Mechanism of manganese(III)-based oxidation of .beta.-keto esters

Snider, Barry B.; Patricia, Jeffrey J.; Kates, Steven A.

doi:10.1021/jo00245a001

Cited by 137 publications

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“…Concentration under vacuum gave the desired product as a crystalline solid, >95 % pure by GC, which was used without further purification. Spectral data agreed with those previously reported (Snider et al, 1988). …”

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confidence: 92%

Chemical communication in mating behaviour of the slave-making ant Polyergus rufescens (Hymenoptera, Formicidae): 3-ethyl-4-methylpentanol as a critical component of the queen sex pheromone

et al. 2008

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The aim of the research reported here was to determine whether 3-ethyl-4-methylpentanol, a minor but crucial component of the sex pheromone of the North American slave-making ant species Polyergus breviceps, was also a component of the sex pheromone of the European congener Polyergus rufescens. Thus, the contents of mandibular glands of P. rufescens virgin queen were extracted and analysed. The main component of the extracts was methyl 6-methylsalicylate and 3-ethyl-4-methylpentanol was identified as one of several minor components. Further analyses showed that the insects produce mainly the (R)-enantiomer of the alcohol. Males responses to various blends of methyl 6-methylsalicylate with the racemate or the pure enantiomers of 3-ethyl-4-methylpentanol were tested in field behavioural bioassays. The data showed that blends of methyl 6-methylsalicylate and 3-ethyl-4-methylpentanol were strongly synergistic, with the most active ratios being biased toward the first component. The addition of other minor components to the binary blend neither increased nor decreased responses by males. Only the (R)-enantiomer of the alcohol was biologically active; its antipode did not inhibit attraction. The results are discussed in terms of the evolution of signals, and are compared with the results previously obtained for the allopatric species Polyergus breviceps.

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confidence: 92%

Chemical communication in mating behaviour of the slave-making ant Polyergus rufescens (Hymenoptera, Formicidae): 3-ethyl-4-methylpentanol as a critical component of the queen sex pheromone

et al. 2008

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“…42 crystallographic analysis conrmed that oxidative cyclization, theoretically possible on carbon 2 or on carbon 4 of naphthoquinones, only took place on carbon 2, probably because of its greater electrophilic nature.…”

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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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“…However, the dimmer [7] was isolated in 65% yield. We found that when the reaction was carried out at room temperature, the oxidative cyclization product 3a could be obtained in moderate yield in 24 h. Therefore, we conducted the oxidative cyclization reaction of MCPs 1 with ethyl 2-methylacetoacetate (1.2 equiv) in the presence of Mn(OAc) 3 (2.5 equiv) in HOAc at room temperature.…”

Section: Introductionmentioning

confidence: 99%

“…A plausible mechanism for the reaction of MCPs 1 with substituted dicarbonyl compounds in the presence of HOAc is shown in Scheme 4. Initiation occurs with the manganese(III) acetate oxidation of substituted dicarbonyl compounds to produce radical 7 [7,8]. The radical intermediate 7 undergoes intermolecular addition to the C@C bond of MCPs to give intermediate 8.…”

Section: Introductionmentioning

confidence: 99%

Mn(III)-based oxidative tandem free-radical cyclizations of methylenecyclopropanes with substituted dicarbonyl compounds

Huang

2007

Journal of Organometallic Chemistry

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Mechanism of manganese(III)-based oxidation of .beta.-keto esters

Cited by 137 publications

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Chemical communication in mating behaviour of the slave-making ant Polyergus rufescens (Hymenoptera, Formicidae): 3-ethyl-4-methylpentanol as a critical component of the queen sex pheromone

Chemical communication in mating behaviour of the slave-making ant Polyergus rufescens (Hymenoptera, Formicidae): 3-ethyl-4-methylpentanol as a critical component of the queen sex pheromone

Mn(OAc)₃ catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

Mn(III)-based oxidative tandem free-radical cyclizations of methylenecyclopropanes with substituted dicarbonyl compounds

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Mechanism of manganese(III)-based oxidation of .beta.-keto esters

Cited by 137 publications

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Chemical communication in mating behaviour of the slave-making ant Polyergus rufescens (Hymenoptera, Formicidae): 3-ethyl-4-methylpentanol as a critical component of the queen sex pheromone

Chemical communication in mating behaviour of the slave-making ant Polyergus rufescens (Hymenoptera, Formicidae): 3-ethyl-4-methylpentanol as a critical component of the queen sex pheromone

Mn(OAc)3 catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

Mn(III)-based oxidative tandem free-radical cyclizations of methylenecyclopropanes with substituted dicarbonyl compounds

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Mn(OAc)₃ catalyzed intermolecular oxidative peroxycyclization of naphthoquinone