21758-00-9Relevant academic research and scientific papers
Alkynylation and Cyanation of Alkenes Using Diverse Properties of a Nitro Group
Asahara, Haruyasu,Sofue, Ayano,Kuroda, Yasuyuki,Nishiwaki, Nagatoshi
, p. 13691 - 13699 (2018/11/30)
In the work being reported here, β-nitrostyrenes bearing an ethoxycarbonyl group at the β-position serve as scaffolds for the synthesis of α,β-difunctionalized alkenes. Nitrocinnamates undergo Michael addition reactions with versatile sp3- and sp2-nucleophiles such as alcohols, Grignard reagents, alkylcopper, and dialkylzinc to afford β-substituted nitroethane derivatives. However, various attempts to obtain a double bond via nitrous acid elimination failed because steric repulsion between the newly introduced sp3/sp2 substituent and the nitro group hampered the required anti-coplanar conformation. This problem was successfully overcome using a smaller sp-nucleophile such as lithium acetylide, potassium cyanide, or trimethylsilyl cyanide. While treatment of the adduct with a strong base did not lead to the elimination of nitrous acid, the weaker triethylamine efficiently afforded functionalized enynes and acrylonitriles in high yields.
Isomerization of 4-aryl-4-methylhex-5-en-2-ones to 5-aryl-4-methylhex-5-en-2-ones by an intramolecular ene-retro ene reaction sequence
Srikrishna, A.,Krishnan, K.,Venkateswarlu, S.,Kumar, P. Praveen
, p. 2033 - 2038 (2007/10/02)
Acid-catalyzed thermal rearrangement of 4-aryl-4-methylhex-5-en-2-ones (products of the Claisen rearrangement of β-methylcinnamyl alcohols and 2-methoxypropene) to isomeric 5-aryl-4-methylhex-5-en-2-ones via an intramolecular ene reaction of the enol taut
