Download PDF
CC BY 4.0 · Synlett 2023; 34(18): 2117-2128
DOI: 10.1055/a-2111-9629
account
Modern Boron Chemistry: 60 Years of the Matteson Reaction

Recent Advances in Catalysis Using Organoborane-Mediated Hydride Abstraction

Joseph P. Gillions
a   School of Chemistry, University of Leicester, Leicester, LE1 7RH, UK
,
Salma A. Elsherbeni
b   Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK
,
Laura Winfrey
a   School of Chemistry, University of Leicester, Leicester, LE1 7RH, UK
,
Lei Yun
a   School of Chemistry, University of Leicester, Leicester, LE1 7RH, UK
,
Rebecca L. Melen∗
c   Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Translational Research Hub, Maindy Road, Cathays, Cardiff, CF24 4HQ, UK
,
Louis C. Morrill∗
b   Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK
,
Alexander P. Pulis∗
a   School of Chemistry, University of Leicester, Leicester, LE1 7RH, UK
› Author AffiliationsA.P.P. thanks the Engineering and Physical Sciences Research Council (EPSRC) for funding (EP/W02151X/1 and EP/Y00146X/1). R.L.M. would like to thank the EPSRC for a research fellowship (EP/R026912/1). J.P.G., L.W., L.Y. and A.P.P. thank the University of Leicester for generous support. L.Y. thanks the China Scholarship Council for funding. S.A.E., R.L.M. and L.C.M. gratefully acknowledge the School of Chemistry, Cardiff University for generous support. S.A.E. thanks the British Council and the Egyptian Cultural Affairs and Missions Sector for a Ph.D. studentship through the Newton-Mosharafa Fund.
› Further Information
   Permissions and Reprints All articles of this category


Dedicated to 60 years of Donald Matteson’s boron homologation

Abstract

C–H functionalization is widely regarded as an important area in the development of synthetic methodology, enabling the design of more time- and atom-efficient syntheses. The ability of electron-deficient organoboranes to mediate hydride abstraction from α-amino C–H bonds is therefore of great interest, as the reactive iminium and hydridoborate moieties generated are able to participate in a range of synthetically useful transformations. In this review, we cover the recent advances made in organoborane-mediated hydride abstraction, and focus on the catalytic applications of electron-deficient boranes in α- or β-functionalization, α,β-difunctionalization, and the dehydrogenation of amines.

1 Introduction

2 α-Functionalization of Amines

3 β-Functionalization of Amines

4 α,β-Difunctionalization of Amines

5 Dehydrogenation of Amines

6 Summary and Future Prospects

Key words

boron - hydride abstraction - amines - iminium - functionalization


Publication History

Received: 31 May 2023

Accepted after revision: 14 June 2023

Accepted Manuscript online:
16 June 2023

Article published online:
04 September 2023

© 2023. This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References and Notes

  • 1 Seyden-Penne J. In Reductions by the Alumino- and Borohydrides in Organic Synthesis. Curran D. Wiley-VCH; New York: 1997: 5
    Google Scholar
  • 2 Sun H.-Y, Hall DG. In Synthesis and Application of Organoboron Compounds . Fernández E, Whiting A. Springer International Publishing; Switzerland: 2015: 221
    CrossrefGoogle Scholar
  • 3 Graham BJ, Raines RT. J. Org. Chem. 2022; in press; DOI DOI: 10.1021/acs.joc.2c01695.
    CrossrefPubMed
  • 4 Ji X, Liu L. Eur. J. Org. Chem. 2022; e202200853
    Crossref
  • 5 Tan X, Wang H. Chem. Soc. Rev. 2022; 51: 2583
    CrossrefPubMed
  • 6 Basak S, Winfrey L, Kustiana BA, Melen RL, Morrill LC, Pulis AP. Chem. Soc. Rev. 2021; 50: 3720
    CrossrefPubMed
  • 7 Ma Y, Loub S.-J, Hou Z. Chem. Soc. Rev. 2021; 50: 1945
    CrossrefPubMed
  • 8 Kumar G, Roy S, Chatterjee I. Org. Biomol. Chem. 2021; 19: 1230
    CrossrefPubMed
  • 9 Walker JC. L, Oestreich M. Synlett 2019; 30: 2216
    Article in Thieme Connect
  • 10 Keess S, Oestreich M. Chem. Sci. 2017; 8: 4688
    CrossrefPubMed
  • 11 Oestreich M. Angew. Chem. Int. Ed. 2016; 55: 494
    CrossrefPubMed
  • 12 Li L, Yang X. Chin. J. Org. Chem. 2023; 43: 1036
    Crossref
  • 13 Webb JD, Laberge VS, Geier SJ, Stephan DW, Crudden CM. Chem. Eur. J. 2010; 16: 4895
    CrossrefPubMed
  • 14 Wilkins LC, Santi N, Luk LY. P, Melen RL. Phil. Trans. R. Soc. A 2017; 375: 20170009
    CrossrefPubMed

