Polymer-Bound Mixed Carboxylic Dithiocarbamic Anhydrides. A New Class of Selective and Recyclable Solid-Phase Acylating Reagents

Article abstract of DOI:10.1021/jo00389a006

Polymer-supported mixed carboxylic dithiocarbamic anhydrides are a new class of regenerable solid-phase reagents for acylating amino groups specifically.The resins were prepared by a four-step synthesis from cross-linked poly(chloromethylstyrene) (Merrifield's resin).The chloromethyl groups were converted to aminomethyl groups by the Gabriel synthesis, and reaction of the aminomethyl resin with carbon disulfide and aqueous sodium hydroxide gave a dithiocarbamate resin.Treatment of this resin with an acyl chloride gave the mixed carboxylic dithiocarbamic anhydride resin.These insoluble anhydrides transfer the acyl group to amines or amino acids in solution at room temperature, yielding a solution of the corresponding amide or peptide.The spent polymeric reagent can be regenerated to the carboxylic dithiocarbamic anhydride by treatment with carbon disulfide and sodium hydroxide followed by acylation.