TBAF-promoted dephenolative transcarbomylation: direct access to substituted carbamates & thiocarbamates.

A mild, metal-free TBAF-catalysed transcarbamoylation of O-phenyl N-alkyl/aryl carbamates enables efficient O- and S-carbamoyl transfer to diverse alcohols and thiols. The protocol delivers carbamates and thiocarbamates in up to 94% yield, tolerating broad functionality and avoiding phosgene, isocyanates and harsh reaction conditions.