2-Trifluoromethyl-1,3-dithianylium triflate: A convenient 'masked' electrophilic pentafluoroethylation reagent

Tetrahedron Letters

Volumn 44, Issue 32, 2003, Pages 5995-5998

  Sevenard, Dmitri V ^a   Kirsch, Peer ^b   Lork, Enno ^a   Röschenthaler, Gerd Volker ^a  

^a UNIVERSITY OF BREMEN   (Germany)

^b MERCK KGAA   (Germany)

Author keywords

Carbenium ions; Desulfurization; Fluorine and compounds; Thioethers; X ray crystal structures

Indexed keywords

2 TRIFLUOROMETHYL 1,3 DITHIANYLIUM TRIFLATE; ALPHA PERFLUOROCARBENIUM; FLUORINE DERIVATIVE; ORGANIC COMPOUND; REAGENT; TRIFLUOROMETHANESULFONIC ACID; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; FLUORODESULFURIZATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANIC CHEMISTRY; PENTAFLUOROETHYLATION; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS; THERMOSTABILITY; X RAY ANALYSIS;

EID: 0038644232     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(03)01478-3     Document Type: Article

References (37)

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10. Selected examples: (a) Olah, G. A.; Pittman, C. U., Jr.; Waack, R.; Doran, M. J. Am. Chem. Soc. 1966, 88, 1488-1499; (b) Olah, G. A.; Pittman, C. U., Jr. J. Am. Chem. Soc. 1966, 88, 3310-3317; (c) Rover-Kevers, M.; Vertommen, L.; Huys, F.; Merényi, R.; Janousek, Z.; Viehe, H. G. Angew. Chem. 1981, 93, 1091-1092; (d) Sürig, T.; Grützmacher, H.-Fr.; Bégué, J. P.; Bonnet-Delpon, D. Org. Mass Spectr. 1993, 28, 254-261; (e) Olah, G. A.; Burrichter, A.; Rasul, G.; Yudin, A. K.; Prakash, G. K. S. J. Org. Chem. 1996, 61, 1934-1939; (f) Laali, K. K.; Tanaka, M.; Hollerstein, S. J. Org. Chem. 1997, 62, 7752-7757; (g) Karpov, V. M.; Mezhenkova, T. V.; Platonov, V. E.; Sinyakov, V. R. J. Fluorine Chem. 2001, 107, 53-57.
11. Selected examples: (a) Olah, G. A.; Pittman, C. U., Jr.; Waack, R.; Doran, M. J. Am. Chem. Soc. 1966, 88, 1488-1499; (b) Olah, G. A.; Pittman, C. U., Jr. J. Am. Chem. Soc. 1966, 88, 3310-3317; (c) Rover-Kevers, M.; Vertommen, L.; Huys, F.; Merényi, R.; Janousek, Z.; Viehe, H. G. Angew. Chem. 1981, 93, 1091-1092; (d) Sürig, T.; Grützmacher, H.-Fr.; Bégué, J. P.; Bonnet-Delpon, D. Org. Mass Spectr. 1993, 28, 254-261; (e) Olah, G. A.; Burrichter, A.; Rasul, G.; Yudin, A. K.; Prakash, G. K. S. J. Org. Chem. 1996, 61, 1934-1939; (f) Laali, K. K.; Tanaka, M.; Hollerstein, S. J. Org. Chem. 1997, 62, 7752-7757; (g) Karpov, V. M.; Mezhenkova, T. V.; Platonov, V. E.; Sinyakov, V. R. J. Fluorine Chem. 2001, 107, 53-57.
12. Selected examples: (a) Olah, G. A.; Pittman, C. U., Jr.; Waack, R.; Doran, M. J. Am. Chem. Soc. 1966, 88, 1488-1499; (b) Olah, G. A.; Pittman, C. U., Jr. J. Am. Chem. Soc. 1966, 88, 3310-3317; (c) Rover-Kevers, M.; Vertommen, L.; Huys, F.; Merényi, R.; Janousek, Z.; Viehe, H. G. Angew. Chem. 1981, 93, 1091-1092; (d) Sürig, T.; Grützmacher, H.-Fr.; Bégué, J. P.; Bonnet-Delpon, D. Org. Mass Spectr. 1993, 28, 254-261; (e) Olah, G. A.; Burrichter, A.; Rasul, G.; Yudin, A. K.; Prakash, G. K. S. J. Org. Chem. 1996, 61, 1934-1939; (f) Laali, K. K.; Tanaka, M.; Hollerstein, S. J. Org. Chem. 1997, 62, 7752-7757; (g) Karpov, V. M.; Mezhenkova, T. V.; Platonov, V. E.; Sinyakov, V. R. J. Fluorine Chem. 2001, 107, 53-57.
