Trifluoromethylation of Alkenyl Bromides and Iodides (Including 5-Iodouracils) with (CF3)2Hgand Cu (“Trifluoromethylcopper”)1

Nowak, Ireneusz; Robins, Morris J.

doi:10.1021/jo062544a

Cited by 56 publications

(26 citation statements)

References 32 publications

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“…13,14,17c As has been recently established, 21 the trifluoromethylation of haloarenes with fluoroform-derived CuCF 3 is a nonradi- The new method compares favorably with the previously reported ones [4][5][6][7][8][9][10][11][12] for perfluoroalkylation of haloalkenes. Apart from the vastly lower cost of the R f sources used, our procedures obviate the need for toxic mercury compounds 7 or expensive DMPU 9b employed in the only two reported methods with a defined substrate scope. 22 In summary, a general new protocol has been developed for the trifluoromethylation and pentafluoroethylation of vinylic bromides and iodides with R f H-derived CuCF 3 and CuC 2 F 5 .…”

Section: Cluster Syn Lettmentioning

confidence: 75%

“…The mono β-substituted iodoethylenes appeared reactive enough to undergo the fluoroalkylation at room temperature (Table 3, entries [1][2][3][4][5][6][7][8]. Importantly, full conversion of these substrates was reached with only 1.1 equivalents of the CuR f reagent not only for R f = C 2 F 5 , but also for R f = CF 3 .…”

Section: Syn Lettmentioning

confidence: 99%

“…[13][14][15] The thus prepared reagents fluoroalkylate a broad variety of substrates in high yield and with excellent selectivities. [13][14][15]17 Notably, there is no need to use toxic CF 3 reagents 7 or expensive DMPU 9b to eliminate the side formation of C 2 F 5 derivatives in the reactions of CHF 3 -derived CuCF 3 . Furthermore, the low cost of our R f Cu reagents makes them potentially suitable for industrial applications.…”

mentioning

confidence: 99%

“…The enhanced thermal stability of the CuC 2 F 5 reagent 14 allowed us to use it in only 10% excess to achieve full conversion for most of the substrates, while running the reactions at 70-80 °C. The data collected in Table 2 show that styryl bromides bearing such substituents as Me (1b-d), MeO (1e), F (1f), Cl (1g,h), and Br (1i,j) in various positions of the aromatic ring undergo clean perfluoroalkylation to give the desired products in ≥90% yield (Table 2, entries [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. The stereochemistry of the starting material is retained in the product.…”

mentioning

confidence: 99%

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Trifluoromethylation and Pentafluoroethylation of Vinylic Halides with Low-Cost RfH-Derived CuRf (Rf = CF3, C2F5)

Lishchynskyi

Mazloomi

Grushin

2014

Synlett

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A variety of vinylic bromides and iodides undergo smooth trifluoromethylation and pentafluoroethylation with R f H-derived CuR f (R f = CF 3 , C 2 F 5 ) to give the corresponding fluoroalkylated olefins. These reactions employing the low-cost CuR f reagents occur in high yield with excellent chemo-and stereoselectivity under mild conditions (23-80 °C). Crystal structures of one trifluoromethyl and one pentafluoroethyl derivative have been determined. Key words trifluoromethylation, pentafluoroethylation, vinylic halides, copper, cross-couplingConsiderable progress has been made in the area of trifluoromethylation of aromatic halides for the synthesis of biologically active compounds and specialty materials. 1,2 Methodologically closely related perfluoroalkylation of vinylic halides, however, remains significantly less developed. Since the original 1960-1970 reports 3 on copper-mediated coupling of perfluoroalkyl iodides (R f I) with haloalkenes, this method has been modified by employing such CF 3 and C 2 F 5 sources as FO 2 SCF 2 I, 4 FO 2 SCF 2 CO 2 Me, 5 FSO 2 (CF 2 ) 2 OCF 2 -CO 2 Me, 6 Hg(CF 3 ) 2 , 7 ClCF 2 CO 2 Me, 8 CF 3 SiR 3 /KF, 9 and C 2 F 5 COX (X = ONa, 10 Ph 11 ). 12 In the vast majority of these reports, however, the scope is undefined, with styryl bromide 4,5a,6,10,11 or chloride 6 being the only vinylic halides explored. Single examples of trifluoromethylation of RCH=CHX (R = H, X = Br 8 and R = C 8 H 17 , X = I 9a ) have been mentioned briefly. One paper 5b describes the trifluoromethylation of structurally alike 4-bromo-3-oxo-Δ 4 -steroids and two more deal with a handful of rather specific 1,2-diiodo-5c and 1,1-dibromoolefin 5d substrates. We are aware of only two reports detailing the scope of this type of transformations. Nowak and Robins 7 have demonstrated trifluoromethylation of 18 vinylic bromides and iodides in 75-95% yield. Regrettably, their method employs toxic Hg(CF 3 ) 2 as the CF 3 source. Hafner and Bräse 9b have modified the Urata-Fuchikami protocol 9a using CF 3 TMS to perform the reaction on five vinylic bromides and six iodides in 23-99% yield. In order to avoid the side formation of C 2

