Synthesis of activated alkenes bearing the difluoromethylenephosphonate group: a range of building blocks for the synthesis of secondary difluorophosphonates

Blades, Kevin; Butt, Afshan H.; Cockerill, G. Stuart; Easterfield, Howard J.; Lequeux, Thierry; Percy, Jonathan M.

doi:10.1039/a907052d

Cited by 17 publications

(6 citation statements)

References 27 publications

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“…A novel and efficient strategy for the synthesis of a class of (α,α-difluoropropargyl)phosphonates via modification of the Corey–Fuchs methodology starting from (diethoxyphosphoryl)difluoroacetic aldehyde has been described. By the action of appropriate bases on the intermediate 3,3-dibromo-1,1-difluoroalkene, the synthesis of bromoalkyne and the generation of (diethoxyphosphoryl)difluoromethyllithium have been achieved for the first time.…”

Section: Discussionmentioning

confidence: 99%

Synthesis of (α,α-Difluoropropargyl)phosphonates via Aldehyde-to-Alkyne Homologation

Pajkert

Röschenthaler

2013

J. Org. Chem.

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An efficient synthetic methodology to a series of novel alkynes bearing a difluoromethylenephosphonate function via a Corey-Fuchs-type sequence starting from (diethoxyphosphoryl)difluoroacetic aldehyde is described. Dehydrobromination of the intermediate (3,3-dibromodifluoroallyl)phosphonate with potassium tert-butoxide gave rise to the corresponding bromoalkyne, whereas upon treatment with lithium base, the generation of ((diethoxyphosphoryl)difluoropropynyl)lithium has been achieved for the first time. The synthetic potential of this lithium reagent was further demonstrated by its reactions with selected electrophiles such as aldehydes, ketones, triflates, chlorophosphines, and chlorosilanes, leading to the corresponding propargyl phosphonates in good to excellent yields. However, in the case, of sterically hindered aldehydes, (α-fluoroallenyl)phosphonates were the solely isolated products.

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Section: Discussionmentioning

confidence: 99%

Synthesis of (α,α-Difluoropropargyl)phosphonates via Aldehyde-to-Alkyne Homologation

Pajkert

Röschenthaler

2013

J. Org. Chem.

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“…However, they have been explored very sparingly with sporadic reports of synthesis incorporating a γ -nitrophosphonate scaffold. [77][78][79][80][81][82][83][84][85] As a research group, we have been pursuing nitroalkene chemistry with great interest realizing the immense application potential of γ -nitrophosphonates. Our group has developed an efficient method for synthesis of γ -nitrophosphonates 203 via diastereo-and enantioselective Michael addition of α-lithiated alkyl phosphonates 202 to a variety of aromatic nitroalkenes 5.…”

Section: γ -Nitrophosphonates Via Michael Addition Of Phosphonates Tomentioning

confidence: 99%

Asymmetric synthesis of $\boldsymbol{\gamma}$ -aminophosphonates: The bio-isosteric analogs of $\boldsymbol{\gamma}$ -aminobutyric acid

2013

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The properties of aminophosphonates as transition state analogs of amino acids, and as antibacterial, antifungal and antiHIV agents attracted considerable attention in recent years. Although many reviews appeared in the literature covering αand β-aminophosphonates, γ-aminophosphonates did not receive sufficient attention despite the fact that parent γ-aminophosphonic acid and its derivatives are bio-isosteric analogs of GABA (γ-amino butyric acid). This review provides a critical summary of the significance of γ-aminophosphonates and various approaches to their synthesis, with particular emphasis to asymmetric versions.

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“…In this communication, we wish to show how a rearrangement-based route affords butyrolactone derivatives 1 (related to building blocks for nucleic acid analogues 1,2 ) and cyclohexenone derivatives 2 (related to deoxyinositol phosphate analogues 3 ). The approach complements our earlier conjugate addition 4,5 and cycloaddition 6 chemistry which was based upon chlorodifluoromethane as a feedstock.…”

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confidence: 90%

A rearrangement-based approach to secondary difluorophosphonates

2000

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Synthesis of activated alkenes bearing the difluoromethylenephosphonate group: a range of building blocks for the synthesis of secondary difluorophosphonates

Cited by 17 publications

References 27 publications

Synthesis of (α,α-Difluoropropargyl)phosphonates via Aldehyde-to-Alkyne Homologation

Synthesis of (α,α-Difluoropropargyl)phosphonates via Aldehyde-to-Alkyne Homologation

Asymmetric synthesis of $\boldsymbol{\gamma}$ -aminophosphonates: The bio-isosteric analogs of $\boldsymbol{\gamma}$ -aminobutyric acid

A rearrangement-based approach to secondary difluorophosphonates

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