RAFT polymerization and thio‐bromo substitution: An efficient way towards well‐defined glycopolymers

Abstract

ABSTRACTDespite an increasing effort to design well‐defined glycopolymers, the convenient synthesis of polymers with higher DPs (>100) and without tedious protection and deprotection steps remains a challenge. Combining the reversible addition fragmentation transfer (RAFT) polymerization and the efficient substitution of primary bromo groups by thiols, we were able to synthesize a set of well‐defined glycopolymers with DPs of up to 115. With the polymerization of the highly reactive monomer (2‐bromoethyl)‐acrylate polymers with low dispersities were obtained that could efficiently be functionalized with various sugar thiol(ate)s. In particular, derivatives of d‐glucose, d‐galactose, and d‐mannose gave excellent degrees of functionalization close to quantitative conversion using only a slight excess of the thiol. This atom efficient synthesis can even be applied for copolymers with acid or base labile components due to the use of unprotected sugar moieties and, hence, the lack of further deprotection steps. Binding studies with the lectin concanavalin A and the subsequent competition studies with α‐d‐methyl‐mannopyranose (αMeMan) proved the effective binding of these derivatives and revealed a DP‐ and carbohydrate‐dependent clustering and dissolution. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3617–3626