3072
Table 3
Hydrogenation of the mixture of 5, 7 and 8
In conclusion, this strategy could be an effective new method for the synthesis of trifluoromethylated
alkanes or β-sulfanyl (trifluoromethyl)alkanes, even if, at the moment, it seems difficult to exceed a
50% yield. It can be noticed that, because of their sulfanyl moiety, the latter compounds can undergo
further functionalization and constitute useful synthetic tools which are under study in our laboratory. On
the other hand, hydrotrifluoromethylation of alkenes with trifluorothioacetates can constitute a valuable
transformation of unsaturated organic substrates since we have demonstrated that the crude photolysis
mixtures can be reduced to a single product.
References
1. (a) Filler, R.; Kobayashi, Y.; Yagulpolskii, Y. L. Organofluorine Compounds in Medicinal Chemistry and Biomedical
Applications; Elsevier: Amsterdam, 1993. (b) Banks, R. E.; Smart, B. E.; Tatlow, J. C. Organofluorine Chemistry: Principles
and Commercial Applications; Plenum Press: New York, 1994. (c) Hudlicky, M.; Pavlath, A. E. Chemistry of Organic
Fluorine Compounds II. A Critical Review; ACS Monograph 187; American Chemical Society: Washington, DC, 1995.
2. McClinton, M. A.; McClinton, D. A. Tetrahedron 1992, 48, 6555–6666.
3. Billard, T.; Langlois, B. R.; Large, S.; Anker, D.; Roidot, N.; Roure, P. J. Org. Chem. 1996, 61, 7545.
4. Billard, T.; Roques, N.; Langlois, B. R. J. Org. Chem. 1999, 64, 3813–3820.
5. Thioesters and alkenes, dissolved in 20 mL of dichloromethane, were introduced in a quartz cylindrical flask (plane faces in
vertical position), fitted with a vertical reflux condenser. Air was blown off from this solution with nitrogen. Then, the stirred
reaction mixture was illuminated by a mercury vapor lamp (Phillips HPK125, 125 W), through the plane walls of the reactor.
6. Fossey, J.; Lefort, D.; Sorba, J. Les Radicaux Libres en Chimie Organique; Masson: Paris, 1993; p. 73.
7. Billard, T.; Langlois, B. Tetrahedron 1999, 55, 8065–8074.
8. Roques, N. Ph.D. Dissertation, University Claude Bernard-Lyon I, Villeurbanne (France), 1996.
1
9. Compounds 5b–e, 9g and 4b were characterized from isolated compounds. For example: 4b: H: 7.24–7.62 (massif, 5H),
3.33 (m, 1H), 2.2–2.5 (massif, 2H), 1.27 (massif, 16H), 0.88 (t, J=6 Hz, 3H). 13C: 133.71, 132.68, 129.14, 127.62, 126.13
(q, J=278 Hz) 42.44 (q, J=2.5 Hz), 39.17 (q, J=27.4 Hz), 33.81 (q, J=1 Hz), 31.91, 29.54, 29.45, 29.32, 29.28, 26.36, 22.72,
1
14.13. 19F: −63.95 (t, J=11.5 Hz). Compound 5b: H: 2.03 (m, 2H), 1.55 (m, 2H), 1.26 (m, 16H), 0.88 (t, J=6.4 Hz, 3H).
13C: 127.42 (q, J=277 Hz), 33.88 (q, J=28 Hz), 32.07, 29.78, 29.71, 29.51, 29.34, 28.87, 22.83, 21.99 (q, J=2 Hz), 14.16. 19F:
−66.9 (t, J=11.3 Hz). The others compounds 4 and 5 were identified by 19F NMR and mass spectrum. By-products 7 and
8 were identified by 19F NMR, mass spectrum and by analogy with the literature (Brookes, C. J.; Coe, P. L.; Pedler, A. E.;
Tatlow, J. C. J. Chem. Soc., Perkin Trans. 1 1978, 202–209.