N-(β,β-Difluorovinyl)oxazolidin-2-ones:
First Synthesis and Application in [3+2]-
and [4+2]-Cycloaddition-Type Reactions

Thanh Binh Nguyen; Arnaud Martel; Robert Dhal; Gilles Dujardin

doi:10.1055/s-0029-1217744

LETTER

N-(β,β-Difluorovinyl)oxazolidin-2-ones: First Synthesis and Application in [3+2]- and [4+2]-Cycloaddition-Type Reactions

Thanh Binh Nguyen, Arnaud Martel, Robert Dhal, Gilles Dujardin*
UCO2M UMR 6011 CNRS, Université du Maine, 72085 Le Mans, France
Fax: +33(243)833344; e-Mail: gilles.dujardin@univ-lemans.fr;

Abstract

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Abstract

N-(β,β-Difluorovinyl)oxazolidin-2-ones were conveniently prepared in good yields in two steps from the parent oxazolidin-2-ones. The [3+2]- and [4+2]-cycloaddition-type reactions with electron-deficient partners were investigated as first application of these new enamides. TMSOTf was efficient in promoting these two reactions, and the corresponding heterocyclic difluoro adducts were obtained in high yields.

Key words

N-(β,β-difluorovinyl)oxazolidin-2-ones - trimethylsilyl trifluoromethanesulfonate - 1,3-dipolar cycloaddition - Diels-Alder reaction - dipolarophile - nitrone - heterodiene

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References

References and Notes

1a Thayer AM. Chem. Eng. News 2006, 84 (23): 15

1b Thayer AM. Chem. Eng. News 2006, 84 (23): 27

2a Purser S. Moore PR. Swallow S. Gouverneur V. Chem. Soc. Rev. 2008, 37: 320

2b Kirk KL. Org. Process Res. Dev. 2008, 12: 305

2c O’Hagan D. Chem. Soc. Rev. 2008, 37: 308

2d Müller K. Faeh C. Diederich F. Science 2007, 317: 1881

2e Sun S. Adejare A. Curr. Top. Med. Chem. 2006, 6: 1457

2f Iseki K. Tetrahedron 1998, 54: 13887

2g Welch JT. Eswarakrishnan S. Fluorine in Bioorganic Chemistry Wiley; New York: 1991.

2h Tozer MJ. Herpin TF. Tetrahedron 1996, 52: 8219

2i Welch JT. Tetrahedron 1987, 43: 3123

3 Singh RP. Schreeve JM. Synthesis 2002, 2561

4 Percy JM. Top. Curr. Chem. 1997, 193: 131

5a Arany A. Crowley PJ. Fawcett J. Hursthouse MB. Kariuki BM. Light ME. Moralee AC. Percy JM. Salafia V. Org. Biomol. Chem. 2004, 2: 455

5b Okano T. Nakajima A. Eguchi S. Synlett 2001, 1449

5c Purrington SZ. Thomas HN. J. Fluorine Chem. 1998, 90: 47

5d Howarth JA. Owton WM. Percy JM. Tetrahedron 1995, 51: 10289

5e Bennette AJ. Percy JM. Synlett 1992, 483

5f Percy JM. Rock MH. Tetrahedron Lett. 1992, 33: 6177

6a Gogsig TM. Sobjerg LS. Lindhardt AT. Jensen KL. Skrydstrup T. J. Org. Chem. 2008, 73: 3404

6b Fang X. Wu YM. Deng J. Wang SW. Tetrahedron 2004, 60: 5487

6c Ichikawa J. Wada Y. Fujiwara M. Sakoda K. Synthesis 2002, 1917

6d Ichikawa J.
J. Fluorine Chem. 2000, 105: 257

6e Ichikawa J. Fujiwara M. Nawata H. Okauchi T. Manami T. Tetrahedron Lett. 1996, 37: 8799

6f Ichikawa J. Ikeura C. Minami T. Synlett 1992, 739

6g Ichikawa J. Hamada S. Sonoda T. Kobayashi H. Tetrahedron Lett. 1992, 33: 337

6h Ichikawa J. Moriya T. Sonoda T. Kobayashi H. Chem. Lett. 1991, 20: 961

6i Ichikawa J. Sonoda T. Kobayashi H. Tetrahedron Lett. 1989, 30: 1641

6j Ichikawa J. Sonoda T. Kobayashi H. Tetrahedron Lett. 1989, 30: 5437

6k Ichikawa J. Sonoda T. Kobayashi H. Tetrahedron Lett. 1989, 30: 6379

6l Tanaka K. Nakai T. Ishikawa N. Tetrahedron Lett. 1978, 4809

6m Percy JM. Tetrahedron Lett. 1990, 31: 3931

7a Fustero S. Sanz-Cervera JF. Aceña JL. Sánchez-Roselló M. Synlett 2009, 525

7b Zhi L, Van Oeveren CA, Chen J.-H, and Higuchi RI. inventors; PCT Int. Appl., WO 2002066475, A220020829.

7c Kudo Y, Katsumata A, Maeda K, Akiyama S, Yaosaka M, Morimoto K, Nakahira K, Ohki T, Hamada N,
Yano T, Noguchi J, and Watanabe S. inventors; PCT Int. Appl., WO 2001068613, A120010920.

7d Okamoto H, and Kato S. inventors; Jpn. Kokai Tokkyo Koho, JP 02178259, A19900711.

7e Haszeldine RN. Tipping AE.
J. Chem. Soc. C 1968, 4: 398

8a Nguyen TB. Vuong TMH. Martel A. Dhal R. Dujardin G. Tetrahedron: Asymmetry 2008, 19: 2084

8b Nguyen TB. Martel A. Dhal R. Dujardin G. Synlett 2008, 2041

8c Nguyen TB. Martel A. Dhal R. Dujardin G. J. Org. Chem. 2008, 73: 2621

8d Nguyen TB. Gaulon C. Chapin T. Tardy S. Tatibouet A. Rollin P. Dhal R. Martel A. Dujardin G. Synlett 2006, 3255

9a Gohier F. Bouhadjera K. Faye D. Gaulon C. Maisonneuve V. Dujardin G. Dhal R. Org. Lett. 2007, 9: 211

9b Gaulon C. Dhal R. Chapin T. Maisonneuve V. Dujardin G. J. Org. Chem. 2004, 69: 4192

9c Gaulon C. Gizecki P. Dhal R. Dujardin G. Synthesis 2003, 2269

9d Gaulon C. Gizecki P. Dhal R. Dujardin G. Synlett 2002, 952

10a Feiring AE. Wonchoba ER. J. Org. Chem. 1992, 57: 7014

10b Dlouba I. Kvicala J. Paleta O. J. Fluorine Chem. 2002, 117: 149

11

Procedures and compounds are described in the Supplementary Information.

12 Dhavale DD. Trombini C. J. Chem. Soc., Chem. Commun. 1992, 1268

13

Only minor adduct 9b, of cis configuration, could be separated from the adduct mixture by column chroma-tography.

14 Amiii H. Kobayashi T. Terasawa H. Uneyama K. Org. Lett. 2001, 3: 3103

15

From the NMR study on adduct 11b, the cis/trans distribution (cis I/cis II/trans I/trans II = 52:22:18:8) was deduced.

Supplementary Material

Supporting Information