Reaction of benzyne with benzene

Stiles, Martin K.; Burckhardt, Urs; Freund, G.

doi:10.1021/jo01286a111

Cited by 28 publications

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“…Currently, there are only a limited number of options to activate benzene sufficiently, including coordination of a transition metal complex to benzene 10 , naphthalene with small resonance energy 11 and the use of benzene derivatives with a sterically induced strained geometry 12 13 14 . Alternatively, exceptionally strong dienophiles or dienes under severe conditions (for example, high temperature and pressure) will undergo Diels–Alder cyclization with benzene 15 16 17 18 19 20 21 , and reactive unsaturated heavier main group analogues of an alkene or alkyne make adducts with arenes under mild conditions 22 23 24 . As a rather peculiar case, 1,4-addition of benzene to a dihydrocyclopent[ a ]indene diradical is also reported 25 .…”

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confidence: 99%

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

2014

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Cyclic polyene with six carbon atoms (benzene) is very stable, whereas cyclic polyene with four carbon atoms (cyclobutadiene) is extremely unstable. The electron-withdrawing pentafluorophenyl group of a substituted cyclobutadiene lowers the energy of the lowest unoccupied molecular orbital, greatly increasing its reactivity as a diene in Diels–Alder reactions with acetylene, ethylene and even benzene. Here we show that the reaction with benzene occurs cleanly at the relatively low temperature of 120 °C and results in the formal fragmentation of benzene into C2H2 and C4H4 units, via a unique Diels–Alder/retro-Diels–Alder reaction. This is a new example of the rare case where breaking the C–C bond of benzene is possible with no activation by a transition metal.

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confidence: 99%

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

2014

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“…Benzyne cycloadditions with alkynes have also been reported. 7 In an early mechanistic work, Roberts has investigated benzyne reactivity with a variety of nucleophiles such as fluorenyl, anilide, acetophenone enolate, and phenylacetylide. 8 Copper- and other transition-metal-catalyzed reactions of alkynes with arynes have been described.…”

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confidence: 99%

Transition-Metal-Free Alkynylation of Aryl Chlorides

Truong

Daugulis

2011

Org. Lett.

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Two sets of conditions have been developed for a base-mediated, transition-metal-free alkynylation of aryl chlorides that proceeds via benzyne intermediates. The first set of conditions involves the use of TMPLi base in a pentane/THF mixture at 25 °C. The second set involves use of a metal alkoxide base in dioxane at elevated temperature. Reasonable functional group tolerance has been observed. Fluoro, trifluoromethyl, silyl, cyano, and alcohol functionalities are compatible with the reaction conditions.

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“…Benzyne species are highly unstable intermediates that can be generated in situ from various precursors. Classical benzyne precursors are represented by benzene derivatives with good leaving groups such as aryl halides,– arene‐diazonium‐2‐carboxylates,– 1,2,3‐benzothiadiazole 1,1‐dioxides, 1‐aminobenzotriazole, and ortho ‐silylaryl triflates (Kobayashi's reagent) . These common benzyne precursors are usually activated by either a metal or a strong base and often require high temperature for benzyne generation.…”

Section: Methodsmentioning

confidence: 99%

Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature

Yoshimura

Fuchs

Middleton

et al. 2017

Chemistry A European J

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New organohypervalent iodine compounds, arylbenziodoxaborole triflates, were prepared from 1-acetoxybenziodoxaboroles and arenes by treatment with trifluoromethanesulfonic acid under mild conditions. Single crystal X-ray crystallography of these compounds revealed a pseudocyclic structure with a short intramolecular interaction of 2.698 to 2.717 Å between oxygen and iodine in the benziodoxaborole ring. These new pseudocyclic aryliodonium salts readily generate aryne intermediates upon treatment with water at room temperature. The generated aryne intermediates react with various substrates to give the corresponding aryne adducts in moderate to good yields. Furthermore, the new benzyne precursors can also work as arylating reagents towards aromatic rings. The aryne intermediates generated from arylbenziodoxaborole triflates selectively react with tert-butyl phenol forming products of ortho arylation in moderate yields.

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Reaction of benzyne with benzene

Cited by 28 publications

References 0 publications

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

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

Transition-Metal-Free Alkynylation of Aryl Chlorides

Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature

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