Iridium-catalyzed (Z)-trialkylsilylation of terminal olefins

Article abstract of DOI:10.1021/jo902678p

(Chemical equation presented) A complex of commercial [Ir(OMe)(cod)] ₂ and 4,4-di-tert-butyl-2,2-bipyridine (dtbpy) catalyzes the Z-selective, dehydrative silylation of terminal alkenes, but not 1,2-disubstituted alkenes, with triethylsilane or benzyldimethylsilane in THF at 40 °C. Yields and Z-stereoselectivity were significantly improved by 2-norbornene, in contrast with other sacrificial alkenes. The reaction is compatible with many functional groups including epoxides, ketones, amides, alcohols, esters, halides, ketals, and silanes. α, β-Unsaturated esters were unreactive. The reaction probably proceeds through a Heck-type mechanism.