Iridium-catalyzed (Z)-trialkylsilylation of terminal olefins.
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 degrees 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. alpha,beta-Unsaturated esters were unreactive. The reaction probably proceeds through a Heck-type mechanism.
Lu
Biao
B
Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, Texas 75390, USA.
Falck
J R
JR
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D007495:Iridium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D009942:Organometallic Compounds; D012821:Silanes; C512918:triethylsilane; D007495:Iridium