Asymmetric synthesis of α-keto esters via Cu(II)-catalyzed aerobic deacylation of acetoacetate alkylation products: An unusually simple synthetic equivalent to the glyoxylate anion synthon

Organic Letters

Volumn 13, Issue 9, 2011, Pages 2426-2429

  Steward, Kimberly M ^a   Johnson, Jeffrey S ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETOACETIC ACID DERIVATIVE; ANION; COPPER; EPOXIDE; ESTER; GLYOXYLIC ACID DERIVATIVE; OXYGEN;

ACYLATION; ALKYLATION; ARTICLE; CATALYSIS; CHEMISTRY; STEREOISOMERISM; SYNTHESIS;

ACETOACETATES; ACYLATION; ALKYLATION; ANIONS; CATALYSIS; COPPER; EPOXY COMPOUNDS; ESTERS; GLYOXYLATES; OXYGEN; STEREOISOMERISM;

EID: 79955596607     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol200649u     Document Type: Article

References (35)

1. Kiefel, M. J.; von Itzstein, M. Chem. Rev. 2002, 102, 471
2. Cooper, A; Meister, G. A. Chem. Rev. 1983, 83, 321
3. Kovacs, L. Rec. Trav. Chim. Pays-Bas 1993, 112, 471
4. Yao, W.; Wang, J. Org. Lett. 2003, 5, 1527
5. Kang, Q.; Zhao, Z. A.; You, S. L. Adv. Synth. Catal. 2007, 349, 1657
6. Select examples of α-keto ester synthesis: Eliel, E.; Hartman, A. J. Org. Chem. 1972, 37, 505
7. Takahashi, T.; Okano, T.; Harada, T.; Imamura, K.; Yamada, H. Synlett 1994, 38, 121
8. Yao, W.; Wang, J. Org. Lett. 2003, 5, 1527
9. Enders, D.; Bonten, M. H.; Raabe, G. Synlett 2007, 51, 885
10. Enders, D; Bonten, M. H.; Raabe, G. Angew. Chem., Int. Ed. 2007, 46, 2314
11. Radosevich, A. T.; Chan, V. S.; Shih, H.-W.; Toste, F. D. Angew. Chem., Int. Ed. 2008, 47, 3755
12. Trost, B. M.; Malhotra, S.; Fried, B. A. J. Am. Chem. Soc. 2009, 131, 1674
13. Nakamura, A.; Lectard, S.; Hashizume, D.; Hamashima, Y.; Sodeoka, M. J. Am. Chem. Soc. 2010, 132, 4036
14. Steward, K. M.; Johnson, J. S. Org. Lett. 2010, 12, 2864 For catalytic, enantioselective synthesis of α-keto amides via umpolung catalysis with glyoxamides, see: Liu, Q.; Perreault, S.; Rovis, T. J. Am. Chem. Soc. 2008, 130, 14066
15. Liu, Q.; Rovis, T. Org. Lett. 2009, 11, 2856
16. Seebach, D. Angew. Chem., Int. Ed. 1979, 18, 239
17. Johnson, J. S. Curr. Opin. Drug Disc. Dev. 2007, 10, 691
18. 1 synthon).
19. Cossy, J.; Belotti, V.; Bellosta, V.; Brocca, D. Tetrahedron Lett. 1994, 35, 6089
20. Vallejos, J.-C.; Capelle, N.; Arzoumanian, H. U.S. Patent 6,057,474, 2000.
21. 2O) of ethyl pyruvate has been estimated to be 16.6: Bell, R. P.; Ridgewell, H. F. F. Proc. Royal Soc. London. Ser. A, Math Phys. Sci. 1967, 298, 178-183
22. Evans, D. A.; Seidel, D. J. Am. Chem. Soc. 2005, 127, 9958
23. See the Supporting Information for details.
24. β-Aryl-γ-nitro-α-keto esters like 3a could not be prepared using an auxiliary-based glyoxylate anion synthetic equivalent because of this elimination. See ref 4e.
25. Watanabe, M.; Murata, K.; Ikariya, T. J. Am. Chem. Soc. 2003, 125, 7508
26. Majima, K.; Takita, R.; Okada, A.; Oshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 15837
27. Tsunoda, T.; Suzuki, M.; Noyori, R. Tetrahedron Lett. 1980, 21, 1357 Subjecting these Michael adducts directly to the aerobic deacylation conditions afforded a complex mixture of products.
28. Saidi, M. R.; Azizi, N.; Akbari, E.; Ebrahimi, F. J. Mol. Catal. Chem-A. 2008, 292, 44
29. Xian, M.; Alaux, S.; Sagot, E.; Gefflaut, T. J. Org. Chem. 2007, 72, 7560
30. Agostinho, M.; Kobayashi, S. J. Am. Chem. Soc. 2008, 130, 2430
31. Momose, T; Muraoka, O. Chem. Pharm. Bull. 1978, 26, 288
32. Trost, B. M.; Bunt, R. C. J. Am. Chem. Soc. 1994, 116, 4089 It is interesting to note that the reaction of malonate esters with cyclohexen-3-yl acetate is a standard test for new allylic alkylation catalysts, but the analogous asymmetric reaction with acetoacetate esters was to the best of our knowledge unknown.
33. Komiya, N.; Naota, T.; Oda, Y.; Murahashi, S. J. Mol. Catal. Chem-A. 1997, 117, 21
34. Schröder, K; Join, B.; Amali, A. J; Junge, K; Ribas, X.; Costas, M.; Beller, M. Angew. Chem., Int. Ed. 2011, 50, 1425
35. Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307