13. Selected examples: (a) Olah, G. A.; Pittman, C. U., Jr.; Waack, R.; Doran, M. J. Am. Chem. Soc. 1966, 88, 1488-1499; (b) Olah, G. A.; Pittman, C. U., Jr. J. Am. Chem. Soc. 1966, 88, 3310-3317; (c) Rover-Kevers, M.; Vertommen, L.; Huys, F.; Merényi, R.; Janousek, Z.; Viehe, H. G. Angew. Chem. 1981, 93, 1091-1092; (d) Sürig, T.; Grützmacher, H.-Fr.; Bégué, J. P.; Bonnet-Delpon, D. Org. Mass Spectr. 1993, 28, 254-261; (e) Olah, G. A.; Burrichter, A.; Rasul, G.; Yudin, A. K.; Prakash, G. K. S. J. Org. Chem. 1996, 61, 1934-1939; (f) Laali, K. K.; Tanaka, M.; Hollerstein, S. J. Org. Chem. 1997, 62, 7752-7757; (g) Karpov, V. M.; Mezhenkova, T. V.; Platonov, V. E.; Sinyakov, V. R. J. Fluorine Chem. 2001, 107, 53-57.
14. Selected examples: (a) Olah, G. A.; Pittman, C. U., Jr.; Waack, R.; Doran, M. J. Am. Chem. Soc. 1966, 88, 1488-1499; (b) Olah, G. A.; Pittman, C. U., Jr. J. Am. Chem. Soc. 1966, 88, 3310-3317; (c) Rover-Kevers, M.; Vertommen, L.; Huys, F.; Merényi, R.; Janousek, Z.; Viehe, H. G. Angew. Chem. 1981, 93, 1091-1092; (d) Sürig, T.; Grützmacher, H.-Fr.; Bégué, J. P.; Bonnet-Delpon, D. Org. Mass Spectr. 1993, 28, 254-261; (e) Olah, G. A.; Burrichter, A.; Rasul, G.; Yudin, A. K.; Prakash, G. K. S. J. Org. Chem. 1996, 61, 1934-1939; (f) Laali, K. K.; Tanaka, M.; Hollerstein, S. J. Org. Chem. 1997, 62, 7752-7757; (g) Karpov, V. M.; Mezhenkova, T. V.; Platonov, V. E.; Sinyakov, V. R. J. Fluorine Chem. 2001, 107, 53-57.
15. Selected examples: (a) Olah, G. A.; Pittman, C. U., Jr.; Waack, R.; Doran, M. J. Am. Chem. Soc. 1966, 88, 1488-1499; (b) Olah, G. A.; Pittman, C. U., Jr. J. Am. Chem. Soc. 1966, 88, 3310-3317; (c) Rover-Kevers, M.; Vertommen, L.; Huys, F.; Merényi, R.; Janousek, Z.; Viehe, H. G. Angew. Chem. 1981, 93, 1091-1092; (d) Sürig, T.; Grützmacher, H.-Fr.; Bégué, J. P.; Bonnet-Delpon, D. Org. Mass Spectr. 1993, 28, 254-261; (e) Olah, G. A.; Burrichter, A.; Rasul, G.; Yudin, A. K.; Prakash, G. K. S. J. Org. Chem. 1996, 61, 1934-1939; (f) Laali, K. K.; Tanaka, M.; Hollerstein, S. J. Org. Chem. 1997, 62, 7752-7757; (g) Karpov, V. M.; Mezhenkova, T. V.; Platonov, V. E.; Sinyakov, V. R. J. Fluorine Chem. 2001, 107, 53-57.
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22. Selected examples: (a) Lokshin, V. A.; Trofimova, N. S.; Voloshin, N. A.; Revinskii, Yu. V.; Shelepin, N. E.; Kurdanov, Kh. A.; Minkin, V. I. Khim. Geterotsikl. Soedin. 1980, 47-50; (b) Stahl, I.; Kühn, I. Chem. Ber. 1983, 116, 1739-1750; (c) Hevesi, L.; Desauvage, S.; Georges, B.; Evrard, G.; Blanpain, P.; Michel, A.; Harkema, S.; van Hummel, J. J. J. Am. Chem. Soc. 1984, 106, 3784-3790; (d) Kirsch, P.; Bremer, M.; Taugerbeck, A.; Wallmichrath, T. Angew. Chem. 2001, 113, 1528-1532 and references cited therein; (e) Kirsch, P.; Huber, F.; Lenges, M.; Taugerbeck, A. J. Fluorine Chem. 2001, 112, 69-72.
