A Diels–Alder super diene breaking benzene into C2H2 and C4H4 units

Inagaki, Yusuke; Nakamoto, Masaaki; Sekiguchi, Akira

doi:10.1038/ncomms4018

Cited by 24 publications

(16 citation statements)

References 35 publications

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“…Diels–Alder reactions with ethylene may be conducted under mild conditions if the diene is destabilized by electronic effects. This usually involves chemistry with reactive species, such as cyclobutadienes, cyclopentadienones, or tetrazines. − In the present study, we show that superelectrophiles may also participate in Diels–Alder reactions with ethylene under mild conditions.…”

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confidence: 51%

Diels–Alder Reactions with Ethylene and Superelectrophiles

et al. 2018

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Diels-Alder reactions have been accomplished with ethylene as the dienophile through the use of inverse-electron demand Diels-Alder chemistry. As a key aspect of the chemistry, the dienes are part of tri- or dicationic superelectrophilic systems. Theoretical calculations reveal that the highly charged superelectrophiles possess exceptionally low lying LUMOs, and this facilitates the cycloaddition chemistry with ethylene. The chemistry has been used to prepare a series of tetrahydroquinoline products. This represents the first application of superelectrophilic activation in a cycloaddition reaction, and a new method of utilizing ethylene as a C building block.

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confidence: 51%

Diels–Alder Reactions with Ethylene and Superelectrophiles

et al. 2018

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“…Another interesting example of acetylene addition is provided by a non-classical Diels-Alder reaction with substituted cyclobutadiene 166 [ 201 ]. The dried acetylene is bubbled into a toluene solution of pentafluorophenyltris(trimethylsilyl)cyclobutadiene to afford the Dewar benzene-like structure 167 ( Scheme 91 ).…”

Section: Acetylene In Organic Synthesismentioning

confidence: 99%

Acetylene in Organic Synthesis: Recent Progress and New Uses

et al. 2018

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Recent progress in the leading synthetic applications of acetylene is discussed from the prospect of rapid development and novel opportunities. A diversity of reactions involving the acetylene molecule to carry out vinylation processes, cross-coupling reactions, synthesis of substituted alkynes, preparation of heterocycles and the construction of a number of functionalized molecules with different levels of molecular complexity were recently studied. Of particular importance is the utilization of acetylene in the synthesis of pharmaceutical substances and drugs. The increasing interest in acetylene and its involvement in organic transformations highlights a fascinating renaissance of this simplest alkyne molecule.

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“…Thus, the utility of the reactions reported so far is quite limited. It has also been demonstrated that the activation of benzene rings can be achieved at ambient temperature with reactive organic molecules , or transition-metal complexes. , These reactions, however, are limited to stoichiometric reactions and not applicable to catalytic reactions. In the situation described above, the development of efficient catalysts, capable of cracking benzene rings into useful C1 compounds at ambient temperature, is urgently required to solve environmental issues derived from benzene derivatives and to achieve industrial benefits.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Oxidative Cracking of Benzene Rings in Water

et al. 2018

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Efficient degradation of harmful benzene rings in water is indispensable for achieving a clean water environment. We report herein unprecedented catalytic oxidative benzene cracking (OBC) in water using a ruthenium(II)–aqua complex having an N-heterocyclic carbene ligand as a catalyst and a cerium(IV) salt as a sacrificial oxidant under mild conditions. The OBC reactions produced carboxylic acids such as formic acid, which can be converted to dihydrogen directly from the OBC solution using a rhodium(III) catalyst with adjustment of the solution pH to 3.3. The OBC reactions can be applied to monosubstituted benzene derivatives such as ethylbenzene, chlorobenzene, and benzoic acid. Initial rates of the OBC reactions showed a linear relationship in the Hammett plot with a negative slope, indicating the electrophilicity of a Ru(III)–oxyl complex as the reactive species in the catalytic OBC reaction. Also, we discuss a plausible mechanism of the catalytic OBC reactions based on the kinetic analysis and the product stoichiometry for the OBC reaction of nonvolatile sodium m-xylene sulfonate. The addition of an electrophilic radical to the aromatic ring to form arene oxide/oxepin is proposed as the initial step of the OBC reaction.

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A Diels–Alder super diene breaking benzene into C2H2 and C4H4 units

Cited by 24 publications

References 35 publications

Diels–Alder Reactions with Ethylene and Superelectrophiles

Diels–Alder Reactions with Ethylene and Superelectrophiles

Acetylene in Organic Synthesis: Recent Progress and New Uses

Catalytic Oxidative Cracking of Benzene Rings in Water

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