Synlett 2022; 33(20): 1961-1967
DOI: 10.1055/a-1890-8375
synpacts

Transition-Metal-Catalyzed Regioselective C–H Borylation of ­Pyridines

Qianlin Sun
,
Yuncong Luo
,
Xin Xu
We are grateful for the financial support provided by the National Natural Science Foundation of China (21871204).


Abstract

The C–H borylation strategy has spurred intense research endeavors due to the high atom- and step-economy it represents and because of the broad range of utilities of the resulting organoboranes. Nevertheless, this powerful transformation has had limited substrate scope and poor regioselectivity when it was applied to Lewis basic substrates (e.g., azines). The basic functionalities in substrates can coordinate to the metal centers, hindering the formation of products. Herein, we provide a brief overview of recent advances in transition-metal-­catalyzed regioselective C–H borylation of pyridines. Attention is paid to the latest contributions, which have demonstrated remarkable ­regioselectivity.

1 Introduction

2 para-Selective C−H Borylation

3 meta-Selective C−H Borylation

4 ortho-Selective C−H Borylation

5 Summary



Publication History

Received: 15 June 2022

Accepted after revision: 03 July 2022

Accepted Manuscript online:
03 July 2022

Article published online:
29 July 2022

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  • References

  • 1 Hall DG. In Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials. Hall DG. John Wiley & Sons; Weinheim: 2006
  • 2 Wang M, Shi Z. Chem. Rev. 2020; 120: 7348
    • 3a Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
    • 3b Iwai T, Sawamura M. ACS Catal. 2015; 5: 5031
    • 3c Xu L, Wang G, Zhang S, Wang H, Wang L, Liu L, Jiao J, Li P. Tetrahedron 2017; 73: 7123
    • 3d Haldar C, Hoque ME, Bisht R, Chattopadhyay B. Tetrahedron Lett. 2018; 59: 1269
    • 4a Wright JS, Scott PJ. H, Steel PG. Angew. Chem. Int. Ed. 2021; 60: 2796
    • 4b Haldar C, Hoque ME, Chaturvedi J, Hassan MM. M, Chattopadhyay B. Chem. Commun. 2021; 57: 13059
  • 5 Bisht R, Haldar C, Hassan MM. M, Hoque ME, Chaturvedi J, Chattopadhyay B. Chem. Soc. Rev. 2022; 51: 5042
    • 6a Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 390
    • 6b Tagata T, Nishida M. Adv. Synth. Catal. 2004; 346: 1655
    • 6c Boller TM, Murphy JM, Hapke M, Ishiyama T, Miyaura N, Hartwig JF. J. Am. Chem. Soc. 2005; 127: 14263
    • 6d Murphy JM, Liao X, Hartwig JF. J. Am. Chem. Soc. 2007; 129: 15434
    • 6e Boebel TA, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 7534
    • 6f Hurst TE, Macklin TK, Becker M, Hartmann E, Kügel W, Parisienne-La Salle J.-C, Batsanov AS, Marder TB, Snieckus V. Chem. Eur. J. 2010; 16: 8155
    • 6g Tajuddin H, Harrisson P, Bitterlich B, Collings JC, Sim N, Batsanov AS, Cheung MS, Kawamorita S, Maxwell AC, Shukla L, Morris J, Lin Z, Marder TB, Steel PG. Chem. Sci. 2012; 3: 3505
    • 6h Hoque ME, Bisht R, Haldar C, Chattopadhyay B. J. Am. Chem. Soc. 2017; 139: 7745
    • 6i Bisht R, Hoque ME, Chattopadhyay B. Angew. Chem. Int. Ed. 2018; 57: 15762
    • 6j Hassan MM. M, Hoque ME, Dey S, Guria S, Roy B, Chattopadhyay B. Synthesis 2021; 53: 3333
    • 6k Chaturvedi J, Haldar C, Bisht R, Pandey G, Chattopadhyay B. J. Am. Chem. Soc. 2021; 143: 7604
    • 6l Hoque ME, Hassan MM. M, Chattopadhyay B. J. Am. Chem. Soc. 2021; 143: 5022
    • 6m Hassan MM. M, Mondal B, Singh S, Haldar C, Chaturvedi J, Bisht R, Sunoj RB, Chattopadhyay B. J. Org. Chem. 2022; 87: 4360
    • 6n Shahzadi HT, Fatima S, Akhter N, Alazmi M, Nawaf A, Said KB, AlGhadhban A, Sulieman AM. E, Saleem RS. Z, Chotana GA. ACS Omega 2022; 7: 11460
    • 6o Hoque ME, Bisht R, Unnikrishnan A, Dey S, Hassan MM. M, Guria S, Rai RN, Sunoj RB, Chattopadhyay B. Angew. Chem. Int. Ed. 2022; 61: e202203539
  • 7 Fischer DF, Sarpong R. J. Am. Chem. Soc. 2010; 132: 5926
  • 8 Balasubramanian M, Keay JG. In Comprehensive Heterocyclic Chemistry II. Katritzky AR, Rees CW, Scriven EF. V. Elsevier; Oxford: 1996
  • 9 Larsen MA, Hartwig JF. J. Am. Chem. Soc. 2014; 136: 4287
  • 10 González-Bello C, Castedo L. In Modern Heterocyclic Chemistry. Alvarez-Builla J, Vaquero JJ, Barluenga J. John Wiley & Sons; Weinheim: 2011
  • 11 Cho J.-Y, Tse MK, Holmes D, Maleczka RE, , Jr.; Smith MR. Science 2002; 295: 305
  • 12 Takagi J, Sato K, Hartwig JF, Ishiyama T, Miyaura N. Tetrahedron Lett. 2002; 43: 5649
  • 13 Mkhalid IA. I, Coventry DN, Albesa-Jove D, Batsanov AS, Howard JA. K, Perutz RN, Marder TB. Angew. Chem. Int. Ed. 2006; 45: 489
  • 14 Obligacion JV, Semproni SP, Chirik PJ. J. Am. Chem. Soc. 2014; 136: 4133
  • 15 Sadler SA, Tajuddin H, Mkhalid IA. I, Batsanov AS, Albesa-Jove D, Cheung MS, Maxwell AC, Shukla L, Roberts B, Blakemore DC, Lin Z, Marder TB, Steel PG. Org. Biomol. Chem. 2014; 12: 7318
  • 16 Murakami K, Yamada S, Kaneda T, Itami K. Chem. Rev. 2017; 117: 9302
    • 17a Yamaguchi J, Yamaguchi AD, Itami K. Angew. Chem. Int. Ed. 2012; 51: 8960
    • 17b Wencel-Delord J, Glorius F. Nat. Chem. 2013; 5: 369
    • 17c Segawa Y, Maekawa T, Itami K. Angew. Chem. Int. Ed. 2015; 54: 66
  • 18 Yang L, Semba K, Nakao Y. Angew. Chem. Int. Ed. 2017; 56: 4853

