Guo Xuanhua, Xu Guangqiang, Yang Rulin, Wang Qinggang
Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China.
Shandong Energy Institute, Qingdao 266101, China.
J Am Chem Soc. 2024 Apr 3;146(13):9084-9095. doi: 10.1021/jacs.3c14091. Epub 2024 Mar 1.
Isotactic polymers have emerged with unique and excellent properties in material sciences. Specific discrimination polymerization provides an ideal pathway to achieve highly isotactic polymers from their racemic monomers, which is of great significance and a challenge in polymeric chemistry. Although an enantioselective catalyst-mediated asymmetric kinetic resolution polymerization (AKRP) process makes it possible, a general and well-defined strategy for catalyst design is still rarely reported. Here, based on a novel dual-ligand strategy, a new type of chiral (BisSalen)Al complex with high enantioselectivity has been described, in which perfect AKRP of racemic phenethylglycolide (Pegl) is achieved for the first time. The more confined asymmetric microenvironment formed by a dual ligand is the key to improve the enantioselectivity of the original catalyst. To illustrate the generality of this strategy, a series of (BisSalen)Al complexes with homo- or heterodual ligands were designed for the AKRP of Pegl.
等规聚合物在材料科学领域展现出独特且优异的性能。特定的判别聚合为从外消旋单体获得高度等规聚合物提供了一条理想途径，这在高分子化学中具有重大意义且颇具挑战性。尽管对映选择性催化剂介导的不对称动力学拆分聚合（AKRP）过程使之成为可能，但关于催化剂设计的通用且明确的策略仍鲜有报道。在此，基于一种新型双配体策略，描述了一种具有高对映选择性的新型手性（双水杨醛）铝配合物，首次实现了外消旋苯乙交酯（Pegl）的完美AKRP。由双配体形成的更受限的不对称微环境是提高原始催化剂对映选择性的关键。为说明该策略的通用性，设计了一系列具有同双配体或异双配体的（双水杨醛）铝配合物用于Pegl的AKRP。
