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Synlett 2002(7): 1134-1136
DOI: 10.1055/s-2002-32607
DOI: 10.1055/s-2002-32607
LETTER
© Georg Thieme Verlag Stuttgart · New YorkCFC- or HFC-Free Approach to α-Substituted β,γ,γ-Trifluoroallyl Alcohols by the Reaction of β-Fluoro-β-trifluoromethylated Enol Tosylate with Grignard Reagents
Further Information
Received
15 April 2002
Publication Date:
07 February 2007 (online)
Publication History
Publication Date:
07 February 2007 (online)

Abstract
The reaction of β-fluoro-β-trifluoromethylated enol tosylate with Grignard reagents giving the corresponding β,γ,γ-trifluoroallyl alcohols as well as heteropoly acid-mediated ethanolysis of the allyl alcohols affording (Z)-β-substituted α-fluoro-α,β-unsaturated esters is described.
Key words
fluorine - trifluoromethyl - Grignard reaction - sulfonates - cleavage - nucleophilic additions - alcohols - esters
- For recent examples, see:
- 1a
Takagi Y.Nakatani T.Itoh T.Oshiki T. Tetrahedron Lett. 2000, 41: 7889 - 1b
Itoh T.Sakabe K.Kudo K.Ohara H.Takagi Y.Kihara H.Zagatti P.Renou M. J. Org. Chem. 1999, 64: 252 - 1c
Peng S.Qing F.-L. J. Chem. Soc., Perkin Trans. 1 1999, 3345 - 1d
Fujita M.Hiyama T. Tetrahedron Lett. 1986, 27: 3659 - 2a
Gillet JP.Sauvêtre R.Normant JF. Synthesis 1986, 355 - 2b
Normant JF.Foulon JP.Masure D.Sauvêtre R.Villieras J. Synthesis 1975, 122 - 3
Tang X.Hu C. Chin. Chem. Lett. 1994, 5: 183 - 4a
Hagiwara T.Fuchikami T. Chem. Lett. 1997, 787 - 4b
Yudin AK.Prakash GKS.Deffieux D.Bradley M.Bau R.Olah GA. J. Am. Chem. Soc. 1997, 119: 1572 - 4c
Fujita M.Obayashi M.Hiyama T. Tetrahedron 1988, 44: 4135 - 4d
Fujita M.Hiyama T. J. Am. Chem. Soc. 1985, 107: 4085 - 5a
Burdon J.Coe PL.Haslock IB.Powell RL. J. Fluorine Chem. 1999, 99: 127 - 5b
Burdon J.Coe PL.Haslock IB.Powell RL. Chem. Commun. 1996, 49 - 6a
Coe PL.Burdon J.Haslock JB. J. Fluorine Chem. 2000, 102: 43 - 6b
Percy JM.Dimartino G. Chem. Commun. 2000, 2339 - 6c
Kanai M.Percy JM. Tetrahedron Lett. 2000, 41: 2453 - 6d
Bainbridge JM.Corr S.Kanai M.Percy JM. Tetrahedron Lett. 2000, 41: 971 - 6e
Dimartino G.Gelbrich T.Hursthouse MB.Light ME.Percy JM.Spencer NS. Chem. Commun. 1999, 2535 - 6f
Bainbridge JM.Brown SJ.Ewing PN.Gibson RR.Percy JM. J. Chem. Soc., Perkin Trans. 1 1998, 2541 - For the reaction of β-fluoro-β-difluoromethylated alkenyl tosylates toward various fluorinated molecules, see:
- 7a
Funabiki K.Fukushima Y.Sugiyama T.Shibata K.Matsui M. Synlett 2001, 1308 - 7b
Funabiki K.Fukushima Y.Matsui M.Shibata K. J. Org. Chem. 2000, 65: 606 - 7c
Funabiki K.Ohtsuki T.Ishihara T.Yamanaka H. J. Chem. Soc., Perkin Trans. 1 1998, 2413 - 7d
Funabiki K.Fukushima Y.Inagaki T.Murata E.Matsui M.Shibata K. Tetrahedron Lett. 1998, 39: 1913 - 7e
Funabiki K.Suzuki C.Takamoto S.Matsui M.Shibata K. J. Chem. Soc., Perkin Trans. 1 1997, 2679 - 7f
Funabiki K.Kurita T.Matsui M.Shibata K. Chem. Lett. 1997, 2679 - 7g
Funabiki K.Ohtake C.Muramatsu H.Matsui M.Shibata K. Synlett 1996, 444 - 7h
Funabiki K.Ohtsuki T.Ishihara T.Yamanaka H. Chem. Lett. 1996, 5 - 7i
Funabiki K.Ohtsuki T.Ishihara T.Yamanaka H. Chem. Lett. 1995, 239 - 7j
Funabiki K.Ohtsuki T.Ishihara T.Yamanaka H. Chem. Lett. 1994, 1705 - 8 For selected examples for the solvolysis of γ,γ-difluoro- or γ-fluoroallyl alcohols
derivatives, see:
Tellier F.Sauvêtre R. Tetrahedron Lett. 1993, 34: 5433 ; and ref. - For the iodine-catalyzed rearrangement of γ-fluoroallyl alcohols derivatives, see:
- 9a
Tellier F.Sauvêtre R. Tetrahedron Lett. 1995, 36: 4223 - 9b
Dubuffet T.Bidon C.Martinet P.Sauvêtre R.Normant JF. J. Orgnomet. Chem. 1990, 393: 161 - H4SiW12O40 was purchased from Merck KGaA and dried at room temperature (1 mmHg) for 2 h before using:
- 10a For a recent example dealing with stereoselective synthesis, see:
Toshima T.Nagai H.Matsumura S. Synlett 1999, 1420 - 10b For reviews on heteropoly acids, see:
Kozhevnikov IV. Chem. Rev. 1998, 98: 171 - 10c Also see:
Mizuno N.Misono M. Chem. Rev. 1998, 98: 199 - 11
Funabiki K.Murata E.Fukushima Y.Matsui M.Shibata K. Tetrahedron 1999, 55: 4637