“…The cleavage of the acyl−S bond of thiolcarbamates by protic solvents and nucleophiles is well-known ,7a and may be related to the biological activity of these compounds 4k. Early routes to thiolcarbamates included acid-mediated addition of alcohols to thiocyanates, the Newman−Kwart rearrangement, and various procedures involving phosgene 8 or other highly energetic reagents . More recently, a variety of methods have been reported, including aminolysis of cyclic thioxocarbonates, carbonate-mediated addition of alkyl halide to carbon disulfide, elaboration of activated carbamoyl derivatives 5a,12 and thiocarbonates, O-to-S allylic rearrangement, rearrangement of N -alkyl carbonimidodithionates, various carbonylation and thiocarbonylation reactions, and thiolation of isocyanates,4k the last being the most general.…”