Nitroalkene

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

Nitroalkenes are synthesized by various means, notable examples include:

• Nitroaldol reactions such as the Knoevenagel condensation:^[1][2][3]

• Nitration of an alkene with nitryl iodide generated in-situ from silver nitrite and elemental iodine:^[4]

• Direct nitration of alkenes with nitric oxide and an aluminum oxide catalyst in acidic conditions:^[5]

• Direct nitration of alkenes with Clayfen (Iron(III) nitrate supported on Montmorillonite clay):^[6]

• Dehydration of nitro-alcohols:^[7]

Reactions

Nitroalkenes are useful intermediates for various chemical functionalities.

• A nitroalkene behaving as a Michael acceptor in the synthesis of Lycoricidine:^[1][8]

• Nitroalkene acting as an activated dienophile toward butadiene in an Diels-Alder cycloaddition:^[1][9]

• The synthesis of pyrrole derivatives via the Barton–Zard reaction:^[10]

• Pericyclic reaction of a nitroalkene yielding an indole:^[11]

• Partial hydrogenation to an alkene baring a hydroxylamine functional group:^[12]

• Reduction to primary amines:^[12][13]

• Asymmetric Stetter reaction:^[14]

References

1. 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. 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): 265–274. 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 the American Chemical Society 131 (31): 10872–10874. doi:10.1021/ja904375q.