19598-21-1Relevant academic research and scientific papers
Manganese(III)-based facile synthesis of 3-cyano-4,5-dihydrofurans and 4-cyano-1,2-dioxan-3-ols using alkenes and acylacetonitrile building blocks
Nguyen, Van-Ha,Nishino, Hiroshi,Kurosawa, Kazu
, p. 899 - 908 (1997)
New 3-cyano-4,5-dihydrofurans and 4-cyano-1,2-dioxan-3-ols were alternatively synthesized in good yields by the oxidation of acylacetonitrile building blocks with manganese(III) acetate in the presence of alkenes without any byproducts. The reaction at reflux temperature gave 3-cyano-4,5-dihydrofurans under an argon atmosphere, while 4-cyano-1,2-dioxan-3-ols were obtained at 23°C under an air atmosphere except for the reaction of styrene with benzoylacetonitrile which afforded 2-cyano-1,4-diphenylbutane-1,4-dione, and the reaction of 1,1-diphenylethene with 2-(2-cyano-1-oxoethyl)-5-methylfuran which yielded 2-cyano-4,4-diphenylbutanolide without any cyclic peroxides. The oxidation of benzoylacetonitrile itself at 23°C under an air atmosphere in the absence of alkene gave benzoic acid. Easy conversion of the 1,2-dioxanes to furans was demonstrated, and mechanisms for the formation of dihydrofurans and dioxanes as well as the unusual transformation to butanedione and butanolide were also discussed.
Mn(III)-based reaction of alkenes with pyrrolidinedione derivatives. Formation of bicyclic peroxides and the related compounds
Nguyen, Van-Ha,Nishino, Hiroshi,Kurosawa, Kazu
, p. 465 - 480 (2007/10/03)
Alkenes (1) and 2,3-pyrrolidinediones (2) were treated with manganese(III) acetate in acetic acid at 23°C under a stream of dry air giving 1-hydroxy-8-aza-2,3-dioxabicyclo[4.3.0]nonan-9-ones (3) in good yields. The reaction at elevated temperature gave 4-ethenyl-2,3-pyrrolidinediones (6) and/or 4-alkyl-2,3-pyrrolidinediones (7) in good yields. A wide variety of 2,3-pyrrolidinediones having an alkoxycarbonyl, cyano, or acyl group at the 4-position were tested to delineate the scope and limitations of these reactions. The mechanisms for the formation of the products were also discussed.
Reaction of Olefins with α-Cyanoacetamide in the Presence of Manganese(III) Acetate
Sato, Hidehiko,Nishino, Hiroshi,Kurosawa, Kazu
, p. 1753 - 1760 (2007/10/02)
2-Butenamides and 2-buten-4-olides are formed by the reaction of phenyl or 4-chlorophenyl-substituted olefins with α-cyanoacetamide in the presence of manganese(III) acetate.On the other hand, aryl substituted olefins having electron-donating groups are oxidized under similar reaction conditions to give 1,5-dihydro-2H-pyrrol-2-ones and 3-ethenyl-2-pyrrolidones.All these reactions also produce glycols or ketones which are given by the direct oxidation of these olefins with manganese(III) acetate.The question whether an intermediate carbocation in the oxidation process cyclized on an oxygen or a nitrogen atom can be explained by the hard and soft acids and bases (HSAB) concept.A possible mechanism for the formation of 2-buten-amides and 2-buten-4-olides is proposed.
