NaOH-Catalyzed Thiolysis of α,β-Epoxyketones in Water. A Key Step in the Synthesis of Target Molecules Starting from α,β -Unsaturated Ketones

Journal of Organic Chemistry

Volumn 69, Issue 7, 2004, Pages 2315-2321

  Fringuelli, Francesco ^a   Pizzo, Ferdinando ^a   Vaccaro, Luigi ^a  

^a UNIVERSITY OF PERUGIA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CONDENSATION; DEHYDRATION; KETONES; PH EFFECTS; STEREOCHEMISTRY;

EPIMERIZATION; THIOLYSIS;

SODIUM COMPOUNDS;

1,5,6,7 TETRAHYDRO 4H 1,2,3 BENZOTRIAZOL 4 ONE; 2 CYCLOHEXENONE; 3,4 EPOXYHEPTAN 2 ONE; ALPHA,BETA EPOXYKETONE; BETA CARBONYL BETA HYDROXYSULFIDE; BETA CARBONYLSULFIDE; CALCHONE OXIDE; ENONE; KETONE; OXIDE; SODIUM HYDROXIDE; SULFIDE; SULFOXIDE; THIOL DERIVATIVE; THIOL GROUP; UNCLASSIFIED DRUG; VINYL DERIVATIVE; VINYL SULFIDE; VINYL SULFOXIDE; WATER;

ALDOL REACTION; ARTICLE; CATALYSIS; CATALYST; DEHYDRATION; EPIMERIZATION; LYSIS; PH; REACTION ANALYSIS; RETROALDOL REACTION; STEREOCHEMISTRY; SYNTHESIS; TEMPERATURE; THIOLYSIS;

EID: 1842609514     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo035804m     Document Type: Article

References (54)

