Abstract
Fluoroolefins, which play an increasingly important role as peptide
mimics in pharmaceuticals and as crop protection agents, are generated
using a fluoro-Julia-Kocienski olefination. Their preparation
can easily be accomplished using a Mitsunobu reaction and subsequent
oxidation to generate the required benzothiazolyl sulfones. The
key step of this process was the electrophilic α-fluorination
of the sulfone with N -fluorobenzenesulfonimide.
The last stage of the successful synthesis of the fluoroolefins
was the modified Julia-Kocienski olefination under basic
conditions. Further functionalization was followed with the application
of a Suzuki reaction.
Key words
fluorine - olefination - sulfones - heterocycles - cross-coupling
References
1a
Bégué JP.
Bonnet-Delpon D.
Bioorganic and Medicinal
Chemistry of Fluorine
Wiley-VCH;
Weinheim:
2008.
1b
Kirsch P.
Modern Fluoroorganic Chemistry: Synthesis,
Reactivity, Applications
Wiley-VCH;
Weinheim:
2004.
1c
Organofluorine
Compounds: Chemistry and Applications
Hiyama T.
Springer;
New York:
2000.
2a
Welch JT.
Tetrahedron
1987,
43:
3123
2b
Welch JT.
Eswarakrishnan S.
Fluorine in Biological Chemistry
Wiley;
New
York:
1991.
3
Müller K.
Faeh C.
Diederich F.
Science
2007,
317:
1881
4
Jeschke P.
ChemBioChem
2004,
5:
570
5
Biffinger JC.
Kim HW.
DiMagno SG.
ChemBioChem
2004,
5:
622
6
Böhm H.-J.
Banner D.
Bendels S.
Kansy M.
Kuhn B.
Müller K.
Obst-Sander U.
ChemBioChem
2004,
5:
637
7
Wiehn MS.
Lindell SD.
Bräse S.
Angew. Chem. Int. Ed.
2008,
47:
8120
8a
Van der Veken P.
Kertèsz I.
Senten K.
Haemers A.
Augustyns K.
Tetrahedron Lett.
2003,
44:
6231
8b
Nakamura Y.
Okada M.
Koura M.
Tojo M.
Saito A.
Sato A.
Taguchi T.
J. Fluorine Chem.
2006,
127:
627
8c
Guan T.
Yoshida M.
Ota D.
Fukuhara T.
Hara S.
J.
Fluorine Chem.
2005,
126:
1185
8d
Pirrung MC.
Han H.
Ludwig RT.
J. Org. Chem.
1994,
59:
2430
8e
Laue KW.
Mück-Lichtenfeld C.
Haufe G.
Tetrahedron
1999,
55:
10413
8f
Daubresse N.
Chupeau Y.
Francesch C.
Lapierre C.
Pollet B.
Rolando C.
Chem. Commun.
1997,
1489
8g
Burkhart JP.
Weintraub PM.
Gates CA.
Resvick RJ.
Vaz RJ.
Friedrich D.
Angelastro MR.
Bey NP.
Bioorg. Med. Chem.
2002,
10:
929
8h
van Steenis JH.
van der Gen A.
J.
Chem. Soc., Perkin Trans. 1
2002,
2117
9a
Bartlett PA.
Otake A.
J.
Org. Chem.
1995,
60:
3107
9b
Allmendinger T.
Furet P.
Hungerbühler E.
Tetrahedron
Lett.
1990,
31:
7297
9c
Allmendinger T.
Felder E.
Hungerbühler E.
Tetrahedron
Lett.
1990,
31:
7301
9d
Welch JT.
Lin J.
Tetrahedron
1996,
52:
291
9e
Okada M.
Nakamura Y.
Saito A.
Sato A.
Horikawa H.
Taguchi T.
Tetrahedron Lett.
2002,
43:
5845
9f
Niida A.
Tomita K.
Mizumoto M.
Tanigaki H.
Terada T.
Oishi S.
Otaka A.
Inui K.
Fuji N.
Org. Lett.
2006,
8:
613
9g
Couve-Bonnaire S.
Cahard D.
Pannecoucke X.
Org. Biomol. Chem.
2007,
5:
1151
9h
Oishi S.
Kamitani H.
Kodera Y.
Watanabe K.
Kobayashi K.
Narumi T.
Tomita K.
Ohno H.
Naito T.
Kodama E.
Matsuoka M.
Fujii N.
Org. Biomol. Chem.
2009,
7:
2872
10
Baudin JB.
Hareau G.
Julia SA.
Ruel O.
Tetrahedron Lett.
1991,
32:
1175
11
Blakemore PR.
Cole WJ.
Kocienski PJ.
Morley A.
Synlett
1998,
26
12
Gosh AK.
Zajc B.
Org. Lett.
2006,
8:
1553
13
Brown HC.
Stocky TP.
J. Am. Chem. Soc.
1977,
99:
8218
14 Compare: Metay E.
Synth.
Commun.
2008,
38:
889
15
Chochrek P.
Wicha J.
Eur. J. Org. Chem.
2007,
2534
16
Ray PC.
Mittapelli V.
Rohatgi A.
Tyagi OD.
Synth. Commun.
2007,
37:
2861
17
Ghosh AK.
Zajc B.
J. Org. Chem.
2009,
74:
8531
18
Stavber G.
Zupan M.
Stavber S.
Tetrahedron
Lett.
2007,
48:
2671
19
Zajc B.
Kake S.
Org. Lett.
2006,
8:
4457
20
Saito A.
Nakagawa M.
Taguchi T.
J.
Fluorine Chem.
2005,
126:
1166
21
Dess DB.
Martin JC.
J. Am. Chem. Soc.
1991,
113:
7277
22
Caijo F.
Mosset P.
Gree R.
Audinot-Bouchez V.
Boutin J.
Renard P.
Caignard D.-H.
Dacquet C.
Eur. J. Org. Chem.
2006,
9:
2181
23
Marck G.
Villiger A.
Buchecker R.
Tetrahedron
Lett.
1994,
35:
3277
24
Ooi T.
Uematsu Y.
Kameda M.
Maruoka K.
Tetrahedron
2006,
62:
11425
25
Zhang F.-J.
J.
Org. Chem.
2000,
65:
3952
26a
Bosanac T.
Yang J.
Wilcox CS.
Angew. Chem. Int. Ed.
2001,
40:
1875
26b
Ali MA.
Tsuada Y.
Chem. Pharm.
Bull.
1992,
40:
2842
26c
Detar DF.
Chu YW.
J.
Am. Chem. Soc.
1955,
77:
4410
27
Yu J.
Gaunt MJ.
Spencer JB.
J.
Org. Chem.
2002,
67:
46
28 Crystallographic data (excluding structure
factors) for the structures reported in this work have been deposited
with the Cambridge Crystallographic Data Centre as supplementary publications
CCDC 755487 (5a ) and CCDC 755489 (7c /8c ). Copies
of the data can be obtained free of charge on application to The
Director, CCDC, 12 Union Road, Cambridge DB2 1EZ, UK [Fax: +44
(1223)336033; e-mail: deposit@ccdc.cam.ac.uk].