Citation: Liu Qianyi, Zhang Lei, Mo Fanyang. Organic Borylation Reactions via Radical Mechanism[J]. Acta Chimica Sinica, ;2020, 78(12): 1297-1308. doi: 10.6023/A20070294 shu

Organic Borylation Reactions via Radical Mechanism

Liu Qianyi ^a ,
Zhang Lei ^a ,
Mo Fanyang ^a,b,,

a.
Department of Energy and Resources Engineering, College of Engineering, Peking University, Beijing 100871, China
b.
Jiangsu Donghai Silicon Industry S & T Innovation Center, Lianyungang 222300, China

Corresponding author: Mo Fanyang, fmo@pku.edu.cn
Received Date: 7 July 2020
Available Online: 31 July 2020
Fund Project: the National Natural Science Foundation of China 21772003the National Natural Science Foundation of China 21933001Project supported by the National Natural Science Foundation of China (Nos. 21772003 and 21933001)

Figures(20)

Organoboronic acids and esters are highly valuable building blocks in cross-coupling reactions and practical intermediates of various functional group transformations. Additionally, organoboronic acids can be utilized directly as small molecule drugs. Therefore, development of efficient methods to synthesize organoboronic compounds is of significant importance. Traditional pathways to synthesize organoboronic compounds mainly rely on electrophilic borylation of organometallic reagent and transition-metal-catalyzed borylation. Radical intermediates have unique chemical properties which are quite different from those of polar intermediates resulted from the heterolysis of chemical bonds and those of the organometallic compounds during transition metal catalysis. As such, borylation based on radical mechanism possesses distinctive reaction process, substrate scope, reaction selectivity, etc., and have great potential in synthesis of organoboronic compounds. In 2010, the Wang's group first reported borylation via a radical mechanism. This method realized an efficient direct conversion of anilines into aryl organoboronic esters. Inspired by this innovative work, more and more borylation methods via radical intermediates have been reported and developed as new avenues for C-B bond formation in the past decade. A series of studies show that organoboronic acids and esters could be efficiently constructed by the reaction of aryl/alkyl radicals with diboron compounds. In this paper, we summarize the recent development of borylation reactions via radical mechanisms, including aryl and alkyl radical borylation. As for aryl radical borylation, the activation of substrates containing C-N, C-O, C-S, C-X (X=halogen) bonds and carboxylic acids to C-B bond is summarized respectively. As for alkyl radical borylation, the activation of substrates containing C-N, C-O, C-X (X=halogen), C-C bonds and carboxylic acids to C-B bond is summarized respectively. Finally, we provide a perspective on the future development direction of this research area.
- radical chemistry,
- borylation reaction,
- diboron compounds,
- aryl radical,
- alkyl radical
1. [1]
  (a) Barth, R. F.; Kabalka, G. W.; Yang, W.; Huo, T.; Nakkula, R. J.; Shaikh, A. L.; Haider, S. A.; Chandra, S. Appl. Radiat. Isotopes 2014, 88, 38; (b) Barth, R. F.; Mi, P.; Yang, W. Cancer Commun. 2018, 38, 35.
