Bromoallenes as allyl dication equivalents in the presence or absence of palladium(0): direct construction of bicyclic sulfamides containing five- to eight-membered rings by tandem cyclization of bromoallenes

Chemistry. 2007;13(6):1692-708. doi: 10.1002/chem.200601373.

Abstract

A highly regioselective synthesis of bicyclic sulfamides is described. Based on our recent discovery that bromoallenes can act as allyl dication equivalents in the presence of a palladium catalyst and alcohol, we investigated tandem cyclization of bromoallenes bearing a sulfamide group. It is found that some bromoallenes act as allyl dication equivalents even in the absence of a palladium(0) catalyst to afford cyclosulfamides containing five- or six-membered rings. While the palladium-free cyclization is dependent on the substrate structure affording the bicyclic sulfamides through the first cyclization onto the proximal or central carbon atom of the bromoallenes, the palladium-catalyzed reaction strongly promotes the first cyclization onto the central allenic carbon atom to afford bicyclic sulfamides containing a seven- or eight-membered ring. Formation of two types of bicyclic sulfamides from single bromoallenes by simply changing the reaction conditions is also described.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkadienes / chemistry*
  • Bridged Bicyclo Compounds / chemical synthesis*
  • Bromine / chemistry*
  • Catalysis
  • Cyclization
  • Models, Chemical
  • Palladium / chemistry*
  • Stereoisomerism
  • Sulfonamides / chemical synthesis*

Substances

  • Alkadienes
  • Bridged Bicyclo Compounds
  • Sulfonamides
  • propadiene
  • Palladium
  • Bromine