Fluorinated styrenes

Kazennikova, G. V.; Talalaeva, T. V.; Zimin, A. V.; Kocheshkov, K. A.

doi:10.1007/bf00909172

Cited by 5 publications

(4 citation statements)

References 4 publications

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“…Although a-(difluoromethyl)styrenes are precursors to polysubstituted fluoroalkene, [12] and novel fluorinated polymers, [13,14] there are no deoxyfluorination strategies reported for these species. [15] They have been prepared by direct fluorination using cesium fluoroxysulfate (CsSO 4 F), [16] however,t he typical approach involves olefination [12,17] or dehydration [13,18] of af luorinecontaining precursor.W eaimed to develop adirect synthesis of a-(difluoromethyl)styrenes through aT olIF 2 -mediated fluorinative rearrangement of phenylallene derivatives.…”

mentioning

confidence: 99%

Fluorinative Rearrangements of Substituted Phenylallenes Mediated by (Difluoroiodo)toluene: Synthesis of α‐(Difluoromethyl)styrenes

Zhao,

Racicot,

Murphy

2017

Angew Chem Int Ed

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Phenylallenes undergo fluorinative rearrangement upon the action of (difluoroiodo)toluene in the presence of 20 mol % BF ⋅OEt to yield α-difluoromethyl styrenes. This unprecedented reaction was entirely chemoselective for the internal allene π bond, and showed remarkable regioselectivity during the fluorination event. Substituted phenylallenes, phenylallenes possessing both phenyl- and α-allenyl substituents, and diphenylallenes were investigated, and good functional-group compatibility was observed throughout. The ease with which allenes can be prepared on a large scale, and the operational simplicity of this reaction allowed us to rapidly access fluorine-containing building blocks that have not been accessed by conventional deoxyfluorination strategies.

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mentioning

confidence: 99%

Fluorinative Rearrangements of Substituted Phenylallenes Mediated by (Difluoroiodo)toluene: Synthesis of α‐(Difluoromethyl)styrenes

Zhao,

Racicot,

Murphy

2017

Angew Chem Int Ed

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“…Although α‐(difluoromethyl)styrenes are precursors to polysubstituted fluoroalkene, and novel fluorinated polymers, there are no deoxyfluorination strategies reported for these species . They have been prepared by direct fluorination using cesium fluoroxysulfate (CsSO 4 F), however, the typical approach involves olefination or dehydration of a fluorine‐containing precursor. We aimed to develop a direct synthesis of α‐(difluoromethyl)styrenes through a TolIF 2 ‐mediated fluorinative rearrangement of phenylallene derivatives.…”

Section: Methodsmentioning

confidence: 99%

Fluorinative Rearrangements of Substituted Phenylallenes Mediated by (Difluoroiodo)toluene: Synthesis of α‐(Difluoromethyl)styrenes

2017

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Phenylallenes undergo fluorinative rearrangement upon the action of (difluoroiodo)toluene in the presence of 20 mol % BF3⋅OEt2 to yield α‐difluoromethyl styrenes. This unprecedented reaction was entirely chemoselective for the internal allene π bond, and showed remarkable regioselectivity during the fluorination event. Substituted phenylallenes, phenylallenes possessing both phenyl‐ and α‐allenyl substituents, and diphenylallenes were investigated, and good functional‐group compatibility was observed throughout. The ease with which allenes can be prepared on a large scale, and the operational simplicity of this reaction allowed us to rapidly access fluorine‐containing building blocks that have not been accessed by conventional deoxyfluorination strategies.

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“…Dehydration of resulting carbinol 6 using phosphorus pentoxide afforded the desired α-(difluoromethyl)styrene 7 in 69% yield (lit. 61%) [15]. h.…”

Section: Page 8 Of 17mentioning

confidence: 97%

“…Although, several methods for the synthesis of difluorometylated derivatives are available [7][8][9][10][11][12][13], only few protocols of FMST synthesis on a large scale have been reported to date [14][15][16]. According to the literature synthetic strategies the difluoromethyl α-substituted styrene was prepared by two-step procedure, where a key step involved a nucleophilic addition of Page 6 of 17 A c c e p t e d M a n u s c r i p t either Gringard's reagent (phenylmagnesium bromide [14]) or organolithium (methyllithium [15]) to corresponding gem-difluorinated ketones. Subsequent dehydration of the resultant difluoromethylated carbinol afforded desired α-difluoromethylated styrene in good to very good overall yields.…”

Section: *Manuscriptmentioning

confidence: 99%