Noncovalent Protection for Direct Synthesis of α-Amino-ω-hydroxyl Poly(ethylene oxide)

Abstract

The synthesis of poly(ethylene oxide) (PEO) with amino end group, a key functionality for PEGylation, is a long-standing challenge. Multistep routes based on postmodification or covalent protection have been adopted to circumvent ethoxylation of the amino group by ethylene oxide (EO). Here, we report a noncovalent protection strategy for one-step synthesis of PEO amine. An amino (di)alcohol is mixed with a small amount of mild phosphazene base and excess triethylborane (Et₃B) before addition of EO. The complexation of the amino group with Et₃B guarantees that polymerization of EO occurs selectively from the hydroxyl group through the bicomponent metal-free catalysis. Simply by precipitation in diethyl ether, the protective Et₃B as well as the catalyst can be removed to afford α-amino-ω-hydroxyl PEO with controlled molar mass, low dispersity, and complete end functionality. The effect of initiator structure and retention of Et₃B on the storage (oxidative) stability of PEO amine is also revealed.