    • For TM–LA bifunctional catalysis for regioselective C–H functionalization reactions, see:
    • 19a Tsai C.-C, Shih W.-C, Fang C.-H, Li C.-Y, Ong T.-G, Yap GP. A. J. Am. Chem. Soc. 2010; 132: 11887
    • 19b Zhang Z, Tanaka K, Yu J.-Q. Nature 2017; 543: 538
    • 19c Nakamura T, Suzuki K, Yamashita M. J. Am. Chem. Soc. 2017; 139: 17763
  • 20 Yang L, Uemura N, Nakao Y. J. Am. Chem. Soc. 2019; 141: 7972
    • 21a Della Ca’ N, Fontana M, Motti E, Catellani M. Acc. Chem. Res. 2016; 49: 1389
    • 21b Davies DL, Macgregor SA, McMullin CL. Chem. Rev. 2017; 117: 8649
    • 21c Lichosyt D, Zhang Y, Hurej K, Dydio P. Nat. Catal. 2019; 2: 114
  • 22 Trouvé J, Zardi P, Al-Shehimy S, Roisnel T, Gramage-Doria R. Angew. Chem. Int. Ed. 2021; 60: 18006
    • 23a Campeau L.-C, Rousseaux S, Fagnou K. J. Am. Chem. Soc. 2005; 127: 18020
    • 23b Dick GR, Woerly EM, Burke MD. Angew. Chem. Int. Ed. 2012; 51: 2667
    • 23c Cook XA. F, de Gombert A, McKnight J, Pantaine LR. E, Willis MC. Angew. Chem. Int. Ed. 2021; 60: 11068
  • 24 Kim JH, Constantin T, Simonetti M, Llaveria J, Sheikh NS, Leonori D. Nature 2021; 595: 677
  • 25 Xu P, Xu X. Organometallics 2019; 38: 3212
  • 26 Luo Y, Jiang S, Xu X. Angew. Chem. Int. Ed. 2022; 61: e202117750
  • 27 Dudnik AS, Weidner VL, Motta A, Delferro M, Marks TJ. Nat. Chem. 2014; 6: 1100