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2025 , Vol. 45 >Issue 2: 498 - 515

DOI: https://doi.org/10.6023/cjoc202406042

综述与进展

C(sp3)—H键对映选择性自由基反应的最新进展

  • 令天鹏 ,
  • 秦海涛 ,
  • 刘峰
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  • a 苏州大学药学院 江苏省神经精神疾病重点实验室和药物化学系 江苏苏州 215123
    b 中国科学院上海有机化学研究所 先进氟氮材料全国重点实验室 上海 200032

收稿日期: 2024-06-28

  修回日期: 2024-09-09

  网络出版日期: 2024-10-18

基金资助

国家自然科学基金(22171200); 江苏省高校重点学科建设(PAPD)

收起

Recent Advances in Enantioselective Radical Reactions of C(sp3)—H Bond

  • Tianpeng Ling ,
  • Haitao Qin ,
  • Feng Liu
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  • a Jiangsu Key Laboratory of Neuropsychiatric Diseases and Department of Medicinal Chemistry, College of Pharmaceutical Sciences, Soochow University, Suzhou, Jiangsu 215123
    b Sate Key Laboratory of Fluorine And Nitrogen Chemisty and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
*E-mail: ;

Received date: 2024-06-28

  Revised date: 2024-09-09

  Online published: 2024-10-18

Supported by

National Natural Science Foundation of China(22171200); Priority Academic Program Development of the Jiangsu Higher Education Institutes(PAPD)

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摘要

碳氢键活化被认为是合成有机化学中最具吸引力的技术之一, 因为它有可能缩短合成路线, 并与传统合成策略相互补. 近年来, 受益于基础知识的显著增长, C(sp3)—H键不对称自由基反应的新想法不断涌现, 随之而来的是大量新的催化方法. 综述了自2020年以来报道的C(sp3)—H键对映选择性自由基反应, 讨论了通过各种途径(如能量转移、单电子转移、氢原子转移等)直接或者间接断裂C—H键形成碳自由基中间体, 随后构建手性C—C、C—N和C—O键的方法.

关键词： 碳氢键; 自由基反应; 对映选择性

本文引用格式

令天鹏 , 秦海涛 , 刘峰 . C(sp3)—H键对映选择性自由基反应的最新进展[J]. 有机化学, 2025 , 45(2) : 498 -515 . DOI: 10.6023/cjoc202406042

Abstract

The activation of carbon-hydrogen bonds is considered one of the most attractive techniques in synthetic organic chemistry due to its potential to shorten synthetic routes and complement traditional synthetic strategies. In recent years, owing to the significant growth in foundational knowledge and advancements in various technologies, new ideas about asymmetric radical reactions have continuously emerged, leading to numerous novel catalytic methods. The enantioselective radical reactions involving C(sp3)—H bonds published since 2020 are reviewed. The methods of directly or indirectly breaking C—H bonds through various pathways, such as energy transfer, single-electron transfer, and hydrogen atom transfer, to form carbon radicals and subsequently construct chiral C—C, C—N, and C—O bonds, are discussed.

