Synlett 2021; 32(09): 845-850
DOI: 10.1055/a-1344-1904
synpacts

Ligand-Driven Advances in Iridium-Catalyzed sp3 C–H Borylation: 2,2′-Dipyridylarylmethane

Margaret R. Jones
,
Funding from Vanderbilt University is gratefully acknowledged. This material is based upon work supported by the National Science Foundation Division of Chemistry under grant no. CHE-1847813. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research.


Abstract

The field of catalytic C–H borylation has grown considerably since its founding, providing a means for the preparation of synthetically versatile organoborane products. Although sp2 C–H borylation methods have found widespread and practical use in organic synthesis, the analogous sp3 C–H borylation reaction remains challenging and has seen limited application. Existing catalysts are often hindered by incomplete consumption of the diboron reagent, poor functional-group tolerance, harsh reaction conditions, and the need for excess or neat substrate. These challenges acutely affect the C–H borylation chemistry of unactivated hydrocarbon substrates, which has lagged in comparison to methods for the C–H borylation of activated compounds. Herein, we discuss recent advances in the sp3 C–H borylation of undirected substrates in the context of two particular challenges: (1) utilization of the diboron reagent and (2) the need for excess or neat substrate. Our recent work on the application of dipyridylarylmethane ligands in sp3 C–H borylation has allowed us to make contributions in this space and has presented an additional ligand scaffold to supplement traditional phenanthroline ligands.



Publication History

Received: 04 December 2020

Accepted after revision: 30 December 2020

Publication Date:
30 December 2020 (online)

© 2020. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References

  • 1 Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
  • 2 Hartwig JF. Acc. Chem. Res. 2012; 45: 864
  • 3 Ros A, Fernández R, Lassaletta JM. Chem. Soc. Rev. 2014; 43: 3229
  • 4 Xu L, Wang G, Zhang S, Wang H, Wang L, Liu L, Jiao J, Li P. Tetrahedron 2017; 73: 7123
  • 5 Kuroda Y, Nakao Y. Chem. Lett. 2019; 48: 1092
  • 6 Crabtree RH. Chem. Rev. 1985; 85: 245
  • 7 Chen H, Schlecht S, Semple TC, Hartwig JF. Science 2000; 287: 1995
  • 8 Janowicz AH, Bergman RG. J. Am. Chem. Soc. 1982; 104: 352
  • 9 Janowicz AH, Bergman RG. J. Am. Chem. Soc. 1983; 105: 3929
  • 10 Waltz KM, Hartwig JF. Science 1997; 277: 211
  • 11 Kawamura K, Hartwig JF. J. Am. Chem. Soc. 2001; 123: 8422
  • 12 Chen H, Hartwig JF. Angew. Chem. Int. Ed. 1999; 38: 3391
  • 13 Liskey CW, Hartwig JF. J. Am. Chem. Soc. 2012; 134: 12422
  • 14 Li Q, Liskey CW, Hartwig JF. J. Am. Chem. Soc. 2014; 136: 8755
  • 15 Jones MR, Fast CD, Schley ND. J. Am. Chem. Soc. 2020; 142: 6488
  • 16 Larsen MA, Oeschger RJ, Hartwig JF. ACS Catal. 2020; 10: 3415
  • 17 Oeschger RJ, Larsen MA, Bismuto A, Hartwig JF. J. Am. Chem. Soc. 2019; 141: 16479
  • 18 Oeschger R, Su B, Yu I, Ehinger C, Romero E, He S, Hartwig J. Science 2020; 368: 736
  • 19 Boller TM, Murphy JM, Hapke M, Ishiyama T, Miyaura N, Hartwig JF. J. Am. Chem. Soc. 2005; 127: 14263
  • 20 Liskey CW, Wei CS, Pahls DR, Hartwig JF. Chem. Commun. 2009; 5603
  • 21 Tamura H, Yamazaki H, Sato H, Sakaki S. J. Am. Chem. Soc. 2003; 125: 16114
  • 22 Jover J, Maseras F. Organometallics 2016; 35: 3221
  • 23 Ahn S, Sorsche D, Berritt S, Gau MR, Mindiola DJ, Baik M.-H. ACS Catal. 2018; 8: 10021
  • 24 Zhong R.-L, Sakaki S. J. Am. Chem. Soc. 2019; 141: 9854
  • 25 Webster CE, Fan Y, Hall MB, Kunz D, Hartwig JF. J. Am. Chem. Soc. 2003; 125: 858
  • 26 Iverson CN, Smith MR. J. Am. Chem. Soc. 1999; 121: 7696
  • 27 Ohmura T, Torigoe T, Suginome M. Organometallics 2013; 32: 6170
  • 28 Liskey CW, Hartwig JF. J. Am. Chem. Soc. 2013; 135: 3375
  • 29 Shi Y, Gao Q, Xu S. J. Am. Chem. Soc. 2019; 141: 10599
  • 30 Ohmura T, Torigoe T, Suginome M. J. Am. Chem. Soc. 2012; 134: 17416
  • 31 Yamamoto T, Ishibashi A, Suginome M. Org. Lett. 2019; 21: 6235
  • 32 Cho SH, Hartwig JF. J. Am. Chem. Soc. 2013; 135: 8157
  • 33 Kawamorita S, Murakami R, Iwai T, Sawamura M. J. Am. Chem. Soc. 2013; 135: 2947
  • 34 Mita T, Ikeda Y, Michigami K, Sato Y. Chem. Commun. 2013; 49: 5601
  • 35 Reyes RL, Iwai T, Maeda S, Sawamura M. J. Am. Chem. Soc. 2019; 141: 6817
  • 36 Lawrence JD, Takahashi M, Bae C, Hartwig JF. J. Am. Chem. Soc. 2004; 126: 15334