Oxidative desulfurization–fluorination of alkanol xanthates. Control of the reaction pathway to fluorination or trifluoromethoxylation

(Note: The full text of this document is currently only available in the PDF Version )

Kiyoshi Kanie, Yoichiro Tanaka, Masaki Shimizu, Manabu Kuroboshi and Tamejiro Hiyama


Abstract

The reagent consisting of 70% HF–py (py = pyridine) and a halonium oxidant converts R–OCS2Me into either R–OCF3 (R = primary) or R–F (R = secondary, tertiary or benzylic) whereas the 50% HF–py system converts R–OCS2Me (R = secondary) into R–OCF3.


References

  1. J. T. Welch, Tetrahedron, 1987, 43, 3123 CrossRef CAS; H. Nohira, Yuki Gosei Kagaku Kyokai Shi, 1991, 49, 467 Search PubMed; N. Yoneda, Tetrahedron, 1991, 47, 5329 CrossRef CAS; J. A. Wilkinson, Chem. Rev., 1992, 92, 505 CrossRef CAS; M. Hudlicky and A. E. Pavlath, Chemistry of Organic Fluorine Compounds II. A Critical Review, ACS Monograph 187, Washington, DC, 1995 and references cited therein Search PubMed.
  2. M. Kuroboshi and T. Hiyama, Yuki Gosei Kagaku Kyokai Shi, 1993, 51, 1124 Search PubMed; M. Kuroboshi and T. Hiyama, Tetrahedron Lett., 1992, 33, 4177 CrossRef CAS; M. Kuroboshi and T. Hiyama, Synlett, 1991, 909 CrossRef CAS; M. Kuroboshi and T. Hiyama, Chem. Lett., 1992, 827 CAS.
  3. M. Kuroboshi, K. Suzuki and T. Hiyama, Tetrahedron Lett., 1992, 33, 4173 CrossRef CAS.
  4. G. A. Olah, J. T. Welch, Y. D. Vankar, M. Nojima, I. Kerekes and J. A. Olah, J. Org. Chem., 1979, 44, 3872 CrossRef CAS.
  5. M. J. Koen, F. L. Guyader and W. B. Motherwell, J. Chem. Soc., Chem. Commun., 1995, 1241 RSC.
  6. C. M. Sharts and W. A. Sheppard, Org. React., 1974, 21, 125 CAS.
  7. β-Fluoroalkyl trifluoromethyl ethers are prepared alternatively by treatment of alkenes with CF3OF, albeit in low yields. See: D. H. R. Barton, L. J. Dankas, A. K. Ganguly, R. H. Hesse, G. Tarzia and M. M. Pechet, J. Chem. Soc., Chem. Commun., 1969, 227 Search PubMed; S. Rozen, Chem. Rev., 1996, 96, 1717 RSC; C. Corvaja, F. Cremonese, W. Navarrini, C. Tonelli and V. Tortelli, Tetrahedron Lett., 1995, 36, 3543 CrossRef CAS.