Silyl ether constitutes a multipurpose (macro)molecular functionality for being, e.g., SuFEx-clickable and easily cleavable as a hydroxyl precursor. Its direct incorporation by anionic polymerization is challenged by its base susceptibility. In this study, a two-component organocatalyst shows strict epoxy-selectivity in the anionic ring-opening polymerization (ROP) of commercially available tert-butyldimethylsilyl (R)-(−)-glycidyl ether (TBSGE). The silyl ether pendant groups are fully preserved in the resultant polyether and readily undergo acidic hydrolysis to yield well-defined linear polyglycerol (PGC). Combination of the ROP with mechanistically distinct polymerization chemistries delivers PGC-based polyurethane and a hybrid amphiphilic block copolymer. The SuFEx reaction with sulfonyl fluoride shows effective tuning of polyTBSGE into a sulfonate-functionalized polyether. We have thus exploited the chemoselectivity of organocatalysis to facilitate access to polymers carrying reactive pendant functionalities.

中文翻译：

---

有机催化硅基缩水甘油醚的选择性开环聚合


甲硅烷基醚构成了一种多用途（大）分子官能团，例如可作为羟基前体进行 SuFEx 点击和轻松裂解。它通过阴离子聚合直接掺入受到其碱敏感性的挑战。在这项研究中，双组分有机催化剂在市售叔丁基二甲基甲硅烷基(R)-(−)-缩水甘油醚(TBSGE)的阴离子开环聚合(ROP)中表现出严格的环氧选择性。甲硅烷基醚侧基完全保留在所得聚醚中，并且易于进行酸水解，产生明确的线性聚甘油（PGC）。 ROP 与机械上不同的聚合化学相结合，可产生基于 PGC 的聚氨酯和混合两亲性嵌段共聚物。 SuFEx 与磺酰氟的反应表明，聚 TBSGE 可以有效地转变为磺酸盐官能化的聚醚。因此，我们利用有机催化的化学选择性来促进获得带有反应性侧基官能团的聚合物。