Unimolecular Anion-Binding Catalysts for Selective Ring-Opening Polymerization of O-carboxyanhydrides
Maosheng Li
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorShuai Zhang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorXiaoyong Zhang
Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
Search for more papers by this authorYanchao Wang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorJinlong Chen
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorCorresponding Author
Youhua Tao
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorCorresponding Author
Xianhong Wang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorMaosheng Li
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorShuai Zhang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorXiaoyong Zhang
Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
Search for more papers by this authorYanchao Wang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorJinlong Chen
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorCorresponding Author
Youhua Tao
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorCorresponding Author
Xianhong Wang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P. R. China
Search for more papers by this authorAbstract
Anion-binding can regulate anion transport in chloride channels through dynamic non-covalent interactions, which gives insights into the designing of new organocatalytic transformations but is surprisingly unexplored in polymerization catalysis. Herein, we describe an effective unimolecular anion-binding organocatalysis where 4-(dimethylamino)pyridine is anchored to a thiourea for ring-opening polymerization of O-carboxyanhydrides (OCAs) to furnish highly isotactic poly(phenyllactic acid) (Ph-PLA) with molecular weight (MW) up to 150.0 kDa, which well addresses the formidable challenge of synthesizing high MW stereoregular polyesters. Calculations and experimental studies indicate a dynamic cooperative anion-binding mechanism, where the dynamic anion-binding interaction of thiourea moiety to propagating species facilitates efficient chain propagation and the synergetic decarboxylation retains high selectivity for OCA ring-opening over side reactions (such as cyclization, epimerization, and transesterification).
Conflict of interest
The authors declare no conflict of interest.
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