SIOC 中文
ACS
Adv search

Acta Chimica Sinica >

0 0

DOI: https://doi.org/10.6023/A26090304

Article

Semi‑Heterogeneous Photoredox‑Catalyzed SO2‑Insertive Multicomponent Cascade Cyclization: DDQ as a Dual HAT/Redox Catalyst for Sulfonyl Phenanthrenes from 2‑Alkynyl Biaryls

  • Zi-Tong Zhang ,
  • Zhe Liao ,
  • Dan-Lu Hu ,
  • Rong-Nan Yi ,
  • Dong-Fang Jiang ,
  • Yu-Cai Tang ,
  • Li-Li Wang ,
  • Wei-Min He
Expand
  • aSchool of Chemistry and Chemical Engineering, University of South China, Hengyang 421001;
    bKey Laboratory of Food & Environment & Drug Monitoring and Testing of Universities in Hunan Province, Hunan Police Academy, Changsha 410138;
    cHunan Provincial University Key Laboratory of the Fundamental and Clinical Research on Functional Nucleic Acid, Changsha Medical University, Changsha 410219;
    dCollege of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde 415000;
    eSchool of Chemical Engineering, Nanjing Forestry University, Nanjing 210037
#These authors contributed equally to this work

Received date: 2026-09-01

  Online published: 2026-09-17

Supported by

Hunan Provincial Natural Science Foundation (No. 2026JJ90135), the Scientific Research Fund of Hunan Provincial Education Department (No. 25A0703 and No.23B0411) and the Changsha Natural Science Foundation (No.104872)

Fold

Abstract

A semi-heterogeneous visible-light photocatalytic system has been developed for the direct construction of sulfonyl phenanthrenes via a multicomponent cascade sulfonylation/cyclization reaction. The protocol employs the inexpensive intrinsic semiconductor CW2 as a heterogeneous photocatalyst and DDQ as a bifunctional homogeneous organocatalyst, enabling the efficient coupling of 2-alkynyl biaryls, Na2S2O5 (as an inorganic SO2 surrogate), and aryldiazonium tetrafluoroborates under mild conditions. This redox-mediator-assisted semiconductor photocatalysis effectively suppresses photogenerated electron-hole recombination and enhances interfacial charge transfer, thus overcoming the intrinsic limitations of conventional single-component semiconductor photocatalysis. The reaction exhibits broad substrate scope with respect to both coupling partners, delivering a wide range of sulfonyl phenanthrenes in good to excellent yields. Importantly, the catalyst system is scalable to gram-level synthesis, and the CW2 photocatalyst can be readily recovered and reused without significant loss of activity. Mechanistic investigations reveal that DDQ plays a crucial dual role in the catalytic cycle: it acts as a HAT catalyst to facilitate phenanthrene ring formation, and simultaneously serves as a redox mediator to sustain the photocatalytic turnover of CW₂. This synergistic interplay between heterogeneous photon harvesting and homogeneous radical/redox mediation is the key to the high efficiency of the cascade process. The protocol offers distinct practical advantages, including the use of commercially available and low-cost catalysts, mild and operationally simple conditions, excellent functional-group tolerance, and catalyst recyclability. This dual-catalytic strategy provides a sustainable and versatile platform for the synthesis of valuable sulfonyl phenanthrenes, with promising potential for applications in medicinal chemistry and functional materials.

Key words： visible-light photocatalysis; semiconductor photocatalysis; sulfonylation reaction; SO2 insertion; phenanthrene

Cite this article

Zi-Tong Zhang , Zhe Liao , Dan-Lu Hu , Rong-Nan Yi , Dong-Fang Jiang , Yu-Cai Tang , Li-Li Wang , Wei-Min He . Semi‑Heterogeneous Photoredox‑Catalyzed SO2‑Insertive Multicomponent Cascade Cyclization: DDQ as a Dual HAT/Redox Catalyst for Sulfonyl Phenanthrenes from 2‑Alkynyl Biaryls[J]. Acta Chimica Sinica, 0 : 0 . DOI: 10.6023/A26090304

