10.1021/acs.joc.7b00811.s001 Kento Iwai Kento Iwai Haruyasu Asahara Haruyasu Asahara Nagatoshi Nishiwaki Nagatoshi Nishiwaki Synthesis of Functionalized 3‑Cyanoisoxazoles Using a Dianionic Reagent American Chemical Society 2017 series nitronate ion cycloaddition dianionic cyano Michael addition azide reactive 3- cyano group dipolar 5- acylated 3- cyanoisoxazoles 5- acyl Synthesi nitroacetate dianionic reagent pyridine ring equivalent Dianionic Reagent ethanolysi nitroacetonitrile 4- aryl group tetrazole Functionalized aci isoxazolo intramolecular nucleophilic substitution quinoline ketone formation Cyanoisoxazole ethyl ester α- chloro 2017-05-04 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Synthesis_of_Functionalized_3_Cyanoisoxazoles_Using_a_Dianionic_Reagent/4986659 A series of 5-acylated 3-cyanoisoxazoles were efficiently synthesized by the Michael addition of dianionic cyano-<i>aci</i>-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-<i>c</i>]­quinoline derivative.