Pd/Cu-cocatalyzed multi-site functionalization of in-situ generated alkenes toward carbazole-based aggregation-induced emission luminogens

doi:10.1016/S1872-2067(24)60164-6

Chinese Journal of Catalysis ›› 2025, Vol. 69: 176-184.DOI: 10.1016/S1872-2067(24)60164-6

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Pd/Cu-cocatalyzed multi-site functionalization of in-situ generated alkenes toward carbazole-based aggregation-induced emission luminogens

Meiqi Zhang^a^,¹, Xueyuan Yan^b^,¹, Zheng Liu^a, Hongyuan Bai^a, Hongwei Ma^a, Genping Huang^b^,^*(), Bo Zhang^c, Dezhu Xu^c, Wenjia Han^d, Li Han^a^,^*(), Tenglong Guo^c^,^*()

^aState Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, Liaoning, China
^bDepartment of Chemistry, School of Science, Tianjin University, Tianjin 300072, China
^cCAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^dState Key Laboratory of Biobased Material and Green Papermaking, Qilu University of Technology, Shandong Academy of Sciences, Jinan 250353, Shandong, China

Received:2024-09-10 Accepted:2024-10-15 Online:2025-02-18 Published:2025-02-10
Contact: *E-mail: hanli@dlut.edu.cn (L. Han), gphuang@tju.edu.cn (G. Huang), guotl1210@dicp.ac.cn (T. Guo).
About author:First author contact:
¹ Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22108272);National Natural Science Foundation of China(22073066);Foundation of State Key Laboratory of Biobased Material and Green Papermaking(GZKF202224)

Abstract

Abstract:

In contrast to the predominant mono or difunctionalization of alkenes, the multi-site functionalization of alkenes involving the synergistic formation of more than two new C−C or C−X bonds is much challenging, especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission (AIE) property has been rarely reported. In present work, the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C-C bonds and C=O bond. A proposed reaction sequence involving C-H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations. Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration, which generated the desired twisted intramolecular charge transfer (TICT) AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends. The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.

Key words: Multi-site functionalization, Carbazoles, Aggregation-induced emission, luminogens, Radical oxygen atom transfer, Microphase separation

Meiqi Zhang, Xueyuan Yan, Zheng Liu, Hongyuan Bai, Hongwei Ma, Genping Huang, Bo Zhang, Dezhu Xu, Wenjia Han, Li Han, Tenglong Guo. Pd/Cu-cocatalyzed multi-site functionalization of in-situ generated alkenes toward carbazole-based aggregation-induced emission luminogens[J]. Chinese Journal of Catalysis, 2025, 69: 176-184.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60164-6

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Figures/Tables 11

Scheme 1. Construction of complex molecules through functionalization of alkenes.

Table 1 Reaction condition optimization of N-methylindole (1a) with 3-chloropropiophenone (2a) and 4-chlorobutyrophenone (3a) a.

Entry	Cu salt	Solvent 1/solvent 2	Temp. 2 (°C)	Yield of 4a ^b (%)
1	Cu(OAc)₂·H₂O	DMF/PhCl	110	61
2	Cu(OAc)₂·H₂O	DMF/PhCl	120	65
3	Cu(OAc)₂·H₂O	DMF/PhCl	130	56
4	CuCl₂·H₂O	DMF/PhCl	120	36
5	Cu(OTf)₂	DMF/PhCl	120	48
6	CuBr	DMF/PhCl	120	30
7	Cu(OAc)₂·H₂O	DMF/Toluene	120	75
8	Cu(OAc)₂·H₂O	DMF/MeCN	120	48
9	Cu(OAc)₂·H₂O	DMF/EtOH	120	0
10	Cu(OAc)₂·H₂O	DMF	120	33
11	Cu(OAc)₂·H₂O	Toluene	120	14
12^c	Cu(OAc)₂·H₂O	DMF/Toluene	120	75
13^d	Cu(OAc)₂·H₂O	DMF/Toluene	120	50
14^e	Cu(OAc)₂·H₂O	DMF/Toluene	120	35

Table 2 Reactions of Indoles (1) with 3-chloropropiophenone (2a) and 4-chlorobutyrophenone (3a)a, b.

Table 3 Reactions of N-methylindole (1a) with β-chloro ketones (2) and γ-chloro ketones (3)a,b.

Table 4 Control experiments of 1a with 2a and 3a.

