2-Halogeno-1,3-dithiane 1,3-dioxide: a diastereoselective carbonyl anion equivalent in reactions with aldehydes

Abstract

The metal anions of 2-halogeno-1,3-dithiane trans-1,3-dioxide react diastereoselectively with aldehydes. The scope and limitations of this reaction have been studied through variations in the metal counter-ion, halogen, aldehyde and reaction temperature, with a view to achieving umpolung asymmetric Darzens type reactions. Chlorohydrins were obtained with high diastereoselectivity by reaction of the lithium anion of 2-chloro-1,3-dithiane dioxide 4 with aromatic aldehydes under equilibrating conditions. Aliphatic aldehydes gave poor selectivities. Attempted stereospecific conversion of the chlorohydrins into epoxides resulted only in reversion to 4 and aldehyde. Use of sodium or potassium bases gave lower yields of chlorohydrins; epoxides were not isolated. It was possible to obtain aromatic bromohydrins with high selectivity using the magnesium anion of 2-bromo-1,3-dithiane 1,3-dioxide 5 as the nucleophile, but once again ring closure to form epoxides failed to compete with the facile retro-aldol process. Use of sodium bases with 5 resulted in capricious reactions from which a single isomer of epoxide could be isolated. There is evidence of decomposition of the target epoxides under the reaction conditions to α-substituted carbonyl compounds and 1,2-dithiolane 1-oxide.

References

1. M. Braun, Angew. Chem., Int. Ed. Engl., 1987, 26, 24.
2. C. H. Heathcock, in, Asymmetric Synthesis, ed. J. D. Morrison, Academic Press, New York, 1984, vol. 3, part B, p. 111.
3. C. H. Heathcock, in, Comp. Org. Synth., ed. C. H. Heathcock, Pergamon Press, Oxford, 1991, vol. II, ch. 1.6.
4. D. A. Evans, J. V. Nelson and T. R. Taber, Top. Stereochem., 1982, 13, 1.
5. S. Masamune, W. Choy, J. S. Petersen and L. R. Sita, Angew. Chem., Int. Ed. Engl., 1985, 24, 1.
6. Y.-C. Wang, A.-W. Hung, C.-S. Chang and T.-H. Yan, J. Org. Chem., 1996, 61, 2038.
7. V. K. Aggarwal, R. Franklin, J. Maddock, G. R. Evans, A. Thomas, M. F. Mahon, K. C. Molloy and M. J. Rice, J. Org. Chem., 1995, 60, 2174.
8. V. K. Aggarwal, A. Thomas and R. J. Franklin, J. Chem. Soc., Chem. Commun., 1994, 1653.
9. K. Y. Ko, W. J. Frazee and E. L. Eliel, Tetrahedron, 1984, 40, 1333.
10. M. Braun and K. Opdenbusch, Angew. Chem., Int. Ed. Engl., 1993, 32, 578.
11. C. Andrebarres, Y. Langlois and M. Gomezpacios, Tetrahedron: Asymmetry, 1990, 1, 571.
12. C. Baldoli, P. Delbuttero, E. Licandro, S. Maiorana and A. Papagni, J. Chem. Soc., Chem. Commun., 1987, 762.
13. L. N. Pridgen, A. F. Abdelmagid, I. Lantos, S. Shilcrat and D. S. Eggleston, J. Org. Chem., 1993, 58, 5107.
14. T. Takahashi, M. Muraoka, M. Capo and K. Koga, Chem. Pharm. Bull., 1995, 43, 1821.
15. A. Abdelmagid, L. N. Pridgen, D. S. Eggleston and I. Lantos, J. Am. Chem. Soc., 1986, 108, 4595.
16. T. Satoh and K. Yamakawa, Synlett, 1992, 455.
17. J. I. Seeman, Chem. Rev., 1983, 83, 83.
18. K. Koh, R. N. Ben and T. Durst, Tetrahedron Lett., 1993, 34, 4473.
19. K. Koh and T. Durst, J. Org. Chem., 1994, 59, 4683.
20. V. K. Aggarwal, J. M. Worrall, H. Adams and R. Alexander, Tetrahedron Lett., 1994, 35, 6167.
21. 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.
22. T. Satoh, T. Oohara, Y. Ueda and K. Yamakawa, J. Org. Chem., 1989, 54, 3130.
23. J. Drabowicz, Synthesis, 1986, 831.
24. V. K. Aggarwal, J. M. Worrall, H. Adams and R. Alexander, J. Chem. Soc., Perkin Trans. 1, following paper.
25. Atomic coordinates, bond lengths and angles, and thermal parameters for compounds 4, 5, 7a and 9a have been deposited with the Cambridge Crystallographic Data Centre. Requests for this material should be accompanied by a full bibliographic reference together with the reference number CCDC 207/58. Further details of the scheme are given in Instructions for Authors ( 1997), J. Chem. Soc., Perkin Trans. 1, 1997, Issue 1.
26. E. L. Eliel, E. M. Olefirowicz, M. T. Alvarez, D. J. Hodgson and D. K. Towle, Heterocycles, 1989, 28, 937.
27. V. K. Aggarwal, I. W. Davies, R. J. Franklin, J. Maddock, M. F. Mahon and K. C. Molloy, J. Chem. Soc., Perkin Trans. 1, 1991, 662.
28. J. T. Doi, R. M. Kessler, D. L. Deleeuw, M. M. Olmstead and W. K. Musker, J. Org. Chem., 1983, 48, 3707.
29. W. Adam and L. Hadjiarapoglou, Tetrahedron Lett., 1992, 33, 469.
30. D. H. R. Barton, D. P. Manly and D. A. Widdowson, J. Chem. Soc., Perkin Trans. 1, 1975, 1568.
31. T. Kumamoto and T. Mukaiyama, Bull. Chem. Soc. Jpn., 1968, 41, 2111.
32. F. A. Davis, L. A. Jenkins and R. L. Billmers, J. Org. Chem., 1986, 51, 1033.
33. H. A. Finkelstein, Chem. Ber., 1910, 43, 1528.
34. J. Hayami, T. Koyanagi and A. Kaji, Bull. Chem. Soc. Jpn., 1979, 52, 1441.
35. J. Bartroli, E. Turmo, J. Belloc and J. Forn, J. Org. Chem., 1995, 60, 3000.
36. H. O. House, D. S. Crumrine, A. Y. Teranishi and H. D. Olmstead, J. Am. Chem. Soc., 1973, 95, 3310.
37. C. Mioskowski and G. Solladie, Tetrahedron, 1980, 36, 227 Solladie found it necessary to use a large excess (17 equiv.) of Bu^tMgBr as base to stabilise the addition products of α-sulfinyl esters with aldehydes.
38. G. M. Sheldrick, University of Gottingen, Germany 1993. SHELXL93, an integrated system for solving and refining crystal structures from diffraction data.
39. R. S. Glass, A. Petsom, G. S. Wilson, R. Martinez and E. Juraristi, J. Org. Chem., 1986, 51, 4337.
40. H. J. Cristau, B. Chabaud, R. Labaudiniere and H. Christol, Synth. Commun., 1981, 11, 423.