From insertion to multicomponent coupling: temperature dependent reactions of arynes with aliphatic alcohols

Thangaraj, Manikandan; Bhojgude, Sachin Suresh; Mane, Manoj V.; Biju, Akkattu T.

doi:10.1039/c5cc08307a

Cited by 52 publications

(33 citation statements)

References 42 publications

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“…Biju reported that the reaction of arynes with alcohols in THF as a solvent preferentially generates three-component assembly product 60 over the alcohol insertion product. 76 Yoshida reported that 59 readily reacts with aryl or alkynyl bromides followed by ring opening to generate o-bromoaryl ether 61. 29 Cyclic thioethers react with arynes in a similar manner as cyclic ethers (Scheme 22).…”

Section: Trapping With Ethers and Thioethersmentioning

confidence: 99%

Aryne-Based Multicomponent Coupling Reactions

Ghorai¹,

Lee²

2020

Synlett

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Multicomponent reactions (MCRs) constitute a powerful synthetic tool to generate a large number of small molecules with high atom economy, which thus can efficiently expand the chemical space with molecular diversity and complexity. Aryne-based MCRs offer versatile possibilities to construct functionalized arenes and benzo-fused heterocycles. Because of their electrophilic nature, arynes couple with a broad range of nucleophiles. Thus, a variety of aryne-based MCRs have been developed, the representative of which are summarized in this account.1 Introduction2 Aryne-Based Multicomponent Reactions2.1 Trapping with Isocyanides2.2 Trapping with Imines2.3 Trapping with Amines2.4 Insertion into π-Bonds2.5 Trapping with Ethers and Thioethers2.6 Trapping with Carbanions2.7 Transition-Metal-Catalyzed Approaches3 Strategies Based on Hexadehydro Diels–Alder Reaction3.1 Dihalogenation3.2 Halohydroxylation and Haloacylation3.3 Amides and Imides3.4 Quinazolines3.5 Benzocyclobutene-1,2-diimines and 3H-Indole-3-imines3.6 Other MCRs of Arynes and Isocyanides4 Conclusion

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Section: Trapping With Ethers and Thioethersmentioning

confidence: 99%

Aryne-Based Multicomponent Coupling Reactions

Ghorai¹,

Lee²

2020

Synlett

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“…1‐Methoxy‐4‐(phenoxymethyl)benzene ( 3 d ) . White solid (35.7 mg, 84 %, Procedure A ), a mixture of petroleum ether/ ethyl acetate=40/ 1 (v/ v) as eluents for column chromatography.…”

Section: Methodsmentioning

confidence: 99%

Base‐Mediated O‐Arylation of Alcohols and Phenols by Triarylsulfonium Triflates

Ming

Tian

Zhang

2019

Chemistry An Asian Journal

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A mild and efficient protocol for O‐arylation of alcohols and phenols (ROH) by triarylsulfonium triflates was developed under transition‐metal‐free conditions. Various alcohols, including primary, secondary and tertiary, and phenols bearing either electron‐donating or electron‐withdrawing groups on the aryl rings were smoothly converted to form the corresponding aromatic ethers in moderate to excellent yields. The reactions were conducted at 50 or 80 °C for 24 h in the presence of a certain base and showed good functional group tolerance. The base‐mediated arylation with asymmetric triarylsulfonium salts could selectively transfer the aryl groups of sulfoniums to ROH, depending on their inherent electronic nature. The mechanistic studies revealed that the reaction might proceed through the nucleophilic attack of the in situ formed alkoxy or phenoxy anions at the aromatic carbon atoms of the C−S bonds of triarylsulfonium cations to furnish the target products.

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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 carboxylgroup arylation protocols since 2004. [30][31][32] Despite the many studies scrutinizing the reactivity of diverse arynophiles, the ability of phosphates to engage in reactions with arynes is absent from the literature. This is remarkable, as the urgent need to access probes for interrogation of phosphate functions, e.g.…”

Section: Introductionmentioning

confidence: 99%

The Aryne Phosphate Reaction

Haas

Wiesler

Dürr‐Mayer

et al. 2021

Preprint

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Condensed phosphates are a critically important class of molecules in biochemistry, with a myriad of derived structures being known. Moreover, non-natural analogues are important for various applications, such as single molecule real time DNA sequencing. Often, 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 an essential endeavour in the field. Here, we scrutinize the potential of phosphates to act as arynophiles, paving the way for follow-up oligophosphorylation reactions. The aryne phosphate reaction is a powerful tool to – depending on the perspective – (oligo)phosphorylate arenes or arylate (oligo-cyclo)phosphates. Based on Kobayashi-type o-silylaryltriflates, the aryne phosphate reaction enables rapid entry into a broad spectrum of arylated products, like monophosphates, diphosphates, phosphodiesters and polyphosphates. The synthetic potential of these new transformations is demonstrated by efficient syntheses of nucleotide analogues and an unprecedented one-flask octaphosphorylation.

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From insertion to multicomponent coupling: temperature dependent reactions of arynes with aliphatic alcohols

Cited by 52 publications

References 42 publications

Aryne-Based Multicomponent Coupling Reactions

Aryne-Based Multicomponent Coupling Reactions

Base‐Mediated O‐Arylation of Alcohols and Phenols by Triarylsulfonium Triflates

The Aryne Phosphate Reaction

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