Oxidative Desulfurization-Difluorination
of Alkyl Aryl Thioethers: Synthesis of ω-Substituted
1,1-Difluoroalkanes

Verena Hugenberg; Günter Haufe

doi:10.1055/s-0028-1087278

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Synlett 2009(1): 106-108
DOI: 10.1055/s-0028-1087278

LETTER

Oxidative Desulfurization-Difluorination of Alkyl Aryl Thioethers: Synthesis of ω-Substituted 1,1-Difluoroalkanes

Verena Hugenberg^a,b, Günter Haufe*^a,b
^a Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstr. 40, 48149 Münster, Germany
^b European Institute of Molecular Imaging (EIMI), Westfälische Wilhelms-Universität Münster, Mendelstr. 11, 48149 Münster, Germany
Fax: +49(251)8339772; e-Mail: haufe@uni-muenster.de;

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Publication History

Received 11 September 2008
Publication Date:
26 November 2008 (online)

Abstract
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Abstract

An efficient new pathway towards ω-substituted gem-difluoroalkanes from corresponding aryl alkyl thioethers by oxidative desulfurization-difluorination with the reagents combination of 1,3-dibromo-5,5-dimethylhydantoin (DBH) as the oxidizer and pyridine-nonakis(hydrogen fluoride) as the fluoride source is described. Two succeeding fluoro-Pummerer-like rearrangements are suggested as a possible reaction mechanism.

Key words

desulfurization - fluorination - oxidation - synthesis - thioethers

References

Selected monographs:
1a Olah GA. Chambers RD. Prakash GKS. Synthetic Fluorine Chemistry Wiley; New York: 1992.

Google Scholar
1b Chemistry of Organic Fluorine Compounds II. A Critical Review Hudlick M. Pavlath AE. ACS Monograph 187, American Chemical Society; Washington: 1995.

Google Scholar
Selected recent monographs:
2a Biomedical Frontiers of Fluorine Chemistry Ojima I. McCarthy JR. Welch JT. ACS Symposium Series 639, American Chemical Society; Washington: 1996.

Google Scholar
2b Bégué JP. Bonnet-Delpon D. Bioorganic and Medicinal Chemistry of Fluorine Wiley; Hoboken: 2008.

Google Scholar
2c Fluorine and Health. Molecular Imaging, Biomedical Materials and Pharmaceuticals Tressaud A. Haufe G. Elsevier; Amsterdam: 2008.

Google Scholar
Selected monographs:
3a Banks RE. Smart BE. Tatlow JC. Organofluorine Chemistry. Principles and Commercial Applications Plenum; New York: 1994.

Google Scholar
3b Kirsch P. Modern Fluoroorganic Chemistry Wiley-VCH; Weinheim: 2004.

Google Scholar
3c Babudri F. Farinola GF. Naso F. Ragni R. Chem. Commun. 2007, 1003

Google Scholar
4a Houben-Weyl Vols. E 10a, E 10b/1, E 10b/2: Baasner B. Hagemann H. Tatlow JC. Thieme; Stuttgart: 1999.

Google Scholar
4b Science of Synthesis Vol. 34: Percy JM. Thieme; Stuttgart: 2006.

Google Scholar
5a Ma J.-A. Cahard D. Chem. Rev. 2004, 104: 6119

Google Scholar
5b Ibrahim H. Togni A. Chem. Commun. 2004, 1147

Google Scholar
5c Pihko PM. Angew. Chem. Int. Ed. 2006, 45: 544 ; Angew. Chem. 2006, 118, 558

Google Scholar
5d Bobbio C. Gouverneur V. Org. Biomol. Chem. 2006, 4: 2065

Google Scholar
5e Shibata N. Ishimaru T. Nakamura S. Toru T. J. Fluorine Chem. 2007, 128: 469

Google Scholar
6a Camps F. Chamorro E. Gasol V. Guerrero A. J. Org. Chem. 1989, 54: 4294

Google Scholar
6b Haufe G. Alvernhe G. Laurent A. Ernet T. Goj O. Kröger S. Sattler A. Org. Synth. 1999, 76: 159

Google Scholar
6c Haufe G. In Science of Synthesis Vol. 34: Percy JM. Thieme; Stuttgart: 2006. p.169-223

