- Novel Synthesis of 2,2,2-Trifluoroethyl Compounds from Homoallylic Alcohols: A Copper(I) Iodide-initiated Trifluoromethyl-Dehydroxylation Process
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Benzyl, prop-2-enyl and allyl chlorodifluoroacetates 3a, bromodifluoroacetates 3b or fluorosulfonyldifluoroacetates 3c, when decomposed in the presence of 1 equivalent of copper(I) iodide at an appropriate temperature in dimethylformamide, gave the corresponding trifluoromethyl derivatives in good to excellent yields.The products can also be obtained directly by ester exchange of XCF2CO2Et (X = FSO2, Cl, Br) 6 and the corresponding alcohols in the presence of KF and CuI.A trifluoromethylation-dehydroxylation mechanism, initiated by CuI, is proposed.
- Duan, Jian-Xing,Chen, Quing-Yun
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- BBDFA: A Practical Reagent for Trifluoromethylation of Allylic and Benzylic Alcohols on Preparative Scale
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We report a safe and readily prepared reagent [1,1′-biphenyl]-4-yl 2-bromo-2,2-difluoroacetate (BBDFA) for Cu-catalyzed trifluoromethylation of allylic or benzylic alcohols. An operationally simple and column-chromatography-free process to prepare BBDFA was developed and demonstrated on >100 g scale. Detailed reaction calorimetry and thermal analysis of the deoxytrifluoromethylation were performed using cinnamyl alcohol as a model substrate, demonstrating that the reactions could be safely implemented on preparative scale.
- Han, Chong,Alabanza, Lady Mae,Kelly, Sean M.,Orsi, Douglas L.,Gosselin, Francis,Altman, Ryan A.
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p. 1695 - 1702
(2019/09/04)
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- The reactions of copper-dibromodifluoromethane-amide systems with alcohols
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1,1,1-Trifluoro-2-arylethanes can be prepared by the trifluoromethyldehydroxylation of benzyl alcohols using the copper-dibromodifluoromethane-amide reaction system, although the yields are low.The mechanism of the reaction may involve chelation of the substrate to copper so that α-substituted benzyl alcohols and other alcohols are unreactive.
- Clark, James H.,McClinton, Martin A.,Blade, Robert J.
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p. 257 - 267
(2007/10/02)
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- A NOVEL AND CONVENIENT METHOD FOR TRIFLUOROMETHYLATION OF ORGANIC HALIDES USING CF3SiR'3/KF/Cu(I) SYSTEM
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Fluoride ion induced cross-coupling reaction of organic halides with trifluoromethyltrialkylsilanes takes place in the presence of Cu(I) salts under mild reaction conditions to give the corresponding trifluoromethylated products in high yields.
- Urata, Hisao,Fuchikami, Takamasa
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