Nitroalkene

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A nitroalkene, or nitro olefin, is a functional group combining the functionality of its constituent parts, an alkene and nitro group, while displaying its own chemical properties through alkene activation, making the functional group useful in specialty reactions such as the Michael reaction or Diels-Alder additions.[1]

Synthesis[edit]

Nitroalkenes are synthesized by various means, notable examples include:

Furfural nitroaldol condensation.png
Nitrogenation of a phenylisopropene.png
Direct nitration of styrene with alumina catalyst.svg
Direct nitration of styrene using FeNO3 on a Clayfen support.png
  • Dehydration of nitro-alcohols:[7]
Dehydration of 2-nitroethanol to nitroethylene via phthalic anhydride.svg

Reactions[edit]

Nitroalkenes are useful intermediates for various chemical functionalities.

Michael acceptor intermediate in Lycoricidine Synthesis.svg
Nitroalkene dienophile in cycloaddition with butadiene.svg
Barton-Zard reaction.png
Pericyclic reaction of a nitroalkene yielding an indole.svg
Partial hydrogenation of a nitrostyrene to an alkene hydroxylamine.svg
Hydrogenation of a nitrostyrene to a primary amine.svg
Asymmetric Stetter Reaction with Nitroalkenes.png

References[edit]

  1. ^ a b c d Furniss, Brian; Hannaford, Antony; Smith, Peter; and Tatchell, Austin (1996). Vogel's Textbook of Practical Organic Chemistry 5th Ed. London: Longman Science & Technical. pp. 635, 768, 1035–1036, & 1121. ISBN 9780582462366. 
  2. ^ Ballini, Roberto; Castagnani, Roberto; Petrini, Marino (1992). "Chemoselective synthesis of functionalized conjugated nitroalkenes". The Journal of Organic Chemistry 57 (7): 2160–2162. doi:10.1021/jo00033a045. 
  3. ^ Worrall, David E. (1929). "Nitrostyrene". Org. Synth. 9: 66. doi:10.15227/orgsyn.009.0066. 
  4. ^ Waldman, Steve; Monte, Aaron, Monte; Bracey, Ann; and Nichols, David (1996). "One-pot Claisen rearrangement/O-methylation/alkene isomerization in the synthesis of ortho-methoxylated phenylisopropylamines". Tetrahedron Letters 37 (44): 7889–7892. doi:10.1016/0040-4039(96)01807-2. 
  5. ^ Mukaiyama, T.; Hata E.; and Yamada, T. (1995). "Convenient and Simple Preparation of Nitroolefins Nitration of Olefins with Nitric Oxide". Chemistry Letters 24 (7): 505–506. doi:10.1246/cl.1995.505. 
  6. ^ Varma, Rajender; Naicker, Kannan; Liesen, Per (1998). "Selective nitration of styrenes with clayfen and clayan: A solvent-free synthesis of β-nitrostyrenes". Tetrahedron Letters 39 (23): 3977–3980. doi:10.1016/S0040-4039(98)00740-0. 
  7. ^ Ranganathan, Darshan; Rao, Bhushan; Ranganathan, Subramania; Mehrotra, Ashok; and Iyengar, Radha (1980). "Nitroethylene: a stable, clean, and reactive agent for organic synthesis". The Journal of Organic Chemistry 45 (7): 1185–1189. doi:10.1021/jo01295a003. 
  8. ^ Jubert, Carole and Knochel, Paul (1992). "Preparation of polyfunctional nitro olefins and nitroalkanes using the copper-zinc reagents RCu(CN)ZnI". The Journal of Organic Chemistry 57 (20): 5431–5438. doi:10.1021/jo00046a027. 
  9. ^ Noboru Ono; Hideyoshi Miyake; Akio Kamimura; and Aritsune, Kaji (1987). "Regioselective Diels–Alder reactions. The nitro group as a regiochemical control element". Perkin Transactions 1: 1929–1935. doi:10.1039/P19870001929. 
  10. ^ Jie Jack Li (2013). Heterocyclic Chemistry in Drug Discovery. New York: Wiley. ISBN 9781118354421.  pp.43-4
  11. ^ Novellino, Luisa; d'Ischia, Marco; and Prota, Giuseppe (1999). "Expedient Synthesis of 5,6-Dihydroxyindole and Derivatives via an Improved Zn(II)-Assisted 2,β-Dinitrostyrene Approach". Synthesis 5: 793–796. doi:10.1055/s-1999-3469. 
  12. ^ a b Masahiko Kohno, Shigehiro Sasao, and Shun-Ichi Murahashi (1990). "Synthesis of Phenethylamines by Hydrogenation of β-Nitrostyrenes". Bulletin of the Chemical Society of Japan 63 (4): 1252–1254. doi:10.1246/bcsj.63.1252. 
  13. ^ Koch, Werner and Reichert, Benno (1935). "Über die katalytische Hydrierung substituierter ω-Nitrostyrole". Archiv der Pharmazie 273 (18-20). doi:10.1002/ardp.19352731802. 
  14. ^ DiRocco, D. A.; Oberg, K. M.; Dalton, D. M.; Rovis, T. (2009). "Catalytic Asymmetric Intermolecular Stetter Reaction of Heterocyclic Aldehydes with Nitroalkenes: Backbone Fluorination Improves Selectivity". Journal of American Chemical Society 131 (31): 10872–10874. doi:10.1021/ja904375q.