Nitroalkene

Nitroalkenes are synthesized by various means, notable examples include:

• Nitroaldol reactions such as the Henry reaction:{{cite journal|author1=Ballini, Roberto |author2=Castagnani, Roberto |author3=Petrini, Marino |title=Chemoselective synthesis of functionalized conjugated nitroalkenes|journal=The Journal of Organic Chemistry|year=1992|volume=57|issue=7|pages=2160–2162|doi=10.1021/jo00033a045}}{{cite journal|last=Worrall|first=David E.|title=Nitrostyrene|journal=Org. Synth.|year=1929|volume=9|pages=66|doi=10.15227/orgsyn.009.0066}}{{cite journal |last1=Chandrasekhar |first1=S. |last2=Shrinidhi |first2=A. |title=Useful Extensions of the Henry Reaction: Expeditious Routes to Nitroalkanes and Nitroalkenes in Aqueous Media |journal=Synthetic Communications |date=2014 |volume=44 |issue=20 |pages=3008–3018 |doi=10.1080/00397911.2014.926373|s2cid=98439096 |url=https://figshare.com/articles/journal_contribution/1053153 }}

:Image:Furfural nitroaldol condensation.png

• Nitration of an alkene with nitryl iodide generated in-situ from silver nitrite and elemental iodine:{{cite journal|author1=Waldman, Steve |author2=Monte, Aaron, Monte |author3=Bracey, Ann |author4=Nichols, David |name-list-style=amp |title=One-pot Claisen rearrangement/O-methylation/alkene isomerization in the synthesis of ortho-methoxylated phenylisopropylamines|journal=Tetrahedron Letters|year=1996|volume=37|issue=44|pages=7889–7892|doi=10.1016/0040-4039(96)01807-2}}

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• Direct nitration of alkenes with nitric oxide and an aluminum oxide catalyst in acidic conditions:{{cite journal|author1=Mukaiyama, T. |author2=Hata E. |author3=Yamada, T. |name-list-style=amp |title=Convenient and Simple Preparation of Nitroolefins Nitration of Olefins with Nitric Oxide|journal=Chemistry Letters|year=1995|volume=24|issue=7|pages=505–506|doi=10.1246/cl.1995.505}}

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• Direct nitration of alkenes with Clayfen (Iron(III) nitrate supported on Montmorillonite clay):{{cite journal|last1=Varma|first1=Rajender|last2=Naicker|first2=Kannan|last3=Liesen|first3=Per|title=Selective nitration of styrenes with clayfen and clayan: A solvent-free synthesis of β-nitrostyrenes|journal=Tetrahedron Letters|date=1998|volume=39|issue=23|pages=3977–3980|doi=10.1016/S0040-4039(98)00740-0}}

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• Dehydration of nitro-alcohols:{{cite journal|author1=Ranganathan, Darshan |author2=Rao, Bhushan |author3=Ranganathan, Subramania |author4=Mehrotra, Ashok |author5=Iyengar, Radha |name-list-style=amp |title=Nitroethylene: a stable, clean, and reactive agent for organic synthesis|journal=The Journal of Organic Chemistry|year=1980|volume=45|issue=7|pages=1185–1189|doi=10.1021/jo01295a003}}

Image:Dehydration of 2-nitroethanol to nitroethylene via phthalic anhydride.svg

Nitroalkenes are useful intermediates for various chemical functionalities.