Google Scholar
7a Purrington ST. Corea ID. J. Org. Chem. 1986, 51: 1080

Google Scholar
7b Saluzzo C. Alvernhe G. Anker D. Haufe G. Tetrahedron Lett. 1990, 31: 663

Google Scholar
7c McCarthy JR. Matthews DP. Barney CL. Tetrahedron Lett. 1990, 31: 973

Google Scholar
7d Saluzzo C. Alvernhe G. Anker D. Haufe G. Tetrahedron Lett. 1990, 31: 2127

Google Scholar
7e Uneyama K. Kanai M. Tetrahedron Lett. 1990, 31: 3583

Google Scholar
7f Haufe G. Alvernhe G. Anker D. Laurent A. Saluzzo C. J. Org. Chem. 1992, 57: 714

Google Scholar
8a Kuroboshi M. Kanie K. Hiyama T. Adv. Synth. Catal. 2001, 343: 235

Google Scholar
8b Shimizu M. Hiyama T. Angew. Chem. Int. Ed. 2005, 44: 214 ; Angew. Chem. 2005, 117, 218

Google Scholar
9a Zupan M. J. Fluorine Chem. 1976, 8: 305

Google Scholar
9b Marat RK. Janzen AF. Can. J. Chem. 1977, 55: 3031

Google Scholar
9c Umemoto T. Tomizawa G. Bull. Chem. Soc. Jpn. 1986, 59: 3625

Google Scholar
9d Brigaud T. Laurent E. Tetrahedron Lett. 1990, 31: 2287

Google Scholar
9e Fuchigami T. Shimojo M. Konno A. Nakagawa K. J. Org. Chem. 1990, 55: 6074

Google Scholar
9f Haufe G. J. Prakt. Chem. 1996, 338: 99

Google Scholar
10a Caddick S. Gazzard L. Motherwell WB. Wilkinson JA. Tetrahedron 1996, 52: 149

Google Scholar
10b Sondej SC. Katzenellenbogen IA. J. Org. Chem. 1986, 51: 3508

Google Scholar
10c Furuta S. Kuroboshi M. Hiyama T. Bull. Chem. Soc. Jpn. 1999, 72: 805

Google Scholar
11a Ayuba S. Fukuhara T. Hara S. Org. Lett. 2003, 5: 2873

Google Scholar
11b Ayuba S. Hiramatsu C. Fukuhara T. Hara S. Tetrahedron 2004, 60: 11445

Google Scholar
12a Nicolaou KC. Dolle RE. Papahatjis DP. Randall JL. J. Am. Chem. Soc. 1984, 106: 4189

Google Scholar
12b Furuta S. Kuroboshi M. Hiyama T. Tetrahedron Lett. 1995, 36: 8243

Google Scholar
12c Furuta S. Kuroboshi M. Hiyama T. Bull. Chem. Soc. Jpn. 1998, 71: 2687

Google Scholar
13 York C. Prakash GKS. Olah GA. Tetrahedron 1996, 52: 9

Crossref Google Scholar
14 Kuroboshi M. Hiyama T. Synlett 1991, 909

Article in Thieme Connect Google Scholar
15 Shimizu M. Maeda T. Fujisawa T. J. Fluorine Chem. 1995, 71: 9

Google Scholar
16a Rozen S. Acc. Chem. Res. 2005, 38: 803

Google Scholar
16b Hagooly A. Rozen S. J. Org. Chem. 2004, 69: 7241

Google Scholar
17a McCharty JR. Peet NP. LeTourneau ME. Inbasekaran M. J. Am. Chem. Soc. 1985, 107: 735

Google Scholar
17b Wnuk SF. Robins MJ. J. Org. Chem. 1990, 55: 4757

Google Scholar
17c Robins MJ. Wnuk SF. J. Org. Chem. 1993, 58: 3800

Google Scholar
17d Aki S. Kita Y. Top. Curr. Chem. 2007, 274: 35

Google Scholar
18a Hugenberg V. Diploma Thesis University of Münster; Germany: 2006.

Google Scholar
18b Hugenberg V. Haufe G. Book of Abstracts 15th European Symposium on Fluorine Chemistry; Prague: 2007. p.210

Google Scholar