Iridium-catalyzed (Z)-trialkylsilylation of terminal olefins

J Org Chem. 2010 Mar 5;75(5):1701-5. doi: 10.1021/jo902678p.

Abstract

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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes / chemistry*
  • Catalysis
  • Cyclization
  • Iridium / chemistry*
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Silanes / chemistry*
  • Stereoisomerism

Substances

  • Alkenes
  • Organometallic Compounds
  • Silanes
  • triethylsilane
  • Iridium