%0 Generic %A Iwai, Kento %A Asahara, Haruyasu %A Nishiwaki, Nagatoshi %D 2017 %T Synthesis of Functionalized 3‑Cyanoisoxazoles Using a Dianionic Reagent %U https://acs.figshare.com/articles/dataset/Synthesis_of_Functionalized_3_Cyanoisoxazoles_Using_a_Dianionic_Reagent/4986656 %R 10.1021/acs.joc.7b00811.s002 %2 https://ndownloader.figshare.com/files/8394725 %K series %K nitronate ion %K cycloaddition %K dianionic cyano %K Michael addition %K azide %K reactive %K 3- cyano group %K dipolar %K 5- acylated 3- cyanoisoxazoles %K 5- acyl %K Synthesi %K nitroacetate %K dianionic reagent %K pyridine ring %K equivalent %K Dianionic Reagent %K ethanolysi %K nitroacetonitrile %K 4- aryl group %K tetrazole %K Functionalized %K aci %K isoxazolo %K intramolecular nucleophilic substitution %K quinoline %K ketone %K formation %K Cyanoisoxazole %K ethyl ester %K α- %K chloro %X A series of 5-acylated 3-cyanoisoxazoles were efficiently synthesized by the Michael addition of dianionic cyano-aci-nitroacetate to α-chloro-α,β-unsaturated ketones followed by intramolecular nucleophilic substitution of the nitronate ion intermediate. In this process, the dianionic reagent serves as the safe synthetic equivalent of the explosive nitroacetonitrile. The 3-cyano group is sufficiently reactive toward ethanolysis and 1,3-dipolar cycloaddition with an azide to afford ethyl ester and tetrazole, respectively. A pyridine ring between the 5-acyl and the 4-aryl group was also constructed. This led to the formation of the isoxazolo­[5,4-c]­quinoline derivative. %I ACS Publications