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DOI: 10.1055/s-0029-1217223
Bromonitromethane: A Versatile Reagent in Organic Synthesis
Dedicated to my dear research advisor Professor Ming Yan.
Publikationsverlauf
Publikationsdatum:
02. Juni 2009 (online)
Biographical Sketches
![](https://www.thieme-connect.de/media/synlett/200910/v288_zhang.jpg)
Introduction
Bromonitromethane (BrCH2NO2) has received considerable attention as a one-carbon synthon for the synthesis of a variety of important organic intermediates. [¹] For examples, it was used in the synthesis of 2-nitrobenzofuran and 2-nitro-2,3-dihydrobenzofuran-3-ols, [²] nitrobenzothio-phenes, and nitrothiazoles, [³] polyfunctionalized nitrocyclopropanes. [4] It has also been utilized in the synthesis of 1-bromo-1-nitroalkan-2-ols [5] and aryl nitromethanes. In addition, it could be used as a bromine donor. [6]
Bromonitromethane is commercially available and can also be easily prepared according to the procedures reported by Fishwick et al. (Scheme [¹] ). [³] A typical procedure is as following: freshly distilled nitromethane was stirred at 0 ˚C and bromine was dropped in 5 seconds. The resulted bromonitromethane could be used without further purification. [¹a]
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Scheme 1
Abstracts
(A) 2-Nitrobenzo[b]furans 4 are prepared by reacting 2-hydroxybenz-aldehydes 1 and bromonitromethane 2 at low temperature. The intermediate 3 is then quantitatively dehydrated by heating in acetic anhydride to provide 4 in good yields. [²] |
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(B) Fishwick and co-workers described the preparation of 3-amino-2-nitrobenzo[b]thiophene (a) starting from 2-sulfanylbenzonitrile and bromonitromethane. [³] Several 3-amino-2-nitrothiophenes were prepared starting from the sodium salt of disubstituted 3-sulfanyl-2-propenenitriles and bromonitromethane. [³] The compounds b were obtained in the yields ranging from 30% to 70%. In another paper, thiophene c was synthesized by Gewald and Hain, starting from disubstituted β-chloroacrylonitrile, sodium sulfide and bromonitromethane. [7] The formation of 5-phenyl-3-amino-2-nitroselenophene (d) was also observed. |
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(C) Recently, Kirsch and co-workers described a one-pot procedure to prepare new 2-aryl-5-nitrothiophenes efficiently from bromonitromethane and 3-chloro-3-aryl-propenals, [¹a] and to prepare substituted 3-amino-2-nitrothiophenes and selenophenes from β-chloroacrylonitriles and bromonitromethane. [¹b] |
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(D) Shen and co-workers described a reaction of aldehydes and bromonitromethane in the presence of tri-n-butylarsine. The reaction provided substituted 1-bromo-1-nitroalkenes in good yields. [8] |
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(E) Concellón and co-workers described an efficient synthesis of 1-bromo-1-nitroalkan-2-ols. The reaction of bromonitromethane and a variety of aldehydes was catalyzed by NaI under mild conditions. While chiral N,N-dibenzyl alaninal was used, the corresponding (1S,2S,3S)-3-dibenzylamino-1-bromo-1-nitrobutan-2-ol was obtained with excellent stereoselectivity. [5] In addition they also reported a samarium-promoted synthesis of (E)-nitroalkenes from 1-bromo-1-nitroalkan-2-ols in good yields. [9] |
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(F) Alcaide and co-workers reported a coupling reaction of azetidine-2,3-diones (α-oxo-β-lactams) and bromonitromethane in aqueous media and in the presence of catalytic amounts of sodium azide. The stereoselectivity of the process was generally good and reasonable anti/syn ratios were achieved by substrate control. Based on the reaction, a simple and efficient synthesis of the potentially bioactive 3-substituted 3-hydroxy-β-lactam moiety has been developed. 2-Azetidinone-tethered 1-halo-1-nitroalkan-2-ols are highly useful building blocks. For example, they can be converted into spiro and fused bicyclic-β-lactams. [¹0] |
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(G) Nitrocyclopropane has been successfully prepared by the reaction of bromonitromethane, potassium carbonate and electrophilic alkenes bearing electron-withdrawing groups both in the α- and β-positions. The method provided good yields and moderate to good diastereoselectivity for linear alkenes. The exo-products were exclusively formed for N-alkylmaleimides. [4b] |
