The Meyer-Schuster rearrangement of ethoxyalkynyl carbinols

Synlett

Volumn , Issue 6, 2007, Pages 949-953

  Lopez, Susana S ^a   Engel, Douglas A ^a   Dudley, Gregory B ^a  

^a FLORIDA STATE UNIVERSITY   (United States)

Author keywords

Alkoxyacetylene; Gold; Meyer schuster; Propargyl alcohol; Rearrangement

Indexed keywords

ALKYNYL GROUP; ETHOXYALKYNYL; METHANOL DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; MEYER SCHUSTER REARRANGEMENT; STEREOCHEMISTRY;

EID: 34247173920     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-973885     Document Type: Article

References (45)

1. (a) Brandsma, L. Acetylenes, Allenes and Cumulenes; Elsevier: Amsterdam, 2003.
2. (b) Modern Acetylene Chemistry; Stang, P. J.; Diederich, F., Eds.; VCH: Weinheim, 1995.
3. Preliminary communication: Engel, D. A.; Dudley, G. B. Org. Lett. 2006, 8, 4027.
4. (a) Kürti, L.; Czakó, B. Strategic Applications of Named Reactions in Organic Synthesis; Elsevier: New York, 2003, 284-285.
5. (b) Swaminathan, S.; Narayanan, K. V. Chem. Rev. 1971, 71, 429.
6. Lewis Acids in Organic Synthesis; Yamamoto, H., Ed.; Wiley-VCH: New York, 2000.
7. Recent reviews with leading references: (a) Dyker, G. Angew. Chem. Int. Ed. 2000, 39, 4237.
8. (b) Hashmi, A. S. K. Gold Bull. 2003, 36, 3.
9. (c) Ma, S.; Yu, S.; Gu, Z. Angew. Chem. Int. Ed. 2006, 45, 200.
10. (d) Asao, N. Synlett 2006, 1645.
11. Selected recent examples: (a) Asao, N.; Sato, K. Org. Lett. 2006, 8, 5361.
12. (b) Staben, S. T.; Kennedy-Smith, J. J.; Huang, D.; Corkey, B. K.; LaLonde, R. L.; Toste, F. D. Angew. Chem. Int. Ed. 2006, 45, 5991.
13. (c) Belting, V.; Krause, N. Org. Lett. 2006, 8, 4489.
14. (d) Wang, S.; Zhang, L. Org. Lett. 2006, 8, 4585.
15. (e) Huang, B.; Yao, X.; Li, C.-J. Adv. Synth. Catal. 2006, 348, 1528.
16. (f) Seregin, I. V.; Gevorgyan, V. J. Am. Chem. Soc. 2006, 128, 12050.
17. (g) Carretin, S.; Blanco, M. C.; Corma, A.; Hashmi, A. S. K. Adv. Synth. Catal. 2006, 348, 1283.
18. (h) Park, S.; Lee, D. J. Am. Chem. Soc. 2006, 128, 10664.
19. (i) Nakamura, I.; Sato, T.; Yamamoto, Y. Angew. Chem. Int. Ed. 2006, 45, 4473.
20. (j) Kang, J.-E.; Kim, H.-B.; Lee, J.-W.; Shin, S. Org. Lett. 2006, 8, 3537.
21. (k) Sun, J.; Conley, M. P.; Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc. 2006, 128, 9705.
22. (l) Liu, Y.; Liu, M.; Guo, S.; Tu, H.; Zhou, Y.; Gao, H. Org. Lett. 2006, 8, 3445.
23. (m) Robles-Machin, R.; Adrio, J.; Carretero, J. C. J. Org. Chem. 2006, 71, 5023.
24. (n) Harrison, T. J.; Kozak, J. A.; Corbella-Pane, M.; Dake, G. R. J. Org. Chem. 2006, 71, 4525.
25. (o) Fürstner, A.; Hannen, P. Chem. Eur. J. 2006, 12, 3006 .
26. Relevant earlier examples: (p) Georgy, M.; Boucard, V.; Campagne, J.-M. J. Am. Chem. Soc. 2005, 127, 14180.
27. (q) Fukuda, Y.; Utimoto, K. Bull. Chem. Soc. Jpn. 1991, 64, 2013.
28. Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863.
29. Ethoxyacetylene was purchased from Sigma-Aldrich as a 40% solution in hexane and used as received.
30. For selected recent examples, see ref. 3a and: (a) Chabardes, P. Tetrahedron Lett. 1988, 29, 6253.
31. (b) Narasaka, K.; Kusama, H.; Hayashi, Y. Chem. Lett. 1991, 1413.
32. (c) Yoshimatsu, M.; Naito, M.; Kawahigashi, M.; Shimizu, H.; Kataoka, T. J. Org. Chem. 1995, 60, 4798.
33. (d) Lorber, C. Y.; Osborn, J. A. Tetrahedron Lett. 1996, 37, 853.
34. Kropp, P. J.; Breton, G. W.; Craig, S. L.; Crawford, S. D.; Durland, W. F. Jr.; Jones, J. E. III; Raleigh, J. S. J. Org. Chem. 1995, 60, 4146.
35. Protic acids in the absence of gold are significantly less effective (ref. 2). Examples of the protic-acid-catalyzed Meyer-Schuster rearrangement of ethoxyalkynyl carbinols: (a) Welch, S. C.; Hagan, C. P.; White, D. H.; Fleming, W. P.; Trotter, J. W. J. Am. Chem. Soc. 1977, 99, 549.
36. (b) Duraisamy, M.; Walborsky, H. M. J. Am. Chem. Soc. 1983, 105, 3252.
37. (c) Crich, D.; Natarajan, S.; Crich, J. Z. Tetrahedron 1997, 53, 7139.
38. 13C NMR, IR, HRMS) were obtained for all compounds. Yields refer to at least 50 mg of material isolated in >95% purity.
39. 2. Identical results were obtained when this catalyst solution was filtered, decanted, or used with the unknown residue in place.
40. 2-Butanone is the recommended solvent in a forthcoming study on the transpositional hydrolysis of propargylic acetates (Prof. Liming Zhang, University of Nevada, Reno, private communication; Yu, M.; Li, G.; Wang, S.; Zhang, L. Adv. Synth Catal. 2007, in press, DOI: 10.1002/adsc.200600579).
41. In fact, simultaneous addition of the solutions of the gold and silver salts to the reaction mixture provided the enoate products with slightly better selectivity, but we consider the sequential addition protocol to be more easily duplicated and thus preferable.
42. Isomerization of the Z-enoates to the E-enoates does not occur under the reaction conditions: extending the reaction time does not have a significant effect on the product ratio, and resubjecting the enoate mixtures to the rearrangement conditions does not change the ratio of stereoisomers. Therefore, we assume that the nonthermodynamic product distribution is purely the result of kinetic control.
43. To the extent that the additive is incorporated into the product, the Meyer-Schuster reaction is not a true 'rearrangement', although it is generally referred to as such in a formal sense for the sake of simplicity.
44. Control experiments confirmed that the rearrangement conditions do not promote transesterification between the ethyl and propyl esters, so the incorporation of the propanol additive is most likely occurring during the course of the rearrangement.
45. For a previous report on the combined use of oxygen-activated alkynes and cationic gold catalysts, see: Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc. 2004, 126, 11806.