Simple and efficient preparation of reagents for thiopyran introduction: Methyl tetrahydro-4-oxo-2H-thiopyran-3-carboxylate, tetrahydro-4H-thiopyran-4- one, and 3,6-dihydro-4-trimethylsilyloxy-2H-thiopyran

Synthesis

Volumn , Issue 10, 2007, Pages 1584-1586

  Ward, Dale E ^a   Rasheed, M Abdul ^a   Gillis, H Martin ^a   Beye, Garrison E ^a   Jheengut, Vishal ^a   Achonduh, George T ^a  

^a UNIVERSITY OF SASKATCHEWAN   (Canada)

Author keywords

4 thianone; Dieckmann cyclization; Heterocyclic ketone; Tetrahydro 4H thiopyran 4 one; Thiopyran synthesis

Indexed keywords

DECARBOXYLATION; DIECKMANN CYCLIZATION; HETEROCYCLIC KETONES; THIOPYRAN SYNTHESIS;

CARBOXYLATION; CYCLIZATION; KETONES; SYNTHESIS (CHEMICAL);

ETHERS;

3,6 DIHYDRO 4 TRIMETHYLSILYLOXY 2H THIOPYRAN; CHLOROFORM; DIMETHYL 3,3' THIOBISPROPANOATE; METHYL TETRAHYDRO 4 OXO 2H THIOPYRAN 3 CARBOXYLATE; PROPANE; REAGENT; SILANE DERIVATIVE; SULFURIC ACID; TETRAHYDRO 4H THIOPYRAN 4 ONE; THIOPYRAN DERIVATIVE; TRIMETHYLCHOLORSILANE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; DECARBOXYLATION; DIECKMANN REACTION; SYNTHESIS;

EID: 34249782829     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-965954     Document Type: Article

References (48)

