多功能多孔有机聚合物负载钯纳米催化剂在炔烃氢羧基化中的应用

doi:10.6023/cjoc202503012

摘要/Abstract

采用自由基三聚制备了一种多功能多孔有机聚合物POP-Nixantphos-PPh₃-PhSO₃Na. 进一步负载Pd(OAc)₂得到Pd/POP-Nixantphos-PPh₃-PhSO₃Na催化剂. 在该催化剂中, 采用了Nixantphos配体提高钯的氢羧基化催化活性. 此外, PPh₃配体用来构建催化剂的多孔框架, 促进钯纳米粒子的分散以及反应物和产物的扩散. 此外, PhSO₃Na基团提高载体的亲水性. 以H₂O为反应溶剂, 在初始CO压力为0.1 MPa的条件下, Pd/POP-Nixantphos-PPh₃-PhSO₃Na能催化炔烃的氢羧基化反应, 得到相应的α,β-不饱和羧酸(76%~96%). 该反应能兼容各种炔烃, 包括二芳炔、芳基烷基炔和二烷基炔. 此外, 该催化剂表现出优异的可循环性, 在5次循环中没有明显的收率损失.

关键词: 氢羧基化反应, 多孔有机聚合物, 多相催化, Pd催化剂

A multifunctional porous organic polymer of POP-Nixantphos-PPh₃-PhSO₃Na was prepared by free radical tri- copolymerization. Further loading of Pd(OAc)₂ led to the catalyst of Pd/POP-Nixantphos-PPh₃-PhSO₃Na. In this catalyst, Nixantphos ligand moieties were employed to enhance the catalytic hydrocarboxylation activity of palladium. Additionally, PPh₃ ligand moieties were utilized to construct a porous framework of catalyst that facilitated the dispersion of Pd nanoparticles as well as the diffusion of reactants and products. Furthermore, the incorporation of PhSO₃Na moieties improved the hydrophilicity of the support. With H₂O as the reaction solvent, under the initial CO pressure of 0.1 MPa, Pd/POP-Nixantphos- PPh₃-PhSO₃Na-catalyzed hydrocarboxylation of alkynes to afford the corresponding α,β-unsaturated carboxylic acids in good yields (76%~96%). Various alkynes, such as diaromatic alkynes, arylalkyl alkynes and dialkyl alkynes, worked well in the process. Additionally, the catalyst showed excellent recyclability with no significant yield loss over five cycles.

Key words: hydrocarboxylation, porous organic polymers, heterogeneous catalysis, Pd catalyst

引用此文

于志起, 陈灿源, 韩佳怡, 周建湖, 王林轩, 岳美娥, 贾肖飞. 多功能多孔有机聚合物负载钯纳米催化剂在炔烃氢羧基化中的应用[J]. 有机化学, 2025, 45(9): 3450-3457.

Zhiqi Yu, Canyuan Chen, Jiayi Han, Jianhu Zhou, Linxuan Wang, Meie Yue, Xiaofei Jia. A Multifunctional Porous Organic Polymer Supported Pd Nanoparticle Catalyst for Hydrocarboxylation of Alkynes[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3450-3457.

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图/表 8

Scheme 1. Heterogeneous catalytic hydrocarboxylation of alkynes

Scheme 2. Synthesis of Pd/POP-Nixantphos-PPh3-PhSO3Na

Figure 1. (a) FT-IR spectra of Pd/POP-Nixantphos-PPh3-PhSO3Na and POP-Nixantphos-PPh3-PhSO3Na; (b) TGA curve of Pd/POP- Nixantphos-PPh3-PhSO3Na; (c) Contact angle measurement of Pd/POP-Nixantphos-PPh3-PhSO3Na; (d) Contact angle measurement of Pd/POP-Nixantphos-PPh3

Figure 2. (a) Pd 3d XPS spectra of Pd/POP-Nixantphos-PPh3-PhSO3Na; (b) P 2p XPS spectra of Pd/POP-Nixantphos-PPh3-PhSO3Na and POP-Nixantphos-PPh3-PhSO3Na

Figure 3. (a) N2 sorption isotherm and pore size distribution of Pd/POP-Nixantphos-PPh3-PhSO3Na; (b) N2 sorption isotherm and pore size distribution of Pd/POP-Nixantphos-PhSO3Na; (c) SEM image; (d) TEM image and (e) EDS elemental mapping images of Pd/POP-Nixantphos-PPh3-PhSO3Na

Figure 4. Various catalysts catalyzed the hydrocarboxylation of diphenylethyne Reaction conditions: diphenylethyne 1a (0.5 mmol), H2O (2 mL), CO (0.1 MPa), 110 ℃, 24 h. (a) Pd/POP-Nixantphos-PPh3-PhSO3Na [14.6 mg, 3.62% (w) Pd], (b) Pd/POP-Nixantphos-PPh3 [14.2 mg, 3.73% (w) Pd], (c) Pd/POP- Nixantphos-PhSO3Na [12.9 mg, 4.12% (w) Pd], (d) Pd/POP-PPh3- PhSO3Na [15.9 mg, 3.32% (w) Pd].

Table 1. Study scope for hydrocarboxylation of various alkynes catalyzed by Pd/POP-Nixantphos-PPh3-PhSO3Naa

Figure 5. (a) Recycling tests of the Pd/POP-Nixantphos-PPh3-PhSO3Na in hydrocarboxylation of diphenylethyne Diphenylethyne 1a (0.5 mmol), Pd/POP-Nixantphos-PPh3-PhSO3Na (14.6 mg), p-toluenesulfonic acid (8.6 mg), H2O (2 mL), CO (0.1 MPa), 110 ℃, 24 h. (b) TEM image, (c) Pd 3d XPS spectra, (d) P 2p of the recovered Pd/POP-Nixantphos-PPh3-PhSO3Na.

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