Stereoselective nucleophilic epoxidation of vinyl sulfoxides: A novel route to enantiopure sulfinyl oxiranes

Journal of Organic Chemistry

Volumn 61, Issue 11, 1996, Pages 3586-3587

  Fernández De La Pradilla, Roberto ^a   Castro, Sonia ^a   Manzano, Pilar ^a   Priego, Julián ^a   Viso, Alma ^b  

^a INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

^b UNIVERSIDAD COMPLUTENSE DE MADRID   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0038121258     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9603845     Document Type: Article

References (23)

1. Taken in part from the M.S. Theses of S.C., P.M., and J.P., Instituto de Química Orgánica, CSIC.
2. (a) For a review, see: Satoh, T.; Yamakawa, K. Synlett 1992, 455-468.
3. (b) Satoh, T.; Oohara, T.; Ueda, Y.; Yamakawa, K. J. Org. Chem. 1989, 54, 3130-3136.
4. (c) For an isolated example of an alternative method, see: Tsuehihashi, G.; Mitamura, S.; Ogura, K. Tetrahedron Lett. 1974, 455-458.
5. Briggs, A. D.; Jackson, R. F. W.; Clegg, W.; Elsegood, M. R. J.; Kelly, J.; Brown, P. A. Tetrahedron Lett. 1994, 35, 6945-6948.
6. For leading references on related nucleophilic epoxidations, see: (a) Jackson, R. F. W.; Standen, S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (b) Linderman, R. J.; Claasen, R. J., II; Viviani, F. Tetrahedron Lett. 1995, 36, 6611-6614. (c) Ambroise, L.; Jackson, R. F. W. Tetrahedron Lett. 1996, 37, 2311-2314.
7. For leading references on related nucleophilic epoxidations, see: (a) Jackson, R. F. W.; Standen, S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (b) Linderman, R. J.; Claasen, R. J., II; Viviani, F. Tetrahedron Lett. 1995, 36, 6611-6614. (c) Ambroise, L.; Jackson, R. F. W. Tetrahedron Lett. 1996, 37, 2311-2314.
8. For leading references on related nucleophilic epoxidations, see: (a) Jackson, R. F. W.; Standen, S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (b) Linderman, R. J.; Claasen, R. J., II; Viviani, F. Tetrahedron Lett. 1995, 36, 6611-6614. (c) Ambroise, L.; Jackson, R. F. W. Tetrahedron Lett. 1996, 37, 2311-2314.
9. See: Paley, R. S.; Weers, H. L.; Fernández de la Pradilla, R.; Castro, S. Tetrahedron Lett. 1995, 36, 3605-3608 and references cited therein.
10. Simple vinyl sulfoxides display a relatively low reactivity with nucleophiles. See, for instance: The Chemistry of Sulphones and Sulphoxides; Patai, S., Rappoport, Z., Stirling, C. J. H., Eds.; John Wiley & Sons: New York, 1988.
11. Substrates 2-5 were prepared in one step from commercially available reagents by the method of Craig. See: Craig, D.; Daniels, K.; McKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Alternatively, 3 could be prepared with high selectivity in two steps according to: Kosugi, H.; Kitaoka, M.; Tagami, K.; Takahashi, A.; Uda, H. J. Org. Chem. 1987, 52, 1078-1082. For the preparation of 1 see: Marino, J. P.; Viso, A.; Fernández de la Pradilla, R.; Fernández, P. J. Org. Chem. 1991, 56, 1349-1351. Racemic 6, available in our laboratories from a previous project, was prepared from 1-hexyne by free radical addition of 2-methyl-2-propanethiol and oxidation. All new products reported here have been fully characterized by spectroscopic techniques.
12. Substrates 2-5 were prepared in one step from commercially available reagents by the method of Craig. See: Craig, D.; Daniels, K.; McKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Alternatively, 3 could be prepared with high selectivity in two steps according to: Kosugi, H.; Kitaoka, M.; Tagami, K.; Takahashi, A.; Uda, H. J. Org. Chem. 1987, 52, 1078-1082. For the preparation of 1 see: Marino, J. P.; Viso, A.; Fernández de la Pradilla, R.; Fernández, P. J. Org. Chem. 1991, 56, 1349-1351. Racemic 6, available in our laboratories from a previous project, was prepared from 1-hexyne by free radical addition of 2-methyl-2-propanethiol and oxidation. All new products reported here have been fully characterized by spectroscopic techniques.
13. Substrates 2-5 were prepared in one step from commercially available reagents by the method of Craig. See: Craig, D.; Daniels, K.; McKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Alternatively, 3 could be prepared with high selectivity in two steps according to: Kosugi, H.; Kitaoka, M.; Tagami, K.; Takahashi, A.; Uda, H. J. Org. Chem. 1987, 52, 1078-1082. For the preparation of 1 see: Marino, J. P.; Viso, A.; Fernández de la Pradilla, R.; Fernández, P. J. Org. Chem. 1991, 56, 1349-1351. Racemic 6, available in our laboratories from a previous project, was prepared from 1-hexyne by free radical addition of 2-methyl-2-propanethiol and oxidation. All new products reported here have been fully characterized by spectroscopic techniques.
14. Forcing reaction conditions (long reaction times, higher temperatures) led to oxidation to the vinyl sulfone and, in some cases, subsequent epoxidation. For the oxidation of sulfoxides with t-BuOOH, see: Breton, G. W.; Fields, J. D.; Kropp, P. J. Tetrahedron Lett. 1995, 36, 3825-3828.
15. Pyne, S. G.; Bloem, P.; Chapman, S. L.; Dixon, C. E.; Griffith, R. J. Org. Chem. 1990, 55, 1086-1093.
16. The qualitative influence of stoichiometry, temperature, concentration, and reaction time on this process was screened. In many cases, very careful monitoring of the reaction by TLC was crucial since vinyl and epoxy sulfoxides present very similar chromatographic mobilities.
17. An authentic sample of enantiomerically pure sulfone 15 was prepared by oxidation (MMPP, MeOH, rt) of epoxy sulfoxide 16.
18. The use of tert-butyl sulfoxides allows for improved stereocontrol us their p-tolyl analogues in some cases. For the preparation of optically pure tert-butyl sulfoxides, see: Khiar, N.; Fernández, I.; Alcudia, F. Tetrahedron Lett. 1994, 35, 5719-5722 and references cited therein.
19. To the best of our knowledge, NaOO-t-Bu has not been used previously for related processes.
20. 2O are underway.
21. s)-1-chloro-n-propyl p-tolyl sulfoxide and n-pentanal by the method of Yamakawa (ref 2) of known stereochemical course. These experiments will be described in detail in a full account of this research.
22. (a) For the α-lithiation of sulfonyl oxiranes, see: Ashwell, M.; Clegg, W.; Jackson, R. F. W. J. Chem. Soc., Perkin Trans. 1 1991, 897-908.
23. (b) For the generation of oxiranyllithium reagents from sulfinyl oxiranes by ligand exchange, see: Satoh, T.; Horiguchi, K. Tetrahedron Lett. 1995, 36, 8235-8238.