1. (a) Press, J. B.; Russell, R. K.; Christiaens, L. E. E. In Comprehensive Heterocyclic Chemistry II, Vol. 2; Bird, C. W., Ed.; Elsevier: Oxford, 1997.
2. (b) Ingall, A. H. In Comprehensive Heterocyclic Chemistry II, Vol. 5; McKillop, A., Ed.; Pergamon: Oxford, 1997.
3. (c) Vedejs, E.; Krafft, G. A. Tetrahedron 1982, 38, 2857.
4. For an overview and list of references, see: (a) Samuel, R.; Nair, S. K.; Asokan, C. V. Synlett 2000, 1804.
5. (b) Ward, D. E.; Gai, Y.; Lai, Y. Synlett 1996, 261.
6. Review: Vartanyan, R. S. Arm. Khim. Zh. 1985, 38, 166.
7. Aldrich Chemical Co., 2005-2006: Cdn $174/5 g of 3. Using the procedure described herein, we estimate the cost of materials (solvents, reagents and other materials) for the preparation of 3 to be ca. $1/g (50 g scale).
8. (a) Ward, D. E.; Guo, C.; Sasmal, P. K.; Man, C. C.; Sales, M. Org. Lett. 2000, 2, 1325.
9. (b) Ward, D. E.; Sales, M.; Man, C. C.; Shen, J.; Sasmal, P. K.; Guo, C. J. Org. Chem. 2002, 67, 1618.
10. (c) Ward, D. E.; Jheengut, V.; Akinnusi, O. T. Org. Lett. 2005, 7, 1181.
11. (d) Ward, D. E.; Gillis, H. M.; Akinnusi, O. T.; Rasheed, M. A.; Saravanan, K.; Sasmal, P. K. Org. Lett. 2006, 8, 2631.
12. From N-methyl-4-piperidone: (a) Johnson, P. Y.; Berchtold, G. A. J. Org. Chem. 1970, 35, 584.
13. (b) Unkovskii, B. V.; Psal'ti, F. I. Khim. Geterotsikl. Soedin., Sb. 1970, 2, 174;
14. Chem. Abstr. 1972, 77, 114188.
15. (c) Garst, M. E.; McBride, B. J.; Johnson, A. T. J. Org. Chem. 1983, 48, 8.
16. From 1,5-dibromo-3-pentanone: (d) Sviridov, S. V.; Vasilevskii, D. A.; Kulinkovich, O. G. Zh. Org. Khim. 1991, 27, 1431.
17. (a) Bennett, G. M.; Scorah, L. V. D. J. Chem. Soc. 1927, 194.
18. (b) Fehnel, E. A.; Carmack, M. J. Am. Chem. Soc. 1948, 70, 1813.
19. (a) Naylor, R. F. J. Chem. Soc. 1949, 2749.
20. (b) Onesta, R.; Castelfranchi, G. Gazz. Chim. Ital. 1959, 89, 1127.
21. (c) Casy, G.; Sutherland, A. G.; Taylor, R. J. K.; Urben, P. G. Synthesis 1989, 767.
22. (d) Rule, N. G.; Detty, M. R.; Kaeding, J. E.; Sinicropi, J. A. J. Org. Chem. 1995, 60, 1665.
23. (e) Matsuyama, H.; Miyazawa, Y.; Takei, Y.; Kobayashi, M. J. Org. Chem. 1987, 52, 1703.
24. (f) Chowdhury, A. Z. M. S.; Khandker, M. M. R.; Bhuiyan, M. M. H.; Hossain, M. K. Pak. J. Sci. Ind. Res. 2001, 44, 63.
25. (a) Barkenbus, C.; Midkiff, V. C.; Newman, R. M. J. Org. Chem. 1951, 16, 232.
26. (b) Traverso, G. Chem. Ber. 1958, 91, 1224.
27. (c) Parham, W. E.; Christensen, L.; Groen, S. H.; Dodson, R. M. J. Org. Chem. 1964, 29, 2211.
28. (d) Harada, K.; Suginose, R.; Kashiwagi, K. Japanese Patent 99198350, 1999; Chem. Abstr. 2001, 134: 131428.
29. 2S: Gershbein, L. L.; Hurd, C. D. J. Am. Chem. Soc. 1947, 69, 241.
30. (b) See also ref. 8e.
31. (a) Kashiwagi, T.; Murakami, M.; Isaka, I.; Ozasa, T. Japanese Patent 74 108119, 1974; Chem. Abstr. 1976, 85: 78006.
32. (b) Duus, F. Tetrahedron 1981, 37, 2633.
33. (c) Liu, H. J.; Ngooi, T. K. Can. J. Chem. 1982, 60, 437.
34. (d) Dowd, P.; Choi, S. C. Tetrahedron 1991, 47, 4847.
35. (e) Tamai, S.; Ushirogochi, H.; Sano, S.; Nagao, Y. Chem. Lett. 1995, 295.
36. (f) Ghosh, A. K.; Liu, W. J. Org. Chem. 1995, 60, 6198.
37. (g) Conroy, J. L.; Sanders, T. C.; Seto, C. T. J. Am. Chem. Soc. 1997, 119, 4285.
38. (h) Li, C.-J.; Chen, D.-L. Synlett 1999, 735.
39. A reaction using 1.1 equiv of NaOMe did not go to completion within 5 h (ca. 90% conversion).
40. (a) Aoki, S.; Fujimura, T.; Nakamura, E. J. Am. Chem. Soc. 1992, 114, 2985.
41. (b) Evans, P. A.; Modi, D. P. J. Org. Chem. 1995, 60, 6662.
42. (c) Biondi, S.; Piga, E.; Rossi, T.; Vigelli, G. Bioorg. Med. Chem. Lett. 1997, 7, 2061.
43. (d) Karisalmi, K.; Rissanen, K.; Koskinen, A. M. P. Org. Biomol. Chem. 2003, 1, 3193.
44. (e) Karisalmi, K.; Koskinen, A. M. P.; Nissinen, M.; Rissanen, K. Tetrahedron 2003, 59, 1421.
45. House, H. O.; Czuba, L. J.; Gall, M.; Olmstead, H. D. J. Org. Chem. 1969, 34, 2324.
46. Na metal was cut into pieces weighing ca. 50-100 mg (3-5 mm per side). The rate of Na consumption depends on the size of pieces; with larger pieces, more time is required to reach 90% conversion.
47. A few specks of Na metal may remain at this point.
48. 13C NMR and confirmed by spiking with authentic samples.