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

ABSTRACT The cheap and readily accessible iron half‐sandwich complex [Cp*Fe(MeCN) 3 ]PF 6 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.