2. [2]
  (a) San Miguel, J. F.; Schlag, R.; Khuageva, N. K.; Dimopoulos, M. A.; Shpilberg, O.; Kropff, M.; Spicka, I.; Petrucci, M. T.; Palumbo, A.; Samoilova, O. S.; Dmoszynska, A.; Abdulkadyrov, K. M.; Schots, R.; Jiang, B.; Mateos, M. V.; Anderson, K. C.; Esseltine, D. L.; Liu, K.; Cakana, A.; Van De Velde, H.; Richardson, P. G. New Engl. J. Med. 2008, 359, 906; (b) Beenen, M. A.; An, C.; Ellman, J. A. J. Am. Chem. Soc. 2008, 130, 6910.
3. [3]
  (a) Chemler, S. R.; Trauner, D.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2001, 40, 4544; (b) Moreno-Maas, M.; Pérez, M.; Pleixats, R. J. Org. Chem. 1996, 61, 2346.
4. [4]
  (a) Miyaura, N.; Suzuki, A., J. Chem. Soc. Chem. Commun. 1979, 866; (b) Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 20, 3437.
5. [5]
  (a) Schneider, N.; Lowe, D. M.; Sayle, R. A.; Tarselli, M. A.; Landrum, G. A. J. Med. Chem. 2016, 59, 4385; (b) Bostrm, J.; Brown, D. G.; Young, R. J.; Keserü, G. M. Nat. Rev. Drug Discov. 2018, 17, 709.
6. [6]
  Torborg, C.; Beller, M. Adv. Synth. Catal. 2009, 351, 3027.
7. [7]
  (a) Liu, M.; Su, S.-J.; Jung, M.-C.; Qi, Y.; Zhao, W.-M.; Kido, J. Chem. Mater. 2012, 24, 3817; (b) Wong, K.-T.; Hung, T. S.; Lin, Y.; Wu, C.-C.; Lee, G.-H.; Peng, S.-M.; Chou, C. H.; Su, Y. O. Org. Lett. 2002, 4, 513.
8. [8]
  (a) Chan, D. M. T.; Monaco, K. L.; Wang, R.-P.; Winters, M. P. Tetrahedron Lett. 1998, 39, 2933; (b) Evans, D. A.; Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937; (c) Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams, J.; Winters, M. P.; Chan, D. M. T.; Combs, A. Tetrahedron Lett. 1998, 39, 2941; (d) Herradura, P. S.; Pendola, K. A.; Guy, R. K. Org. Lett. 2000, 2, 2019.
9. [9]
  Petasis, N. A.; Akritopoulou, I. Tetrahedron Lett. 1993, 34, 583.
10. [10]
  Wu, P.; Givskov, M.; Nielsen, T. E. Chem. Rev. 2019, 119, 11245.
11. [11]
  (a) Brown, H. C.; Cole, T. E. Organometallics. 1983, 2, 1316; (b) Brown, H. C.; Srebnik, M.; Cole, T. E. Organometallics. 1986, 5, 2300.
12. [12]
  Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995, 60, 7508.
13. [13]
  Li, Z.; Zheng, J.; Li, C.; Wu, W.; Jiang, H. Chin. J. Chem. 2019, 37, 140.
14. [14]
  Yoshida, H. ACS Catal. 2016, 6, 1799.
15. [15]
  Li, S.; Li, J.; Xia, T.; Zhao, W. Chin. J. Chem. 2019, 37, 462.
16. [16]
  He, Z.; Fan, M.; Xu, J.; Hu, Y.; Wang, L.; Wu, X.; Xia, C.; Liu, C. Chin. J. Org. Chem. 2019, 39, 3438.
17. [17]
  Wang, M.; Shi, Z. Chem. Rev. 2020, DOI: 10.1021/acs.chemrev.9b00384. doi: 10.1021/acs.chemrev.9b00384.
18. [18]
  (a) Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Science 2000, 287, 1995; (b) Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J. M.; Hartwig, J. F. Chem. Rev. 2010, 110, 890; (c) Jiang, Z.-T.; Wang, B.-Q.; Shi, Z.-J. Chin. J. Chem. 2018, 36, 950; (d) Zhan, M.; Song, P.; Jiao, J.; Li, P. Chin. J. Chem. 2020, 38, 665.
19. [19]
  (a) (a) Xiao, L. Li, J.-H, Wang, T. Acta Chim. Sinica, 2019, 77, 841(in Chinese). (肖丽, 李嘉恒, 王挺, 化学学报 2019, 77, 841.) (b) Ye, S.-Q, Wu, J. Acta Chim. Sinica, 2019, 77, 814(in Chinese). (叶盛青, 吴劼, 化学学报 2019, 77, 814.)
