(1R,3R)-2-Methylene-1,3-dithiolane 1,3-dioxide: a highly reactive and highly selective chiral ketene equivalent in cycloaddition reactions with a broad range of dienes

Abstract

The chiral ketene equivalent trans-2-methylene-1,3-dithiolane 1,3-dioxide has been prepared in racemic and enantiomerically pure form in four steps. The key step in the asymmetric synthesis utilised a Modena asymmetric oxidation of 2-benzyloxymethyl-1,3-dithiolane which gave the trans bis-sulfoxide with high diastereocontrol (91∶9 in favour of trans) and high enantiocontrol (>97% ee). The ketene equivalent shows high selectivity (>97∶3) in Diels–Alder reactions with a range of simple dienes (cyclopentadiene, furan, 1-methoxybutadiene, Danishefsky’s diene, 1-methoxycyclohexa-1,3-diene) and shows high reactivity as it is able to undergo cycloadditions with notoriously unreactive dienes (cyclohexa-1,3-diene, 90∶10 selectivity; 2H-pyran-2-one, 94∶6 selectivity). Dihydropyridines also participated in cycloaddition reaction but with only moderate selectivity (73∶27). The Diels–Alder adducts can be readily deprotected to return the carbonyl group using a two step sequence involving reduction followed by hydrolysis.