23. Selected examples: (a) Lokshin, V. A.; Trofimova, N. S.; Voloshin, N. A.; Revinskii, Yu. V.; Shelepin, N. E.; Kurdanov, Kh. A.; Minkin, V. I. Khim. Geterotsikl. Soedin. 1980, 47-50; (b) Stahl, I.; Kühn, I. Chem. Ber. 1983, 116, 1739-1750; (c) Hevesi, L.; Desauvage, S.; Georges, B.; Evrard, G.; Blanpain, P.; Michel, A.; Harkema, S.; van Hummel, J. J. J. Am. Chem. Soc. 1984, 106, 3784-3790; (d) Kirsch, P.; Bremer, M.; Taugerbeck, A.; Wallmichrath, T. Angew. Chem. 2001, 113, 1528-1532 and references cited therein; (e) Kirsch, P.; Huber, F.; Lenges, M.; Taugerbeck, A. J. Fluorine Chem. 2001, 112, 69-72.
24. Selected examples: (a) Lokshin, V. A.; Trofimova, N. S.; Voloshin, N. A.; Revinskii, Yu. V.; Shelepin, N. E.; Kurdanov, Kh. A.; Minkin, V. I. Khim. Geterotsikl. Soedin. 1980, 47-50; (b) Stahl, I.; Kühn, I. Chem. Ber. 1983, 116, 1739-1750; (c) Hevesi, L.; Desauvage, S.; Georges, B.; Evrard, G.; Blanpain, P.; Michel, A.; Harkema, S.; van Hummel, J. J. J. Am. Chem. Soc. 1984, 106, 3784-3790; (d) Kirsch, P.; Bremer, M.; Taugerbeck, A.; Wallmichrath, T. Angew. Chem. 2001, 113, 1528-1532 and references cited therein; (e) Kirsch, P.; Huber, F.; Lenges, M.; Taugerbeck, A. J. Fluorine Chem. 2001, 112, 69-72.
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28. 4NBr (186.2222) as standard.
29. max=27.5°, Mo-Kα radiation (λ=71.073 pm), T=-100°C. The structure was solved by direct methods and refined using the SHELX program system (Sheldrick, G. M. SHELX-97, University of Göttingen, 1997). All non-hydrogen atoms were refined anisotropically. The positions of hydrogen atoms were calculated as a riding model. Crystallographic data (excluding structure factors) have been deposited with Cambridge Crystallographic Data Centre as supplementary publication no. 186353. Copies of the data can be obtained, free of charge, via the Internet http://www.ccdc.cam.ac.uk, or on application to the director; CCDC, 12 Union Road, Cambridge CB2 1EZ, UK. Tel.: (+44)1223-336-408; fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk.
30. DFT calculation: B3LYP/6-31G*; the optimized structures have only positive eigen frequencies. Gaussian 98, Revision A.6: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian, Inc., Pittsburgh, PA, USA, 1998.
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34. Umemoto T. Chem. Rev. 96:1996;1757-1777.
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36. +: found 342.1968; calcd 342.1982, 4.1 (10.0) ppm, 1.4 (10.0) mmu.
37. 5) were also obtained: Sevenard, D. V.; Kolomeitsev, A. A.; Kalinovich, N.; Königsmann, M. H.; Kirsch, P.; Röschenthaler, G.-V., unpublished results.