Key words： C—H bond; radical reaction; enantioselectivity

参考文献

[1]
Capaldo, L.; Ravelli, D.; Fagnoni, M. Chem. Rev. 2022, 122, 1875.
[2]
Zhang, Y.; Zhang, T.; Das, S. Chem 2022, 8, 1.
[3]
Chen, X. M.; Kramer, S. Chem. Catal. 2024, 4, 100854.
[4]
Xu, G. Q.; Wang, W. D.; Xu, P. F. J. Am. Chem. Soc. 2024, 146, 1209.
[5]
Zhang, Z. X.; Chen, P. H.; Liu, G. S. Chem. Soc. Rev. 2022, 51, 1640.
[6]
Li, M. L.; Wang, J. Synthesis 2022, 54, 4734.
[7]
Yu, X.; Zhang, Z. Z.; Niu, J. L.; Shi, B. F. Org. Chem. Front. 2022, 9, 1458.
[8]
Font, M.; Gulías, M. Angew. Chem., Int. Ed. 2022, 61, e202112848.
[9]
Docherty, J. H.; Liste, T. M.; Mcarthur, G.; Findlay, M. T.; Legarda, P. D.; Kenyon, J.; Choudhary, S.; Larrosa, I. Chem. Rev. 2023, 123, 7692.
[10]
Rodríguez, R. I.; Mollari, L.; Alemán, J. Angew. Chem., Int. Ed. 2021, 60, 4555.
[11]
Xu, P.; Fan, W. Z.; Chen, P. H.; Liu, G. S. J. Am. Chem. Soc. 2022, 144, 13468.
[12]
Zhang, Q. L.; Liang, K.; Guo, C. Angew. Chem., Int. Ed. 2022, 61, e202210632.
[13]
Hu, H.; Shi, Z. X.; Guo, X. C.; Zhang, F. H.; Wang, Z. B. J. Am. Chem. Soc. 2024, 146, 5316.
[14]
Shu, X. M.; Huan, L. T.; Huang, Q.; Huo, H. H. J. Am. Chem. Soc. 2020, 142, 19058.
[15]
Huan, L. T.; Shu, X. M.; Zu, W. S.; Zhong, D.; Huo, H. H. Nat. Commun. 2021, 12, 3536.
[16]
Shu, X. M.; Zhong, D.; Huang, Q.; Huan, L. T.; Huo, H. H. Nat. Commun. 2023, 14, 125.
[17]
Galisteo, S. C.; Sch?rgenhumer, J.; Hervieu, C.; Nevado, C. Angew. Chem., Int. Ed. 2024, 63, e202313717.
[18]
(a) Zhang, W.; Shu, X. M.; Huan, L. T.; Cheng, B. Q.; Huo, H. H. Org. Biomol. Chem., 2021, 19, 9407.
[18]
(b) Shu, X. M.; Zhong, D.; Lin, Y. M.; Qin, X.; Huo, H. H. J. Am. Chem. Soc. 2022, 144, 8797.
[19]
Xu, S.; Ping, Y. Y.; Li, W.; Guo, H. Y.; Su, Y. Y.; Li, Z. Y.; Wang, M. Y.; Kong, W. Q. J. Am. Chem. Soc. 2023, 145, 5231.
[20]
Hu, Y. W.; Hervieu, C.; Merino, E.; Nevado, C. Angew. Chem., Int. Ed. 2024, 63, e202319158.
[21]
Xu, J. T.; Li, Z. L.; Xu, Y. M.; Shu, X. M.; Huo, H. H. ACS Catal. 2021, 11, 13567.
[22]
Cheng, X. K.; Li, T. T.; Liu, Y. T.; Lu, Z. ACS Catal. 2021, 11, 11059
[23]
Fu, L.; Zhang, Z. H.; Chen, P. H.; Lin, Z. Y.; Liu, G. S. J. Am. Chem. Soc. 2020, 142, 12493.
[24]
Liu, L.; Guo, K. X.; Tian, Y.; Yang, C. J.; Gu, Q. S.; Li, Z. L.; Ye, L.; Liu, X. Y. Angew. Chem., Int. Ed. 2021, 60, 26710.
[25]
Wang, C. Y.; Qin, Z. Y.; Huang, Y. L.; Hou, Y. M.; Jin, R. X.; Li, C.; Wang, X. S. Org. Lett. 2020, 22, 4006.
[26]
Guo, R.; Xiao, H. J.; Li, S. J.; Luo, Y. X.; Bai, J. H.; Zhang, M. Z.; Guo, Y. L.; Qi, X. T.; Zhang, G. Z. Angew. Chem., Int. Ed. 2022, 61, e202208232.
[27]
Fan, W. Z.; Zhao, X. Y.; Deng, Y. S.; Chen, P. H.; Wang, F.; Liu, G. S. J. Am. Chem. Soc. 2022, 144, 21674.
