Organocatalytic Asymmetric Double Addition of Kojic Acids to 2‐Nitroallylic Carbonates. Issue 3 (18th January 2022)

• Record Type: Journal Article
• Authors: Kovalevsky, Ruslan A.; Smirnov, Maxim V.; Kucherenko, Alexander S.; Bykova, Kseniya A.; Shikina, Elizaveta V.; Zlotin, Sergei G.
• Is Part Of: European journal of organic chemistry. Volume 2022:Issue 3(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-18
• Subjects: Asymmetric catalysis -- Asymmetric synthesis -- Kojic acid -- Michael addition -- Nitroallylic carbonates; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202101435
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: 2‐Nitroallylic carbonates were first applied as promising bis‐electrophilic C3 synthons for bifunctional squaramide catalyzed asymmetric domino reaction with kojic acid derivatives to afford so far inaccessible nitro compounds bearing two hydroxypyranone units. The reaction products undergo non‐catalytic epimerization at the carbon atom next to the nitro group. Plausible mechanism of the epimerization based on reversible formation of intermediate aci‐nitro compound is proposed. The double addition products were transformed to configurationally stable acetates and to chiral nitro glutarates, promising precursors to chiral amino glutaric acid derivatives. Abstract : Chiral nitro compounds containing two hydroxypyranone units were enantioselectively produced from kojic acid derivatives and 2‐nitroallylic carbonates in the presence of bifunctional tertiary amine‐squaramide organocatalyst. The reaction products were converted to corresponding acetates and nitro glutarates via acylation or oxidative fragmentation reactions.