99613-44-2Relevant academic research and scientific papers
Catalytic Rearrangement of O-Cholesteryl S-Alkyl Dithiocarbonates to S-Alkyl S-Cholesteryl Dithiocarbonates by Phenols
Harano, Kazunobu,Miyoshi, Kouichirou,Hisano, Takuzo
, p. 1861 - 1868 (2007/10/02)
Phenolysis of O-cholesteryl S-alkyl dithiocarbonates gave the corresponding S-alkyl S-cholesteryl dithiocarbonates.The rearrangements obeyed first-order rate laws and the rates were affected by the acidity of the phenols.A plot of the substituent effect of the S-alkyl moiety against the Tafts ?* values was roughly linear. ortho-Substituted phenols such as 2-chlorophenol or 2,6-dimethylphenol considerably retarted the rearrangement.The role of phenols and the reaction behavior of O-cholesteryl S-alkyl dithiocarbonates are discussed on the basis of kinetic and molecular orbital calculation data indicating that the rearrangement may proceed by specific solvation of phenols at the thiocarbonyl sulfur atom.Keywords: O-cholesteryl S-alkyl dithiocarbonate; homoallylic participation; phenol-catalyzed rearrangement; S-cholesteryl S-alkyl dithiocarbonate; hydrogen bonding; phenolysis; frontier molecular orbital; reaction rate
