State Key Laboratory of Supramolecular Structureand Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, 230009, China.
Nat Commun. 2023 Feb 2;14(1):566. doi: 10.1038/s41467-023-36327-0.
Immobilizing organocatalyst onto helical polymers not only facilitates the catalyst recycling from homogeneous reactions, but also boosts enantioselectivity. In this work, achiral organoiodine-functionalized single left- and right-handed helical polyisocyanides were prepared from the same monomers, which catalyzed three asymmetric oxidations gave the desired products in high yields and excellent enantioselectivity. The enantiomeric excess of the target products was up to 95%. Remarkably, the enantioselectivity can be switched by reversing the helicity of the polymer backbone. The polymer catalysts can be facilely recovered and recycled in different asymmetric oxidations with maintained excellent activity and enantioselectivity.
将有机催化剂固定在螺旋聚合物上不仅便于从均相反应中回收催化剂，而且还可以提高对映选择性。在这项工作中，从相同的单体制备了非手性有机碘官能化的单一左、右手螺旋聚异氰化物，它们催化了三种不对称氧化反应，以高产率和优异的对映选择性得到了所需的产物。目标产物的对映体过量高达 95%。值得注意的是，通过反转聚合物主链的手性可以切换对映选择性。聚合物催化剂可以在不同的不对称氧化反应中简便地回收和再循环，同时保持优异的活性和对映选择性。
