A Multifunctional Porous Organic Polymer Supported Pd Nanoparticle Catalyst for Hydrocarboxylation of Alkynes

doi:10.6023/cjoc202503012

Abstract

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

Cite this article

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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Fig. & Tab. 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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