Entry	Condition	Yield^a (%)
1	standard condition	75
2	without TEMPO	13
3	under 0.1 MPa N₂	55
4	without TEMPO under 0.1 MPa N₂	0

Scheme 2. Proposed mechanism.

Fig. 1. Calculated energy profile for the transformation between radical D and 7.

Table 5 Reactions of 4a with aryl-1,2-diamine (9)a,b.

Fig. 2. (A) PL spectra of 10a in THF/H2O mixtures with different fw. λex: 365 nm, concentration: 50 μmol/L. (B) plots for the αAIE and maximum emission wavelength versus the water fraction of 10a, αAIE = I/I0, I0 = PL intensity in pure THF. Inset: fluorescence images (50 μmol/L in THF) followed by water fraction taken under the irradiation with 365 nm UV.

Fig. 3. (A) PL spectra of 10a in different polarities of solvents (50 μmol/L in THF). λex: 365 nm. (B) Emission spectra of polymer films doped with 1.0 wt% 10a. λex: 365 nm. Inset: images of polymer films doped with 10a taken under irradiation with 365 nm UV using a hand-held UV lamp.

Fig. 4. Fluorescence photos of 1.0 wt% 10a-doped PS/PAN blended thin films with different ratios of PS (wPS), observed using a microscope (200 μm) and taken under the irradiation with 365 nm UV from a hand-held UV lamp.

