A mild, palladium-catalyzed method for the dehydrohalogenation of alkyl bromides: synthetic and mechanistic studies

J Am Chem Soc. 2012 Aug 29;134(34):14232-7. doi: 10.1021/ja306323x. Epub 2012 Aug 20.


We have exploited a typically undesired elementary step in cross-coupling reactions, β-hydride elimination, to accomplish palladium-catalyzed dehydrohalogenations of alkyl bromides to form terminal olefins. We have applied this method, which proceeds in excellent yield at room temperature in the presence of a variety of functional groups, to a formal total synthesis of (R)-mevalonolactone. Our mechanistic studies have established that the rate-determining step can vary with the structure of the alkyl bromide and, most significantly, that L(2)PdHBr (L = phosphine), an intermediate that is often invoked in palladium-catalyzed processes such as the Heck reaction, is not an intermediate in the active catalytic cycle.

Publication types

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

MeSH terms

  • Alkanes / chemistry*
  • Alkenes / chemical synthesis*
  • Bromine / chemistry*
  • Catalysis
  • Halogenation
  • Palladium / chemistry*
  • Phosphines / chemistry


  • Alkanes
  • Alkenes
  • Phosphines
  • Palladium
  • phosphine
  • Bromine