含氟配体修饰UiO-67-Pd催化生物基糠醇氧化芳基化反应的电子调控效应

doi:10.1016/S1872-2067(24)60207-X

摘要/Abstract

摘要：

作为一种高附加值的单体分子, 芳基呋喃(AFs)广泛应用于光电材料、天然产物、药物分子和生物燃料等领域. 该化合物通常以芳基硼酸和芳基卤化物为原料, 通过钯催化Suzuki偶联的方式合成得到. 然而, 使用含卤素原料有违绿色化学的理念. 因而, 利用易得、可再生的生物基呋喃和芳基硼酸作为底物, 通过钯催化氧化偶联将是一种很有前途的替代方法.尤其是, 该方法具有无卤、过程经济性高、使用氧气作为氧化剂的优点,近年来受到广泛关注. 然而, 现有的均相催化体系存在催化剂分离和回收难、需要使用有毒配体和共氧化剂, 且均相催化氧化芳基化的Heck插入或亲电钯化过程易伴生富电子呋喃环和伯羟基的氧化等副反应. 因此, 发展基于电子和空间协同效应的高效非均相钯催化体系具有重要的意义.

本文以菲罗啉/联吡啶和多氟取代的苯基配体作为混合连接剂, 发展了新颖的UiO-67-Pd(F)催化剂, 实现了生物基糠醇连续选择性芳基化制备芳基呋喃化合物的过程. 粉末X射线衍射、傅里叶变换红外光谱和透射电镜等研究发现, 使用多氟取代苯基配体修饰后的UiO-67未改变其拓扑结构, 但为钯催化活性中心提供了一个稳定的配位环境. X射线光电子能谱、同步辐射X射线吸收谱和理论计算结果表明, UiO-67-Pd(F)催化剂中含氟配体的引入使得电子通过F-Zr₆簇-Pd途径转移, 有效地调节了钯活性中心的缺电子性质, 有利于呋喃类底物的吸附和活化. 在最佳反应条件下, Heck插入步骤的FAs转化率为72.2%, 单芳基呋喃(MAF)选择性为74.8%. 随后的亲电钯化反应中MAF的转化率为85.3%, 最终AFs的选择性为74.8%. 值得注意的是, 该UiO-67-Pd(F)多相催化剂的活性是现有文献报道中的较好均相体系(Pd(CH₃CN)₂Cl₂或Pd(OAc)₂)的50倍以上. 此外, UiO-67-Pd(F)催化剂在Heck插入和亲电钯化反应中均展现出良好的底物适用性. 机理研究表明: 该C-H芳基化过程存在烯丙基钯中间体, C-C键断裂反应存在呋喃氧鎓离子中间体, 意味着该UiO-67-Pd(F)催化糠醇氧化芳基化反应遵循连续Heck插入和亲电钯化机理. 理论计算结果表明, 菲罗啉有利于钯中心与呋喃环π配位活化; 而联吡啶对钯的位阻影响较小, 有利于第二步的亲电钯化. UiO-67-Pd(F)参与Heck插入和亲电钯化过程的能垒图进一步证实了C=C键反式插入、转金属步骤分别为决速步. 此外, UiO-67-Pd(F)催化剂具有良好的重复使用性和稳定性, 循环使用五次, 催化活性以及催化剂理化性质未见明显改变. 研究同时发现, UiO-67-Pd(F)催化无卤合成的呋喃-苯聚合物比传统Suzuki偶联法获得的材料具有更优的光电性能.

综上所述, 本文报道了一种调节非均相催化剂的金属活性中心电荷的策略, 为合成高附加值芳基呋喃光电材料单体催化剂的设计提供了借鉴.

