Citation: Xiao Li, Li Jiaheng, Wang Ting. Visible-Light-Induced N-Radical Directed Remote Functionalization of sp³ C-H Bonds[J]. Acta Chimica Sinica, ;2019, 77(9): 841-849. doi: 10.6023/A19050183 shu

Visible-Light-Induced N-Radical Directed Remote Functionalization of sp³ C-H Bonds

Xiao Li ^a,, ,
Li Jiaheng ^b ,
Wang Ting ^b,,

a.
Biogen, 115 Broadway, Cambridge, Massachusetts 02142, United States
b.
Department of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, New York 12222, United States

Corresponding author: Xiao Li, xiao.221@buckeyemail.osu.edu Wang Ting, twang3@albany.edu
Received Date: 15 May 2019
Available Online: 14 September 2019

Figures(21)

The selective functionalization of unactivated sp³ carbon-hydrogen (C-H) bond is an attractive strategy in modern organic transformation. The hydrogen atom transfer (HAT) catalysis has recently shown its advances in remotely selective activation of an inert C-H bond with great functional group compatibility, generating new carbon-carbon (C-C) bonds and carbon-heteroatom (C-O, C-N, C-X) bonds. Therefore, the remote sp³ C-H functionalization has become an intensively investigated research area, drawing extensive attention in synthetic community. Particularly, the 1, 5-hydrogen atom abstraction of nitrogen radicals, the key step of the Hoffman-L ffler-Freytag (HLF) reaction, has been widely applied in the preparation of heterocycles. Comparing to the well-studied area of nucleophilic N-species, N-centered radical based reactions are still underdeveloped. The limited utility is partially due to the required use of hazardous radical initiators, elevated temperatures, or high-energy UV irradiation for the generation of N-radicals. Recently, visible-light photoredox catalysis has been leading efficient accesses to Nitrogen-radicals under mild conditions. The visible-light-induced nitrogen radical formation has also stimulated the development of the remote sp³ C-H functionalization by photoredox catalysis. The classic HLF reaction requires pre-functionalization at N-center in the substrate to promote the formation of N-radical. Recently, a direct N-H single electron transfer (SET) oxidation was realized by photoredox catalysis in Knowles and Rovis's group, generating N-radicals efficiently. The processes significantly simplified the preparation of the HLF reaction substrates and broaden the application of this classic reaction. In addition, the visible-light-induced nitrogen radical-directed reaction on modified imines provided possibilities for the remote sp³ C-H functionalization of ketones, as ketone is the product of imine hydrolysis. Moreover, the application of chiral Lewis acid catalysis combined with visible-light photoredox catalysis enabled the asymmetric alkylation of the unactivated remote sp³ C-H position, which achieves both regioselective and stereoselective functionalization. In conclusion, this strategy takes advantage of mild generation of N-radicals upon visible-light excitation. Subsequent 1, 5-hydrogen atom transfer (1, 5-HAT) and intermolecular radical coupling would realize the remote functionalization of unactivated sp³ C-H bonds. The strategies have been successfully applied in remote C(sp³)-H amidation, fluorination, chlorination, iodination, alkylation, vinylation, allylation, oxygenation, thioetherification, cyanation and alkynylation. In this review, we focus on visible-light-induced nitrogen radical directed functionalization of remote sp³ C-H bonds, summarized the methodologies, and briefly reviewed their synthetic applications in pharmaceuticals and natural products.
- visible-light,
