Extremely rapid postfunctionalization of maleate and fumarate main chain polyesters in the presence of TBD

Unsaturated polyester (UP) scaffold, poly (butylene maleate) (P1), possessing an electron-deficient double bond in the main chain was prepared and utilized as a precursor for thiol- and aza-Michael addition reactions. From a detailed catalyst search (amidine and guanidine bases), 1,5,7-triazabicyclo [4.4.0]dec-5-ene (TBD) proved to be the most efficient catalyst for thiol-Michael addition reactions since pendant thioether functional polyesters were achieved quantitatively within 1 min. Furthermore, P1 was allowed to react with primary and secondary amines through aza-Michael addition reactions, followed by thiol-Michael addition reaction thus affording the synthesis of pendant amine and thioether functional polyesters. [Display omitted] •An extremely rapid postfunctionalization of the unsaturated polyester backbone with maleate and fumarate units.•Thiol-Michael addition reactions catalyzed by TBD proceeds quantitatively to yield thioether functional polyester at room temperature within 1 min.•Mixed pendant amine and thioether functional polyester were also achieved using sequential aza- and thiol-Michael reactions.