Citation: Zhongyan Cao, Shengnan Jin, Yuxia Wang, Yiyi Chen, Xianqiang Kong, Yuanqing Xu. Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors[J]. University Chemistry, ;2025, 40(4): 245-252. doi: 10.12461/PKU.DXHX202405186 shu

Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors

1.
College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004 China;
2.
School of Chemical Engineering and Materials, Changzhou Institute of Technology, Changzhou 213032 China

Received Date: 9 May 2024
Revised Date: 1 August 2024

Phenols, produced at an annual volume exceeding ten million tons, are widely used in various key organic transformations due to their low cost. In introductory chemistry courses, the reactions of phenols typically involve substitutions at the electron-rich aromatic ring or the hydroxyl oxygen, leaving the inert C―O bond intact in the final products. To expand the utility of phenols, researchers have developed metal-catalyzed strategies that cleave the C―O bond by introducing activating groups at the oxygen atom, enabling efficient deoxygenative coupling reactions. However, these methods often require harsh conditions and may result in metal contamination, limiting their use in pharmaceutical and other sensitive applications. To address these limitations, recent studies have demonstrated that simple phenol derivatives can selectively cleave the inert C―O bond under mild conditions, using light or electricity to generate aryl radicals. The high reactivity and selectivity of these radicals enable novel and efficient chemical transformations, offering new strategies for the application of phenols in organic synthesis. This paper reviews recent advancements in using trifluoromethanesulfonates, phosphates, and carbonates of phenols as aryl radical precursors, discussing the challenges and breakthroughs in constructing complex molecules with high precision. This review aims to broaden the knowledge of advanced students in the field.
- Phenols,
- Inert C-O bond,
- Selective cleavage,
- Aryl radicals,
- Photosynthesis,
- Electrosynthesis
1. [1]
  Zakzeski, J.; Bruijnincx, P. C. A.; Jongerius, A. L.; Weckhuysen, B. M. Chem. Rev. 2010, 110 (6), 3552.
2. [2]
  Schutyser, W.; Renders, T.; Van den Bosch, S.; Koelewijin, S. F.; Beckham, G. T.; Sels, B. F. Chem. Soc. Rev. 2018, 47, 852.
3. [3]
4. [4]
  Zeng, H.; Qiu, Z.; Domínguez-Huerta, A.; Hearne, Z.; Chen, Z.; Li, C.-J. ACS Catal. 2017, 7 (1), 510.
5. [5]
  Qiu, Z.; Li, C.-J. Chem. Rev. 2020, 120 (18), 10454.
6. [6]
  Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113 (7), 5322.
7. [7]
  Ravelli, D.; Protti, S.; Fagnoni, M. Chem. Rev. 2016, 116 (17), 9850.
8. [8]
  Romero, N. A.; Nicewicz, D. A. Chem. Rev. 2016, 116 (17), 10075.
9. [9]
  Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117 (21), 13230.
10. [10]
  Tang, S.; Liu, Y.; Lei, A. Chem 2018, 4, 27.
11. [11]
  Ma, C.; Fang, P.; Liu, Z.; Xu, S.; Xu, K.; Cheng, X.; Lei, A.; Xu, H.; Zeng, C. C.; Mei, T.-S. Sci. Bull. 2021, 66 (23), 2412.
12. [12]
  Cheng, X.; Lei, A. W.; Mei, T.-S.; Xu, H.-C.; Xu, K.; Zeng, C. CCS Chem. 2022, 4 (4), 1120.
13. [13]
  Kavsovs, N.; Gevorgyan, V. Chem. Soc. Rev. 2021, 50, 2244.
14. [14]
  Kong, X.; Chen, Y.; Chen, X.; Ma, C.; Chen, M.; Wang, W.; Xu, Y.-Q.; Ni, S.-F.; Cao, Z.-Y. Nat. Commun. 2023, 14, 6933.
15. [15]
  Jutand, A.; Negri, S.; Mosleh, A. J. Chem. Soc. Chem. Commun. 1992, 1729.
16. [16]
