Reaction of C-silyl-P-chloro-alkylidenephosphoranes with carbonyl compounds

Kolodiazhna, Olga O.; Kolodiazhnyi, Oleg I.

doi:10.1080/10426507.2015.1054932

Cited by 4 publications

(16 citation statements)

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“…Dissociation of 2-halo-1,2λ 5 -oxaphosphetanes is enhanced by reducing the electron-accepting properties of substituents and also by increasing priority solvent. The 2-halo-1,2λ 5 -oxaphosphetanes containing electron-accepting groups at C(4) are distinctly stabler than oxaphosphetanes with alkyl groups in this position [25][26][27].…”

Section: Synthesis Of 2-halo-12λ 5 -Oxaphosphetanementioning

confidence: 99%

“…Substitution of electron withdrawing CF3 group at C4 atom by hydrogen atom destabilizes the oxaphosphetane cycle and considerably reinforces the ionization of Р-С1 bond. The stability of 2-halogenoxaphosphetanes decreases, and positive values δР and ionization of Р-С1 bond increases in the sequence of substituents at С4 atom: СF3 > С6Н4F-4 >-C6N5 > С6Н4ОMе > H (Table 4) [25,30,31]. Chemical shifts of phosphorus in 2-bromo-1,2λ 5 -oxaphosphetanes (δР =+20-+75 ppm) were in the weaker fields relatively to chemical shifts of chloro-oxaphosphetanes.…”

Section: Properties Of Oxaphosphetanesmentioning

confidence: 99%

“…2-Fluoro-1,2λ 5 oxaphosphetanes containing two alkyl groups at C3 as well eliminated hydrogen fluoride and afforded the allylphosphonates 42 (Scheme 26, Table 8). The reaction occurs by the 1,4-elimination as shown in Scheme 26 [25]. Opposite to 2,2,2-triphenyloxaphosphetanes, upon heating, the decyclization of 2-fluorooxaphosphetanes led to the formation of phosphorylated alkenes 41,42.…”

Section: Properties Of Oxaphosphetanesmentioning

confidence: 99%

“…13 С-NMR signals of С-3 and С-4 carbons were found at 30 and 90 ppm, correspondingly. The 31 P-NMR signals of 2-chloro-1,2λ 5 -oxaphosphetanes 19 at δP +48 ppm (R 1 = iPrO) and at δP = 60 ppm (R 1 = Et2N) correspond to tetracoordinate phosphorus included in fourmembered phosphetane cycle (Table 1) [25,32]. Sotiropulos and Bertrand [33] reported the addition of phosphacumulene ylides 20 bearing the diazo group to isocyanates, leading to the formation of products 22.…”

Section: Synthesis Of 2-halo-12λ 5 -Oxaphosphetanementioning

confidence: 99%

“…These compounds are much distinguished from unstable adducts of carbonyl compounds with triphenylphosphonium ylides. Cycloadducts of P-fluoroylides with carbonyl compounds, 2-fluoro-1,2λ 5 -oxaphosphetanes, are also much more stable than 2-chloro-or 2-bromo-1,2λ 5 -oxaphosphetanes [25][26][27][28][29][30][31]. The stability of 2-fluoro-oxaphosphetanes is explained by the high electronegativity of the fluorine atom, compared to the electronegativities of chlorine and bromine.…”

Section: Synthesis Of 2-halo-12λ 5 -Oxaphosphetanementioning

confidence: 99%

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Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ5-oxaphosphetanes

Kolodiazhna

Kolodiazhnyi

2016

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Abstract:Results of research into four-membered 2-halo-1,2λ 5 -oxaphosphetane phosphorus(V)-heterocycles are presented. The preparation of 2-halo-1,2λ 5 -oxaphosphetanes by reaction of Phaloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-сycloaddition of ylides to aldehydes was proposed on the base of low-temperature NMR investigations. 2-Halo-1,2λ 5 -oxaphosphetanes were isolated as individual compounds and their structures were confirmed by 1 Н-, 13 C-, 19 F-and 31 Р-NMR spectra. These compounds are convenient reagents for preparing of various organic and organophosphorus compounds hardly available by other methods. Chemical and physical properties of the 2-halo-1,2λ 5 -oxaphosphetanes are reviewed. The 2-chloro-1,2λ 5 -oxaphosphetanes, rearrange with formation of 2-chloroalkylphosphonates or convert into trans-phosphorylated alkenes depending on the substituents at the α-carbon atom. Prospective synthetic applications of 2-halo-1,2λ 5 -oxaphosphetanes are analyzed. The 2-halo-1,2λ 5 -oxaphosphetanes may be easily converted to various alkenylphosphonates: allylor vinylphosphonates, phosphorus ketenes, thioketenes, ketenimines.

