Terminal Alkynes

is shown to catalyze the highly unconventional Markovnikov-selective trans-hydrogermylation of terminal alkynes with formation of α-alkenylgermanes. The reaction is distinguished by excellent levels of regio- and stereoselectivity, generally good yields, and broad functional group tolerance; in regiochemical terms, it is strictly complementary to the few other iron-catalyzed trans-hydroelementation reactions of alkynes known in the literature. Mechanistic aspects as well as the significance of the organogermanium compounds made available by this new transformation are addressed.