Room temperature acylketene formation 1,3-dioxin-4-ones via silver(I) activation of phenylthioacetoacetate in the presence of ketones

Journal of Organic Chemistry

Volumn 75, Issue 17, 2010, Pages 6054-6056

  May, Aaron E ^a   Hoye, Thomas R ^a  

^a University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MECHANISTIC STUDIES; ROOM TEMPERATURE;

SILVER; SILVER COMPOUNDS;

KETONES;

1,3 DIOXANE DERIVATIVE; KETENE DERIVATIVE; KETONE DERIVATIVE; SILVER;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; ROOM TEMPERATURE;

DIOXINS; KETONES; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; SILVER; STEREOISOMERISM; SULFHYDRYL COMPOUNDS; TEMPERATURE;

EID: 77956152360     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo101372v     Document Type: Article

References (20)

1. For a review on application of acylketene intermediates to natural product synthesis, see: Reber, K. P.; Tilley, S. D.; Sorensen, E. J. Chem. Soc. Rev. 2009, 38, 3022-3034
2. Chiang, Y.; Guo, H. X.; Kresge, A. J.; Tee, O. S. J. Am. Chem. Soc. 1996, 118, 3386-3391
3. Wentrup, C.; Heilmayer, W.; Kollenz, G. Synthesis 1994, 1219-1248
4. Hyatt, J. A.; Feldman, P. L.; Clemens, R. J. J. Org. Chem. 1984, 49, 5105-5108
5. Horner, L.; Spietschka, E. Chem. Ber. 1952, 85, 225-229
6. Freiermuth, B.; Wentrup, C. J. Org. Chem. 1991, 56, 2286-2289
7. Koltsova, S. V.; Feshin, V. P. Russ. J. Org. Chem. 2001, 37, 1616-1620
8. Bell, K.; Sadasivam, D. V.; Gudipati, I. R.; Ji, H.; Birney, D. Tetrahedron Lett. 2009, 50, 1295-1297
9. Park, P. U.; Broka, C. A.; Johnson, B. F.; Kishi, Y. J. Am. Chem. Soc. 1987, 109, 6205-6207
10. Booth, P. M.; Fox, C. M.; Ley, S. V. J. Chem. Soc., Perkin Trans. 1 1987, 121-129
11. Hoye, T. R.; Danielson, M. E.; May, A. E.; Zhao, H. Angew. Chem., Int. Ed. 2008, 47, 9743-9746
12. For comparisons of mercury, silver, and copper salts for the activation of thioesters, see: Masamune, S.; Hayase, Y.; Schilling, W.; Chan, W.; Bates, G. S. J. Am. Chem. Soc. 1977, 99, 6756-6758
13. For the synthesis of 12 (by refluxing 2,2,6-trimethyl-4 H -1,3-dioxin-4-one with thiophenol) see: Clemens, R. J.; Hyatt, J. A. J. Org. Chem. 1985, 50, 2431-2435
14. Douglas, K. T.; Yaggi, N. F. J. Chem. Soc., Chem. Commun. 1980, 15, 728-730
15. Douglas, K. T.; Alborz, M.; Rullo, G. R.; Yaggi, N. F. J. Chem. Soc., Chem. Commun. 1982, 245-246
16. Competitive trapping of acetylketene with a 20-fold excess of cyclohexanone vs pentanol leads to a ∼300:1 ratio of alcohol trapping over ketone trapping. See: Birney, D. M.; Xu, X. L.; Ham, S.; Huang, X. M. J. Org. Chem. 1997, 62, 7114-7120
17. 3 in these reactions, it is noteworthy that use of silver phosphate or silver triflate was also found to effect this transformation.
18. tBu), which lock the species into the less reactive s-trans conformation (Leung-Toung, R.; Wentrup, C. J. Org. Chem. 1992, 57, 4850 - 4858), and (ii) acetylketene dimerizes and oligomerizes upon being warmed from -77 K by itself and reacts with alcohol traps between -90 and -50 °C. (6)
19. 3 was observed instead.
20. 1H NMR spectroscopy) amounts of the acetylketene homodimer, dehydroacetic acid (3-acetyl-2-hydroxy-6-methyl-4 H -pyran-4-one), along with other byproducts.