- radical,
- remote functionalization
1. [1]
  Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322. doi: 10.1021/cr300503r
2. [2]
  Hoplinson, M. N.; Sahoo, B.; Li, J.-L.; Glorius, F. Chem.-Eur. J. 2014, 20, 3874. doi: 10.1002/chem.201304823
3. [3]
  Kärkäs, M. D.; Porco, J. A. Jr.; Stephenson, C. R. J. Chem. Rev. 2016, 116, 9683. doi: 10.1021/acs.chemrev.5b00760
4. [4]
  Xuan, J.; Xiao, W.-J. Angew. Chem., Int. Ed. 2012, 51, 6828. doi: 10.1002/anie.201200223
5. [5]
  Narayanam, J. M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40, 102. doi: 10.1039/B913880N
6. [6]
  Yoon, T. P. ACS Catal. 2013, 3, 895. doi: 10.1021/cs400088e
7. [7]
  Nicewicz, D. A.; Nguyen, T. M. ACS Catal. 2014, 4. 355. doi: 10.1021/cs400956a
8. [8]
  Fukuzumi, S.; Ohkubo, K. Org. Biomol. Chem. 2014, 12, 6059. doi: 10.1039/C4OB00843J
9. [9]
  Hari, D. P.; König, B. Chem. Commun. 2014, 50, 6688. doi: 10.1039/C4CC00751D
10. [10]
  Martin, M. L.; Santos-Juanes, L.; Arques, A.; Amat, A. M.; Miranda, M. A. Chem. Rev. 2012, 112, 1710. doi: 10.1021/cr2000543
11. [11]
  Nicewicz, D. A.; Romero, N. A. Chem. Rev. 2016, 116, 10075. doi: 10.1021/acs.chemrev.6b00057
12. [12]
  Chen, J.-R.; Hu, X.-Q.; Lu, L.-Q.; Xiao, W.-J. Chem. Soc. Rev. 2016, 45, 2044. doi: 10.1039/C5CS00655D
13. [13]
  Twilton, J.; Le, C.; Zhang, P.; Shaw, M. H.; Evans, R. W.; MacMillan, D. W. C. Nat. Rev. Chem. 2017, 1, 52. doi: 10.1038/s41570-017-0052
14. [14]
  Tellis, J. C.; Kelly, C. B.; Primer, D. N.; Jouffroy, M.; Patel, N. R.; Molander, G. A. Acc. Chem. Res. 2016, 49, 1429. doi: 10.1021/acs.accounts.6b00214
15. [15]
  Chen, Y.-Y.; Lu, L.-Q.; Yu, D.-G.; Zhu, C.-J.; Xiao, W.-J. Sci. China Chem. 2019, 62, 24. doi: 10.1007/s11426-018-9399-2
16. [16]
  He, J.; Wasa, M.; Chan, K. S.; Shao, Q.; Yu, J.-Q. Chem. Rev. 2016, 117, 8754.
17. [17]
  Gutekunst, W. R.; Baran, P. S. Chem. Soc. Rev. 2011, 40, 1976. doi: 10.1039/c0cs00182a
18. [18]
  Yamaguchi, J.; Yamaguchi, A. D.; Itami, K. Angew. Chem., Int. Ed. 2012, 51, 8960. doi: 10.1002/anie.201201666
19. [19]
  Huang, Z.; Lim, H. N.; Mo, F.; Young, M. C.; Dong, G. Chem. Soc. Rev. 2015, 44, 7764. doi: 10.1039/C5CS00272A
20. [20]
21. [21]
  Chiba, S.; Chen, H. Org. Biomol. Chem. 2014, 12, 4051. doi: 10.1039/C4OB00469H
22. [22]
  Robertson, J.; Pillai, J.; Lush, R. K. Chem. Soc. Rev. 2001, 30, 94. doi: 10.1039/b000705f
23. [23]
  Mayer, J. M. Acc. Chem. Res. 2010, 44, 36.
24. [24]
  Protti, S.; Fagnoni, M.; Ravelli, D. ChemCatChem 2015, 7, 1516. doi: 10.1002/cctc.201500125
25. [25]
  Wolff, M. E. Chem. Rev. 1963, 63, 55. doi: 10.1021/cr60221a004
26. [26]
  Qin, Q.; Yu, S. Org. Lett. 2015, 17, 1894. doi: 10.1021/acs.orglett.5b00582
27. [27]
  Choi, G. J.; Zhu, Q.; Miller, D. C.; Gu, C. J.; Knowles, R. R. Nature 2016, 539, 268. doi: 10.1038/nature19811
28. [28]
  Chu, J. C. K.; Rovis, T. Nature 2016, 539, 272. doi: 10.1038/nature19810
29. [29]
  Chen, D.-F.; Chu, J. C. K.; Rovis, T. J. Am. Chem. Soc. 2017, 139, 14897. doi: 10.1021/jacs.7b09306
30. [30]
  Yuan, W.; Zhou, Z.; Gong, L.; Meggers, E. Chem. Commun. 2017, 53, 8964. doi: 10.1039/C7CC04941B
31. [31]
  Shu, W.; Nevado, C. Angew. Chem., Int. Ed. 2017, 56, 1881. doi: 10.1002/anie.201609885
32. [32]
  Chen, H.; Guo, L.; Yu, S. Org. Lett. 2018, 20, 6255. doi: 10.1021/acs.orglett.8b02737
33. [33]
  Shen, X.; Zhao, J.; Yu, S. Org. Lett. 2018, 20, 5523. doi: 10.1021/acs.orglett.8b02540
34. [34]
  Xia, Y.; Wang, L.; Studer, A. Angew. Chem., Int. Ed. 2018, 57, 12940. doi: 10.1002/anie.201807455
35. [35]
  Dauncey, E. M.; Morcillo, S. P.; Douglas, J. J.; Sheikh, N. S.; Leonori, D. Angew. Chem., Int. Ed. 2018, 57, 744. doi: 10.1002/anie.201710790
