Synlett
DOI: 10.1055/s-0043-1775465
letter
First-Row Transition-Metal Catalysis for Organic Synthesis

Modular Access to 1,3-Diboronates via Cu-Catalyzed Borylalkylation of Activated Alkenes

Quan-Hong Zhao
,
Xin-Yue Chai
,
Yanjie Yang
,
Zhuo Zhang
,
Yuan Huang  ∗

The authors are grateful for the financial support that was provided by the National Natural Science Foundation of China (Grant No. 22001203, 22471209), the Key Research and Development Projects of Shaanxi Province (Grant No. 2023-YBSF-186), the Youth Project of Basic Science Research Institute of Shaanxi Province (Grant No. 22JHQ013), the Fundamental Research Funds for the Central Universities (Grant No. xtr052024013, xyz2022023080), and the funds from Xi’an Jiaotong University (XJTU).
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Abstract

1,3-Bis-(boryl)alkanes are useful building blocks in organic synthesis, which enables a series of functionalizations to build up molecular complexity for the synthesis of target molecules. However, modular and practical synthesis of such building blocks remains a challenge. Herein, we report an efficient method for the synthesis of 1,3-diboronates via Cu-catalyzed borylalkylation of alkenes using iodomethyl boronate as the electrophile. This reaction provides a wide range of 1,3-bis-(boryl)alkanes in high efficiency under simple reaction conditions. Notably, this reaction exhibits high modularity, and large-scale reaction further demonstrated its practicability.

Key words

1,3-diboronates - borylalkylation - Cu catalysis - boron compounds - modular synthesis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1775465.
  • Supporting Information


Publication History

Received: 18 December 2024

Accepted after revision: 06 March 2025

Article published online:
17 July 2025

© 2025. Thieme. All rights reserved

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  • References

    • 2a Kabatas S, Agüi-Gonzalez P, Saal K.-A, Jähne S, Opazo F, Rizzoli SO, Phan NT. N. Angew. Chem. Int. Ed. 2019; 58: 3438
      Search in Google Scholar
    • 2b Wade CR, Broomsgrove AE. J, Aldridge S, Gabbaï FP. Chem. Rev. 2010; 110: 3958
      Search in Google Scholar
    • 2c Fu Y, Qiu F, Zhang F, Mai Y, Wang Y, Fu S, Tang R, Zhuang X, Feng X. Chem. Commun. 2015; 51: 5298
      Search in Google Scholar
    • 3a Grams RJ, Santos WL, Scorei IR, Abad-García A, Rosenblum CA, Bita A, Cerecetto H, Viñas C, Soriano-Ursúa MA. Chem. Rev. 2024; 124: 2441
      Search in Google Scholar
    • 3b Messner K, Vuong B, Tranmer GK. Pharmaceuticals 2022; 15: 264
      Search in Google Scholar
    • 3c Das BC, Thapa P, Karki R, Schinke C, Das S, Kambhampati S, Banerjee SK, Van Veldhuizen P, Verma A, Weiss LM, Evans T. Future Med. Chem. 2013; 5: 653
      Search in Google Scholar
    • 4a Endo K, Hirokami M, Shibata T. J. Org. Chem. 2010; 75: 3469
      Search in Google Scholar
    • 4b Coombs JR, Zhang L, Morken JP. Org. Lett. 2015; 17: 1708
      Search in Google Scholar
    • 4c Shi Y, Hoveyda AH. Angew. Chem. Int. Ed. 2016; 55: 3455
      Search in Google Scholar
    • 4d Crudden CM, Ziebenhaus C, Rygus JP. G, Ghozati K, Unsworth PJ, Nambo M, Voth S, Hutchinson M, Laberge VS, Maekawa Y, Imao D. Nat. Commun. 2016; 7: 11065
      Search in Google Scholar
    • 4e Ferris GE, Hong K, Roundtree IA, Morken JP. J. Am. Chem. Soc. 2013; 135: 2501
      Search in Google Scholar
    • 7a Fawcett A, Nitsch D, Ali M, Bateman JM, Myers EL, Aggarwal VK. Angew. Chem. Int. Ed. 2016; 55: 14663
      Search in Google Scholar
    • 7b Blair DJ, Tanini D, Bateman JM, Scott HK, Myers EL, Aggarwal VK. Chem. Sci. 2017; 8: 2898
      Search in Google Scholar
    • 7c Pujol A, Whiting A. J. Org. Chem. 2017; 82: 7265
      Search in Google Scholar
    • 7d Wang D, Mück-Lichtenfeld C, Studer A. J. Am. Chem. Soc. 2020; 142: 9119
      Search in Google Scholar
    • 7e Tan BB, Hu M, Ge S. Angew. Chem. Int. Ed. 2023; 62: e202307176
      Search in Google Scholar
  • 9 You C, Studer A. Angew. Chem. Int. Ed. 2020; 59: 17245
    Search in Google Scholar
  • 10 Sun S.-Z, Talavera L, Spieß P, Day CS, Martin R. Angew. Chem. Int. Ed. 2021; 60: 11740
    Search in Google Scholar

      • Selected reviews:
    • 11a Hemming D, Fritzemeier R, Westcott SA. Santos W. L, Steel PG. Chem. Soc. Rev. 2018; 47: 7477
      Search in Google Scholar
    • 11b Yang X, Kalita SJ, Maheshuni S, Huang YY. Coord. Chem. Rev. 2019; 392: 35
      Search in Google Scholar
    • 11c Whyte A, Torelli A, Mirabi B, Zhang A, Lautens M. ACS Catal. 2020; 10: 11578
      Search in Google Scholar
    • 11d Zhu Y.-S, Li J.-X, Zhao H.-T, Su B. Chin. J. Chem. 2024; 42: 3588
      Search in Google Scholar

      • Selected examples:
    • 11e Chen B, Cao P, Liao Y, Wang M, Liao J. Org. Lett. 2018; 20: 1346
      Search in Google Scholar
    • 11f Ito H, Kosaka Y, Nonoyama K, Sasaki Y, Sawamura M. Angew. Chem. Int. Ed. 2008; 47: 7424
      Search in Google Scholar
    • 11g Zhong C, Kunii S, Kosaka Y, Sawamura M, Ito H. J. Am. Chem. Soc. 2010; 132: 11440
      Search in Google Scholar
    • 11h Su W, Gong T.-J, Lu X, Xu M.-Y, Yu C.-G, Xu Z.-Y, Yu H.-Z, Xiao B, Fu Y. Angew. Chem. Int. Ed. 2015; 54: 12957
      Search in Google Scholar
  • 12 Larouche-Gauthier R, Elford TG. Aggarwal V. K. J. Am. Chem. Soc. 2011; 133: 16794
    Search in Google Scholar
  • 13 Armstrong RJ, Niwetmarin W, Aggarwal VK. Org. Lett. 2017; 19: 2762
    Search in Google Scholar