关键词: 生物基呋喃, 催化氧化芳基化, UiO-67-Pd(F)催化剂, 配体调控, 电荷分离

Abstract:

An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol (FA) to aryl furans (AFs), a versatile monomer of photoelectric materials, in the presence of UiO-67-Pd(F) with phenanthroline/ bipyridine, and poly-F substituted phenyl ligands as the mixture linkers. The results of control experiments and theoretical calculations reveal that the −F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr₆ clusters bridges, which favors the adsorption and activation of the furan ring. Furthermore, the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation, respectively. As a result, the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects. Under the optimized conditions, 72.2% FA conversion and 74.8% mono aryl furan (MAF) selectivity are shown in the Heck-type insertion. Meanwhile, 85.3% of MAF is converted, affording 74.8% selectivity of final product (AFs) in the subsequent electrophilic palladation reaction. This process efficiency is remarkably higher than that with homogeneous catalysts. In addition, furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F) show significantly better properties than that from conventional Suzuki coupling method. Therefore, the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.

Key words: Bio-based furan, Catalytic oxidative arylation, UiO-67-Pd(F) catalyst, Ligand regulation, Charge separation

郭栋稳, 曾国辉, 龙金星, 尹标林. 含氟配体修饰UiO-67-Pd催化生物基糠醇氧化芳基化反应的电子调控效应[J]. 催化学报, 2025, 69: 230-240.

Dongwen Guo, Guohui Zeng, Jinxing Long, Biaolin Yin. Switching electronic effects of UiO-67-Pd using fluorinated ligands for catalytic oxidative arylation of bio-based furfuryl alcohol[J]. Chinese Journal of Catalysis, 2025, 69: 230-240.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60207-X

https://www.cjcatal.com/CN/Y2025/V69/I2/230

图/表 10

Fig. 1. Synthesis and application of aryl furan scaffolds.

Scheme 1. The synthesis of FBs-1 and FBs-2.

Fig. 2. (a) XRD patterns of UiO-67, UiO-67-Phen(F)-Pd, UiO-67-Bpy(F)-Pd, and simulated. (b) FT-IR spectra of UiO-67-Phen-Pd, UiO-67-Phen(F)-Pd, UiO-67-Bpy-Pd, UiO-67-Bpy(F)-Pd, and UiO-67. (c) SEM images of UiO-67-Phen(F)-Pd. (d,e) TEM images of UiO-67-Phen(F)-Pd. (f) The EDX spectra of UiO-67-Phen(F)-Pd. (g) SEM images of UiO-67-Phen(F)-Pd. (h,i) TEM images of UiO-67-Phen(F)-Pd. (j) The EDX spectra of UiO-67-Phen(F)-Pd. The EDX elemental mapping images of UiO-67-Phen(F)-Pd (k?q) and UiO-67-Bpy(F)-Pd (r?x).

Fig. 3. XPS spectra of UiO-67-Phen-Pd, UiO-67-Phen(F)-Pd, UiO-67-Bpy-Pd, and UiO-67-Bpy(F)-Pd: Pd 3d (a), Zr 3d (b), and F 1s (c). (d) Pd K-edge XANES spectra of UiO-67-Phen(F)-Pd and reference samples (Pd foil and PdO). (e) FT k3-weighted Pd K-edge EXAFS curves of UiO-67-Phen(F)-Pd, UiO-67-Bpy(F)-Pd and reference samples (Pd foil and PdO). (f) FT-EXAFS R space fitting curves of UiO-67-Phen(F)-Pd. (g) Pd K-edge XANES spectra of UiO-67-Bpy(F)-Pd and reference samples (Pd foil and PdO). (h) Pd k-space spectra of UiO-67-Phen(F)-Pd, UiO-67-Bpy(F)-Pd and reference samples (Pd foil and PdO). (i) FT-EXAFS R space fitting curves of UiO-67-Bpy(F)-Pd.

Fig. 4. The differential charge density of UiO-67-Phen-Pd, UiO-67-Phen(F)-Pd, UiO-67-Bpy-Pd, and UiO-67-Bpy(F)-Pd.

Fig. 5. The TDOS and PDOS for UiO-67-Phen-Pd (a), UiO-67-Phen(F)-Pd (b), UiO-67-Bpy-Pd (c), and UiO-67-Bpy(F)-Pd (d).

Table 1 Catalytic performance of the continuous oxidative arylation of furfuryl alcohol derivative (a) under various catalysts a.

