RSS-Feed abonnieren
DOI: 10.1055/s-2002-35625
Direct α-Fluorination of Ketones Using N-F Reagents
Publikationsverlauf
Publikationsdatum:
20. November 2002 (online)
![](https://www.thieme-connect.de/media/synthesis/200217/lookinside/thumbnails/10.1055-s-2002-35625-1.jpg)
Abstract
The use of 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Accufluor TM NFTh) as a fluorine atom transfer reagent and methanol as solvent enabled direct regiospecific fluorofunctionalization of the α-carbonyl position in ketones without prior activation of the target molecules. Methoxy or hydroxy substituted derivatives of 1-indanone, 1-tetralone and oxo derivatives of thiophene, benzo[b]thiophene, benzofuran and benzopyran were regiospecifically transformed to the corresponding α-fluoro derivatives in high yield, while 2α-fluoro-5α-cholestan-3-one (28) and 16α-fluoro-3β-hydroxy-5α-androstan-17-one (30) were regio- and stereospecifically obtained starting directly from the corresponding keto steroids.
Key words
fluorination - ketones - Accufluor TM NFTh - keto steroids
-
1a
Banks RE.Smart BE.Tatlow JC. In Organofluorine Chemistry. Principles and Commercial Applications Plenum Press; New York: 1994. -
1b
Hudlicky M.Pavlath AE. In Chemistry of Organic Fluorine Compounds II. A Critical Review ACS Monograph 187; Washington: 1995. -
1c
Hiyama T. In Organofluorine Compounds. Chemistry and Applications Springer-Verlag; Berlin: 2000. - 2
Baasner B.Hagemann H.Tatlow JC. In Methods of Organic Chemistry (Houben-Weyl): Organofluorine Compounds Vol. E 10a,10b: Thieme; New York: 1999. -
3a
Lal GS.Pez GP.Syvret RG. Chem. Rev. 1996, 96: 1737 -
3b
Taylor SD.Kotoris CC.Hum G. Tetrahedron 1999, 55: 12431 -
3c
Furin GG.Fainzilberg AA. Russian Chem. Rev. 1999, 68: 653 -
4a
Organofluorine Compounds in Medicinal Chemistry
and Biomedicinal Applications
Filler R.Kobayashi Y.Yagupolskii LM. Elsevier; Amsterdam: 1993. -
4b
Resnati G.Soloshnok VA. In Fluoroorganic Chemistry: Synthetic Challenges and Biomedicinal Rewards, Tetrahedron Symposia-in-Print No. 58 52: Elsievier; Amsterdam: 1996. p.1 -
4c
Smart BE. J. Fluorine Chem. 2001, 109: 3 -
5a
Rozen S.Filler R. Tetrahedron 1985, 41: 1111 ; and references therein -
5b
Davis FA.Kasu PVN. Org. Prep. Proced. Int. 1999, 31: 125 ; and references therein -
6a
Differding E.Lang RW. Tetrahedron Lett. 1988, 29: 6087 -
6b
Davis FA.Han W.Murphy CK. J. Org. Chem. 1995, 60: 4730 -
6c
Davis FA.Zhou P.Murphy CK.Sundarababu G.Qi H.H’an W.Przeslawski RM.Chen BC.Carrol PJ. J. Org. Chem. 1998, 63: 2273 -
6d
Liu Z.Shibata N.Takeuchi Y. J. Org. Chem. 2000, 65: 7583 -
6e
Cahard D.Audouard C.Plaquevent J.-C.Roques N. Org. Lett. 2000, 2: 3699 -
6f
Shibata N.Suzuki E.Asahi T.Shiro M. J. Am. Chem. Soc. 2001, 123: 7001 -
6g
Enders D.Faure S.Potthoff M.Runsink J. Synthesis 2001, 15: 2307 - 7
Stavber S.Zupan M. Tetrahedron Lett. 1996, 37: 3591 - 8
Stavber S.Jereb M.Zupan M. Chem. Commun. 2000, 1323 - 9
Ohloff G. In Scent and Fragrances Springer-Verlag; Berlin: 1994. -
10a
Meyer MD.Hancock AA.Tietje K.Sippy KB.Giardina WJ.Kervin JF. Bioorg. Med. Chem. Lett. 1995, 5: 2287 -
10b
Meyer MD.Hancock AA.Tietje K.Sippy KB.Prasad R.Stout DM.Arendsen DL.Donner BG.Carrol WA. J. Med. Chem. 1997, 40: 1049 -
10c
Perrone R.Berardi F.Leopoldo M.Tottorella V.Fornaretto MG.Caccia C.McArthur RA. J. Med. Chem. 1996, 39: 3195 -
10d
Ragot JP.Steeneck C.Alcaraz M.-L.Taylor JK. J. Chem. Soc., Perkin Trans. 1 1999, 1073 -
11a
Hamanaka N.Takahashi K.Nagao Y.Torisu K.Tokumoto H.Kondo K. Bioorg. Med. Chem. Lett. 1995, 5: 1083 -
11b
Mu YQ.Gibbs RA. Bioorg. Med. Chem. 1997, 5: 1327 - 12
Gilicinski AG.Pez GP.Syvret RG.Lal GS. J. Fluorine Chem. 1992, 59: 157 - 13
Thomas MG.Suckling CJ.Pitt AR.Suckling KE. J. Chem. Soc., Perkin Trans. 1 1999, 3191 - 14
Rozen S.Menahem Y. J. Fluorine Chem. 1980, 16: 19 - 15
Molines H.Wakselman C. J. Chem. Soc., Chem. Commun. 1975, 232 - 16
Shapiro B.Chrysam MM. J. Org. Chem. 1973, 38: 880 - 17
Leroy J. J. Org. Chem. 1981, 46: 206