51384-78-2Relevant academic research and scientific papers
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
supporting information; experimental part, 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
An Efficient One Pot Synthesis of α-Iodo-α,β-unsaturated Esters, Ketones and Nitriles via Arsonium Salts
Huang, Yao-Zeng,Shi, Li-Lan,Li, Sao-Wei,Huang, Rong
, p. 2639 - 2646 (2007/10/02)
A number of α-iodo-α,β-unsaturated compounds 3 were synthesized under mild conditions via corresponding readily available arsonium salts 1 in one pot reaction.
Elimination from Diastereomeric Methyl 3-Acetoxy-2-halogeno- and 2,3-Dihalogeno-3-phenylpropanoates
Cabaleiro, Mercedes C.,Garay, Raul O.
, p. 1473 - 1476 (2007/10/02)
The rates of elimination of a number of erythro- and threo-PhCHYCXHCO2Me in methanolic triethylamine have been measured.The kinetic evidence together with the stereochemical results suggest that elimination of the dihalogeno-compounds occurs by an (E1cB)I process for the erythro-substrates and by a concerted pathways for the threo-isomers.In the case of the acetoxy derivatives the former mechanism seems to be operative for both stereoisomers.
