Manganese(III) acetate initiated oxidative free radical reaction between 1,4-naphthoquinones and ethyl nitroacetate

Chuang, Che Ping; Wu, Yi; Jiang, Ming Chyuan

doi:10.1016/s0040-4020(99)00646-8

Cited by 43 publications

(17 citation statements)

References 21 publications

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“…"Activated" nitro compounds (a-nitroketones, nitroacetamides [23] or nitroacetates), [24,25] on treatment with an alkene and Mn III , according to the reported rationalisation, follow two parallel reaction paths: the intermediate Mn III nitronate reacts with the alkene to give either the expected radical addition or the dehydrated cycloadduct. In the first reaction, Mn III behaves as a monoelectronic oxidant, in the other, as a dehydrating agent.…”

Section: Introductionmentioning

confidence: 98%

Synthesis of 4,5‐Dihydroisoxazoles by Condensation of Primary Nitro Compounds with Alkenes by Using a Copper/Base Catalytic System

Cecchi

Sarlo

Machetti

2008

Chemistry A European J

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A new procedure for the synthesis of 4.5-dihydroisoxazoles by condensation of primary nitro compounds with olefins by using a copper/base catalytic system is described. The catalytic effect of copper(II) salts is evidenced by comparison of the reaction rates. Thus, activated nitro compounds react faster than with organic catalysis by tertiary amines, whereas nitroalkanes, unable to condense with dipolarophiles in the presence of the base alone, undergo the reaction on addition of a copper(II) catalyst. The observed occurrence of induction periods in most reactions is ascribed to an equilibrium preceding the rate-determining step, and gives a hint as to the proposed reaction mechanism. The results indicate that this method might be of practical and general utility for synthetic practice.

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Section: Introductionmentioning

confidence: 98%

Synthesis of 4,5‐Dihydroisoxazoles by Condensation of Primary Nitro Compounds with Alkenes by Using a Copper/Base Catalytic System

Cecchi

Sarlo

Machetti

2008

Chemistry A European J

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“…-Nitro compounds, such as nitroacetates [30], nitroketones, and nitroamides [31] were also used for Mn(OAc) 3 mediated free radical addition to alkenes. The intramolecular cyclization reaction that was carried out with -unsubstituted nitroacetates was shown by Snider to afford mixtures of isoxazolines by dehydration to a nitrile oxide that underwent cycloaddition, as well as isoxazoline oxides or cyclopropanes by oxidative cyclization.…”

Section: Chmentioning

confidence: 99%

Manganese(III) Acetate: A Versatile Reagent in Organic Chemistry

Demir¹,

Emrullahoğlu

2007

COS

106

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Free radical reactions have become increasingly important, as well as a very attractive tool, in organic synthesis within the last two decades, due to their powerful, selective, specific, and mild reaction abilities. Mn(OAc)3 mediated oxidative free radical reactions have been extensively developed in the last twenty years. Numerous regio-, chemo-, and stereoselective synthetic methods have been developed in both inter-and intramolecular reactions, and have detailed the progress of Mn(OAc)3 mediated oxidative free radical reactions since the end of the 19 th century. The new literature about the new synthetic methods on Mn(OAc)3 mediated carbon-carbon bond formation and carbon-oxygen bond formation reactions has not been extensively reviewed. The present paper summarizes the recent developments in oxidative free radical reactions mediated by Mn(OAc)3. Mn(OAc)3 mediated reactions of conjugated systems (e.g., alkenes, alkynes, 1,3-alkadienes, l,3-alkadiynes, 1-alken-3-ynes) with -dicarbonyl compounds, Mn(OAc)3 mediated alkylation, such as the oxidative addition of an aldehyde or ketone to alkenes, Mn(OAc)3 mediated free-radical cyclization of alkenes with active methylene compounds in the presence of oxygen to afford the cyclic peroxides; lactone synthesis by the Mn(OAc)3 mediated oxidative addition of carboxylic acids to alkenes, Mn(OAc)3 mediated cyclization of -(methylthio)acetamides, enamides, and -keto carboxamides to afford cyclic products.Mn(OAc)3 oxidative free-radical cyclizations of allylic -dicarbonyl compounds, for example, the cyclization of allylic -ketoesters to afford the corresponding -lactone. The reaction of alkenes with sodium azide in the presence of acetic acid was investigated to afford 1.2-diazides. The selective oxidation of enones led to '-acetoxy-enones by Mn(OAc)3 oxidation. In general, Mn(OAc)3 oxidations are characterized by higher '-regioselectivity and chemical yields, and milder reaction conditions, in turn tolerating many sensitive functional groups. The use of Mn(OAc)3 in combination with other carboxylic acids or manganese(II) carboxylates extends this methodology to the preparation of a variety of '-acyloxyenones that are otherwise inaccessible in a one-step procedure.

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“…Isoxazoles and 2-pyrazoles can be easily obtained by oxidation of isoxazolines [12][13][14][15][16][17] and 2-pyrazolines [18], respectively. Several methods have been reported for oxidation of isoxazolines and 2-pyrazolines including Pd-C-acetic acid [19], carbon-activated oxygen [20], cobalt soap of fatty acids [21] [23], manganese dioxide [24], potassium permanganate [24,25], silver nitrate [26], iodobenzene diacetate [27], zirconium nitrate [28], nickel peroxide [29], chromite [16], N-bromosuccinimide (NBS) [30], manganese triacetate [31], sodium bicarbonate-dimethylformamide [32], 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) [33], sodium carbonate-methanol [10], and tetrakis pyridine nickel(II) dichromate [34]. However, many of these methods have such disadvantages as long reaction times, low yields, and toxicity because of the elements present in the reagents used.…”

Section: Introductionmentioning

confidence: 99%

Mild and efficient oxidation of 2-pyrazolines and isoxazolines by trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxalane–NH4Cl–HOAc in water–MeCN

Khosravi

2014

Res Chem Intermed

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Manganese(III) acetate initiated oxidative free radical reaction between 1,4-naphthoquinones and ethyl nitroacetate

Cited by 43 publications

References 21 publications

Synthesis of 4,5‐Dihydroisoxazoles by Condensation of Primary Nitro Compounds with Alkenes by Using a Copper/Base Catalytic System

Synthesis of 4,5‐Dihydroisoxazoles by Condensation of Primary Nitro Compounds with Alkenes by Using a Copper/Base Catalytic System

Manganese(III) Acetate: A Versatile Reagent in Organic Chemistry

Mild and efficient oxidation of 2-pyrazolines and isoxazolines by trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxalane–NH4Cl–HOAc in water–MeCN

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