A xanthate transfer radical process for the introduction of the Trifluoromethyl group

Organic Letters

Volumn 3, Issue 7, 2001, Pages 1069-1071

  Bertrand, Frédérique ^a   Pevere, Virginie ^b   Quiclet Sire, Béatrice ^a   Zard, Samir Z ^a,c  

^a INSTITUT DE CHIMIE DES SUBSTANCES NATURELLES   (France)

^b Rhodia Recherches   (France)

^c CNRS   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001477881     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0156446     Document Type: Article

References (27)

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20. For a review of this work, see: (a) Zard, S. Z. Angew. Chem., Int. Ed. Engl. 1997, 36, 672-685.
21. (b) Quiclet-Sire, B.; Zard, S. Z. Phosphorus, Sulfur Silicon 1999, 153-154, 137-134.
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25. The synthesis of O-ethyl-S-trifluoromethyl xanthate using the photo-chemical decomposition of the corresponding S-trifluoroacetyl xanthate as well as one example of UV mediated addition to 1-decene have been claimed in a patent: Langlois, B.; Roques, N.; Wakselman, C.; Tordeux, M.; Forat, G. (Rhône-poulenc Agrochimie) WO 9626185.
26. Typical experimental procedure: (a) Synthesis of 1a. To an ice-cooled solution of trifluoroacetic anhydride (13.3 mL; 90.1 mmol) in anhydrous acetonitrile (40 mL) was added dropwise a solution of sodium O-phenethyl xanthate (10 g; 45.0 mmol) in anhydrous acetonitrile under an inert atmosphere. Once the addition was complete, the mixture was heated to reflux for 15 min; then three portions of lauroyl peroxide (907 mg; 4.5 mmol) were added at intervals of 1.5 h. The solvent was then evaporated under reduced pressure and the residue taken up in dichloromethane. The organic layer was washed with saturated sodium bicarbonate, dried, and evaporated. Chromatography of the residue on silica (heptane) did not give a totally pure material, so further purification was accomplished by distillation in a Kugelruhr apparatus (80 °C/0.1 Torr) to give the desired xanthate in 38% yield as a pale yellow oil. (b) General procedure for the radical additions to olefin: A solution of the xanthate (1 mmol) and olefin (2-5 mmol) in 1,2-dichloroethane (ca. 1 mL) was heated to reflux for 15 min; then lauroyl peroxide (2.5 mol %) was added every 1.5 h until almost complete consumption of the xanthate. The solvent was then removed under reduced pressure and the residue purified by chromatography on silica.
27. Ly, T.-M.; Quiclet-Sire, B.; Sortais, B.; Zard, S. Z. Tetrahedron Lett. 1999, 40, 2533-2536.