20. [20]
  Mo, F.; Jiang, Y.; Qiu, D.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2010, 49, 1846.
21. [21]
  Qiu, D.; Jin, L.; Zheng, Z.; Meng, H.; Mo, F.; Wang, X.; Zhang, Y.; Wang, J. J. Org. Chem. 2013, 78, 1923.
22. [22]
  (a) Yu, J.; Zhang, L.; Yan, G. Adv. Synth. Catal. 2012, 354, 2625; (b) Zhu, C.; Yamane, M. Org. Lett. 2012, 14, 4560; (c) Erb, W.; Hellal, A.; Albini, M.; Rouden, J.; Blanchet, J. Chem. Eur. J. 2014, 20, 6608; (d) Marciasini, L. D.; Vaultier, M.; Pucheault, M. Tetrahedron Lett. 2014, 55, 1702; (e) Zhao, C.-J.; Xue, D.; Jia, Z.-H.; Wang, C.; Xiao, J. Synlett 2014, 25, 1577; (f) Ahammed, S.; Nandi, S.; Kundu, D.; Ranu, B. C. Tetrahedron Lett. 2016, 57, 1551; (g) Qi, X.; Jiang, L.-B.; Zhou, C.; Peng, J.-B.; Wu, X.-F. ChemistryOpen 2017, 6, 345; (h) Xu, Y.; Yang, X.; Fang, H. J. Org. Chem. 2018, 83, 12831.
23. [23]
  Teders, M.; Gómez-Suárez, A.; Pitzer, L.; Hopkinson, M. N.; Glorius, F. Angew. Chem. Int. Ed. 2017, 56, 902.
24. [24]
  Ma, Y.; Pang, Y.; Chabbra, S.; Reijerse, E. J.; Schnegg, A.; Niski, J.; Leutzsch, M.; Cornella, J. Chem. Eur. J. 2020, 26, 3738.
25. [25]
  Chen, K.; Cheung, M. S.; Lin, Z.; Li, P. Org. Chem. Front. 2016, 3, 875.
26. [26]
  Liu, W.; Yang, X.; Gao, Y.; Li, C.-J. J. Am. Chem. Soc. 2017, 139, 8621.
27. [27]
  Jin, S.; Dang, H. T.; Haug, G. C.; He, R.; Nguyen, V. D.; Nguyen, V. T.; Arman, H. D.; Schanze, K. S.; Larionov, O. V. J. Am. Chem. Soc. 2020, 142, 1603.
28. [28]
  Candish, L.; Teders, M.; Glorius, F. J. Am. Chem. Soc. 2017, 139, 7440.
29. [29]
  Cheng, W.-M.; Shang, R.; Zhao, B.; Xing, W.-L.; Fu, Y. Org. Lett. 2017, 19, 4291.
30. [30]
  Dai, P.-F.; Ning, X.-S.; Wang, H.; Cui, X.-C.; Liu, J.; Qu, J.-P.; Kang, Y.-B. Angew. Chem. Int. Ed. 2019, 58, 5392.
31. [31]
  Berger, F.; Plutschack, M. B.; Riegger, J.; Yu, W.; Speicher, S.; Ho, M.; Frank, N.; Ritter, T. Nature 2019, 567, 223.
32. [32]
  Huang, C.; Feng, J.; Ma, R.; Fang, S.; Lu, T.; Tang, W.; Du, D.; Gao, J. Org. Lett. 2019, 21, 9688.
33. [33]
  Zhang, J.; Wu, H.-H.; Zhang, J. Eur. J. Org. Chem. 2013, 2013, 6263.
34. [34]
  Hong, J.; Liu, Q.; Li, F.; Bai, G.; Liu, G.; Li, M.; Nayal, O. S.; Fu, X.; Mo, F. Chin. J. Chem. 2019, 37, 347.
35. [35]
  Chen, K.; Zhang, S.; He, P.; Li, P. Chem. Sci. 2016, 7, 3676.
36. [36]
  Mfuh, A. M.; Doyle, J. D.; Chhetri, B.; Arman, H. D.; Larionov, O. V. J. Am. Chem. Soc. 2016, 138, 2985.
37. [37]
  Mukai, K.; de Sant'Ana, D. P.; Hirooka, Y.; Mercado-Marin, E. V.; Stephens, D. E.; Kou, K. G. M.; Richter, S. C.; Kelley, N.; Sarpong, R. Nat. Chem. 2018, 10, 38.
38. [38]
  Zhang, L.; Jiao, L. J. Am. Chem. Soc. 2017, 139, 607.
39. [39]
  Zhang, L.; Jiao, L. Chem. Sci. 2018, 9, 2711.
40. [40]
  Pinet, S.; Liautard, V.; Debiais, M.; Pucheault, M. Synthesis 2017, 49, 4759.
41. [41]
  Hu, D.; Wang, L.; Li, P. Org. Lett. 2017, 19, 2770.
42. [42]
  Fawcett, A.; Pradeilles, J.; Wang, Y.; Mutsuga, T.; Myers, E. L.; Aggarwal, V. K. Science 2017, 357, 283.
43. [43]
  Wang, J.; Shang, M.; Lundberg, H.; Feu, K. S.; Hecker, S. J.; Qin, T.; Blackmond, D. G.; Baran, P. S. ACS Catal. 2018, 8, 9537.
