The insertion of arynes into the O–H bond of aliphatic carboxylic acids

Wen, Chunxiao; Chen, Qian; He, Zhenwen; Yan, Xinxing; Zhang, Changyuan; Du, Zhiyun; Zhang, Kun

doi:10.1016/j.tetlet.2015.08.019

“…Until 2015, Chen, Zhang, and co-workers could solve this inactivity problem on aliphatic carboxylic acids. As shown in Scheme b, they noticed that sodium carboxylates, generated from NaOH and aliphatic carboxylic acids, have enhanced nucleophilicity over their acid form . Consequently, a combination of aliphatic carboxylic acid and its sodium salt in the reaction with arynes could furnish the corresponding products 5-42 along with a small amount of C–OH bond insertion products.…”

Section: Nucleophilic Addition Reactionsmentioning

confidence: 99%

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

Shi

¹

,

Li

²

,

Li

³

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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“…However,no exclusive aryne-based O-arylation has ever been described in the synthesis of organophosphorous compounds.M ore generally," there are limited examples of O-arylation transformations" [6] using arynes (Scheme 1, B), overall restricted to few hydroxyl and carboxyl-group arylation protocols since 2004. [30][31][32] Despite the many studies scrutinizing the reactivity of diverse arynophiles,t he ability of phosphates to engage in reactions with arynes is absent from the literature.T his is remarkable,a st he urgent need to access probes for interrogation of phosphate functions,f or example,i na nalytical biochemistry,h as driven innovative synthesis strategy development in the past years. [33][34][35][36][37] Here,wepresent adetailed study of the phosphate aryne reaction.…”

Section: Introductionmentioning

confidence: 99%

The Aryne Phosphate Reaction**

Haas

¹

,

Wiesler

²

,

Dürr‐Mayer

³

et al. 2021

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Condensed phosphates are ac ritically important class of molecules in biochemistry.Non-natural analogues are important for various applications,s uch as single-molecule real-time DNAs equencing.O ften, such analogues contain more than three phosphate units in their oligophosphate chain. Consequently,investigations into phosphate reactivity enabling new ways of phosphate functionalization and oligophosphorylation are essential. Here,w es crutinizet he potential of phosphates to act as arynophiles,paving the way for follow-up oligophosphorylation reactions.The aryne phosphate reaction is ap owerful tool to-depending on the perspective-(oligo)phosphorylate arenes or arylate (oligo-cyclo)phosphates. Based on Kobayashi-type o-silylaryltriflates,t he aryne phosphate reaction enables rapid entry into ab road spectrum of arylated products,l ike monophosphates,d iphosphates,p hosphodiesters and polyphosphates.T he synthetic potential of these new transformations is demonstrated by efficient syntheses of nucleotide analogues and an unprecedented one-flask octaphosphorylation.

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“…More generally, “there are limited examples of O‐arylation transformations” [6] using arynes (Scheme 1 , B), overall restricted to few hydroxyl and carboxyl‐group arylation protocols since 2004. [ 30 , 31 , 32 ]…”

Section: Introductionmentioning

confidence: 99%

The Aryne Phosphate Reaction**

Haas

¹

,

Wiesler

²

,

Dürr‐Mayer

³

et al. 2021

View full text Add to dashboard Cite

Condensed phosphates are ac ritically important class of molecules in biochemistry.Non-natural analogues are important for various applications,s uch as single-molecule real-time DNAs equencing.O ften, such analogues contain more than three phosphate units in their oligophosphate chain. Consequently,investigations into phosphate reactivity enabling new ways of phosphate functionalization and oligophosphorylation are essential. Here,w es crutinizet he potential of phosphates to act as arynophiles,paving the way for follow-up oligophosphorylation reactions.The aryne phosphate reaction is ap owerful tool to-depending on the perspective-(oligo)phosphorylate arenes or arylate (oligo-cyclo)phosphates. Based on Kobayashi-type o-silylaryltriflates,t he aryne phosphate reaction enables rapid entry into ab road spectrum of arylated products,l ike monophosphates,d iphosphates,p hosphodiesters and polyphosphates.T he synthetic potential of these new transformations is demonstrated by efficient syntheses of nucleotide analogues and an unprecedented one-flask octaphosphorylation.

show abstract

The insertion of arynes into the O–H bond of aliphatic carboxylic acids

Cited by 14 publications

References 42 publications

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

The Aryne Phosphate Reaction**

The Aryne Phosphate Reaction**

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