1. (a) Li C. J.; Chang T. H. In Organic Reactions in Aqueous Media; Wiley: New York, 1997.
2. (b) Fringuelli, F.; Piermatti, O.; Pizzo, F. In Organic Synthesis in Water; Grieco P. A., Ed.; Blackie Academic and Professional: London, 1998; pp 223-261.
3. (c) Fringuelli F.; Matteucci M.; Piermatti O.; Pizzo F.; Burla M. C. J. Org. Chem. 2001, 66, 4461-4466.
4. (d) Amantini D.; Fringuelli F.; Pizzo F.; Vaccaro L. J. Org. Chem. 2001, 66, 4463-4467.
5. (e) Amantini D.; Fringuelli F.; Piermatti, O.; Pizzo F.; Vaccaro L. Green Chem. 2001, 3, 229-332.
6. (f) Amantini D.; Fringuelli F.; Pizzo F. J. Org. Chem. 2002, 67, 7238-7243.
7. (g) Fringuelli F.; Pizzo F.; Rucci, M.; Vaccaro L. J. Org. Chem. 2003, 68, 7041-7045.
8. (h) Fringuelli, F.; Pizzo, F.; Tortoioli, S.; Vaccaro, L. Green Chem. 2003, 5, 436-440.
9. (i) Amantini, D.; Fringuelli, F.; Pizzo, F.; Tortoioli, S.; Vaccaro, L. Synlett 2003, 2292-2296.
10. (j) Amantini, D.; Fringuelli, F.; Piermatti, O.; Pizzo, F.; Vaccaro, L. J. Org. Chem. 2003, 68, 9263-9268.
11. For recent papers, see: (a) Fringuelli F.; Pizzo F.; Vaccaro L. Synthesis 2000, 646-650.
12. (b) Fringuelli F.; Pizzo F.; Vaccaro L. J. Org. Chem. 2001, 66, 3544-3548.
13. (c) Fringuelli F.; Pizzo; Vaccaro L. Tetrahedron Lett. 2001, 42, 1131-1134.
14. (d) Fringuelli F.; Pizzo F.; Vaccaro L. J. Org. Chem. 2001, 66, 4719-4722.
15. (e) Fringuelli F.; Pizzo F.; Tortoioli, S.; Vaccaro L. Adv. Synth. Catal. 2002, 344, 379-384.
16. (f) Fioroni, G.; Fringuelli, F.; Pizzo, F.; Vaccaro, L. Green Chem. 2003, 5, 425-428
17. (h) Fringuelli F.; Pizzo F.; Tortoioli, S.; Vaccaro L. J. Org. Chem. 2003, 68, 8248-8251.
18. Watanabe, S.; Mori, E.; Nagai, H.; Iwamura, T.; Iwama, T.; Kataoka, T. J. Org. Chem. 2000, 65, 8893-8898.
19. Sasmal, P. K.; Maier, M. E. J. Org. Chem. 2003, 68, 824-831.
20. Pearson, W. H.; Hines, J. V. J Org. Chem. 2000, 65, 5785-5793.
21. (a) Arimori, S.; Kouno, R.; Okauchi, T.; Minami, T.J. Org. Chem. 2002, 67, 7303-7308.
22. (b) Pearson, W. H.; Mi, Y.; Young Lee, I.; Stoy, P. J. Am. Chem. Soc. 2001, 123, 6724-6725.
23. (c) Hayes, P.; Maignan, C. Tetrahedron: Asymmetry 1999, 10, 1041-1050.
24. Yoshida, T.; Ito, A.; Murase, M.; Totani, E. Chem. Pharm. Bull. 2001, 49, 1198-1202.
25. Tietze, L. F.; Hartfiel, U.; Hübsch, T.; Voss, E.; Bogdanowicz-Szwed, K.; Wichmann, J. Liebigs Ann. Chem. 1991, 275-281.
26. (a) Arroyo, Y.; de Paz, M.; Rodriguez, J. F.; Sanz-Tejedor, M. A.; García Ruano, J. L. J. Org. Chem. 2002, 67, 5638-5643.
27. (b) García Ruano, J. L.; Tito, A.; Peromingo, M. T. J. Org. Chem. 2002, 67, 981-987.
28. (c) Marino, J. P.; Rubio, M. B.; Cao, G.; de Dios, A. J. Am. Chem. Soc. 2002, 124, 13398-13399.
29. (d) Kita, Y.; Higuchi, K.; Yoshida, Y.; Iio, K.; Kitagaki, S.; Ueda, K.; Akai, S.; Fujioka, H. J. Am. Chem. Soc. 2001, 123, 3214-3222.
30. (e) Carreño, M. C.; Hernández-Sánchez, R.; Mahugo, J.; Urbano, A. J. Org. Chem. 1999, 64, 1387-1390.
31. (f) Carreytero, J. C.; García Ruano, J. L.; Martín Cabrejas, L. M. J. Org. Chem. 1997, 8, 22215-2225.
32. (g) Carreño, M. C. Chem. Rev. 1995, 95, 1717-1760.
33. (h) Posner, G. H. Acc. Chem. Res. 1987, 20, 72-78.
34. (a) Yechezkel, T.; Ghera, E.; Ostercamp, D.; Hassner, A. J. Org. Chem. 1995, 60, 5135-5142.
35. (b) Durman, J.; Grayson, J. I.; Hunt, P. G.; Warren, S. J. Chem. Soc., Perkin Trans. 1 1986, 1939-1945 and reference cited herein.
36. (c) Abul-Hajj, Y. J. J. Med. Chem. 1986, 29, 582-584.
37. (d) McKervey, M. A.; Ratananukul, P. Tetrahedron Lett. 1983, 24, 117-120.
38. (e) Monteiro, H. J.; Gemal, A. L. Synthesis 1975, 437-438 and reference cited therein.
39. (f) Mukaiama, T.; Adachi, T.; Kumamoto, T. Bull. Chem. Soc. Jpn. 1971, 44, 3155-3158.
40. (g) Tobias, M. A.; Strong, J. G.; Napier, R. PJ. Org. Chem. 1970, 35, 1709-1711.
41. (h) Wilgus, H. S., III; Frauenglass, E.; Chiesa, P. P.; Nawn, G. H.; Evans, F. J.; Gates, J. W., Jr. Can. J. Chem. 1966, 44, 603-609.
42. (a) Lauret, C. Tetrahedron: Asymmetry 2001, 12, Report No. 52, 2359-2383.
43. (b) McElroy, A. B.; Warren, S. Tetrahedron Lett. 1985, 26, 5709-5712.
44. Bernasconi, C. F.; Ketner, R. J.; Brown, S. D.; Chen, X.; Rappoport. Z. J. Org. Chem. 1999, 64, 8829-8839.
45. (b) Yabroff, D. L. Ind. Eng. Chem. 1940, 32, 257-262.
46. Bordwell, F. G.; Hughes, D. L. J. Org. Chem. 1982, 47, 3224-3232.
47. DeCollo, T. V.; Lees, W. J. J. Org. Chem. 2001, 66, 4244-4249.
48. a value is expected to be higher. (1S)-Camphorthiol is completely soluble in water at pH ≥ 13 in 0.5 M concentration.
49. We have also considered the possibility of a Brønsted acid catalysis and we have performed the thiolsysis of 1 with 2a and 2b at pH 2.0. After 24 h at 30 °C 2a gave complete conversion to anti-3a, while after 72 h 2b gave 90% conversion to anti-3b. This result can be justified on the basis of the higher nucleophilicity of alkylthiol with respect to aryl ones.
50. β-Hydroxy-α-thiophenyl cyclohexanones derivatives, upon treatment with strong bases (ethylthiolate or methoxide ions or lithium diisopropylamide) in organic solvents, give exclusive retroaldol condensation. It is also reported that C-α epimerization under strong base conditions (ethylthiolate or methoxide ions) occurs via retroaldol condensation: (a) Caine, D.; Crews, E.; Salvino, J. M. Tetrahedron Lett. 1983, 24, 2083-2086.
51. (b) Silvermann, R. B. J. Am. Chem. Soc. 1981, 103, 3, 5939-5941.
52. 4 gave lower yields due to some carbonization, while p-TsOH gave excellent results in conditions apparently milder than those utilizing HCl but with a very long reaction time. In this work, we have preferred the aqueous HCl procedure that allowed the one-pot protocol to be realized, and the use of p-TsOH is indeed viable.
53. Fox, D. J.; House, D.; Warren S. Angew. Chem., Int. Ed. 2002, 41 2462-2482.
54. At 30 °C after 1 h a 3:1 mixture of hydroxy sulfide and vinyl sulfide was isolated. After heating to reflux for an additional 1 h, only vinyl sulfide product was obtained.