聚合型膦配体在除草剂灵思科中的合成应用

doi:10.6023/A24060186

摘要/Abstract

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.

关键词: 聚合型膦配体, Suzuki-Miyaura偶联反应, 均相催化, 异相循环

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.

Key words: polymeric phosphorus ligand, Suzuki-Miyaura coupling, homogeneous catalysis, heterogeneous recycling

引用此文

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.

Wenfeng Dong, Nan Wang, He Yang, Guangqing Xu, Wenjun Tang. A Polymeric Phosphorus Ligand for the Synthesis of Herbicide Rinskor[J]. Acta Chimica Sinica, 2024, 82(9): 940-953.

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图/表 11

图1. 聚合型膦配体PolyBIDIME的设计

Figure 1. The design of recyclable polymeric phosphorus ligand PolyBIDIME

图2. PolyBIDIME及钯络合物的合成

Figure 2. Synthesis of PolyBIDIME and its Pd complex

图3. 膦谱核磁分析

Figure 3. 31P-NMR analysis

Entries^a	Ligand/Catalyst	Base	Solvent	Yield^b/%
1	BIDIME/Pd(OAc)₂	Na₂CO₃	toluene	30
2	BIDIME/Pd(OAc)₂	DIPEA	toluene	46
3	BIDIME/Pd(OAc)₂	DIPEA	CH₃CN	67
4	BIDIME/Pd(OAc)₂	DIPEA	V(CH₃CN)∶V(H₂O)=4∶1	91
5^c	BIDIME/Pd(OAc)₂	DIPEA	V(CH₃CN)∶V(H₂O)=4∶1	10
6	6/Pd(OAc)₂	DIPEA	V(CH₃CN)∶V(H₂O)=4∶1	76
7^d	6/Pd(OAc)₂	DIPEA	CH₃CN	93
8^d	7	DIPEA	CH₃CN	94

表1. 偶联反应条件优化

Table 1. Optimization of coupling conditions

图4. 催化剂循环过程中反应收率和转化率

Figure 4. Yields and conversions over catalyst cyclings

图5. 催化剂循环过程中催化剂质量

Figure 5. Weight of catalysts over catalyst cyclings

图6. 催化循环过程中钯含量和钯总量

Figure 6. Palladium content and total palladium content during catalyst recyclings

图7. 催化剂中配体氧化态含量占比

Figure 7. The proportion of oxidized ligands during catalyst recyclings

图8. 偶联反应过程跟踪(转化率vs反应时间, 钯络合物7/Pd(OAc)2- BIDIME, 1 mol% Pd loading)

Figure 8. The reaction profile of cross-coupling (conversion vs reaction time, complex 7/Pd(OAc)2-BIDIME, 1 mol% Pd loading)

表2. 反应作用范围a

Table 2. Reaction scope

图9. 聚合BIDIME的合成应用

Figure 9. Synthetic applications of PolyBIDIME

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