References

1. For a review see: S. Ranganathan, D. Ranganathan and A. K. Mehrotra, Synthesis, 1977, 289.
2. (a) E. Viera and P. Vogel, Helv. Chim. Acta, 1983, 66, 1865; (b) J. L. Reymond and P. Vogel, J. Chem. Soc., Chem. Commun., 1990, 1070; (c) P. Vogel, D. Fattori, F. Gasparini and C. Le Drain, Synlett, 1990, 173; (d) J. L. Reymond and P. Vogel, Tetrahedron: Asymmetry, 1990, 1, 729.
3. (a) J. Mattay, J. Mertes and G. Maas, Chem. Ber., 1989, 122, 327; (b) W. R. Roush, A. P. Essenfeld, J. S. Warmus and B. B. Brown, Tetrahedron Lett., 1989, 20, 7305.
4. (a) C. Maignan and R. A. Raphael, Tetrahedron, 1983, 39, 3245; (b) R. V. Williams and X. Lin, J. Chem. Soc., Chem. Commun., 1989, 1872; (c) N. Katagiri, S. Ise, N. Watanabe and C. Kaneko, Chem. Pharm. Bull., 1990, 38, 3242; (d) O. De Lucci, D. Fabbri and V. Lucchini, Synlett, 1991, 565 For a review see O. De Lucchi and L. Pasquato, Tetrahedron, 1988, 44, 6755.
5. (a) C. Maignan and F. Belkasmioui, Tetrahedron Lett., 1988, 29, 2823; (b) A. W. M. Lee, W. H. Chan and M. S. Wong, J. Chem. Soc., Chem. Commun., 1988, 1585.
6. (a) H. B. Kagan and B. Ronan, Tetrahedron: Asymmetry, 1991, 2, 75; (b) H. B. Kagan and B. Ronan, Tetrahedron: Asymmetry, 1992, 3, 115.
7. R. Lopez and J. C. Carretero, Tetrahedron: Asymmetry, 1991, 2, 93.
8. Y. Arai, S. Kuwayama, Y. Takeuchi and T. Koizumi, Synth. Commun., 1986, 16, 233.
9. J. Martynow, M. Dimitroff and A. G. Fallis, Tetrahedron Lett., 1993, 34, 8201.
10. V. K. Aggarwal, M. Lightowler and S. D. Lindell, Synlett, 1992, 730.
11. For a preliminary account see: V. K. Aggarwal, J. Drabowicz, R. S. Grainger, Z. Gültekin, M. Lightowler and P. L. Spargo, J. Org. Chem., 1995, 60, 4962.
12. The experimental details for this synthesis are described in: V. K. Aggarwal, R. S. Grainger, H. Adams and P. L. Spargo, J. Org. Chem., 1998, 63, 3481.
13. K. R. Dahnke and L. A. Paquette, Org. Synth., 1992, 71, 175.
14. V. K. Aggarwal, I. W. Davies, R. Franklin, J. Maddock, M. F. Mahon and K. C. Molloy, J. Chem. Soc., Perkin Trans. 1, 1994, 2363.
15. V. K. Aggarwal, S. Schade and H. Adams, J. Org. Chem., 1997, 62, 1139.
16. (a) F. Di Furia, G. Modena and R. Seraglia, Synthesis, 1984, 325; (b) F. Di Furia, G. Licini and G. Modena, Gazz. Chim. Ital., 1990, 120, 165; (c) M. Corich, F. Di Furia, G. Licini and G. Modena, Tetrahedron Lett., 1992, 33, 3043.
17. V. K. Aggarwal, G. Evans, E. Moya and J. Dowden, J. Org. Chem., 1992, 57, 6390.
18. V. Conte, F. Di Furia, G. Licini, G. Modena, G. Sbampato and G. Valle, Tetrahedron: Asymmetry, 1991, 2, 257.
19. (a) N. Komatsu, M. Hashizume, T. Sugita and S. Uemura, J. Org. Chem., 1993, 58, 4529; (b) A. Scettri, F. Bonadies, A. Lattanzi, A. Senatore and A. Soriente, Tetrahedron: Asymmetry, 1996, 7, 657; (c) A. Lattanzi, F. Bonadies, A. Senatore, A. Soriente and A. Scettri, Tetrahedron: Asymmetry, 1997, 8, 2473.
20. (a) S. Kobayashi, Y. Fujishita and T. Mukaiyama, Chem. Lett., 1990, 1455; (b) S. Kobayashi, M. Furuya, A. Ohtsuba and T. Mukaiyama, Tetrahedron: Asymmetry, 1992, 2, 115.
21. Full crystallographic details, excluding structure factor tables, have been deposited at the Cambridge Crystallographic Data Centre (CCDC). For details of the deposition scheme, see ‘Instructions for Authors’, J. Chem. Soc., Perkin Trans. 1, available via the RSC Web pages (http//www.rsc.org/authors). Any request to the CCDC for this material should quote the full literature citation and the reference number 207/241.
22. (a) For other examples of selective Diels–Alder reactions resulting from the difference in size between a sulfinyl oxygen a lone pair see: A. Waldner, Tetrahedron Lett., 1989, 30, 3061; (b) ref. 9; (c) M. J. Fisher, W. J. Hehre, S. D. Kahn and L. E. Overman, J. Am. Chem. Soc., 1988, 110, 4625; (d) For an example where addition occurs syn to a sulfinyl oxygen see: A. M. Naperstkow, J. B. Macaulay, M. J. Newlands and A. G. Fallis, Tetrahedron Lett., 1989, 30, 5077.
23. M. A. McCarrick, Y. D. Wu and K. N. Houk, J. Am. Chem. Soc., 1992, 114, 1499.
24. R. J. Sundberg and J. D. Bloom, J. Org. Chem., 1981, 46, 4836.
25. For reviews on Diels–Alder reactions of dihydropyridines see: D. M. Stout and A. I. Meyers, Chem. Rev., 1982, 82, 223 see also B. Weinstein, L. C. Lin and F. W. Fowler, J. Org. Chem., 1980, 45, 1657; E. W. Baxter, D. Labaree, S. Chao and P. S. Mariano, J. Org. Chem., 1989, 54, 2893; G. R. Krow, J. T. Carey, K. C. Cannon and K. J. Henz, Tetrahedron Lett., 1982, 23, 2527.
26. See summary in: F. Fringuelli and A. Taticchi, Dienes in the Diels–Alder Reaction, Wiley, Toronto, 1990.
27. D. A. Evans, W. L. Scott and L. K. Truesdale, Tetrahedron Lett., 1972, 13, 121.
28. For a review see: K. Afarinkia, V. Vinader, T. D. Nelson and G. H. Posner, Tetrahedron, 1992, 48, 9111.
29. For a review on sulfoxide reduction see: M. Madesclaire, Tetrahedron, 1988, 44, 6537.
30. (a) D. O. Spry, J. Chem. Soc., Chem. Commun., 1973, 671; (b) D. O. Spry, Tetrahedron Lett., 1973, 14, 2413.
31. F. Mohanazadeh, A. R. Momeni and Y. Ranjbar, Tetrahedron Lett., 1994, 35, 6127.
32. G. V. Kaiser, R. D. G. Cooper, R. E. Koehler, C. F. Murphy, J. A. Webber, I. G. Wright and E. M. Van Heyningen, J. Org. Chem., 1970, 35, 2430.
33. J. Drabowicz and S. Oae, Synthesis, 1977, 404.
34. A. Nayak, B. Nanda, N. B. Das and R. P. Sharma, J. Chem. Res. (S), 1994, 100.
35. (a) E. De Guchteneere, D. Fattori and P. Vogel, Tetrahedron, 1992, 48, 10 603; (b) F. Emery and P. Vogel, J. Org. Chem., 1995, 60, 5843; (c) V. Moritz and P. Vogel, Tetrahedron Lett., 1992, 33, 5243; (d) P. Renaud and J. P. Vionnet, J. Org. Chem., 1993, 58, 5895; (e) P. Vogel and J. L. Reymond, J. Chem. Soc., Chem. Commun., 1990, 1070; (f) Y. Chen and P. Vogel, Tetrahedron Lett., 1992, 33, 4917.
36. G. M. Sheldrick, University of Gottingen, Germany, 1993. SHELXL93, an integrated system for solving and refining crystal structures from diffraction data.
37. E. J. Corey and T.-P. Loh, J. Am. Chem. Soc., 1991, 113, 8966 see also: C. Le Drian and A. E. Greene, J. Am. Chem. Soc., 1982, 104, 5473.
38. E. Vicira and P. Vogel, Helv. Chim. Acta, 1982, 65, 1701.