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(H) Ley and co-workers reported the first organocatalytic enantioselective nitrocyclopropanation of 2-cyclohexen-1-one and bromonitro-methane with good yields and enantioselectivities. 5-(Pyrrolidin-2-yl)-1H-tetrazole was used as the efficient catalyst. [¹¹ ] Recently, the same group developed a general organocatalytic synthesis of chiral nitrocyclopropanes from bromonitromethane and a variety of cyclic and acyclic enones. [¹²] Wang and co-workers reported the same reaction catalyzed by chiral primary amines. Good yields and excellent enantioselectivities were achieved. [¹³] Very recently, Yan and co-workers reported an efficient synthesis of chiral 4-bromo-4-nitroketones via the asymmetric conjugate addition of bromonitromethane to alkyl vinyl ketones. [¹4] |
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(I) Córdova and co-workers described a novel organocatalytic nitrocyclopropanation of α,β-unsaturated aldehydes with bromonitromethane. 1-Nitro-2-formylcyclopropanes were obtained in good yields and with excellent enantioselectivities. [¹5] Recently, Yan and co-workers used MeOH-AcONa instead of CHCl3-Et3N resulting in better yields for a variety for substrates. [¹6] |
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1a
Rodríguez Dominguez JC.Thomae D.Seck P.Kirsch G. Synlett 2008, 286 -
1b
Thomae D.Rodríguez Dominguez JC.Kirsch G.Seck P. Tetrahedron 2008, 64: 3232 -
2a
Ohishi Y.Doi Y.Nakanishi T. Chem. Pharm. Bull. 1984, 32: 4260 -
2b
Tromelin A.Demerseman P.Royer R. Synthesis 1985, 1074 - 3
Fishwick BR.Rowles DK.Stifling CJM. J. Chem. Soc., Perkin Trans. 1 1986, 1171 -
4a
Braish TF.Castaldi M.Chan S.Fox DE.Keltonic T.McGarry J.Hawkins JM.Norris T.Rose PR.Sieser JE.Sitter BJ.Watson HJr. Synlett 1996, 1100 -
4b
Ballini R.Fiorini D.Palmieri A. Synlett 2003, 1704 - 5
Concellón JM.Rodríguez-Solla H.Concellón C.García-Granda S.Díaz MR. Org. Lett. 2006, 8: 5979 - 6
Sherrill ML. J. Am. Chem. Soc. 1924, 46: 2753 - 7
Gewald K.Hain U. Monatsh. Chem. 1992, 123: 455 - 8
Shen Y.Yang B. Synth. Commun. 1993, 23: 1 - 9
Concellón JM.Bernad PL.Rodríguez-Solla H.Concellón C. J. Org. Chem. 2007, 72: 5421 - 10
Alcaide B.Almendros P.Luna A.Torres MR. Org. Biomol. Chem. 2008, 6: 1635 - 11
Hansen HM.Longbottom DA.Ley SV. Chem. Commun. 2006, 4838 - 12
Wascholowski V.Hansen HM.Longbottom DA.Ley SV. Synthesis 2008, 1269 - 13
Lv J.Zhan J.Wang Y. Chem. Eur. J. 2009, 15: 972 - 14
Dong L.-t.Lu R.-j.Du Q.-s.Zhang J.-m.Liu S.-p.Xuan Y.-n.Yan M. Tetrahedron 2009, 65: 4124 - 15
Vesely J.Zhao GL.Bartoszewicz A.Córdova A. Tetrahedron Lett. 2008, 49: 4209 -
16a (a)
Zhang J.-m.Hu Z.-p.Zhao S.-q.Yan M. Tetrahedron 2009, 65: 802 -
16b (b)
Zhang J.-m.Hu Z.-p.Dong L.-t.Xuan Y.-n.Lou C.-l.Yan M. Tetrahedron: Asymmetry 2009, 20: 355
References
-
1a
Rodríguez Dominguez JC.Thomae D.Seck P.Kirsch G. Synlett 2008, 286 -
1b
Thomae D.Rodríguez Dominguez JC.Kirsch G.Seck P. Tetrahedron 2008, 64: 3232 -
2a
Ohishi Y.Doi Y.Nakanishi T. Chem. Pharm. Bull. 1984, 32: 4260 -
2b
Tromelin A.Demerseman P.Royer R. Synthesis 1985, 1074 - 3
Fishwick BR.Rowles DK.Stifling CJM. J. Chem. Soc., Perkin Trans. 1 1986, 1171 -
4a
Braish TF.Castaldi M.Chan S.Fox DE.Keltonic T.McGarry J.Hawkins JM.Norris T.Rose PR.Sieser JE.Sitter BJ.Watson HJr. Synlett 1996, 1100 -
4b
Ballini R.Fiorini D.Palmieri A. Synlett 2003, 1704 - 5
Concellón JM.Rodríguez-Solla H.Concellón C.García-Granda S.Díaz MR. Org. Lett. 2006, 8: 5979 - 6
Sherrill ML. J. Am. Chem. Soc. 1924, 46: 2753 - 7
Gewald K.Hain U. Monatsh. Chem. 1992, 123: 455 - 8
Shen Y.Yang B. Synth. Commun. 1993, 23: 1 - 9
Concellón JM.Bernad PL.Rodríguez-Solla H.Concellón C. J. Org. Chem. 2007, 72: 5421 - 10
Alcaide B.Almendros P.Luna A.Torres MR. Org. Biomol. Chem. 2008, 6: 1635 - 11
Hansen HM.Longbottom DA.Ley SV. Chem. Commun. 2006, 4838 - 12
Wascholowski V.Hansen HM.Longbottom DA.Ley SV. Synthesis 2008, 1269 - 13
Lv J.Zhan J.Wang Y. Chem. Eur. J. 2009, 15: 972 - 14
Dong L.-t.Lu R.-j.Du Q.-s.Zhang J.-m.Liu S.-p.Xuan Y.-n.Yan M. Tetrahedron 2009, 65: 4124 - 15
Vesely J.Zhao GL.Bartoszewicz A.Córdova A. Tetrahedron Lett. 2008, 49: 4209 -
16a (a)
Zhang J.-m.Hu Z.-p.Zhao S.-q.Yan M. Tetrahedron 2009, 65: 802 -
16b (b)
Zhang J.-m.Hu Z.-p.Dong L.-t.Xuan Y.-n.Lou C.-l.Yan M. Tetrahedron: Asymmetry 2009, 20: 355
References
![](https://www.thieme-connect.de/media/synlett/200910/v288_s1.gif)
Scheme 1
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