• A nitroalkene behaving as a Michael acceptor in the synthesis of Lycoricidine:{{cite journal|author1=Jubert, Carole |author2=Knochel, Paul |name-list-style=amp |title=Preparation of polyfunctional nitro olefins and nitroalkanes using the copper-zinc reagents RCu(CN)ZnI|journal=The Journal of Organic Chemistry|year=1992|volume=57|issue=20|pages=5431–5438|doi=10.1021/jo00046a027}}

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• Nitroalkene acting as an activated dienophile toward butadiene in a Diels-Alder cycloaddition:{{cite journal|author1=Noboru Ono |author2=Hideyoshi Miyake |author3=Akio Kamimura |author4=Aritsune, Kaji |name-list-style=amp |title=Regioselective Diels–Alder reactions. The nitro group as a regiochemical control element|journal=Perkin Transactions|year=1987|volume=1|pages=1929–1935|doi=10.1039/P19870001929}}

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• The synthesis of pyrrole derivatives via the Barton–Zard reaction:{{cite book | author =Jie Jack Li | title =Heterocyclic Chemistry in Drug Discovery | publisher =Wiley | location =New York | year =2013|isbn =9781118354421| url =https://books.google.com/books?id=p_fM6CuK6xcC}} pp.43-4

Image:Barton-Zard reaction.svg

• Pericyclic reaction of a nitroalkene yielding an indole:{{cite journal|author1=Novellino, Luisa |author2=d'Ischia, Marco |author3=Prota, Giuseppe |name-list-style=amp |title=Expedient Synthesis of 5,6-Dihydroxyindole and Derivatives via an Improved Zn(II)-Assisted 2,β-Dinitrostyrene Approach|journal=Synthesis|year=1999|volume=1999|issue=5 |pages=793–796|doi=10.1055/s-1999-3469}}

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• Partial hydrogenation to an alkene baring a hydroxylamine functional group:{{cite journal|author1=Masahiko Kohno |author2=Shigehiro Sasao |author3=Shun-Ichi Murahashi |name-list-style=amp |title=Synthesis of Phenethylamines by Hydrogenation of β-Nitrostyrenes|journal=Bulletin of the Chemical Society of Japan|year=1990|volume=63|issue=4|pages=1252–1254|doi=10.1246/bcsj.63.1252|doi-access=free}}

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• Reduction to primary amines:{{cite journal|author1=Koch, Werner |author2=Reichert, Benno |name-list-style=amp |title=Über die katalytische Hydrierung substituierter ω-Nitrostyrole|journal=Archiv der Pharmazie|year=1935|volume=273|issue=18–20|doi=10.1002/ardp.19352731802|pages=265–274|s2cid=95731916 }}

File:Hydrogenation of a nitrostyrene to a primary amine.svg

• Asymmetric Stetter reaction:{{cite journal|author1=DiRocco, D. A. |author2=Oberg, K. M. |author3=Dalton, D. M. |author4=Rovis, T. |title=Catalytic Asymmetric Intermolecular Stetter Reaction of Heterocyclic Aldehydes with Nitroalkenes: Backbone Fluorination Improves Selectivity|journal=Journal of the American Chemical Society|year=2009|volume=131|issue=31|pages=10872–10874|doi=10.1021/ja904375q |pmid=19722669 |pmc=2747345}}

Image:Asymmetric Stetter Reaction with Nitroalkenes.png

The related nitroalkynes are rather unstable, easily losing nitrogen dioxide radicals, rearranging to nitriles over −40 °C, or adding nucleophiles. Fewer than 20 had been synthesized before 2014. Nitration of metalloalkynes requires nearly-bare nitronium, i.e. nitronium tetrafluoroborate or nitric anhydride. In contrast, Tilden's reagent suffices to nitrosylate metalloalkynes; the products then oxidize to nitroalkenes in peroxyacids. Protected nitroalkene dehydroiodination occurs delicately in the gas phase.{{cite journal|url=https://www.researchgate.net/profile/Philip-Pagoria/publication/273040611_Nitroalkynes_A_Unique_Class_of_Energetic_Materials/links/587420e108ae329d621d3995/Nitroalkynes-A-Unique-Class-of-Energetic-Materials.pdf|via=ResearchGate|journal=Synthesis|title=Nitroalkynes: A Unique Class of Energetic Materials|first1=G. Kenneth|last1=Widler|first2=Philip F.|last2=Pagoria|first3=K. Peter C.|last3=Vollhardt|year=2014|publisher=Thieme|location=New York, NY}}

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Category:Functional groups