Synthesis of Trifluorostyrene Derivatives by Palladium‐Catalyzed Cross‐Coupling of Lithium Trimethoxy(trifluorovinyl)borate with Aryl Bromides

Duric, Sasa; Schmidt, Bernd; Ninnemann, Nina M.; Lentz, Dieter; Tzschucke, Carl Christoph

doi:10.1002/chem.201103067

Cited by 23 publications

(10 citation statements)

References 68 publications

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“…3 For the synthesis of multisubstituted fluorine-containing alkenes, 4 fluoroalkylated alkenylboronates are essential building blocks that can be readily used in transition-metal-catalyzed transformations, especially in Suzuki−Miyaura cross-couplings. 5 However, step-economic, versatile, and stereoselective synthetic methods toward trisubstituted and tetrasubstituted fluoroalkylborylated alkenes have been extremely limited thus far. For example, in 2001, Shimizu et al developed a lithium reagent mediated strategy that can afford CF 3 -containing tetrasubstituted alkenes through stepwise C−C and C−B bond formation (Scheme 1a).…”

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confidence: 99%

Fluoroalkylation–Borylation of Alkynes: An Efficient Method To Obtain (Z)-Tri- and Tetrasubstituted Fluoroalkylated Alkenylboronates

et al. 2018

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Efficient methods for the synthesis of fluoroalkylated alkenylboronates are very limited, despite their importance in modern organic synthesis. Herein, we report a palladium-catalyzed trans-fluoroalkylation–borylation of alkynes with fluoroalkyl iodides and B2pin2. The reaction tolerates a series of difluoroalkyl iodides and perfluoroalkyl iodides and can enable coupling with a variety of alkynes, including internal and terminal alkynes, with high efficiency, high functional group compatibility, and high regio- and stereoselectivities. Preliminary mechanistic studies reveal that a trans-fluoroalkylated alkenyl iodide is the key intermediate, which subsequently undergoes borylation to produce the trans-fluoroalkylated alkenylboronate.

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confidence: 99%

Fluoroalkylation–Borylation of Alkynes: An Efficient Method To Obtain (Z)-Tri- and Tetrasubstituted Fluoroalkylated Alkenylboronates

et al. 2018

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“…(8)). Morken and Burton [12] showed that (2,2-dibromo)hexafluoropropane could also be used to generate the internal propenylzinc reagent in situ, which could be utilized (Negishi coupling) for the preparation of b,b-difluoro-a-(trifluoromethyl)styrenes (Eq.…”

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confidence: 93%

“…(4)). Lentz and coworkers [8] also reported the synthesis of trifluorostyrene derivatives by palladium-catalyzed coupling of lithium trimethoxy(trifluorovinyl)borate with aryl bromides (Eq. (5)).…”

mentioning

confidence: 96%

Stereospecific synthesis of (E)- and (Z)-1-chloro-1,2-difluorostyrenes

Lim

Burton

2014

Journal of Fluorine Chemistry

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“…Pd(0)-catalyzed cross-coupling reactions of trifluorovinylzinc, tin, or borate reagents emerged in the 1980s as more direct synthetic methods [24][25][26][27][28][29][30][31][32][33]. A synthetic route involving a more stable trifluorovinyl borate has recently been developed to replace the zinc or tin reagents [34,35]. Alternative routes to synthesize (α,β,β-trifluoro)styrenes via the cross-coupling of chlorotrifluoroethylene with arylboronic acids have recently been reported [36,37].…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

Ohashi

Ogoshi

2014

Catalysts

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Abstract:In this review, we summarize our recent development of palladium(0)-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C-F bond of tetrafluoroethylene (TFE) to palladium(0) was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II) iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0)/PR 3 -catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II) fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C-F bond. In addition, our strategy utilizing the synergetic effect of Pd(0) and lithium iodide could be applied to the C-F bond cleavage of unreactive hexafluorobenzene (C 6 F 6 ), leading to the first Pd(0)-catalyzed cross-coupling reaction of C 6 F 6 with diarylzinc compounds.

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Synthesis of Trifluorostyrene Derivatives by Palladium‐Catalyzed Cross‐Coupling of Lithium Trimethoxy(trifluorovinyl)borate with Aryl Bromides

Cited by 23 publications

References 68 publications

Fluoroalkylation–Borylation of Alkynes: An Efficient Method To Obtain (Z)-Tri- and Tetrasubstituted Fluoroalkylated Alkenylboronates

Fluoroalkylation–Borylation of Alkynes: An Efficient Method To Obtain (Z)-Tri- and Tetrasubstituted Fluoroalkylated Alkenylboronates

Stereospecific synthesis of (E)- and (Z)-1-chloro-1,2-difluorostyrenes

Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

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