      • Organoborane-catalyzed processes that do not include direct hydride abstraction from C–H to B–H, such as pericyclic 1,n-hydride shifts, are beyond the scope of this review. For examples, see:
    • 15a Zhou R, Paradies J. Eur. J. Org. Chem. 2021; 6334
      Crossref
    • 15b Zhang B.-B, Peng S, Wang F, Lu C, Nie J, Chen Z, Yang G, Ma C. Chem. Sci. 2022; 13: 775
      CrossrefPubMed
    • 15c Wang J, Zhou H, Wei J, Liu F, Wang T. Chem. Commun. 2022; 58: 6910
      CrossrefPubMed
    • 15d Wicker G, Schoch R, Paradies J. Org. Lett. 2021; 23: 3626
      CrossrefPubMed
  • 16 Borane-mediated α-O C(sp3)–H hydride abstraction has been proposed, see: Liang X.-S, Li R.-D, Sun W, Zhong L, Wang X.-C. ACS Catal. 2022; 12: 9153
    CrossrefPubMed
  • 17 Borane-mediated NH hydride abstraction has been proposed, see: Dipika, Sharma YB, Pant S, Dhaked DK, Guru MM. Org. Chem. Front. 2022; 9: 3428
    CrossrefPubMed
  • 18 Chan JZ, Yesilcimen A, Cao M, Zhang Y, Zhang B, Wasa M. J. Am. Chem. Soc. 2020; 142: 16493
    CrossrefPubMed
  • 19 Tian J.-J, Sun W, Li R.-R, Tian G.-X, Wang X.-C. Angew. Chem. Int. Ed. 2022; 61: e202208427
    CrossrefPubMed
  • 20 Zhang Z.-Y, Ren J, Zhang M, Xu X.-F, Wang X.-C. Chin. J. Chem. 2021; 39: 1641
    CrossrefPubMed
  • 21 Zhang Z.-Y, Liu Z.-Y, Guo R.-T, Zhao Y.-Q, Li X, Wang X.-C. Angew. Chem. Int. Ed. 2017; 56: 4028
    CrossrefPubMed
  • 22 Klose I, Di Mauro G, Kaldre D, Maulide N. Nat. Chem. 2022; 14: 1306
    CrossrefPubMed
  • 23 Chen Y, Wan H.-L, Huang Y, Liu S, Wang F, Lu C, Nie J, Chen Z, Yang G, Ma C. Org. Lett. 2020; 22: 7797
    CrossrefPubMed
  • 24 Chang Y, Cao M, Chan JZ, Zhao C, Wang Y, Yang R, Wasa M. J. Am. Chem. Soc. 2021; 143: 2441
    CrossrefPubMed
  • 25 Fang H, Xie K, Kemper S, Oestreich M. Angew. Chem. Int. Ed. 2021; 60: 8542
    CrossrefPubMed
  • 26 Zou C.-P, Ma T, Qiao X.-X, Wu X.-X, Li G, He Y, Zhao X.-J. Org. Biomol. Chem. 2023; 21: 4393
    CrossrefPubMed
  • 27 Zhang M, Wang X.-C. Angew. Chem. Int. Ed. 2021; 60: 17185
    CrossrefPubMed
  • 28 He Y, Liu Q, Du Z, Xu Y, Cao L, Zhang X, Fan X. J. Org. Chem. 2022; 87: 14840
    CrossrefPubMed
  • 29 Organoborane-mediated α-N hydride abstraction may also be invoked at one point in the mechanism proposed in: Zhang S, Xu H, He J, Zhang Y. Adv. Synth. Cat. 2021; 363: 5319
    CrossrefPubMed
  • 30 Hashimoto T, Asada T, Ogoshi S, Hoshimoto Y. Sci. Adv. 2022; 8: eade0189
    CrossrefPubMed
  • 31 Stephan D. J. Am. Chem. Soc. 2021; 143: 20002
    CrossrefPubMed