Entry	Step	Catalyst	Conversion of (a)/(c) (%)	Selectivity of (b)/(d) (%)	Yield of (b)/(d) (%)	TOF ^e (h⁻¹)
1	I	None	0	0	0	—
2		UiO-67	0	0	0	—
3		UiO-67-Phen-Pd	40.3	56.8	22.9	11.9
4		UiO-67-Phen(F)-Pd	72.2	74.8	54.0	21.3
5		UiO-67-Bpy(F)-Pd	63.4	36.3	23.0	18.7
6 ^b		UiO-67-Phen(F) + Pd(TFA)₂	21.6	30.4	6.6	—
7 ^c		Pd(CH₃CN)₂Cl₂	38.1	37.5	14.3	0.4
8	II	None	0	0	0	—
9		UiO-67	0	0	0	—
10		UiO-67-Bpy-Pd	54.6	70.3	38.3	24.1
11		UiO-67-Phen(F)-Pd	77.4	41.7	32.3	34.2
12		UiO-67-Bpy(F)-Pd	85.3	86.5	73.8	37.7
13 ^b		UiO-67-Bpy(F) + Pd(TFA)₂	40.8	27.4	11.2	—
14 ^d		Pd(OAc)₂	46.6	67.9	31.6	0.7

Fig. 6. (a) The energy diagram and reaction pathways for the C?H arylation of a in the presence of UiO-67-Phen-Pd and UiO-67-Phen(F)-Pd catalysts. (b) The energy diagram and reaction pathways for the C?C bond cleavage of c in the presence of UiO-67-Bpy-Pd and UiO-67-Bpy(F)-Pd catalysts.

Fig. 7. The recyclability experiments of UiO-67-Phen(F)-Pd (a) and UiO-67-Bpy(F)-Pd (b). (c) The hot filtration tests of UiO-67-Phen(F)-Pd and UiO-67-Bpy(F)-Pd. XRD patterns (d) and XPS spectra (e) of used UiO-67-Phen(F)-Pd and UiO-67-Bpy(F)-Pd. The TEM images of fresh UiO-67-Phen(F)-Pd (f), used UiO-67-Phen(F)-Pd (g), fresh UiO-67-Bpy(F)-Pd (h), and used UiO-67-Bpy(F)-Pd (i).

Fig. 8. (a) Solid-state UV-vis absorption spectra of FBs-1 and FBs-2. Tauc plots for band gap calculation of FBs-1 (b) and FBs-2 (c). (d) Photoluminescence spectra of FBs-1 and FBs-2.

