Facile H–D exchange of the bridgehead methyls of bicyclo[2.2.2]octan-2,5-diones. Evidence for a carbon analogue of the acyloin rearrangement Academic Article uri icon

  •  
  • Overview
  •  
  • Research
  •  
  • Identity
  •  
  • Additional Document Info
  •  
  • View All
  •  

abstract

  • Hexamethyltwistyl-2,5-dione 4 has been synthesized and its H–D exchange studied in t-BuOK/t-BuOD at 125 °C. We find that the bridgehead methyl at C-3 undergoes exchange 7 × 105 times faster than the bridgehead methyl of bicyclo[2.2.1]heptan-2-one (fenchone). This result, along with a previous study, establishes the first examples of the carbon analogue of the acyloin rearrangement of alicyclic systems.

publication date

  • September 1, 1985