Facile Endoperoxypropellane Synthesis by Manganese(III) Acetate‐Mediated Aerobic Oxidation

Asahi, Kentaro; Nishino, Hiroshi

doi:10.1002/ejoc.200701232

Cited by 22 publications

(8 citation statements)

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“…5,38,39 At high temperature, under anaerobic conditions, a dihydrofuran ring is obtained, and at room temperature under aerobic conditions, oxygen trapping led to a 1,2-dioxane ring. Catalytic quantities of Mn(OAc) 3 are sufficient for this mechanism, summarized in Scheme 2.…”

Section: 41mentioning

confidence: 99%

Mn(OAc)₃ catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

et al. 2017

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Manganese(III) acetate-mediated peroxycyclization between 2-hydroxy-3-methylnaphthoquinone and various alkenes was performed to obtain dihydronaphtho[2,3-c][1,2]dioxine-5,10(3H,10aH)-diones. The reactivity of symmetrical or unsymmetrical 1,1-disubstituted alkenes and monosubstituted alkenes allowed the synthesis of more than 50 original molecules. Focusing on the excellent reactivity of 2-hydroxy-3-methylnaphthoquinone, we describe the first example of Mn(OAc) 3 reactivity with nitrosubstituted alkenes. The scope, limitations and stereochemistry of the products synthesized are discussed. Starting from monosubstituted alkenes, the instability of a pair of diastereoisomers was observed, leading to ring opening.

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Section: 41mentioning

confidence: 99%

Mn(OAc)₃ catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

et al. 2017

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“…The aerobic oxidation might be explained by a radical chain mechanism. To rationalize our experimental results, we presume the formation of Mn(III)-enolate complex A in situ undergoing single-electron transfer (SET) to give 1,3-dicarbonyl radical B and the reduced Mn(II) ( Scheme 5 ) [ 31 , 32 , 33 , 34 , 35 , 36 ]. This is the initiation step of the radical chain reaction.…”

Section: Resultsmentioning

confidence: 76%

“…In connection with our current investigation of the Mn(OAc) 3 -assisted aerobic oxidation [ 31 , 32 , 33 , 34 , 35 , 36 ], we found the double hydroperoxyalkylaton of barbituric acids [ 37 ], pyrazolidine-3,5-diones ( Scheme 1 ) [ 38 , 39 ], 4-hydroxy-1 H -quinolin-2-ones [ 40 ], and tetronic acid [ 41 ]. The reaction could not be stopped at the monohydroperoxyalkylation stage.…”

Section: Introductionmentioning

confidence: 94%

Mn(III)-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

et al. 2011

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The Mn(III)-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.

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“…At this time, the cyclization is controlled by the kinetics and thermodynamics, and also the nucleophilicity of the carbonyl oxygen. We previously reported the reactions using tricarbonyl substrates, giving dihydro‐2 H ‐pyrans, dihydrofuro[2, 3‐ b ]furans, azadioxa[4.3.3]‐, azadioxa[5.3.3]‐, azadioxa[6.3.3]‐, and azatrioxa[4.4.3]‐propellanes . In this paper, we concentrated on the reaction using the 3‐acetyl‐1‐arylalkane‐1,4‐dione derivatives and examined the difference in the reactivity for the nucleophilicity of the carbonyl oxygen.…”

Section: Introductionmentioning

confidence: 99%

Mn(III)‐Based Oxidative Cyclization of Alkenes Using Tricarbonyl System

et al. 2018

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The Mn(III)-based oxidation of 1,1-disubstituted ethenes with 2-(2-aryl-2-oxoethyl)malonates, 2-acetyl-4-aryl-4-oxobutanoates, and 3-acetyl-1-arylpentane-1,4-diones was evaluated. The reaction using the malonates mainly gave the 2,3-dihydro-4Hpyran-4,4-dicarboxylates along with g-lactones. A similar reaction using the acetyloxobutanoates and acetylpentanediones produced the 2,3,3a,6a-tetrahydrofuro[2, 3-b]furans and the corresponding dihydropyrans. The cyclization was strongly affected by the nucleophilicity of the carbonyl oxygen in the carbocation intermediate, and the kinetic and thermodynamic controls of the following reaction. The structure determination and the mechanisms are discussed.[a] T.

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Facile Endoperoxypropellane Synthesis by Manganese(III) Acetate‐Mediated Aerobic Oxidation

Cited by 22 publications

References 59 publications

Mn(OAc)₃ catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

Mn(OAc)₃ catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

Mn(III)-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

Mn(III)‐Based Oxidative Cyclization of Alkenes Using Tricarbonyl System

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Facile Endoperoxypropellane Synthesis by Manganese(III) Acetate‐Mediated Aerobic Oxidation

Cited by 22 publications

References 59 publications

Mn(OAc)3 catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

Mn(OAc)3 catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

Mn(III)-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

Mn(III)‐Based Oxidative Cyclization of Alkenes Using Tricarbonyl System

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Mn(OAc)₃ catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

Mn(OAc)₃ catalyzed intermolecular oxidative peroxycyclization of naphthoquinone