A Practical Synthesis of 1,2-Nitroamines
by Michael Addition of N-Nucleophiles to Nitroalkenes

Raphaël Robiette; Trieu-Van Tran; Alex Cordi; Bernard Tinant; Jacqueline Marchand-Brynaert

doi:10.1055/s-0030-1258176

PAPER

A Practical Synthesis of 1,2-Nitroamines by Michael Addition of N-Nucleophiles to Nitroalkenes

Raphaël Robiette*^a, Trieu-Van Tran^a, Alex Cordi^b, Bernard Tinant^a, Jacqueline Marchand-Brynaert*^a
^a Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, Place Louis Pasteur 1, 1348 Louvain-la-Neuve, Belgium
Fax: +3210474168; e-Mail: raphael.robiette@uclouvain.be; e-Mail: jacqueline.marchand@uclouvain.be;
^b Institut de Recherches Servier, Rue des Moulineaux 11, 92150 Suresnes, France

Abstract

All articles of this category

Abstract

A practical method for the synthesis of α-nitroamines by Michael addition of azide to nitroalkene has been developed. This reaction proceeds in high yields under very mild conditions (phase-transfer catalysis) and is found to be general; good yields are obtained with both aryl and alkyl derivatives as well as with 1,1-disubstituted ones.

Key words

azides - amines - Michael addition - nitroalkenes - nitroamines

Full Text

References

<A NAME="RP06310SS-1">1</A> For a review on nitroamines, see: Lucet D. Le Gall T. Mioskowski C. Angew. Chem. Int. Ed. 1998, 37: 2580

For reviews on Nef oxidation, see:

<A NAME="RP06310SS-2A">2a</A> Ballini R. Petrini M. Tetrahedron 2004, 60: 1017

<A NAME="RP06310SS-2B">2b</A> Pinnick H. Org. React. 1990, 38: 655

For the synthesis of 1,2-diamines from nitroamines, see:

<A NAME="RP06310SS-3A">3a</A> Anderson JC. Chapman HA. Synthesis 2006, 3309

<A NAME="RP06310SS-3B">3b</A> Yamada K. Moll G. Shibasaki M. Synlett 2001, 980

<A NAME="RP06310SS-3C">3c</A> Anderson JC. Blake AJ. Howell GP. Wilson C. J. Org. Chem. 2005, 70: 649

<A NAME="RP06310SS-3D">3d</A> Imagawa K. Hata E. Yamada T. Mukaiyama T. Chem. Lett. 1996, 4: 291

<A NAME="RP06310SS-4">4</A> For recent advances on this reaction, see: Westermann B. Angew. Chem. Int. Ed. 2003, 42: 151

For some recent reports on enantioselective aza-Henry reaction, see:

<A NAME="RP06310SS-5A">5a</A> Wang L. Tan C. Liu X. Feng X. Syntlett 2008, 2075

<A NAME="RP06310SS-5B">5b</A> Gomez-Bengoa Enrique LA. López R. Mugica-Mendiola I. Oiarbide M. Palomo C. J. Am. Chem. Soc. 2008, 130: 7955

<A NAME="RP06310SS-5C">5c</A> Robak MT. Trincado M. Ellman JA. J. Am. Chem. Soc. 2007, 129: 15110

<A NAME="RP06310SS-5D">5d</A> Rossi L. Bianchi G. Feroci M. Inesi A. Synlett 2007, 2505

<A NAME="RP06310SS-5E">5e</A> Palomo C. Oiarbide M. Halder R. Laso A. López R. Angew. Chem. Int. Ed. 2006, 45: 117

<A NAME="RP06310SS-6A">6a</A> Wang L. Tan C. Liu X. Feng X. Synlett 2008, 2075

<A NAME="RP06310SS-6B">6b</A> Pahadi NK. Ube H. Terada M. Tetrahedron Lett. 2007, 48: 8700

<A NAME="RP06310SS-6C">6c</A> Anderson JC. Blake AJ. Howell GP. Wilson C. J. Org. Chem. 2005, 70: 549

<A NAME="RP06310SS-6D">6d</A> Ruano J.-LG. Topp M. López-Cantarero J. Alemán J. Remuiñán MJ. Cid MB. Org. Lett. 2005, 7: 4407 ; and references cited therein

For some recent reports, see:

<A NAME="RP06310SS-7A">7a</A> Ooi T. Takada S. Doda K. Maruoka K. Angew. Chem. Int. Ed. 2006, 45: 7606

<A NAME="RP06310SS-7B">7b</A> Lalonde MP. Chen Y. Jacobsen EN. Angew. Chem. Int. Ed. 2006, 45: 6366

<A NAME="RP06310SS-7C">7c</A> Tsogoeva SB. Wei S. Chem. Commun. 2006, 1451

<A NAME="RP06310SS-7D">7d</A> Huang H. Jaconsen EN. J. Am. Chem. Soc. 2006, 128: 7170 ; and references cited therein

<A NAME="RP06310SS-8A">8a</A> Nielsen M. Zhuang W. Jorgensen KA. Tetrahedron 2007, 63: 5849