参考文献

[1]	B. Zheng, L. Huo, Small methods, 2021, 5, 2100493.
[2]	W. Zhang, C. Song, J. Wang, S. Cai, M. Gao, Y. Feng, T. Lu, Chin. J. Catal., 2023, 52, 176-186.
[3]	O. Gidron, Y. Diskin-Posner, M. Bendikov, J. Am. Chem. Soc., 2010, 132, 2148-2150.
[4]	C. Li, H Cai, B Zhang, W. Li, G. Pei, T. Dai, A. Wang, T. Zhang, Chin. J. Catal., 2015, 36, 1638-1646.
[5]	F. S. Han, Chem. Soc. Rev., 2013, 42, 5270-5298.
[6]	S. Yang, C. Sun, Z. Fang, B. Li, Y. Li, Z. Shi, Angew. Chem. Int. Ed., 2008, 47, 1473-1476.
[7]	G. Albano, A. Punzi, M. A. M. Capozzi, G. M. Farinola, Green Chem., 2022, 24, 1809-1894.
[8]	K. Yamaguchi, H. Kondo, J. Yamaguchi, K. Itami, Chem. Sci., 2013, 4, 3753-3757.
[9]	R. Srinivasan, R. S. Kumaran, N. S. Nagarajan, RSC Adv., 2014, 14, 47697-47700.
[10]	Z. Wang, W. Luo, L. Lu, B. Yin, J. Org. Chem., 2018, 83, 10080-10088.
[11]	I. Banerjee, K. C. Ghosh, S. Sinha, J. Chem. Sci., 2019, 131, 71.
[12]	G. Huang, B. Yin, Adv. Synth. Catal., 2019, 361, 5576-5586.
[13]	G. Huang, L. Lu, H. Jiang, B. Yin, Chem. Commun., 2017, 53, 12217-12220.
[14]	K. Jiang,; H. Wang, Y. Xie, H. Jiang, M. Lei, B. Yin, ACS Catal., 2023, 13, 3520-3531.
[15]	J. Ding, H. Wang, K. Shen, X. Wei, L. Chen, Y. Li, Chin. J. Catal., 2024, 60, 351-359.
[16]	H. Zhou, S. Kitagawa, Chem. Soc. Rev., 2014, 43, 5415-5418.
[17]	L. Huang, S. Mo, X. Zhao, J. Zhou, X. Zhou, Y. Zhang, Y. Fan, Q. Xie, B. Li, J. Li, Appl. Catal. B, 2024, 352, 124019.
[18]	O. Shelonchik, N. Lemcoff, R. Shimoni, A. Biswas, E. Yehezkel, D. Yesodi, I. Hod, Y. Weizmann, Nat. Commun., 2024, 15, 1154.
[19]	L. Tao, C. Zhou, W. Pan, R. Liu, C. Liao, G. Jiang, Appl. Catal. B, 2024, 357, 124298.
[20]	X. Zhang, Z. Huang, M. Ferrandon, D. Yang, L. Robison, P. Li, T. C. Wang, M. Delferro, O. K. Farha, Nat. Catal., 2018, 1, 356-362.
[21]	J. Zhou, M. Liang, J. Chen, ACS Catal., 2023, 13, 10261-10281.
[22]	S. Chen, W. Li, W. Jiang, J. Yang, J. Zhu, L. Wang, H. Ou, Z. Zhuang, M. Chen, X. Sun, D. Wang, Y. Li, Angew. Chem. Int. Ed., 2022, 61, e202114450.
[23]	J. Wu, Z. Wang, X. Jin, S. Zhang, T. Li, Y. Zhang, H. Xing, Y. Yu, H. Zhang, X. Gao, H. Wei, Adv. Mater., 2021, 33, 2005024.
[24]	J. Zheng, L. Löbbert, S. Chheda, N. Khetrapal, J. Schmid, C. A. Gaggioli, B. Yeh, R. Bermejo-Deval, R. K. Motkuri, M. Balasubramanian, J. L. Fulton, O. Y. Gutiérrez, J. I. Siepmann, M. Neurock, L. Gagliardi, J. A. Lercher, J. Catal., 2022, 413, 176-183.
[25]	G. Chelucci, R. P. Thummel, Chem. Rev., 2022, 102, 3129-3170.
[26]	H. Kwong, H. Yeung, C. Yeung, W. Lee, C. Lee, W. Wong, Coord. Chem. Rev., 2007, 251, 2188-2222.
[27]	L. Duan, L. Wang, F. Li, F. Li, L. Sun, Acc. Chem. Res., 2015, 48, 2084-2096.
[28]	X. Feng, Y. Ren, H. Jiang, Coord. Chem. Rev., 2021, 438, 213907.
[29]	H. B. Aiyappa, J. Thote, D. B. Shinde, R. Banerjee, S. Kurungot, Chem. Mater., 2016, 28, 4375-4379.
