State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024, China.
Angew Chem Int Ed Engl. 2021 Mar 8;60(11):5994-6002. doi: 10.1002/anie.202011259. Epub 2021 Feb 4.
Unprecedented enantioselective resolution copolymerization of racemic cis-internal epoxides and anhydrides was mediated by dinuclear aluminum complexes with multiple chirality, affording optically active polyesters with two contiguous stereogenic centers, and the unreacted substrates in good enantioselectivity. Unexpected stereoconvergence is observed in this resolution copolymerization, where the selectivity factor for the enantioselective formation of copolymer significantly exceeds the kinetic resolution coefficient based on the unreacted epoxide at various conversions. Catalytic activity and copolymer enantioselectivity are strongly influenced by the phenolate ortho-substituents of the ligand set, as well as the axial linker and its chirality. An enantiopure binaphthol-linked bimetallic Al complex allows stereoconvergent access to the stereoregular semi-crystalline polyesters and a concomitant kinetic resolution of the epoxide substrates.
通过双核铝配合物介导的具有多种手性的非对映选择性环氧化物和酸酐的外消旋顺式内环氧化物的空前聚合反应，得到了具有两个连续手性中心的光学活性聚酯，同时未反应的底物具有良好的对映选择性。在这种分辨率共聚反应中观察到了意想不到的立体汇聚，其中共聚的对映选择性形成的选择性因子显著超过基于各种转化率的未反应环氧化物的动力学拆分系数。催化剂活性和共聚物对映选择性强烈受配体的酚盐邻位取代基以及轴向连接基团及其手性的影响。手性纯联萘酚连接的双金属铝配合物允许通过立体汇聚途径获得立体规整的半结晶聚酯，并同时对环氧化物底物进行动力学拆分。
