Synthesis of N,N‐Disubstituted Thiocarbamates from Thiocarbamoyl Fluorides with Alcohols/Phenols/Thiophenols/Thioalcohols Through Copper Catalysis

Abstract

AbstractTraditional methods for preparing N,N‐disubstituted thiocarbamates require highly toxic, flammable and volatile reagents, or their derivatives. Recently, we developed a general method for thiocarbamoyl fluorides from safe, cheap, and easily available starting materials. Reported reactions involving thioyl fluoride with nucleophiles are very scarce. In this report, copper catalyzed reaction of thiocarbamoyl fluorides with phenols/thiophenols/alcohols/thioalcohols under Na2CO3 at 50 °C or at 80 °C in CH3CN were first developed, affording the corresponding N,N‐disubstituted thiocarbamates in moderate to excellent yields. When alcohols are cheap and their boiling points are less than 120 °C or they are water‐soluble, CuCl catalyzed reaction of thiocarbamoyl fluorides with alcohols at 50 °C was also developed. The reaction has good functional group tolerance. Methoxy, methyl, chloro, bromo, nitro, even ester functional groups were all tolerated. Control reactions demonstrated that copper catalyst played the key role on the success of these novel reactions.