TY - DATA T1 - Synthesis of Functionalized 3‑Cyanoisoxazoles Using a Dianionic Reagent PY - 2017/05/04 AU - Kento Iwai AU - Haruyasu Asahara AU - Nagatoshi Nishiwaki UR - https://acs.figshare.com/articles/journal_contribution/Synthesis_of_Functionalized_3_Cyanoisoxazoles_Using_a_Dianionic_Reagent/4986659 DO - 10.1021/acs.joc.7b00811.s001 L4 - https://ndownloader.figshare.com/files/8394728 KW - series KW - nitronate ion KW - cycloaddition KW - dianionic cyano KW - Michael addition KW - azide KW - reactive KW - 3- cyano group KW - dipolar KW - 5- acylated 3- cyanoisoxazoles KW - 5- acyl KW - Synthesi KW - nitroacetate KW - dianionic reagent KW - pyridine ring KW - equivalent KW - Dianionic Reagent KW - ethanolysi KW - nitroacetonitrile KW - 4- aryl group KW - tetrazole KW - Functionalized KW - aci KW - isoxazolo KW - intramolecular nucleophilic substitution KW - quinoline KW - ketone KW - formation KW - Cyanoisoxazole KW - ethyl ester KW - α- KW - chloro N2 - 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. ER -