References

[1] (a) Bortolato, T.; Cuadros, S.; Simionato, G.; Dell’Amico, L., Chem. Commun. 2022, 58, 1263; (b) Bellotti, P.; Huang, H.-M.; Faber, T.; Glorius, F., Chem. Rev. 2023, 123, 4237; (c) Khalid, S.; Bilal, M.; Rasool, N.; Imran, M., Chin. Chem. Lett. 2024, 35, 109498; (d) Hou, J.-C.; Cai, W.; Ji, H.-T.; Ou, L.-J.; He, W.-M., Chin. Chem. Lett. 2025, 36, 110469; (e) Zhao, Y.; Xing, T.; Duan, Y.; Zhao, Q., Acta Chim. Sinica 2025, 83, 773; (f) Zhang, Z.; Qiao, L.; Sun, K.; Li, X.; Jiang, Z.; Chen, X.; Cao, Z.-Y.; Qu, L.; Yu, B., Org. Biomol. Chem. 2026, 24, 5819.
[2] (a) Xin, C.; Jiang, J.; Deng, Z.-W.; Ou, L.-J.; He, W.-M., Acta Chim. Sinica 2024, 82, 1109; (b) Li, W.; Li, L.; Guan, L.; Zhang, X.; You, J.; Shen, S.; Zhao, Y.; Duan, C., Acta Chim. Sinica 2025, 83, 596; (c) Jiang, D.; Yang, C.; Man, X.; Li, X.; Wang, H.; Song, Y.; Qi, Z., Org. Biomol. Chem. 2026, 24, 152; (d) Qiao, L.; Zhang, Z.; Wu, Y.; Sun, K.; Li, X.; Chen, X.; Qu, L.; Yu, B., Org. Lett. 2026, 28, 9077; (e) Zhao, W.; Wu, Q.; Zhang, Q.; Qin, Y.; Zhao, Y.; Yang, Z.; Zhu, Y.; Ren, T.; Wang, Q., J. Org. Chem. 2026, 91, 11469; (f) Zhu, M.; Chen, L.; Jiang, D.-F.; Huang, H.; Deng, G.-J., Org. Lett. 2026, 28, 10576; (g) Wu, Y.; Ye, X.; Qiao, L.; Sun, K.; Li, X.; Cao, Z.-Y.; Chen, X.; Qu, L.; Yu, B., Org. Lett. 2026, 28, 10635; (h) Wang, X.; An, J.; Qiao, L.; Xiang, P.; Sun, K.; Yu, B., ChemPhotoChem 2026, 10, e70264; (i) Yi, R.; He, W., Chin. J. Org. Chem. 2024, 44, 1035.
[3] (a) Liu, Q.-H.; Kang, S.-L.; Cui, Z.-S.; Liu, Y.-H.; Zhang, M.; Zhang, Z.-H., Green Chem. 2024, 26, 4803; (b) Peng, Q.-H.; Peng, J.; Cai, Y.-L.; Wang, Z.-L.; Yi, R.-N.; Shen, C.; He, W.-M., Acta Chim. Sinica 2025, 83, 1013; (c) Liu, D.; Kadierya, A.; Zhang, Q.; Li, J.; Fan, Y.; Abulikemu, A. R., Acta Chim. Sinica 2025, 83, 319; (d) Wu, C.; Wu, S.; Huang, Q.; Sun, K.; Huang, X.; Wang, J.; Yu, B., Chin. Chem. Lett. 2025, 36, 110250; (e) Li, H.-C.; Zhang, M.; Lv, Q.; Sun, K.; Chen, X.-L.; Qu, L.; Yu, B., Chin. Chem. Lett. 2025, 36, 110579; (f) Song, H.-K.; Yang, H.-B.; Jing, J.; Li, H.-C.; Sun, K.; Yang, Z.; Li, H.-J.; Chen, X.; Qu, L.; Yu, B., J. Org. Chem. 2026, 91, 6840; (g) Zeng, Y.-Y.; Jiang, J.; Wen, Y.-C.; Zhuang, C.-L.; Ou, L.-J.; Yang, Z.; Zhu, H.-T.; Wang, Z.-L.; He, W.-M., Chin. Chem. Lett. 2026, 37, 111776; (h) Zheng, K.; Shen, H.; Ma, X.; Chen, C.; Shen, C., Adv. Synth. Catal. 2026, 368, e70646.
