The Dimerization of Gaseous Benzyne

“…As short-lived intermediates, , arynes possess some unique properties. The triple bond on an aryne is somewhere between a double and a triple bond.…”

Section: Introductionmentioning

confidence: 99%

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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Arynes are among the most active organic intermediates and have found numerous applications in expeditious preparation of substituted arenes. In the past 20 years, chemists have witnessed a resurgence in aryne chemistry, which is mainly attributed by the extensive utilization of Kobayashi's method, a fluoride-induced removal of the TMS group with concomitant departure of its ortho OTf group on o-silylaryl triflates. Nowadays, o-silylaryl triflates are the most frequently employed aryne precursors. This review provides an overview of the history of Kobayashi's method, its methodological achievements, and its applications in the synthesis of natural products, bioactive molecules, and polycyclic aromatic hydrocarbons.

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“…[36] Monitoring of the dimerization of gaseous benzyne produced by flash photolysis of solid benzene diazonium carboxylate 5 in an evacuated tube by both UV and mass spectrometry permitted the determination of a preliminary rate of dimerization to biphenylene as equal to or greater than 8 ± 10 8 l mol −1 s −1 . [37] This value was considered to be within a factor of 3 of the true bimolecular rate constant, which is just a little short of a rate measured a few years later by flash photolysis of phthalic anhydride vapour in Ne and Ar, 4.6 ± 1.2 × 10 9 l mol −1 s −1 . [38] The photolysis of either 9, 10, or phthaloyl peroxide 11 in the presence of tetraphenylcyclopentadienone (tetracyclone) yielded 1,2,3,4-tetraphenylnaphthalene, formed via Diels-Alder addition of benzyne followed by cheletropic extrusion of CO (Scheme 7).…”

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confidence: 95%

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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The Dimerization of Gaseous Benzyne

Cited by 39 publications

References 2 publications

The nature of the “triple bond” of 1,2-benzyne

The nature of the “triple bond” of 1,2-benzyne

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

The Benzyne Story

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