  Liu, W.; Yang, X.; Gao, Y.; Li, C.-J. J. Am. Chem. Soc. 2017, 139 (25), 8621.
17. [17]
  Dou, Q.; Geng, L.; Cheng, B.; Li, C.-J.; Zeng, H. Chem. Commun. 2021, 57, 8429.
18. [18]
  Yan, B.; Zhou, Y.; Wu. J.; Ran, M.; Li, H.; Yao, Q. Org. Chem. Front. 2021, 8, 5244.
19. [19]
  Wang, S.; Wang, H.; König, B. Chem 2021, 7, 1653.
20. [20]
  Ratushnyy, M.; Kvasovs, N.; Sarkar, S.; Gevorgyan, V. Angew. Chem. Int. Ed. 2020, 59 (26), 10316.
21. [21]
  Jin, S.; Dang, H. T.; Haug, G. C.; He, H. R.; Nguyen, V. D.; Nguyen, V. T.; Arman, H. D.; Schanze, K. S.; Larionov, O. V. J. Am. Chem. Soc. 2020, 142 (3), 1603.
1. [1]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
2. [2]
  Zhongyan Cao , Youzhi Xu , Menghua Li , Xiao Xiao , Xianqiang Kong , Deyun Qian . Electrochemically Driven Denitrative Borylation and Fluorosulfonylation of Nitroarenes. University Chemistry, 2025, 40(4): 277-281. doi: 10.12461/PKU.DXHX202407017
3. [3]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
4. [4]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
5. [5]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
6. [6]
  Yuan GAO , Yiming LIU , Chunhui WANG , Zhe HAN , Chaoyue FAN , Jie QIU . A hexanuclear cerium oxo cluster stabilized by furoate: Synthesis, structure, and remarkable ability to scavenge hydroxyl radicals. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 491-498. doi: 10.11862/CJIC.20240271
7. [7]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
8. [8]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
9. [9]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
10. [10]
  Wei Zhong , Dan Zheng , Yuanxin Ou , Aiyun Meng , Yaorong Su . K原子掺杂高度面间结晶的g-C₃N₄光催化剂及其高效H₂O₂光合成. Acta Physico-Chimica Sinica, 2024, 40(11): 2406005-. doi: 10.3866/PKU.WHXB202406005
11. [11]
  Jiajia Li , Xiangyu Zhang , Zhihan Yuan , Zhengyang Qian , Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073
12. [12]
  Yongqing Kuang , Jie Liu , Jianjun Feng , Wen Yang , Shuanglian Cai , Ling Shi . Experimental Design for the Two-Step Synthesis of Paracetamol from 4-Hydroxyacetophenone. University Chemistry, 2024, 39(8): 331-337. doi: 10.12461/PKU.DXHX202403012
13. [13]
  Min LIU , Huapeng RUAN , Zhongtao FENG , Xue DONG , Haiyan CUI , Xinping WANG . Neutral boron-containing radical dimers. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 123-130. doi: 10.11862/CJIC.20240362
14. [14]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
15. [15]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
16. [16]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
17. [17]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
18. [18]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
19. [19]
  Rui Gao , Ying Zhou , Yifan Hu , Siyuan Chen , Shouhong Xu , Qianfu Luo , Wenqing Zhang . Design, Synthesis and Performance Experiment of Novel Photoswitchable Hybrid Tetraarylethenes. University Chemistry, 2024, 39(5): 125-133. doi: 10.3866/PKU.DXHX202310050
20. [20]
  Jiapei Zou , Junyang Zhang , Xuming Wu , Cong Wei , Simin Fang , Yuxi Wang . A Comprehensive Experiment Based on Electrocatalytic Nitrate Reduction into Ammonia: Synthesis, Characterization, Performance Exploration, and Applicable Design of Copper-based Catalysts. University Chemistry, 2024, 39(6): 373-382. doi: 10.3866/PKU.DXHX202312081

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(95)
HTML views(37)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142