THE INVENTION OF RADICAL REACTIONS. PART XV. SOME MECHANISTIC ASPECTS OF THE DECARBOXYLATIVE REARRANGEMENT OF THIOHYDROXAMIC ESTERS

Article abstract of DOI:10.1016/S0040-4020(01)86878-2

Esters (mixed anhydrides) derived from aliphatic or alicyclic carboxylic acids (RCO2H) and thiohydroxamic acids 2 or 3 undergo a thermally or photochemically induced radical chain reaction to give sulphides 4 with loss of carbon dioxide.On irradiation at low temperature however, the chain reaction is essentially suppressed.Under these conditions moderate to good yields of dimers R-R are obtained from primary acids.The mechanistic and synthetic implications of these observations are discussed.