References

[1]	M. J. Kim, K. Targos, D. E. Holst, D. J. Wang, Z. K. Wickens, Angew. Chem. Int. Ed., 2024, 63, e202314904.
[2]	B. C. Lee, C.-F. Liu, L. Q. H. Lin, K. Z. Yap, N. Song, C. H. M. Ko, P. H. Chan, M. J. Koh, Chem. Soc. Rev., 2023, 52, 2946-2991.
[3]	R. I. McDonald, G. Liu, S. S. Stahl, Chem. Rev., 2011, 111, 2981-3019.
[4]	G. Yin, X. Mu, G. Liu, Acc. Chem. Res., 2016, 49, 2413-2423.
[5]	J. Derosa, T. Kang, V. T. Tran, S. R. Wisniewski, M. K. Karunananda, T. C. Jankins, K. L. Xu, K. M. Engle, Angew. Chem. Int. Ed., 2020, 59, 1201-1205.
[6]	Z. Wu, J. Meng, H. Liu, Y. Li, X. Zhang, W. Zhang, Nat. Chem., 2023, 15, 988-997.
[7]	J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, H. S. Kwok, X. Zhan, Y. Liu, D. Zhu, B. Z. Tang, Chem. Commun., 2001, 1740-1741.
[8]	J. Mei, N. L. C. Leung, R. T. K. Kwok, J. W. Y. Lam, B. Z. Tang, Chem. Rev., 2015, 115, 11718-11940.
[9]	Y. Chen, S. Chen, H. Yu, Y. Wang, M. Cui, P. Wang, P. Sun, M. Ji, Adv. Healthcare Mater. 2022, 11, 2201158.
[10]	Y. Gu, H. Lai, Z.-Y. Chen, Y. Zhu, Z. Sun, X. Lai, H. Wang, Z. Wei, L. Chen, L. Huang, Y. Zhang, F. He, L. Tian, Angew. Chem. Int. Ed., 2023, 62, e202303476.
[11]	X. Wan, C. Li, M. Zhang, Y. Chen, Chem. Soc. Rev., 2020, 49, 2828-2842.
[12]	Z. Xu, D. Wu, C. Fang, Y. Li, Des. Monomers Polym., 2023, 26, 90-105.
[13]	L. A. T. Allen, P. Natho, Org. Biomol. Chem., 2023, 21, 8956-8974.
[14]	H. Uoyama, K. Goushi, K. Shizu, H. Nomura, C. Adachi, Nature, 2012, 492, 234-238.
[15]	D. Zhang, X. Song, A. J. Gillett, B. H. Drummond, S. T. E. Jones, G. Li, H. He, M. Cai, D. Credgington, L. Duan, Adv. Mater., 2020, 32, 1908355.
[16]	A. Banerjee, S. Kundu, A. Bhattacharyya, S. Sahu, M. S. Maji, Org. Chem. Front., 2021, 8, 2710-2771.
[17]	J. K. Laha, N. A. Dayal, Org. Lett., 2015, 17, 4742-4745.
[18]	T. Guo, Y. Lin, D. Pan, X. Zhang, W. Zhu, X. Cai, G. Huang, H. Wang, D. Xu, F. E. Kühn, B. Zhang, T. Zhang, Nat. Commun., 2023, 14, 6076.
[19]	H. Y. Li, Q. D. Jiang, X. M. Jie, Y. P. Shang, Y. F. Zhang, L. J. Goossen, W. P. Su, ACS Catal., 2018, 8, 4777-4782.
[20]	D. K. Tiwari, M. Phanindrudu, S. B. Wakade, J. B. Nanuboluc, D. K. Tiwari, Chem. Commun., 2017, 53, 5302-5305.
[21]	J.-L. Zhan, M.-W. Wu, F. Chen, B. Han, J. Org. Chem., 2016, 81, 11994-12000.
[22]	X. Jie, Y. Shang, X. Zhang, W. Su, J. Am. Chem. Soc., 2016, 138, 5623-5633.
[23]	R. A. Smits, H. D. Lim, A. Hanzer, O. P. Zuiderveld, E. Guaita, M. Adami, G. Coruzzi, R. Leurs, I. J. P. de Esch, J. Med. Chem., 2008, 51, 2457-2467.
[24]	A. K. Parhi, Y. Zhang, K. W. Saionz, P. Pradhan, M. Kaul, K. Trivedi, D. S. Pilch, E. J. LaVoie, Bioorg. Med. Chem. Lett., 2013, 23, 4968-4974.
[25]	Y. B. Kim, Y. H. Kim, J. Y. Park, S. K. Kim, Bioorg. Med. Chem. Lett., 2004, 14, 541-544.
[26]	X. Hui, J. Desrivot, C. Bories, P. M. Loiseau, X. Franck, R. Hocquemiller, B. Figadère, Bioorg. Med. Chem. Lett., 2006, 16, 815-820.
[27]	C. Betschart, S. Hintermann, D. Behnke, S. Cotesta, M. Fendt, C. E. Gee, L. H. Jacobson, G. Laue, S. Ofner, V. Chaudhari, S. Badiger, C. Pandit, J. Wagner, D. Hoyer, J. Med. Chem., 2013, 56, 7590-7607.
[28]	F. A. R. Rodrigues, I. d. S. Bomfim, B. C. Cavalcanti, C. D. Ó. Pessoa, J. L. Wardell, S. M. S. V. Wardell, A. C. Pinheiro, C. R. Kaiser, T. C. M. Nogueira, J. N. Low, L. R. Gomes, M. V. N. de Souza, Bioorg. Med. Chem. Lett., 2014, 24, 934-939.
[29]	S. Ammermann, C. Hrib, P. G. Jones, W.-W. du Mont, W. Kowalsky, H.-H. Johannes, Org. Lett., 2012, 14, 5090-5093.
[30]	L. Wang, W. Guo, X. Zhang, X.-D. Xia, W.-J. Xiao, Org. Lett., 2012, 14, 740-743.
[31]	W. Wang, Y. Shen, X. Meng, M. Zhao, Y. Chen, B. Chen, Org. Lett., 2011, 13, 4514-4517.
[32]	R. Arora, B. Mirabi, A. G. Durant, C. Bozal-Ginesta, A. D. Marchese, A. Aspuru-Guzik, M. Lautens, J. Am. Chem. Soc., 2023, 145, 26623-26631.
[33]	Y. Yu, H. Xing, Z. Zhou, J. Liu, H. H. Y. Sung, I. D. Williams, J. E. Halpert, Z. Zhao, B. Z. Tang, Sci. China Chem., 2022, 65, 135-144.
[34]	W. Z. Yuan, Y. Gong, S. Chen, X. Y. Shen, J. W. Y. Lam, P. Lu, Y. Lu, Z. Wang, R. Hu, N. Xie, H. S. Kwok, Y. Zhang, J. Z. Sun, B. Z. Tang, Chem. Mater., 2012, 24, 1518-1528.
[35]	F. P. Wenzl, P. Pachler, C. Suess, A. Haase, E. J. W. List, P. Poelt, D. Somitsch, P. Knoll, U. Scherf, G. Leising, Adv. Funct. Mater., 2004, 14, 441-450.
[36]	J. E. Slota, E. Elmalem, G. Tu, B. Watts, J. Fang, P. M. Oberhumer, R. H. Friend, W. T. S. Huck, Macromolecules, 2012, 45, 1468-1475.

Pd/Cu-cocatalyzed multi-site functionalization of in-situ generated alkenes toward carbazole-based aggregation-induced emission luminogens

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