[28]
Cai, C. Y.; Lai, X. L.; Wang, Y.; Hu, H. H.; Song, J. S.; Yang, Y.; Wang, C.; Xu, H. C. Nat. Catal. 2022, 5, 943.
[29]
Deng, Y. S.; Lu, R. H.; Chen, P. H.; Liu, G. S. Chem. Commun. 2023, 59, 4656.
[30]
Chen, H.; Jin, W. W.; Yu, S. Y. Org. Lett. 2020, 22, 5910.
[31]
Athavale, S. V.; Gao, S. L.; Das, A.; Mallojjala, S. C.; Alfonzo, E.; Long, Y. M.; Hirschi, J. S.; Arnold, F. H. J. Am. Chem. Soc. 2022, 144, 19097.
[32]
Mao, R.; Gao, S. L.; Qin, Z. Y.; Rogge, T.; Wu, S. J.; Li, Z. Q.; Das, A.; Houk, K. N.; Arnold, F. H. Nat. Catal. 2024, 7, 585.
[33]
Nakafuku, K. M.; Zhang, Z. X.; Wappes, E. A.; Stateman, L. M.; Chen, A. D.; Nagib, D. A. Nat. Chem. 2020, 12, 697.
[34]
Dai, L.; Chen, Y. Y.; Xiao, L. J.; Zhou, Q. L. Angew. Chem., Int. Ed. 2023, 62, e202304427.
[35]
Chen, X. M.; Lian, Z.; Kramer, S. Angew. Chem., Int. Ed. 2023, 62, e202217638.
[36]
Yang, C. J.; Zhang, C.; Gu, Q. S.; Fang, J. H.; Su, X. L.; Ye, L.; Sun, Y.; Tian, Y.; Li, Z. L.; Liu, X. Y. Nat. Catal. 2020, 3, 539.
[37]
Lazib, Y.; Retailleau, P.; Saget, T.; Darses, B.; Dauban, P. Angew. Chem., Int. Ed. 2021, 60, 21708.
[38]
Ye, C. X.; Shen, X.; Chen, S. M.; Meggers, E. Nat. Chem. 2022, 14, 566.
[39]
Kim, S.; Song, S. L.; Zhang, J. B.; Kim, D.; Hong, S.; Chang, S. J. Am. Chem. Soc. 2023, 145, 16238.
[40]
Mai, B. K.; Neris, N. M.; Yang, Y.; Liu, P. J. Am. Chem. Soc. 2022, 144, 11215.
[41]
Cao, M.; Wang, H. L.; Ma, Y. G.; Tung, C. H.; Liu, L. J. Am. Chem. Soc. 2022, 144, 15383.
[42]
Rui, J. Y.; Zhao, Q.; Huls, A. J.; Soler, J.; Paris, J. C.; Chen, Z. H.; Reshetnikov, V.; Yang, Y. F.; Guo, Y. S.; Garcia-Borràs, M.; Huang, X. Y. Science 2022, 376, 869.
[43]
Bryliakov, K. P. ACS Catal. 2023, 13, 10770.
[44]
Ottenbacher, R. V.; Bryliakova, A. A.; Shashkov, M. V.; Talsi, E.P.; Bryliakov, K. P. T. ACS Catal. 2021, 11, 5517.
[45]
Zhang, K.; Yu, A. Q.; Chu, X.; Li, F. D.; Liu, J.; Liu, L.; Bai, W. J.; He, C.; Wang, X. Q. Angew. Chem., Int. Ed. 2022, 61, e202204290.
[46]
Mao, Y. L.; Zhang, W. J.; Fu, Z. Y.; Liu, Y. Q.; Chen, L.; Lian, X.; Zhuo, D.; Wu, J. W.; Zheng, M. Y.; Liao, C. S. Angew. Chem., Int. Ed. 2023, 62, e202305250.
[47]
Harwood, L. A.; Xiong, Z. Y.; Christensen, K. E.; Wang, R. Y.; Wong, L. L.; Robertson, J. J. Am. Chem. Soc. 2023, 145, 27767.
[48]
Zhou, X. J.; Wang, M. Y.; Zhao, L.; He, Y. Q.; Wang, Z. Q.; Li, J. J.; Deng, G. Z.; Wan, N. W.; Chen, Y. Z. ACS Catal. 2023, 13, 15948.
[49]
Xi, J. J.; Zhu, X. T.; Bao, H. L. Synthesis 2024, 56, 1393.
[50]
Zhao, Q.; Chen, Z. L.; Soler, J.; Chen, X. H.; Rui, J. Y.; Ji, N. T. L.; Yu, Q. L. E.; Yang, Y. F.; Garcia-Borràs, M.; Huang, X. Y. Nat. Synth. 2024, 3, 958.
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