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Section: Cluster Syn Lettmentioning

confidence: 75%

Section: Syn Lettmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Trifluoromethylation and Pentafluoroethylation of Vinylic Halides with Low-Cost RfH-Derived CuRf (Rf = CF3, C2F5)

Lishchynskyi

Mazloomi

Grushin

2014

Synlett

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“…Procedures reported by the groups of Yagupolskii [15] and Burton [16] to form [CuCF 3 ] involve toxic mercury-or cadmium-CF 3 species, whereas the method reported by Kobayashi et al [17] requires pressurized gaseous CF 3 I. Chambers and co-workers utilized sodium trifluoroacetate as a cheap and widely available starting material to access [CuCF 3 ] by CuIpromoted decarboxylation at 160 8C.…”

Section: Introductionmentioning

confidence: 99%

Copper‐Catalyzed Trifluoromethylation of Aryl Iodides with Potassium (Trifluoromethyl)trimethoxyborate

Knauber

Arikan

Röschenthaler

et al. 2011

Chemistry A European J

266

107

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Potassium (trifluoromethyl)trimethoxyborate is introduced as a new source of CF(3) nucleophiles in copper-catalyzed trifluoromethylation reactions. The crystalline salt is stable on storage, easy to handle, and can be obtained in near-quantitative yields simply by mixing B(OMe)(3), CF(3)SiMe(3), and KF. The trifluoromethylation reagent allows the conversion of various aryl iodides into the corresponding benzotrifluorides in high yields under mild, base-free conditions in the presence of catalytic quantities of a Cu(I)/1,10-phenanthroline complex.

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Nucleophilic Additions of Perfluoroalkyl Groups

Beier

Zibinsky²,

Prakash

2016

Organic Reactions

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The trifluoromethyl and perfluoroalkyl functional groups possess significant thermal, chemical, and metabolic stability, as well as high lipophilicity and electronegativity. These physicochemical properties render fluorinated carbon residues indispensable in diverse applications, such as agrochemistry, drug design, and material chemistry. The generation and properties of nucleophilic perfluoroalkyl reagents as well as the scope and limitations of their additions to various electrophilic partners is described in this chapter.

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Trifluoromethylation of Alkenyl Bromides and Iodides (Including 5-Iodouracils) with (CF₃)₂Hgand Cu (“Trifluoromethylcopper”)¹

Cited by 56 publications

References 32 publications

Trifluoromethylation and Pentafluoroethylation of Vinylic Halides with Low-Cost RfH-Derived CuRf (Rf = CF3, C2F5)

Trifluoromethylation and Pentafluoroethylation of Vinylic Halides with Low-Cost RfH-Derived CuRf (Rf = CF3, C2F5)

Copper‐Catalyzed Trifluoromethylation of Aryl Iodides with Potassium (Trifluoromethyl)trimethoxyborate

Nucleophilic Additions of Perfluoroalkyl Groups

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