Reactions of copper(I) halide complexes of trivalent phosphorus with vinylic halides

Axelrad, George; Laosooksathit, Surin; Engel, Robert

doi:10.1021/jo00338a028

Cited by 38 publications

(10 citation statements)

References 2 publications

(2 reference statements)

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“…Since the pioneering early work by Kosolapoff and McCullough in 1951, various synthetic methods for vinylphosphonate motifs have been developed over the past decades. The direct C–P bond forming approaches toward the synthesis of vinylphosphonates include transition-metal-catalyzed cross-coupling reactions of alkylphosphites with vinyl halides (Scheme , a), metal-promoted hydrophosphorylation reactions of terminal alkynes with dialkylphosphites (Scheme , b), and silver-mediated radical phosphonation reaction (Scheme , c) . Metalation of alkynylphosphonates via zirconation or titanation, yielding metallacycle intermediates, followed by hydrolysis of the intermediate, is an efficient route for the stereoselective synthesis of vinylphosphonates (Scheme , d).…”

Section: Introductionmentioning

confidence: 99%

Utility of Bifunctional N-Heterocyclic Phosphine (NHP)-Thioureas for Metal-Free Carbon–Phosphorus Bond Construction toward Regio- and Stereoselective Formation of Vinylphosphonates

et al. 2015

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An efficient and practical protocol for completely regioselective and highly stereoselective synthesis of vinyldiazaphosphonates from N-heterocyclic phosphine (NHP) and allenes via phospha-Michael/intramolecular nucleophilic substitution reaction has been developed. This transformation enabled the synthesis of valuable densely functionalized vinyldiazaphosphonates with a β-, γ-unsaturated ester moiety under mild reaction conditions. Synthetic utility of vinyldiazaphosphonates was demonstrated by a series of synthetic manipulations.

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Section: Introductionmentioning

confidence: 99%

Utility of Bifunctional N-Heterocyclic Phosphine (NHP)-Thioureas for Metal-Free Carbon–Phosphorus Bond Construction toward Regio- and Stereoselective Formation of Vinylphosphonates

et al. 2015

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“…The reaction of aryl halides of decreased reactivity may be promoted by Ni salts (at higher temperatures) [44,45]. Vinyl halides may react in the presence of Cu (I) bromide [46].…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Phosphinic Acid Derivatives; Traditional Versus up-to-Date Synthetic Procedures

Keglevich

Kiss²,

Mucsi³

2014

Chem Sci J

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Synthetic methods for the preparation of phosphinic derivatives (esters and amides) are summarized. The basic method is, when phosphinic chlorides are reacted with alcohols or amines. These reactions take place under mild conditions, but utilize expensive chlorides, need a solvent, and a base has to be added to remove the HCl formed. On conventional heating, the phosphinic acids resist undergoing derivatizations by nucleophiles. However, on microwave (MW) irradiation, the phosphinic acids could be esterified by alcohols. The direct esterification does not require an extra solvent, it is atomic efficient, but needs a relatively higher temperature. The similar amidations were reluctant. Phosphinic acids may also be esterified by alkylation that may be promoted by combined phase transfer catalysis and MW irradiation. It is also possible to convert the phosphinic acids by different reagents (e.g. by the T3P  reactant) to a more reactive intermediate that is ready to react with alcohols or amines. Other methods, such as preparation by the Arbuzov reaction or by fragmentation-related phosphorylation are also discussed.

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“…At the same time, Axelrad (Axelrad et al, 1981a , b ) demonstrated that phosphite- or phosphine- ligated copper(I) chloride complexes could mediate the transformation of alkenyl bromides to the corresponding chlorides, although under harsh conditions and using a stoichiometric amount of the copper complex (Figure 17 , middle).…”

Section: Halogen Exchange In Alkenyl Halidesmentioning

confidence: 99%

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: A Review

et al. 2018

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Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical, and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter, or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

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Reactions of copper(I) halide complexes of trivalent phosphorus with vinylic halides

Cited by 38 publications

References 2 publications

Utility of Bifunctional N-Heterocyclic Phosphine (NHP)-Thioureas for Metal-Free Carbon–Phosphorus Bond Construction toward Regio- and Stereoselective Formation of Vinylphosphonates

Utility of Bifunctional N-Heterocyclic Phosphine (NHP)-Thioureas for Metal-Free Carbon–Phosphorus Bond Construction toward Regio- and Stereoselective Formation of Vinylphosphonates

Synthesis of Phosphinic Acid Derivatives; Traditional Versus up-to-Date Synthetic Procedures

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: A Review

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