91358-53-1Relevant academic research and scientific papers
TMSCN/DBU-mediated facile redox transformation of α,β- unsaturated aldehydes to carboxylic acid derivatives
Kaise, Hiromi,Shimokawa, Jun,Fukuyama, Tohru
supporting information, p. 727 - 729 (2014/03/21)
Redox transformation of an α,β-unsaturated aldehyde to a carboxylic acid derivative by means of a combination of TMSCN and DBU was investigated. In addition to the wide use of the carboxylic acid derivatives provided by this reaction, temperature-dependent control of the kinetic or thermodynamic protonation pattern was found to selectively switch the stereochemistry of the acyl group in the product.
The synthesis of α-azidoesters and geminal triazides
Klahn, Philipp,Erhardt, Hellmuth,Kotthaus, Andreas,Kirsch, Stefan F.
supporting information, p. 7913 - 7917 (2014/08/05)
Three simple methods for the synthesis of geminal triazides are described: Starting from 1) 3-oxocarboxylic acids, 2) iodomethyl ketones, or 3) terminal olefins, a range of triazidomethyl ketones can be constructed under mild oxidative reaction conditions by the use of IBX-SO3K, a sulfonylated derivative of 2-iodoxybenzoic acid (IBX), and NaN3 as an azide source. This is the first report of representatives of this novel class of triazide compounds: Despite their high nitrogen content, the geminal triazides are easy to handle, even when preparative-scale syntheses are performed. (Caution: These procedures still require protective measures!) The triazides are now broadly available for further studies regarding their properties and reactivity. Furthermore, we show how the method can be used to provide α-azidoesters, which are potential building blocks for amino acids. Either/or: Geminal triazides are rapidly constructed with broad scope by the use of oxocarboxylic acids, iodomethyl ketones, or terminal olefins as starting substrates in oxidative azidations with a mild derivative of 2-iodoxybenzoic acid and sodium azide. Along with this little-studied class of organic azides, α-azidoesters were also synthesized.
A substrate-driven approach to determine reactivities of α,β-unsaturated carboxylic esters towards asymmetric bioreduction
Tasnádi, Gábor,Winkler, Christoph K.,Clay, Dorina,Sultana, Nargis,Fabian, Walter M. F.,Hall, Mélanie,Ditrich, Klaus,Faber, Kurt
, p. 10362 - 10367 (2012/10/08)
The degree of C=C bond activation in the asymmetric bioreduction of α,β-unsaturated carboxylic esters by ene-reductases was studied, and general recommendations to render these "borderline-substrates" more reactive towards enzymatic reduction are proposed. The concept of "supported substrate activation" was developed. In general, an additional α-halogenated substituent proved to be beneficial for enzymatic activity, whereas β-alkyl or β-aryl substituents were detrimental for the reactivity of nonhalogenated substrates, and α-cyano groups showed little effect. The alcohol moiety of the ester functionality was found to have a strong influence on the reaction rate. Overall, activities were determined by both steric and electronic effects. Biotransformation: The asymmetric bioreduction of α,β-unsaturated carboxylic esters by ene-reductases could be tuned by varying the degree of C=C bond activation (see scheme). An additional α-halogenated substituent proved to be beneficial for enzymatic activity, whereas β-alkyl or β-aryl substituents were detrimental for the reactivity of nonhalogenated substrates. Copyright
IODOARYLATION OF ACRYLONITRILE AND ACRYLIC ESTERS WITH ARENEDIAZONIUM SALTS
Ganushchak, N. I.,Obushak, N. D.,Polishchuk, O. P.
, p. 2291 - 2295 (2007/10/02)
In the reaction of acrylic esters and acrylonitrile with arenediazonium salts in the presence of alkali-metal iodides the products from addition of the aryl radical and iodine at the double bond are formed.An effective method is proposed for the synthesis of 1-iodo-1-methoxycarbonyl(cyano)-2-arylalkanes, which enter readily into nucleophilic substitution of iodine.When boiled with an alcohol solution of alkali, they are transformed into derivatives of cinnamic acid.
