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

  • 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.
  • 加载中
    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.

  • 加载中
    1. [1]

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

    2. [2]

      Xinxin Wu . 基础有机化学教学中自由基重排反应的课程设计及其课程思政元素的融入. University Chemistry, 2025, 40(6): 316-325. doi: 10.12461/PKU.DXHX202408055

    3. [3]

      Tongyan Yu Pan Xu . Visible-Light Photocatalyzed Radical Rearrangement Reaction. University Chemistry, 2025, 40(7): 169-176. doi: 10.12461/PKU.DXHX202409070

    4. [4]

      Yuanyuan Ping Wangqing Kong . 光催化碳氢键官能团化合成1-苯基-1,2-乙二醇. University Chemistry, 2025, 40(6): 238-247. doi: 10.12461/PKU.DXHX202408092

    5. [5]

      Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018

    6. [6]

      Min LIUHuapeng RUANZhongtao FENGXue DONGHaiyan CUIXinping WANG . Neutral boron-containing radical dimers. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 123-130. doi: 10.11862/CJIC.20240362

    7. [7]

      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

    8. [8]

      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

    9. [9]

      Dan Liu . 可见光-有机小分子协同催化的不对称自由基反应研究进展. University Chemistry, 2025, 40(6): 118-128. doi: 10.12461/PKU.DXHX202408101

    10. [10]

      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

    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]

      CCS Chemistry | 超分子活化底物自由基促进高效选择性光催化氧化

      . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.

    13. [13]

      Yuan GAOYiming LIUChunhui WANGZhe HANChaoyue FANJie 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

    14. [14]

      Nan Xiao Fang Sun . 二芳基硫醚化合物的构建及应用. University Chemistry, 2025, 40(6): 360-363. doi: 10.12461/PKU.DXHX202407099

    15. [15]

      Lili Jiang Shaoyu Zheng Xuejiao Liu Xiaomin Xie . Copper-Catalyzed Oxidative Coupling Reactions for the Synthesis of Aryl Sulfones: A Fundamental and Exploratory Experiment for Undergraduate Teaching. University Chemistry, 2025, 40(7): 267-276. doi: 10.12461/PKU.DXHX202408004

    16. [16]

      Lina Feng Guoyu Jiang Xiaoxia Jian Jianguo Wang . Application of Organic Radical Materials in Biomedicine. University Chemistry, 2025, 40(4): 253-260. doi: 10.12461/PKU.DXHX202405171

    17. [17]

      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

    18. [18]

      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

    19. [19]

      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

    20. [20]

      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

Metrics
  • PDF Downloads(357)
  • Abstract views(10333)
  • HTML views(3148)

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

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索
Address:Zhongguancun North First Street 2,100190 Beijing, PR China Tel: +86-010-82449177-888
Powered By info@rhhz.net

/

DownLoad:  Full-Size Img  PowerPoint
Return