<A NAME="RP06310SS-8B">8b</A> Kamimura A. Kadowaki A. Nagata Y. Uno H. Tetrahedron Lett. 2006, 47: 2471

<A NAME="RP06310SS-8C">8c</A> Wang J. Li H. Zu L. Wang W. Org. Lett. 2006, 8: 1391

<A NAME="RP06310SS-8D">8d</A> Yan M.-C. Tu Z. Lin C. Ko S. Hsu J. Yao CF. J. Org. Chem. 2004, 69: 1565

<A NAME="RP06310SS-8E">8e</A> Molteni M. Volonterio A. Zanda M. Org. Lett. 2003, 5: 3887

<A NAME="RP06310SS-8F">8f</A> Lucet D. Sabelle S. Kostelitz O. Le Gall T. Mioskowski C. Eur. J. Org. Chem. 1999, 2583

<A NAME="RP06310SS-8G">8g</A> Enders D. Wiedemann J. Synthesis 1996, 1443

<A NAME="RP06310SS-9">9</A> For a review on benzotriazole, see: Katritzky AR. Xiangfu L. Yang JZ. Denisko OV. Chem. Rev. 1998, 98: 409

The structure of 3b has been confirmed by X-ray crystallography. The X-ray data have been deposited at the Cambridge Crystallographic Data Centre (deposition number: CCDC 769007). These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033, E-mail: deposit@ccdc.cam.ac.uk].

This is consistent with a previous study on addition of benzotriazole on nitroalkene. See ref. 8c.

<A NAME="RP06310SS-12">12</A> Katritzky AR. Perumal S. Fan WQ. J. Chem. Soc., Perkin Trans. 2 1990, 2059

<A NAME="RP06310SS-13">13</A> Yadav JS. Reddy AR. Rao YG. Narsaiah AV. Reddy BVS. Synthesis 2007, 3447

Total conversion was obtained in dichloroethane at 60 ˚C after 5 h.

<A NAME="RP06310SS-15">15</A> For early report on addition of hydroxylamine to nitroalkene, see: Hurd CD. Patterson J. J. Chem. Soc., Chem. Commun. 1953, 285

A test reaction showed that the reaction does not proceed in the absence of catalyst.

<A NAME="RP06310SS-17">17</A> Quiclet B. Zard SZ. Synthesis 2005, 3319

For one example of addition of azide using TMSN₃, see 8a.

<A NAME="RP06310SS-19">19</A> For a review on azides, see: Scriven EFV. Turnbull K. Chem. Rev. 1988, 88: 351

<A NAME="RP06310SS-20">20</A> Salunkhe AM. Ramachandran PV. Brown HC. Tetrahedron 2002, 58: 10059

<A NAME="RP06310SS-21A">21a</A> Staudinger H. Meyer J. Helv. Chim. Acta 1919, 2: 635

<A NAME="RP06310SS-21B">21b</A> Leffler JE. Temple RD. J. Am. Chem. Soc. 1967, 89: 5235

<A NAME="RP06310SS-21C">21c</A> Vaultier M. Knouzi N. Carrie R. Tetrahedron Lett. 1983, 24: 763

<A NAME="RP06310SS-21D">21d</A> Venturini A. Gonzalez J. J. Org. Chem. 2002, 67: 9088

<A NAME="RP06310SS-21E">21e</A> Chen J. Forsyth CJ. Org. Lett. 2003, 5: 1281

<A NAME="RP06310SS-22A">22a</A> Arcelli A. Cerè V. Peri F. Pollicino S. Ricci A. Tetrahedron 2001, 57: 3439

<A NAME="RP06310SS-22B">22b</A> Racouchot S. Ollivier J. Salaün J. Synlett 2000, 1729

<A NAME="RP06310SS-23">23</A> Denmark SE. Kesler BS. Moon YC. J. Org. Chem. 1992, 57: 4912

<A NAME="RP06310SS-24">24</A> Wen-Wei L. Yeong-Jiunn J. Yeh W. Ju-Tsung L. Shin-Ru H. Lian-Yong W. Ching-Fa Y. J. Org. Chem. 2001, 66: 1984

<A NAME="RP06310SS-25">25</A> Nielsen M. Zhuang W. Jørgensen KA. Tetrahedron 2007, 63: 5849

<A NAME="RP06310SS-26">26</A> Boyer JH. J. Am. Chem. Soc. 1951, 73: 4248

In the case of 4b, the reaction mixture was poured into H₂O, extracted with CH₂Cl₂, and the CH₂Cl₂ extract was concentrated under reduced pressure.

<A NAME="RP06310SS-28A">28a</A> Benalil A. Carboni B. Vaultier M. Tetrahedron 1991, 47: 8177

<A NAME="RP06310SS-28B">28b</A> Hsiao Y. Hegedus LS. J. Org. Chem. 1997, 62: 3586

<A NAME="RP06310SS-29">29</A> Plössl K. Chandra R. Qu W. Lieberman BP. Kung M.-P. Zhou R. Huang B. Kung HF. Nucl. Med. Biol. 2008, 35: 83