Alkane desaturation by concerted double hydrogen atom transfer to benzyne

Niu, Dawen; Willoughby, Patrick H.; Woods, Brian P.; Baire, Beeraiah; Hoye, Thomas R.

doi:10.1038/nature12492

Cited by 136 publications

(82 citation statements)

References 27 publications

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“…Recent examples include the construction of very large polycyclic aromatic hydrocarbons 9,10 , the use of pyridynes as building blocks 11 or the chemical modification of graphene sheets 12 and carbon nanotubes 13 . Moreover, recent approaches to generate benzynes by cycloisomerization of triyne precursors revealed unexpected opportunities in aryne chemistry [14][15][16][17] . Despite this broad range of practical applications, their structural characterization has been the subject of debate and remains a challenge.…”

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confidence: 99%

On-surface generation and imaging of arynes by atomic force microscopy

et al. 2015

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Reactive intermediates are involved in many chemical transformations. However, their characterization is a great challenge because of their short lifetimes and high reactivities. Arynes, formally derived from arenes by the removal of two hydrogen atoms from adjacent carbon atoms, are prominent reactive intermediates that have been hypothesized for more than a century. Their rich chemistry enables a widespread use in synthetic chemistry, as they are advantageous building blocks for the construction of polycyclic compounds that contain aromatic rings. Here, we demonstrate the generation and characterization of individual polycyclic aryne molecules on an ultrathin insulating film by means of low-temperature scanning tunnelling microscopy and atomic force microscopy. Bond-order analysis suggests that a cumulene resonance structure is the dominant one, and the aryne reactivity is preserved at cryogenic temperatures. Our results provide important insights into the chemistry of these elusive intermediates and their potential application in the field of on-surface synthesis.

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confidence: 99%

On-surface generation and imaging of arynes by atomic force microscopy

et al. 2015

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“…Recently, Hoye and coworkers reported a strongly related process leading to the desaturation of alkanes promoted by benzynes. [9] Thus, species II, generated through a hexadehydroDiels-Alder (HDDA) reaction [10] from triyne I, is able to accept two vicinal hydrogen atoms from a suitable alkane 2H donor (i.e., a cyclic hydrocarbon) to produce the bicyclic species III (Scheme 2). This transformation is compatible with different HDDA-generated 1,2-benzynes and cyclic alkanes or heterocycles (from cyclopentane or tetrahydrofuran to cyclooctane) and can even occur at room temperature.…”

Section: Introductionmentioning

confidence: 99%

“…This level was chosen because it was previously used by Hoye and coworkers [9] and also by us [11] to study these particular DGTR. Reactants and products were characterized by frequency calculations at the M06-2X/6-311 1 G(d,p) level, and have positive definite Hessian matrices.…”

Section: Introductionmentioning

confidence: 99%

“…This transformation is compatible with different HDDA-generated 1,2-benzynes and cyclic alkanes or heterocycles (from cyclopentane or tetrahydrofuran to cyclooctane) and can even occur at room temperature. According to Density Functional Theory (DFT) calculations, [9,11] the II ! III transformation can be viewed as a concerted DGTR which proceeds with relatively low activation barriers (DG 6 ¼ in the range of 17 to 27 kcal/mol).…”

Section: Introductionmentioning

confidence: 99%

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Interplay between aromaticity and strain in double group transfer reactions to 1,2-benzyne

Fernández

Cossío

2016

J. Comput. Chem.

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Density Functional Theory calculations are used to explore the double hydrogen atom transfer from different alkanes to 1,2-benzyne. State-of-the-art calculations including the Activation Strain Model of reactivity, Energy Decomposition Analysis, and Valence Bond methods, reveal the origins of the relatively low activation barriers computed for these processes compared to the analogous reaction involving acetylene. In addition, the interplay between the in-plane aromaticity of the corresponding transition states and the variation of the π-aromaticity associated with the benzyne moiety as well as their influence on the barrier heights of the transformations are analyzed in detail.

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“…Hoyle reported that other than alcohols, mediumsized cycloalkanes and even THF are good hydrogen donors to reduce arynes [16]. Okuma also reported [17] that α-amino acid methyl esters derived from phenylalanine and aspartic acid resulted in significant dehydrogenation (product E, Figure 4) after annulation to indolin-3-ones.…”

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confidence: 97%

Transfer Hydrogenation vs Nucleophilic Addition: Aryne Reaction with Alcohols

Dubrovskiy¹

2017

MOJBOC

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CommentaryMOJ Biorg Org Chem 2017, 1(1): 00004 manner [7]. As an illustrative example, when carbodiimide, a not well recognized nucleophile, and methanol are both present, aryne would selectively react with the former [8]. This seemingly counterintuitive "inertness" of benzyne toward aliphatic alcohols, along with some others highlighted in our recent review [9], constitutes a long-standing curiosity for aryne chemists, both synthetically and mechanistically.

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Alkane desaturation by concerted double hydrogen atom transfer to benzyne

Cited by 136 publications

References 27 publications

On-surface generation and imaging of arynes by atomic force microscopy

On-surface generation and imaging of arynes by atomic force microscopy

Interplay between aromaticity and strain in double group transfer reactions to 1,2-benzyne

Transfer Hydrogenation vs Nucleophilic Addition: Aryne Reaction with Alcohols

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