Reaction of phosphoranes with formate esters. New method for synthesis of vinyl ethers

Subramanyam, V.; Silver, E.H.; Soloway, Albert H.

doi:10.1021/jo00869a048

Cited by 29 publications

(5 citation statements)

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“…Despite the synthetic applicability of β-alkoxyacrylates, they are mainly prepared by conjugate addition of alcohols/phenols to propiolate esters (Figure a). ,− , Other less employed alternatives (Figure b) consist of esterification of alcohols with 3-alkoxyacryloyl chloride, Wittig reaction between (phosphanylidene)acetates and alkyl formates, addition/elimination of alcohols to β-iodo- or β-methoxyacrylates, ,,, and Reformatsky reaction with bromoacetates . The existence of a single methodology for obtaining this synthon has led us to search for a new possible route via a retrosynthetic analysis with two disconnections (Scheme ): the first based on O-alkylation of a formylacetate derivative followed by a Claisen condensation.…”

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confidence: 99%

TiCl₄/Et₃N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates

2016

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A methodology to build (E)-β-alkoxy- and (E)-β-aryloxyacrylate moieties from acetate and formate esters promoted by the TiCl/EtN system is presented. The reaction is compatible with a broad range of structural skeletons and elapses through an unusual condensation pathway. Taking into account the obtained results, we propose a plausible mechanism involving a bimetallic titanium intermediate for this type of transformation.

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confidence: 99%

TiCl₄/Et₃N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates

2016

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“…Upon deprotonation, phosphonate 7 (in the absence of aldehyde) underwent dimerisation to olefin 28 . While the exact mechanism is not known, it may involve a reactive carbene intermediate formed by α-elimination of the phosphonate as described in previous reports [ 23 ]. Alternatively, a base-promoted autoxidation of phosphonate 7 in the presence of trace amounts of oxygen, followed by olefination may be taking place ( Scheme 8 ) [ 24 – 26 ].…”

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confidence: 99%

Facile synthesis of 7-alkyl-1,2,3,4-tetrahydro-1,8-naphthyridines as arginine mimetics using a Horner–Wadsworth–Emmons-based approach

Lippa

Murphy

Barrett

2020

Beilstein J. Org. Chem.

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Integrin inhibitors based on the tripeptide sequence Arg–Gly–Asp (RGD) are potential therapeutics for the treatment of idiopathic pulmonary fibrosis (IPF). Herein, we describe an expeditious three-step synthetic sequence of Horner–Wadsworth–Emmons olefination, diimide reduction, and global deprotection to synthesise cores for these compounds in high yields (63–83% over 3 steps) with no need for chromatography. Key to this transformation is the phosphoramidate protecting group, which is stable to metalation steps.

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“…Upon deprotonation, phosphonate 7 (in the absence of aldehyde) underwent dimerisation to olefin 28. While the exact mechanism is not known, it may involve a reactive carbene intermediate formed by α-elimination of the phosphonate as described in previous reports [23]. Alternatively, a base-promoted autoxidation of phosphonate 7 in the presence of trace amounts of oxygen, followed by olefination may be taking place (Scheme 8) [24][25][26].…”

Section: Reaction Scopementioning

confidence: 88%

Facile Synthesis of 7-Alkyl-1,2,3,4-tetrahydro-[1,8]-naphthyridines as Arginine Mimetics Using a Horner–Wadsworth–Emmons Based Approach

Lippa¹,

Murphy²,

Barrett³

2020

Preprint

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Integrin inhibitors based on the tripeptide sequence Arg-Gly-Asp (RGD) are potential therapeutics for the treatment of idiopathic pulmonary fibrosis (IPF). Herein, we describe an expeditious three-step synthetic sequence of Horner–Wadsworth–Emmons olefination, diimide reduction and global deprotection to synthesise cores for these compounds in high yields (63–83% over 3 steps) with no need for chromatography. Key to this transformation is the phosphoramidate protecting group, which is stable to metalation steps.

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Reaction of phosphoranes with formate esters. New method for synthesis of vinyl ethers

Cited by 29 publications

References 5 publications

TiCl₄/Et₃N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates

TiCl₄/Et₃N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates

Facile synthesis of 7-alkyl-1,2,3,4-tetrahydro-1,8-naphthyridines as arginine mimetics using a Horner–Wadsworth–Emmons-based approach

Facile Synthesis of 7-Alkyl-1,2,3,4-tetrahydro-[1,8]-naphthyridines as Arginine Mimetics Using a Horner–Wadsworth–Emmons Based Approach

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Reaction of phosphoranes with formate esters. New method for synthesis of vinyl ethers

Cited by 29 publications

References 5 publications

TiCl4/Et3N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates

TiCl4/Et3N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates

Facile synthesis of 7-alkyl-1,2,3,4-tetrahydro-1,8-naphthyridines as arginine mimetics using a Horner–Wadsworth–Emmons-based approach

Facile Synthesis of 7-Alkyl-1,2,3,4-tetrahydro-[1,8]-naphthyridines as Arginine Mimetics Using a Horner–Wadsworth–Emmons Based Approach

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TiCl₄/Et₃N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates

TiCl₄/Et₃N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates