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High-Activity Organocatalysts for Polyether Synthesis via Intramolecular Ammonium Cation Assisted SN 2 Ring-Opening Polymerization.
Angew Chem Int Ed Engl. 2020 Jun 20 [Online ahead of print]AC

Abstract

This manuscript describes a kind of bifunctional organocatalyst with unprecedented reactivity for the synthesis of polyethers via ring-opening polymerization (ROP) of epoxides under mild conditions. The bifunctional catalyst incorporates two 9-borabicyclo[3.3.1]nonane centers on the two ends as Lewis acidic sites for epoxide activation and a quaternary ammonium halide in the middle as the initiating site. The catalyst could be easily prepared in two steps from commercially available stocks on up to kilogram scale with ≈100 % yield. The organoboron catalyst mediated ROP of epoxides displays living behavior with low catalyst loading (5 ppm) and enables the synthesis of polyethers with molecular weights of over a million grams per mole (>106 g mol-1). Based on the investigations on crystal structure of catalyst, MALDI-TOF, and 11 B NMR spectroscopy, an intramolecular ammonium cation assisted SN 2 mechanism is proposed and verified by DFT calculations.

Authors+Show Affiliations

MOE Laboratory of Macromolecular Synthesis and Functionalization, Adsorption and Separation Materials and Technologies of Zhejiang Province, Department of Polymer Science and Engineering, Zhejiang University, Zhe Da Road 38, Hangzhou, 310027, China.MOE Laboratory of Macromolecular Synthesis and Functionalization, Adsorption and Separation Materials and Technologies of Zhejiang Province, Department of Polymer Science and Engineering, Zhejiang University, Zhe Da Road 38, Hangzhou, 310027, China.MOE Laboratory of Macromolecular Synthesis and Functionalization, Adsorption and Separation Materials and Technologies of Zhejiang Province, Department of Polymer Science and Engineering, Zhejiang University, Zhe Da Road 38, Hangzhou, 310027, China.MOE Laboratory of Macromolecular Synthesis and Functionalization, Adsorption and Separation Materials and Technologies of Zhejiang Province, Department of Polymer Science and Engineering, Zhejiang University, Zhe Da Road 38, Hangzhou, 310027, China.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

32562445

Citation

Yang, Guan-Wen, et al. "High-Activity Organocatalysts for Polyether Synthesis Via Intramolecular Ammonium Cation Assisted SN 2 Ring-Opening Polymerization." Angewandte Chemie (International Ed. in English), 2020.
Yang GW, Zhang YY, Xie R, et al. High-Activity Organocatalysts for Polyether Synthesis via Intramolecular Ammonium Cation Assisted SN 2 Ring-Opening Polymerization. Angew Chem Int Ed Engl. 2020.
Yang, G. W., Zhang, Y. Y., Xie, R., & Wu, G. P. (2020). High-Activity Organocatalysts for Polyether Synthesis via Intramolecular Ammonium Cation Assisted SN 2 Ring-Opening Polymerization. Angewandte Chemie (International Ed. in English). https://doi.org/10.1002/anie.202002815
Yang GW, et al. High-Activity Organocatalysts for Polyether Synthesis Via Intramolecular Ammonium Cation Assisted SN 2 Ring-Opening Polymerization. Angew Chem Int Ed Engl. 2020 Jun 20; PubMed PMID: 32562445.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - High-Activity Organocatalysts for Polyether Synthesis via Intramolecular Ammonium Cation Assisted SN 2 Ring-Opening Polymerization. AU - Yang,Guan-Wen, AU - Zhang,Yao-Yao, AU - Xie,Rui, AU - Wu,Guang-Peng, Y1 - 2020/06/20/ PY - 2020/02/23/received PY - 2020/6/21/pubmed PY - 2020/6/21/medline PY - 2020/6/21/entrez KW - DFT calculations KW - organocatalysts KW - polyethers KW - ring-opening polymerization JF - Angewandte Chemie (International ed. in English) JO - Angew. Chem. Int. Ed. Engl. N2 - This manuscript describes a kind of bifunctional organocatalyst with unprecedented reactivity for the synthesis of polyethers via ring-opening polymerization (ROP) of epoxides under mild conditions. The bifunctional catalyst incorporates two 9-borabicyclo[3.3.1]nonane centers on the two ends as Lewis acidic sites for epoxide activation and a quaternary ammonium halide in the middle as the initiating site. The catalyst could be easily prepared in two steps from commercially available stocks on up to kilogram scale with ≈100 % yield. The organoboron catalyst mediated ROP of epoxides displays living behavior with low catalyst loading (5 ppm) and enables the synthesis of polyethers with molecular weights of over a million grams per mole (>106 g mol-1). Based on the investigations on crystal structure of catalyst, MALDI-TOF, and 11 B NMR spectroscopy, an intramolecular ammonium cation assisted SN 2 mechanism is proposed and verified by DFT calculations. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/32562445/High-Activity_Organocatalysts_for_Synthesis_of_Polyether_via_Intramolecular_Ammonium_Cation-Assisted_SN2_Ring-Opening_Polymerization L2 - https://doi.org/10.1002/anie.202002815 DB - PRIME DP - Unbound Medicine ER -
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