Imidazole-Assisted Intramolecular Phenoxythiocarbonylation of Tertiary Alcohols. A Key Reaction for the Deoxygenation of α-Trifluoromethylarylmethyl Alcohols

Article abstract of DOI:10.3987/COM-94-S(B)77

The deoxygenation of α-trifluoromethylarylmethyl alcohols failed under catalytic hydrogenation conditions.However, these alcohols can be deoxygenated via their thionocarbonate intermediates followed by homolytic reductive cleavage of the C-O bond.The formation of the phenyl thionocarbonate esters is sterically dependent.Consequently, secondary α-trifluoromethyl arylmethyl alcohols can be smoothly converted to thionocarbonates, but tertiary alcohols cannot.Exceptions to this lack of reactivity are the aryl 4-substituted imidazolyl trifluoromethyl carbinols, which do form the thionocarbonates under these conditions.