Photochemical transformations.  LII.  Benzyne

Chapman, O. L.; Mattes, K. C.; McIntosh, C. L.; Pacansky, J.; Calder, G. V.; Orr, G F

doi:10.1021/ja00799a060

Cited by 152 publications

(80 citation statements)

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“…[19,20] The recent elucidation of the mode of action of the highly potent enediyne anticancer drugs, [21] which involves a rearrangement of enediyne 15 to p-benzyne (14), known as Bergman cycloaromatization after its discoverer Robert G. Bergman, [22] led to a renaissance for all three benzyne isomers 12Ϫ14 and an even greater interest in their electronic and spectroscopic properties. [23Ϫ25] o-Benzyne has been investigated in detail in cryogenic matrices by UV/Vis [26] and FT-IR spectroscopy [27] and by gas-phase microwave spectroscopy. [28] Chapman first matrix-isolated o-benzyne in argon at 8 K by photolyzing benzocyclobutenedione 16 (Scheme 1).…”

Section: Benzocyclopropenone and O-benzynementioning

confidence: 99%

Inner-Phase Stabilization of Reactive Intermediates

Warmuth

2001

Eur. J. Org. Chem.

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Molecular container compounds are spherical, hollow molecules with inner cavities (inner phases) that are large enough to accommodate a single guest molecule. These inner phases are superb environments for the stabilization and spectroscopic investigation of important reactive intermediates. The surrounding host protects the incarcerated reactive intermediate from dimerization or from a reaction with bulk‐phase reactants that are too large to enter the inner phase by passing through a portal in the host shell.

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Section: Benzocyclopropenone and O-benzynementioning

confidence: 99%

Inner-Phase Stabilization of Reactive Intermediates

Warmuth

2001

Eur. J. Org. Chem.

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“…[47] The first matrix-isolation experiments with IR-spectroscopic observation of benzyne were reported in 1973 using phthaloyl proxide and benzocyclobutenedione as precursors. [48] o-Benzyne has now been characterized very thoroughly by IR spectroscopy [49] in noble gas matrices, which is reviewed herein, [19,25] as are the gas-phase microwave, [31,50] photoelectron and UV spectroscopic, [24] and mass spectrometric [25] investigations. Also the 1,2-naphthyne 5 and 2,3-naphthyne have been characterized by IR and UV spectroscopy.…”

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confidence: 99%

“…At higher temperatures it reacts irreversibly with the hemicarcerand host via Diels-Alder addition to benzene moieties. [53] The combined evidence from microwave, [31,50] NMR, [53a] and IR spectroscopy [48,49] as well as theoretical calculations [17,53b] indicates that o-benzyne can be described as a resonance hybrid of the acetylene 3 and the cumulene 14, being closer to the acetylenic structure (Eqn 4).…”

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confidence: 99%

The Benzyne Story

Wentrup¹

2010

Aust. J. Chem.

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The history of o-benzyne from its early beginnings as an unobservable reactive intermediate until its present status as a very well characterized but still theoretically challenging molecule with important applications in synthesis is reviewed. The m- and p-benzynes, tridehydrobenzenes, and benzdiynes are also known, and p-benzyne is a key intermediate in the action of a potent class of ene-diyne anti-tumour compounds.

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“…[11,12] Phthalic anhydrides have frequently been used to generate 1 a and its derivatives in inert gas matrices. [13][14][15] Iodoarenes, on the other hand, undergo photochemical or thermal cleavage of the CÀI bond and are thus precursors for aryl radicals and diradicals. [15][16][17] A general problem in the matrix photolysis of iodoarenes is the rapid thermal recombination of the aryl radicals with the iodine atoms which thus lowers the yield of the radicals.…”

mentioning

confidence: 99%