[4] (a) Dan, X.; Yang, Q.; Xing, L.; Tang, Y.; Wang, W.; Cai, Y., Org. Lett. 2023, 25, 4124; (b) Hou, J.-C.; Ji, H.-T.; Lu, Y.-H.; Wang, J.-S.; Xu, Y.-D.; Zeng, Y.-Y.; He, W.-M., Chin. Chem. Lett. 2024, 35, 109514; (c) He, X.; Liu, F.; Tu, T., Chin. Chem. Lett. 2025, 36, 110621; (d) Peng, M.; Jiang, J.; Wang, Y.-H.; Li, T.; Yang, Z.; Zhu, H.-T.; He, W.-M., J. Org. Chem. 2025, 90, 18255; (e) Peng, Q.-H.; Cai, Y.-L.; Dai, H.; Zhuang, C.-L.; Wang, S.-H.; Yang, Z.; Wang, Z.-L.; Jiang, J.; He, W.-M., J. Org. Chem. 2025, 90, 14786; (f) Zheng, K.; Chen, C.; Wang, Y.; Xu, H.; Ge, K.; Shen, C., Org. Lett. 2025, 27, 4747; (g) Song, H.; Meng, J.; Li, S.; Li, C.; Song, Y.; Jiang, X., CCS Chem. 2026, DOI:10.31635/ccschem.026.202608407.
[5] (a) Chen, B.; Xu, J.; Wang, Z.; Yang, L.; Liu, Q.; Zhang, P., Green Chem. 2025, 27, 10656; (b) Jiang, D.; Liu, F.; Yang, C.; Li, X.; Zhou, H.; Wang, H.; Qi, Z., Org. Chem. Front. 2025, 12, 5862; (c) Zuo, D.; Xu, H.; Tang, S.; Hua, M.; Song, C.; Li, Y.; Zhao, J.; Yang, B.; Li, P., Org. Lett. 2025, 27, 5471; (d) Yang, Z.; Jin, Y.; Du, Q.; Ran, L.; Wei, W., Eur. J. Org. Chem. 2026, 29, e70748; (e) Jin, Y.; Huang, J.; Zhang, Y.; Yue, H.; Wei, W.; Yang, Z.; Ran, L.; Yi, D., J. Org. Chem. 2026, 91, 10856; (f) Wang, Q.-L.; He, C.-D.; Huang, H.; Yin, L.; Jiang, D.-F.; Wei, H.; Hu, X.-M.; Yu, M.; Cai, J., Adv. Synth. Catal. 2026, 368, e70579; (g) Wan, X.; Xie, B.; Huang, H.; Deng, G.-J., Green Chem. 2026, 28, 13321; (h) Hou, Y.; Wang, Y.; Jin, Y.; Yue, H.; Li, X.; Ran, L.; Wei, W.; Yi, D., J. Org. Chem. 2026, 91, 11840.
[6] (a) Wang, F.; Xie, X.; Ye, B.; Wang, L.; Zhu, B., Adv. Synth. Catal. 2026, 368, e70306;(b) Liu, P.; Huang, F.; Lu, Q.; Liang, T., Eur. J. Org. Chem. 2026, 29, e70660.
[7] (a) Guo, G.; Li, X.; Ma, J.; Shi, Y.; Lv, J.; Yang, D., Chin. Chem. Lett. 2024, 35, 110024; (b) Ren, Y.; Song, C.; Hua, M.; Zhao, J.; Li, P., Org. Lett. 2025, 27, 1574; (c) Cui, H.; Qiao, X.; Shi, T.; Wei, W.; Yue, H.; Wang, Z.; Ma, Z.; Yang, Z., Chem. Commun. 2025, 61, 17890; (d) Yang, Z.; Yue, H.; Ma, C.; Jian, Y.; Wei, W.; Yi, D., J. Org. Chem. 2026, 91, 4460; (e) Lv, Y.; Huang, J.; Yue, H.; Wei, W.; Yang, Z.; Ran, L.; Yi, D., J. Org. Chem. 2026, 91, 10738; (f) Wu, Q.; Huang, N.; Zhang, J.; Zhang, P.; Zhao, J.; Li, P., Org. Chem. Front. 2026, 13, 3335; (g) Cai, Y.-L.; Zhang, Z.-T.; Ding, R.; Li, J.; Jiang, J.; Yang, Z.; Tang, Y.-C.; He, W.-M., J. Org. Chem. 2026, 91, 11164; (h) Li, T.; Ouyang, W.; Yi, R.; Tang, Y.; Yang, Z.; Wu, C.; He, W., Chin. J. Org. Chem. 2026, 46, 1668; (i) Ding, L.; Li, Y.; Jiang, D.-F.; Ying, J.; Ji, X.; Huang, H., Org. Lett. 2026, DOI:10.1021/acs.orglett.6c03144.
[8] Zhao C.; Rakesh K. P.; Ravidar L.; Fang W.-Y.; Qin, H.-L., Eur. J. Med.Chem. 2019, 162, 679.
