近日，中国科学院化学所王煜团队报道了手性偶氮-降冰片烯的高区域选择性和反选择开环复分解聚合。该研究于2026年6月24日发表在《中国高分子科学杂志》上。

开环复分解聚合（ROMP）中的立体化学控制对于调控聚合物性能至关重要。尽管已有若干研究通过催化剂设计实现了对非对称单体的可调区域选择性，但在明确区域化学的同时实现高反式选择性仍然是一项挑战。

研究组报道了使用一种易于制备的苯基亚胺钨催化剂，对源自Vince内酰胺的手性氮杂降冰片烯单体进行ROMP。所得聚合物表现出高的头-头区域选择性和高的反式选择性，这与此前工作形成鲜明对比——在之前的工作中，钌基催化剂从同一单体主要得到顺式选择性的聚合物。

此外，结合研究组先前报道的聚合物，比旋光度测定和圆二色谱表明，不同的立体构型显著影响了来自同一手性单体的聚合物的光学活性和手性表达。这项工作为ROMP中的立体化学控制提供了一种互补策略，为设计和合成结构明确的手性聚合物提供了有价值的见解。

附：英文原文

Title: Highly Regio- and trans-Selective Ring-opening Metathesis Polymerization of Chiral Aza-norbornene with a Simple Phenylimido-Tungsten Catalyst

Author: Xun Ci, Jing Bai, Yu Wang, Wei You

Issue&Volume: 2026-06-24

Abstract: Stereochemical control in ring-opening metathesis polymerization (ROMP) is essential for tailoring polymer properties. While several existing studies have achieved tunable regioselectivity with asymmetric monomers through catalyst design, yet achieving high trans-selectivity alongside defined regiochemistry remains challenging. Here we report the ROMP of a chiral aza-norbornene monomer derived from Vince lactam using a readily prepared phenylimido tungsten catalyst. The resulting polymer exhibited high head-to-head regioselectivity and high trans-selectivity, which stands in stark contrast to our previous work where Ru-based catalysts afforded predominantly cis-selective polymers from the same monomer. Moreover, together with our previously reported polymers, specific rotation measurements and circular dichroism spectra demonstrated that varied stereochemical configurations significantly influenced the optical activity and chiral expression of polymers derived from the same chiral monomer. This work provides a complementary approach to stereochemical control in ROMP, offering valuable insights for design and synthesis of structurally well-defined chiral polymers.

DOI: 10.1007/s10118-026-3696-4

Source: https://www.cjps.org/en/article/doi/10.1007/s10118-026-3696-4/