36. [36]
  Jiang, H.; Studer, A. Angew. Chem., Int. Ed. 2018, 57, 1692. doi: 10.1002/anie.201712066
37. [37]
  Morcillo, S. P.; Dauncey, E. M.; Kim, J. H.; Douglas, J. J.; Sheikh, N. S.; Leonori, D. Angew. Chem., Int. Ed. 2018, 57, 12945. doi: 10.1002/anie.201807941
38. [38]
  Wappes, E. A.; Vanitcha, A.; Nagib, D. A. Chem. Sci. 2018, 9, 4500. doi: 10.1039/C8SC01214H
39. [39]
  Wu, K.; Wang, L.; Colón-Rodríguez, S.; Flechsig, G.; Wang, T. Angew. Chem., Int. Ed. 2019, 58, 1774. doi: 10.1002/anie.201811004
40. [40]
  Xu, B.; Tambar, U. K. ACS Catal. 2019, 9, 4727.
1. [1]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
2. [2]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
3. [3]
  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
4. [4]
  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
5. [5]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
6. [6]
  Jie Li , Huida Qian , Deyang Pan , Wenjing Wang , Daliang Zhu , Zhongxue Fang . Efficient Synthesis of Anethaldehyde Induced by Visible Light. University Chemistry, 2024, 39(4): 343-350. doi: 10.3866/PKU.DXHX202310076
7. [7]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
8. [8]
  Yurong Tang , Yunren Shi , Yi Xu , Bo Qin , Yanqin Xu , Yunfei Cai . Innovative Experiment and Course Transformation Practice of Visible-Light-Mediated Photocatalytic Synthesis of Isoquinolinone. University Chemistry, 2024, 39(5): 296-306. doi: 10.3866/PKU.DXHX202311087
9. [9]
  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
10. [10]
  Xinyu Zhu , Meili Pang . Application of Functional Group Addition Strategy in Organic Synthesis. University Chemistry, 2024, 39(3): 218-230. doi: 10.3866/PKU.DXHX202308106
11. [11]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
12. [12]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
13. [13]
  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
14. [14]
  Honglian Liang , Xiaozhe Kuang , Fuping Wang , Yu Chen . Exploration and Practice of Integrating Ideological and Political Education into Physical Chemistry: a Case on Surface Tension and Gibbs Free Energy. University Chemistry, 2024, 39(10): 433-440. doi: 10.12461/PKU.DXHX202405073
15. [15]
  Huan LI , Shengyan WANG , Long Zhang , Yue CAO , Xiaohan YANG , Ziliang WANG , Wenjuan ZHU , Wenlei ZHU , Yang ZHOU . Growth mechanisms and application potentials of magic-size clusters of groups Ⅱ-Ⅵ semiconductors. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1425-1441. doi: 10.11862/CJIC.20240088
16. [16]
  Xin Lv , Hongxing Zhang , Kaibo Duan , Wenhui Dai , Zhihui Wen , Wei Guo , Junsheng Hao . Lighting the Way Against Cancer: Photodynamic Therapy. University Chemistry, 2024, 39(5): 70-79. doi: 10.3866/PKU.DXHX202309090
17. [17]
  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
18. [18]
  Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-. doi: 10.3866/PKU.WHXB202310034
19. [19]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-. doi: 10.3866/PKU.WHXB202405016
20. [20]
  Tengjiao Wang , Tian Cheng , Rongjun Liu , Zeyi Wang , Yuxuan Qiao , An Wang , Peng Li . Conductive Hydrogel-based Flexible Electronic System: Innovative Experimental Design in Flexible Electronics. University Chemistry, 2024, 39(4): 286-295. doi: 10.3866/PKU.DXHX202309094

Get Citation

PDF

XML

Metrics

PDF Downloads(49)
Abstract views(1805)
HTML views(383)

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

Visible-Light-Induced N-Radical Directed Remote Functionalization of sp3 C-H Bonds

Metrics

通讯作者: 陈斌, bchen63@163.com

Visible-Light-Induced N-Radical Directed Remote Functionalization of sp³ C-H Bonds