CC BY-NC-ND 4.0 · SynOpen 2020; 04(04): 116-122
DOI: 10.1055/s-0040-1705980
paper

Ammonia–Borane-Mediated Reduction of Nitroalkenes

Chiara Faverio
,
Monica Fiorenza Boselli
,
Laura Raimondi
,
M.B. thanks MIUR for funding through project PRIN 2017 ‘NATURECHEM’. M.B. thanks Università degli Studi di Milano for the PSR 2019-financed project ‘Catalytic Strategies for the Synthesis of High Added-Value Molecules from Bio-Based Starting Materials’. M.B. thanks the ITN-EID project Marie Sklodowska-Curie Actions Innovative Training Network - TECHNOTRAIN H2020-MSCA-ITN-2018 Grant Agreement 812944. www.technotrain-ITN.eu.


Abstract

Ammonia borane (AB) has been successfully employed in the reduction of nitroalkenes. A variety of nitrostyrenes and alkyl-substituted­ nitroalkenes were chemoselectively reduced to the corresponding nitroalkanes, in short reaction time, with an atom-economic, simple experimental procedure that also works with α- and β-substituted nitroolefins.

Supporting Information



Publication History

Received: 21 September 2020

Accepted after revision: 09 October 2020

Publication Date:
25 November 2020 (online)

© 2020. This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-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-nc-nd/4.0/)

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  • References

  • 1 Kumar R, Karkamar A, Bowden M, Autrey T. Chem. Soc. Rev. 2019; 48: 5350
    • 2a Staubitz A, Robertson AP. M, Sloan ME, Manners I. Chem. Rev. 2010; 110: 4023
    • 2b Alpaydin CY, Gulbay SK, Colpan CO. Int. J. Hydrogen Energy 2020; 45: 3414
  • 3 Ramachandran PV, Kulkarnia AS. Int. J. Hydrogen Energy 2017; 42: 1451
    • 4a Bhunya S, Malakar T, Ganguly G, Paul A. ACS Catal. 2016; 6: 7907
    • 4b Han D, Anke F, Trose M, Breweries T. Coord. Chem. Rev. 2019; 380: 260
    • 4c Colebatch AL, Weller AS. Chem. Eur. J. 2019; 25: 1379
    • 5a Rossin A, Peruzzini M. Chem. Rev. 2016; 116: 8848
    • 5b Boom DH. A, Jupp AR, Slootweg JC. Chem. Eur. J. 2019; 25: 9133
    • 5c Melen RL. Chem. Soc. Rev. 2016; 45: 775
  • 6 Yang X, Fox T, Berke H. Chem. Commun. 2011; 47: 2053
  • 7 Chong CC, Rao B, Kinjo K. ACS Catal. 2017; 7: 5814
  • 8 The formation of the dimer 3a,b is due to the attack of a molecule of reduced nitroalkane on to a molecule of unreacted nitroalkene still present in solution. The two diastereoisomers are always formed as a 1:1 mixture.
  • 9 After chromatographic purification, the product was isolated in 63% yield; unreacted starting material (10%), the dimeric adduct (18%) and unidentified decomposition products were also obtained.
  • 10 Preliminary studies using (thio)urea derivatives of cinchona alkaloid derivatives afforded product 21 in good yields and up to 21% e.e. Further studies and the use of new, ‘ad hoc’ designed chiral catalysts are necessary to improve the enantioselectivity of the process, and studies are under way in our group.
  • 11 Yang X, Fox T, Berke H. Org. Biomol. Chem. 2012; 10: 852
  • 12 When the reduction to produce 2 and 22 was performed in CD3OD, in both cases the formation of the α,α-bisdeuterated nitroalkane was detected (see NMR spectra in the Supporting Information). However, these preliminary studies with deuterated solvents or reagents were not conclusive; the use of a protic solvent, such as methanol, and the acidity of the protons in a position of the nitroalkane make possible different scenarios for the protonation step and more carefully designed studies are needed to clarify the mechanistic details.
  • 13 Vojáčková P, Chalupa D, Prieboj J, Nečas J, Švenda J. Org. Lett. 2018; 20: 7085
  • 14 Dong X, Teng H, Wang C. Org. Lett. 2009; 11: 1265
  • 15 Marčeková M, Gerža P, Šoral M, Moncol J, Berkeš D, Kolarovič A, Jakubec P. Org. Lett. 2019; 21: 4580
  • 16 Mahesh S, Adebomi V, Muneeswaran ZP, Raj M. Angew. Chem. Int. Ed. 2020; 59: 2793
  • 17 Rezazadeh S, Devannah V, Watson DA. J. Am. Chem. Soc. 2017; 139: 8110
  • 18 Cai S, Zhang S, Zhao Y, Wang DZ. Org. Lett. 2013; 15: 2660
  • 19 Xianga J, Sunb E, Liana C, Yuana W, Zhua J, Wanga Q, Deng J. Tetrahedron 2012; 68: 4609
  • 20 Wangand J, Evano G. Org. Lett. 2016; 18: 3542
  • 21 McNamara YM, Cloonan SM, Knox AJ. S, Keating JJ, Butler SG, Peters GH, Meegan MJ, Williams DC. Bioorg. Med. Chem. 2011; 19: 1328
  • 22 Cai S, Zhao X, Wang X, Liu Q, Li Z, Wang DZ. Angew. Chem. Int. Ed. 2012; 51: 8050
  • 23 Zhang Z, Schreiner PR. Synthesis 2007; 2559
  • 24 Chandrasekhar S, Shrinidhi A. Synth. Commun. 2014; 44: 3008
  • 25 Matsubara R, Kim H, Sakaguchi T, Xie W, Zhao X, Nagoshi Y, Wang C, Tateiwa M, Ando A, Hayashi M, Yamanaka MTsuneda T. Org. Lett. 2020; 22: 1182
  • 26 Padilla-Salinas R, Walvoord RR, Tcyrulnikov S, Kozlowski MC. Org. Lett. 2013; 15: 3966
  • 27 Hostmann T, Molloy JJ, Bussmann K, Gilmour R. Org. Lett. 2019; 21: 10164