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

Kolodiazhna, Olga O.; Kolodiazhnyi, Oleg I.

doi:10.1080/10426507.2015.1054932

Cited by 3 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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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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Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ5-oxaphosphetanes

Kolodiazhna

Kolodiazhnyi

2016

Molecules

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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 P-haloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-cycloaddition 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 H-, 13 C-, 19 F-and 31 P-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-chloroalkyl-phosphonates 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 3 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

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

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

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

Cited by 3 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

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

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