[9] (a) Huang, A.-X.; Li, R.; Lv, Q.-Y.; Yu, B., Chem - Eur. J. 2024, 30, e202402416; (b) Tan, Y.-Y.; He, L.-H.; He, W.-M., Chin. Chem. Lett. 2024, 35, 109986; (c) Yang, W.; Zhang, Z.; Yang, Z.; Chen, X.; Qiao, L.; Chen, X.; Sun, K.; Qu, L.; Yu, B., J. Org. Chem. 2025, 90, 16403; (d) Lu, G.; Zhang, T.; Cheng, X.; Qian, K.; Wang, Y.; Wan, X., Org. Chem. Front. 2025, 12, 1885; (e) Shi, T.; Tian, M.; Zhu, Y.; Sun, L.; Liu, F.; Chen, S.; Hao, E.; Sun, K.; Wang, X., J. Org. Chem. 2025, 90, 3435; (f) Gao, S.-J.; Huang, X.-Y.; Li, X.-Y.; Ge, D.; Ma, M.; Shen, Z.-L.; Chu, X.-Q., J. Org. Chem. 2025, 90, 3373; (g) He, T.; Kong, C.; Tang, Y.; Yang, Z.; Huang, S., Org. Lett. 2026, 28, 6109.
[10] Ye S.; Wu, J. Chem. Commun. 2012, 48, 10037.
[11] Zheng D.; An Y.; Li Z.; Wu, J., Angew. Chem. Int.Ed. 2014, 53, 2451.
[12] (a) Xiao, W.; Chen, J.-Q.; Wu, J., Chem. Soc. Rev. 2025, 54, 6832 (b) Zhang, Z.-T.; Yang, Y.; Li, J.; Zhou, Q.; Yang, Z.; Tang, Y.-C.; Jiang, J.; He, W.-M., J. Org. Chem. 2026, DOI:10.1021/acs.joc.6c01820.
[13] (a) Chen, S.-Y.; Wang, Y.-S.; Han, X.; Zhang, Z.-D.; Li, Z.-K.; Lu, D.-L.; Li, S., Org. Chem. Front. 2024, 11, 1169; (b) Xiao, W.; Tang, Z.; He, F.-S.; Wu, J., Adv. Synth. Catal. 2024, 366, 3041; (c) Tian, M.-Y.; Liu, J.-Q.; Wu, C.; Wang, Y.-Z.; Kong, S.-L.; Li, C.; Zhang, Y.-B.; Yang, W.; Zheng, Y.-G.; Tang, K.; Wei, W.-T., Org. Lett. 2026, 28, 6115; (d) Peng, W.; Mi, J.; Liu, G.; Xiao, W.; Wu, J., Adv. Synth. Catal. 2026, 368, e70711; (e) Luo, Y.; Fan, J.-H.; Liu, Y., J. Org. Chem. 2026, 91, 5895.
[14] Pu T.; Yue H.; Zhang Z.; Gao H.; Wang P.-L.; Miao T.,J. Org. Chem. 2024, 89, 17664.
[15] Tian H.-D.; Fu Z.-H.; Li C.; Lin H.-C.; Li M.; Ni S.-F.; Wen L.-R.; Zhang, L.-B. Org. Lett. 2022, 24, 9322.
[16] (a) Wang, Y.-H.; He, L.-H.; Tan, Y.-Y.; Zhang, Z.-T.; Xu, Y.-D.; Ding, R.; Jiang, J.; He, W.-M., Adv. Sci. 2026, 13, e15993;(b) Lu, J.-J.; Zhang, Z.-T.; Ou, L.-J.; Jiang, D.-F.; Tang, Y.; Peng, J.-M.; He, W.-M., J. Org. Chem. 2026, 91, 5577.
[17] (a) He, W.; Yi, R.; Yang, Z.; Wu, Z.; He, W.-M., Chin. J. Org. Chem. 2025, 45, 3534; (b) Wen, Y.-C.; Hou, J.-C.; Zhou, Q.; Wang, S.-H.; Jiang, J.; Yang, Z.; Zhu, H.-T.; Wang, Z.-L.; He, W.-M., Chin. Chem. Lett. 2025, 36, 111795; (c) Wen, Y.-C.; Zhu, L.-J.; Yi, R.-N.; Shen, C.; Zhu, H.-T.; Wang, Z.-L.; He, W.-M., Acta Chim. Sinica 2025, 83, 1124; (d) Yan, D.; He, W.; Tang, Y.; Xin, C.; Yang, Z.; Chen, X., Chin. J. Org. Chem. 2026, 46, 2327; (e) Tang, Y.; Huang, J.; Liang, J.; Long, N.; Liu, J.; Yin, Q.; Jiang, D.-F.; Zhu, H.-T.; He, W.-M., J. Org. Chem. 2026, 91, 6440; (f) Peng, J.; Yang, Y.; Cai, Y.-L.; Yi, R.-N.; Jiang, D.-F.; Tang, Y.-C.; Wu, c.; Ye, L.-W.; He, W.-M., Acta Chim. Sinica 2026, 84; (g) Jiang, D.-F.; Xiong, X.; Ou, L.-J.; Tang, Y.-C.; He, W.-M., Adv. Synth. Catal. 2026, 368, e70695.
[18] (a) Hou, Z.-W.; Li, L.; Wang, L., Org. Chem. Front. 2021, 8, 4700 (b) Xiong, Y.; Zhou, Z.; Zhang, Y.; Chen, J.-Q.; Wu, J., Org. Lett. 2025, 27, 8915.
Options
Outlines

/

〈 〉