Organocatalytic ring-opening polymerization of morpholinones: new strategies to functionalized polyesters.

The oxidative lactonization of N-substituted diethanolamines with the Pd catalyst [LPd(OAc)]2(2+)[OTf(-)]2 generates N-substituted morpholin-2-ones. The organocatalytic ring-opening polymerization of N-acyl morpholin-2-ones occurs readily to generate functionalized poly(aminoesters) with N-acylated amines in the polyester backbone. The thermodynamics of the ring-opening polymerization depends sensitively on the hybridization of the nitrogen of the heterocyclic lactone. N-Acyl morpholin-2-ones polymerize readily to generate polymorpholinones, but the N-aryl or N-alkyl substituted morpholin-2-ones do not polymerize. Experimental and theoretical studies reveal that the thermodynamics of ring opening correlates to the degree of pyramidalization of the endocyclic N-atom. Deprotection of the poly(N-Boc-morpholin-2-one) yields a water-soluble, cationic polymorpholinone.