[30]	W. Zhong, R. Sa, L. Li, Y. He, L. Li, J. Bi, Z. Zhuang, Y. Yu, Z. Zou, J. Am. Chem. Soc., 2019, 141, 7615-7621.
[31]	C. Kaes, A. Katz, M. W. Hosseini, Chem. Rev., 2020, 100, 3553-3590.
[32]	H. Li, Y. Zhou, C. Chen, Y. Li, Z. Liu, M. Wu, M. Hong, Inorg. Chem., 2024, 63, 21548-21554.
[33]	M. Lv, C. Cui, N. Huang, M. Wu, Q. Wang, T. Gao, Y. Zheng, H. Li, W. Liu, Y. Huang, T. Ma, L. Ye, Angew. Chem. Int. Ed., 2024, 63, e202315802.
[34]	H. Wang, X. Liu, W. Yang, G. Mao, Z. Meng, Z. Wu, H. Jiang, J. Am. Chem. Soc., 2022, 144, 22008-22017.
[35]	S. Cheng, J. Ouyang, M. Li, Y. Diao, J. Yao, F. Li, Y. Lee, H. Ho-Yung SUNG, I. Williams, Z. Xu, Y. Quan, Angew. Chem. Int. Ed., 2023, 62, e202300993.
[36]	L. Li, J. Kong, H. Zhang, S. Liu, Q. Zeng, Y. Zhang, H. Ma, H. He, J. Long, X. Li, Appl. Catal. B, 2020, 279, 119343.
[37]	E. H. Kim, M. H. Lee, J. Kim, E. C. Ra, J. H. Lee, J. S. Lee, Chin. J. Catal., 2023, 47, 214-221.
[38]	S. Dutta, A. Gurumoorthi, S. Lee, S. W. Jang, N. Kumari, Y. Hong, W. Choi, C. Y. Son, I. S. Lee, Angew. Chem. Int. Ed., 2023, 62, e202303890.
[39]	Y. An, Y. Liu, H. Bian, Z. Wang, P. Wang, Z. Zheng, Y. Dai, M. Whangbo, B. Huang, Sci. Bull., 2019, 64, 1502-1509.
[40]	A. M. Ebrahim, T. J. Bandosz, ACS Appl. Mater. Interfaces, 2012, 5, 10565-10573.
[41]	L. Zhong, X. Liao, H. Cui, H. Luo, Y. Lv, P. Liu, Appl. Catal. B, 2024, 342, 123421.
[42]	D. Guo, K. Jiang, H. Gan, Y. Ren, J. Long, Y. Li, B. Yin, Angew. Chem. Int. Ed., 2023, 62, e202304662.
[43]	M. Yang, J. Yu, A. Zimina, B. B. Sarma, J. D. Grunwaldt, H. Zada, L. Wang, J. Sun, Angew. Chem. Int. Ed., 2024, 63, e202312292.
[44]	Z. Cui, T. Fan, L. Chen, R. Fang, C. Li, Y. Li, Sci. China Chem., 2021, 64, 109-115.
[45]	V. E. Diyuk, A. N. Zaderko, L. M. Grishchenko, S. Afonin, R. Mariychuk, O. Y. Boldyrieva, V. A. Skryshevsky, M. Kaňuchová, V. V. Lisnyak, Appl. Nanosci., 2022, 12, 637-650.
[46]	L. Peng, Y. Yu, S. Gao, M. Wang, J. Zhang, R. Zhang, W. Jia, Y. Sun, H. Liu, ACS Catal., 2024, 14, 6623-6632.
[47]	M. Soorholtz, L. C. Jones, D. Samuelis, C. Weidenthaler, R. J. White, M. M. Titirici, D. A. Cullen, T. Zimmermann, M. Antonietti, J. Maier, R. Palkovits, B. F. Chmelka, F. Schüth, ACS Catal., 2016, 6, 2332-2340.
[48]	Y. Zhao, H. Zhou, W. Chen, Y. Tong, C. Zhao, Y. Lin, Z. Jiang, Q. Zhang, Z. Xue, W. C. Cheong, B. Jin, F. Zhou, W. Wang, M. Chen, X. Hong, J. Dong, S. Wei, Y. Li, Y. Wu, J. Am. Chem. Soc., 2019, 141, 10590-10594.
[49]	Q. Deng, J. Lu, G. Sheng, Y.-C. Zhang, J. Wang, Z. Zeng, T. Yoskamtorn, S. C. Edman Tsang, ACS Catal., 2023, 13, 14356-14366.
[50]	B. Hammer, K. Norskov, Nature, 1995, 376, 238-240.
[51]	M. S. Kazantsev, A. A. Beloborodova, A. D. Kuimov, I. P. Koskin, E. S. Frantseva, T. V. Rybalova, I. K. Shundrina, C. S. Becker, E. A. Mostovich, Org. Electron., 2018, 56, 208-215.