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Section: Synthesis Of 2-halo-12λ 5 -Oxaphosphetanementioning

confidence: 99%

Section: Properties Of Oxaphosphetanesmentioning

confidence: 99%

Section: Properties Of Oxaphosphetanesmentioning

confidence: 99%

Section: Synthesis Of 2-halo-12λ 5 -Oxaphosphetanementioning

confidence: 99%

Section: Synthesis Of 2-halo-12λ 5 -Oxaphosphetanementioning

confidence: 99%

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Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ5-oxaphosphetanes

Kolodiazhna

Kolodiazhnyi

2016

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42.8.18 Alkylphosphonous Acids and Derivatives (Update 2025)

Stankevič,

Sowa

2025

Knowledge Updates 2025/1

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This is an update to the previous Science of Synthesis contribution (from 2009), describing newly developed methods for the synthesis of alkylphosphonous acids and their derivatives. Various synthetic methodologies have been developed, depending on the structure of the final compound. The majority of examples describe mutual interconversions within the product class, with other transformations having been developed far less extensively.

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Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ5-oxaphosphetanes

Kolodiazhna¹,

Kolodiazhnyi²

2016

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Abstract:Results of research into four-membered 2-halo-1,2λ 5 -oxaphosphetane phosphorus(V)-heterocycles are presented. The preparation of 2-halo-1,2λ 5 -oxaphosphetanes by reaction of Phaloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-сycloaddition of ylides to aldehydes was proposed on the base of low-temperature NMR investigations. 2-Halo-1,2λ 5 -oxaphosphetanes were isolated as individual compounds and their structures were confirmed by 1 Н-, 13 C-, 19 F-and 31 Р-NMR spectra. These compounds are convenient reagents for preparing of various organic and organophosphorus compounds hardly available by other methods. Chemical and physical properties of the 2-halon-1,2λ 5 -oxaphosphetanes are reviewed. The 2-chloro-1,2λ 5 -oxaphosphetanes, rearrange with formation of 2-chloroalkylphosphonates or convert into trans-phosphorylated alkenes depending on the substituents at the α-carbon atom. Prospective synthetic applications of 2-halo-1,2λ 5 -oxaphosphetanes are analyzed. The 2-halo-1,2λ 5 -oxaphosphetanes may be easily converted to various alkenylphosphonates: allyl-or vinylphosphonates, phosphorus ketenes, thioketenes, ketenimines.

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Reaction of C-silyl-P-chloro-alkylidenephosphoranes with carbonyl compounds

Cited by 4 publications

References 20 publications

Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ<sup>5</sup>-oxaphosphetanes

Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ<sup>5</sup>-oxaphosphetanes

42.8.18 Alkylphosphonous Acids and Derivatives (Update 2025)

Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ<sup>5</sup>-oxaphosphetanes

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Reaction of C-silyl-P-chloro-alkylidenephosphoranes with carbonyl compounds

Cited by 4 publications

References 20 publications

Synthesis, Properties and Stereochemistry of 2-Halo-1,2&lambda;<sup>5</sup>-oxaphosphetanes

Synthesis, Properties and Stereochemistry of 2-Halo-1,2&lambda;<sup>5</sup>-oxaphosphetanes

42.8.18 Alkylphosphonous Acids and Derivatives (Update 2025)

Synthesis, Properties and Stereochemistry of 2-Halo-1,2&lambda;<sup>5</sup>-oxaphosphetanes

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Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ<sup>5</sup>-oxaphosphetanes

Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ<sup>5</sup>-oxaphosphetanes

Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ<sup>5</sup>-oxaphosphetanes