44. [44]
  Wei, D.; Liu, T.-M.; Zhou, B.; Han, B. Org. Lett. 2020, 22, 234.
45. [45]
  (a) Wu, J.; He, L.; Noble, A.; Aggarwal, V. K. J. Am. Chem. Soc. 2018, 140, 10700; (b) Sandfort, F.; Strieth-Kalthoff, F.; Klauck, F. J. R.; James, M. J.; Glorius, F. Chem. Eur. J. 2018, 24, 17210.
46. [46]
  Hu, J.; Wang, G.; Li, S.; Shi, Z. Angew. Chem. Int. Ed. 2018, 57, 15227.
47. [47]
  Friese, F. W.; Studer, A. Angew. Chem. Int. Ed. 2019, 58, 9561.
48. [48]
  Wu, J.; Bär, R. M.; Guo, L.; Noble, A.; Aggarwal, V. K. Angew. Chem. Int. Ed. 2019, 58, 18830.
49. [49]
  Cheng, Y.; Mück-Lichtenfeld, C.; Studer, A. Angew. Chem. Int. Ed. 2018, 57, 16832.
50. [50]
  Liu, Q.; Hong, J.; Sun, B.; Bai, G.; Li, F.; Liu, G.; Yang, Y.; Mo, F. Org. Lett. 2019, 21, 6597.
51. [51]
  Zhang, L.; Wu, Z.-Q.; Jiao, L. Angew. Chem. Int. Ed. 2020, 59, 2095.
52. [52]
  Zhang, J.-J.; Duan, X.-H.; Wu, Y.; Yang, J.-C.; Guo, L.-N. Chem. Sci. 2019, 10, 161.
53. [53]
  Neeve, E. C.; Geier, S. J.; Mkhalid, I. A. I.; Westcott, S. A.; Marder, T. B. Chem. Rev. 2016, 116, 9091.
1. [1]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
2. [2]
  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
3. [3]
  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
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]
  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
6. [6]
  Yanan Liu , Yufei He , Dianqing Li . Preparation of Highly Dispersed LDHs-based Catalysts and Testing of Nitro Compound Reduction Performance: A Comprehensive Chemical Experiment for Research Transformation. University Chemistry, 2024, 39(8): 306-313. doi: 10.3866/PKU.DXHX202401081
7. [7]
  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
8. [8]
  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
9. [9]
  Shasha Liu , Yongmei Liu , Youqin Li , Juan Wang , Lisen Sun , Jinfen Zhang , Xiang Gao , Xingwen Sun . “Cognitive Experience-Strengthening Foundation-Frontier Innovation”: Construction and Practice of the Chemistry Experimental Curriculum System for Fudan University. University Chemistry, 2024, 39(7): 180-187. doi: 10.12461/PKU.DXHX202405095
10. [10]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
11. [11]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
12. [12]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
13. [13]
  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
14. [14]
  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
15. [15]
  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
16. [16]
  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
17. [17]
  Dan Li , Hui Xin , Xiaofeng Yi . Comprehensive Experimental Design on Ni-based Catalyst for Biofuel Production. University Chemistry, 2024, 39(8): 204-211. doi: 10.3866/PKU.DXHX202312046
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]
  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
20. [20]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079

Get Citation

PDF

XML

Metrics

PDF Downloads(310)
Abstract views(7418)
HTML views(2418)

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