Insertion of Arynes into P–O Bonds: One-Step Simultaneous Construction of C–P and C–O Bonds

Qi, Na; Ning, Zengping; Allu, Srinivasa Rao; J, Gao; Guo, Jingjie; He, Yun

doi:10.1021/acs.orglett.6b03283

Cited by 46 publications

(28 citation statements)

References 52 publications

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“…Two equivalents of NaOH in water were used in the hydrolysis of a series of ethyl phosphinates ( 58 ) carried out with stirring at 80 °C for 6–12 h. The sodium salt formed during the alkaline hydrolysis was converted to free acid ( 5 ) by treatment with hydrochloric acid in the second step ( Scheme 29 ) [ 110 ].…”

Section: Alkaline and Basic Hydrolysismentioning

confidence: 99%

The Hydrolysis of Phosphinates and Phosphonates: A Review

Harsági

Keglevich

2021

Molecules

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Phosphinic and phosphonic acids are useful intermediates and biologically active compounds which may be prepared from their esters, phosphinates and phosphonates, respectively, by hydrolysis or dealkylation. The hydrolysis may take place both under acidic and basic conditions, but the C-O bond may also be cleaved by trimethylsilyl halides. The hydrolysis of P-esters is a challenging task because, in most cases, the optimized reaction conditions have not yet been explored. Despite the importance of the hydrolysis of P-esters, this field has not yet been fully surveyed. In order to fill this gap, examples of acidic and alkaline hydrolysis, as well as the dealkylation of phosphinates and phosphonates, are summarized in this review.

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Section: Alkaline and Basic Hydrolysismentioning

confidence: 99%

The Hydrolysis of Phosphinates and Phosphonates: A Review

Harsági

Keglevich

2021

Molecules

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“…Following this procedure, phenylphosphate 27 was synthesized in 88% yield. 2-Naphtylphosphate 28 was accessed from the corresponding naphtyne precursor in 65% yield and 3,4dimethylphenylphosphate (29) was isolated in a yield of 92%. Garg's indole 4,5-indolyne-precursor was transformed to indolylphosphate 30 in 41% yield, in a regioisomeric ratio of 96:4 (5-30:4-30).…”

Section: Synthesis Of (Pyro)phosphomonoestersmentioning

confidence: 99%

“…[26][27][28] Moreover, He presented a σ-P-O-bond insertion of arynes into organophosphinic acids (9). [29] In summary, the broad spectrum of aryne reactivity can be exploited with phosphorous functionalities towards diversely arylated products enabling C-P -bond formation. However, no exclusive aryne-based Oarylation has ever been described in the synthesis of organophosphorous compounds.…”

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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“…In 2016, He, Guo and co‐workers reported the σ‐insertion reaction of arynes with phosphinic acid and their analogues (Scheme 23). [34] A variety of ortho ‐hydroxy‐substituted arylphosphine oxides, phosphinates, and phosphonates were obtained in moderate to good yields. Likewise, the mechanistic pathway involved the crucial four‐membered ring intermediates that were initiated by O‐arylations.…”

Section: Reactions Of Aryne With Organophosphorus(v) Compoundsmentioning

confidence: 99%

Reactions of Organophosphorus Compounds with Arynes: Reactivity and Mechanism

et al. 2020

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Aryl phosphorus compounds have found versatile applications in materials, medicinal and synthetic chemistry. As a powerful tool, aryne chemistry has been widely utilized in constructing aryl C−P bonds under mild conditions; this has enabled facile access to a variety of structurally diverse aryl–phosphorus compounds with good efficiency. The present review aims to offer a comprehensive overview of the chemistry between arynes and organophosphorus compounds, with emphasis placed on reactivity modes and mechanistic aspects. According to the valency of phosphorus atoms, this paper is divided into two main sections, reactions of arynes with organophosphorus(III) compounds and those with organophosphorus(V) compounds.magnified image

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Insertion of Arynes into P–O Bonds: One-Step Simultaneous Construction of C–P and C–O Bonds

Cited by 46 publications

References 52 publications

The Hydrolysis of Phosphinates and Phosphonates: A Review

The Hydrolysis of Phosphinates and Phosphonates: A Review

The Aryne Phosphate Reaction

Reactions of Organophosphorus Compounds with Arynes: Reactivity and Mechanism

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