Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective
- Norio Shibata,
- Andrej Matsnev and
- Dominique Cahard
Beilstein J. Org. Chem. 2010, 6, No. 65, doi:10.3762/bjoc.6.65
Graphical Abstract
Scheme 1: Preparation of the first electrophilic trifluoromethylating reagent and its reaction with a thiophe...
Scheme 2: Synthetic routes to S-CF3 and Se-CF3 dibenzochalcogenium salts.
Scheme 3: Synthesis of (trifluoromethyl)dibenzotellurophenium salts.
Scheme 4: Nitration of (trifluoromethyl)dibenzochalcogenium salts.
Scheme 5: Synthesis of a sulphonium salt with a bridged oxygen.
Scheme 6: Reactivity of (trifluoromethyl)dibenzochalcogenium salts.
Scheme 7: Pd(II)-Catalyzed ortho-trifluoromethylation of heterocycle-substituted arenes by Umemoto’s reagents....
Scheme 8: Mild electrophilic trifluoromethylation of β-ketoesters and silyl enol ethers.
Scheme 9: Enantioselective electrophilic trifluoromethylation of β-ketoesters.
Scheme 10: Preparation of water-soluble S-(trifluoromethyl)dibenzothiophenium salts.
Scheme 11: Method for large-scale preparation of S-(trifluoromethyl)dibenzothiophenium salts.
Scheme 12: Triflic acid catalyzed synthesis of 5-(trifluoromethyl)thiophenium salts.
Scheme 13: Trifluoromethylation of β-ketoesters and dicyanoalkylidenes by S-(trifluoromethyl)benzothiophenium ...
Scheme 14: Synthesis of chiral S-(trifluoromethyl)benzothiophenium salt 18 and attempt of enantioselective tri...
Scheme 15: Synthesis of O-(trifluoromethyl)dibenzofuranium salts.
Scheme 16: Photochemical O- and N-trifluoromethylation by 20b.
Scheme 17: Thermal O-trifluoromethylation of phenol by diazonium salt 19a. Effect of the counteranion.
Scheme 18: Thermal O- and N-trifluoromethylations.
Scheme 19: Method of preparation of S-(trifluoromethyl)diphenylsulfonium triflates.
Scheme 20: Reactivity of some S-(trifluoromethyl)diarylsulfonium triflates.
Scheme 21: One-pot synthesis of S-(trifluoromethyl)diarylsulfonium triflates.
Scheme 22: One-pot synthesis of Umemoto’s type reagents.
Scheme 23: Preparation of sulfonium salts by transformation of CF3− into CF3+.
Scheme 24: Selected reactions with the new Yagupolskii reagents.
Scheme 25: Synthesis of heteroaryl-substituted sulfonium salts.
Scheme 26: First neutral S-CF3 reagents.
Scheme 27: Synthesis of Togni reagents. aYield for the two-step procedure.
Scheme 28: Trifluoromethylation of C-nucleophiles with 37.
Scheme 29: Selected examples of trifluoromethylation of S-nucleophiles with 37.
Scheme 30: Selected examples of trifluoromethylation of P-nucleophiles with 35 and 37.
Scheme 31: Trifluoromethylation of 2,4,6-trimethylphenol with 35.
Scheme 32: Examples of O-trifluoromethylation of alcohols with 35 in the presence of 1 equiv of Zn(NTf2)2.
Scheme 33: Formation of trifluoromethyl sulfonates from sulfonic acids and 35.
Scheme 34: Organocatalytic α-trifluoromethylation of aldehydes with 37.
Scheme 35: Synthesis of reagent 42 and mechanism of trifluoromethylation.
Scheme 36: Trifluoromethylation of β-ketoesters and dicyanoalkylidenes with 42.
