研究论文

聚合型膦配体在除草剂灵思科中的合成应用

  • 董文锋 ,
  • 王楠 ,
  • 杨贺 ,
  • 徐广庆 ,
  • 汤文军
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  • a 国科大杭州高等研究院化学和材料科学学院 杭州 310024
    b 中国科学院上海有机化学研究所生命过程小分子调控全国实验室 上海 200032
    c 上海科技大学物质科学与技术学院 上海 201210

收稿日期: 2024-06-06

  网络出版日期: 2024-07-12

基金资助

国家重点研发计划(2022YFA1503702); 国家重点研发计划(2021YFF0701601); 国家自然科学基金(82188101)

A Polymeric Phosphorus Ligand for the Synthesis of Herbicide Rinskor

  • Wenfeng Dong ,
  • Nan Wang ,
  • He Yang ,
  • Guangqing Xu ,
  • Wenjun Tang
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  • a School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024
    b State key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
    c School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210

Received date: 2024-06-06

  Online published: 2024-07-12

Supported by

National Key R&D Program of China(2022YFA1503702); National Key R&D Program of China(2021YFF0701601); National Natural Science Foundation of China(82188101)

摘要

高钯催化剂用量仍然是含杂环的复杂Suzuki-Miyaura偶联反应中的挑战性问题. 为降低钯催化剂用量, 提高催化转化数, 本工作报道一种可循环使用的聚合型膦配体PolyBIDIME及其钯络合物的制备和催化应用. 通过对膦配体单体及钯络合物、聚合型膦配体及钯络合物的核磁鉴定和钯催化剂在Suzuki-Miyaura偶联反应中的循环试验, PolyBIDIME钯络合物在除草剂灵斯科的关键偶联反应中表现出优异的可循环使用次数(10次)和高达1000的转化总数, 展现出潜在的工业应用价值. 核磁和催化剂重量分析表明聚合型膦配体的部分氧化可能是催化剂循环使用中催化反应效率逐步下降的原因.

本文引用格式

董文锋 , 王楠 , 杨贺 , 徐广庆 , 汤文军 . 聚合型膦配体在除草剂灵思科中的合成应用[J]. 化学学报, 2024 , 82(9) : 940 -953 . DOI: 10.6023/A24060186

Abstract

A recyclable polymeric phosphorus ligand, PolyBIDIME, and its palladium complexes was designed and introduced to address the high loadings of palladium catalysts in complex Suzuki-Miyaura coupling reaction. PolyBIDIME, a supported BI-DIME ligand on a polyamide chain, was designed as a soluble ligand in organic solvent applicable to homogeneous catalysis, but insoluble or less soluble in certain solvents for easy recovery from reaction conditions. This polymeric phosphorus ligand was designed in order to provide a practical and efficient example of “homogeneous catalysis and heterogeneous recycling in order to achieve a higher turnover number”. PolyBIDIME was synthesized by polymerization of 6-vinyl BIDIME with N-isopropylacrylamide in the presence of 2,2'-azobis(isobutyronitrile) (AIBN). The structure of the polymeric ligand was well characterized by 1H, 31P NMR, and gel permeation chromatography (GPC). The palladium complex of PolyBIDIME was prepared and characterized as Pd(PolyBIDIME)2Cl2, which was applied as the catalyst to the key Suzuki-Miyaura cross-coupling reaction of herbicide rinskor. Under optimized conditions, the Pd-PolyBIDIME catalyst provided high yields of the coupling product, excellent recyclability (10 times), and high total turnover numbers (up to 1000), showing great potential for industrial applications. The Pd-PolyBIDIME was also applicable as the catalyst to a range of Suzuki-Miyaura couplings, showing great compatibility to steric hindrance and functional groups. Further synthetic applications were demonstrated in the synthesis of herbicides boscalid and fluxapyroxad as Suzuki-Miyaura cross-coupling catalyst, as well as in the synthesis of naproxen as a carbonylation catalyst, showcasing the high potential of Pd-PolyBIDIME as a cross-coupling catalyst in industrial settings. Detailed NMR studies and catalyst weight analysis were conducted to rationalize the catalyst recycling process. Results showed that slight physical loss of the palladium catalyst was confirmed during each run, while partial oxidation of the phosphorus ligand increased gradually after each run, which could be the main reason for the gradual decrease in catalytic efficiency during catalyst recycling.

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