Lewis base catalyzed enantioselective aldol addition of acetaldehyde-derived silyl enol ether to aldehydes

Journal of Organic Chemistry

Volumn 70, Issue 24, 2005, Pages 10190-10193

  Denmark, Scott E ^a   Bui, Tommy ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; AROMATIC COMPOUNDS; CATALYSIS; CATALYST SELECTIVITY; CATALYSTS; ETHERS;

ALDOL ADDITION; ENANTIOSELECTIVITY; ENOL ETHERS; LACTONE;

ALDEHYDES;

ACETALDEHYDE; ALDEHYDE; ALPHA CHLOROHYDRIN; BENZALDEHYDE; KETONE; LEWIS BASE; PHOSPHORAMIDIC ACID; SILANE DERIVATIVE; SILYL ETHER; SODIUM BOROHYDRIDE; TRIMETHYLSILYL DERIVATIVE; UNCLASSIFIED DRUG;

ADDITION REACTION; ALDOL REACTION; ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL STRUCTURE; DIASTEREOISOMER; ENANTIOSELECTIVITY; NUCLEAR OVERHAUSER EFFECT; POLYMERIZATION; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; REPRODUCIBILITY; TEMPERATURE;

EID: 28044459433     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0517500     Document Type: Article

References (43)

1. For reviews on catalytic, enantioselective aldol reactions, see: (a) Shibasaski, M.; Erasmus, M. V.; Groger, H. Chem. Eur. J. 1998, 7, 1137-1141,
2. (b) Nelson, S. G. Tetrahedron: Asymmetry 1998, 9, 357-389.
3. Wong, C.-H.; Machajewski, T. D. Angew. Chem., Int. Ed. 2000, 39, 1352-1374.
4. Evans, D, A,; Johnson, J. S. Acc. Chem. Res. 2000, 33, 325-335.
5. (e) Alcaide, B.; Almendros, P. Angew. Chem., Int. Ed. 2003, 42, 858-860,
6. (f) Carreira, E. M. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; John Wiley & Sons: New York, 2000; p 513,
7. (e) Carreira, E. M, In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A, Yamamoto, H., Eds.; Springer: Heidelberg, 1999; Vol. 3, Chapter 29.1.
8. (f) Modern Aldol Reactions; Mahrwald, R., Ed.; Wiley-VCH: Weinheim, 2004.
9. Heathcock, C. H. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Chapter 1.5, pp 133-179.
10. Barbas, C. F., III; Cordova, A.; Notz, W. J. Org. Chem. 2002, 67, 301-303.
11. Nielsen, A. J. Am. Chem. Soc. 1957, 79, 2518-2524.
12. (a) Merger, F.; Fouquet, G.; Platz, R. Liebigs Ann. Chem. 1979, 1591-1601.
13. (b) Day, A. R.; Lin, I. J. Am. Chem. Soc. 1952, 74, 5133-5135.
14. (c) Mahrwald, R. In Modern Aldol Reactions; Mahrwald, R., Ed.; Wiley-VCH: Weinheim, 2004; Vol. 2; Chapter 8.
15. (a) Silvestri, M. G.; Desantis, G.; Mitchell, M.; Wong, C.-H. In Topics in Stereochemistry; Denmark, S. E., Ed.; Wiley-Interscience: New York, 2003; Vol. 23, Chapter 5.
16. (b) Fessner, W.-D. In Modern Aldol Reactions; Mahrwald, R., Ed.; Wiley-VCH: Weinheim, 2004; Vol. 1; Chapter 5.
17. Wong, C.-H.; Gijsen, H. J. M. J. Am. Chem. Soc. 1994, 116, 8422-8423.
18. (a) MacMillan, D. W. C.; Northrup, A. B. J. Am. Chem. Soc. 2002, 124, 6798-6799.
19. (b) Notz, W.; Tanaka, F.; Barbas, C. F., III. Acc. Chem. Res. 2004, 37, 580-591. The use of chiral amines in catalytic asymmetric aldol reactions of ketones and aldehydes, see:
20. (c) List, B. In Modern Aldol Reactions; Mahrwald, R., Ed.; Wiley-VCH: Weinheim, 2004; Vol. 1, Chapter 4.
21. (d) List, B. Tetrahedron 2002, 58, 5573-5590.
22. Barbas, C. F., III; Mase, N.; Tanaka, F. Angew. Chem., Int. Ed. 2004, 43, 2420-2423.
23. MacMillan, D. W. C.; Northrup, A. B. Science 2004, 305, 1752-1755.
24. (a) Denmark, S. E.; Fujimori, S. In Modern Aldol Reactions; Mahrwald, R., Ed,; Wiley-VCH: Weinheim, 2004; Vol. 2, Chapter 7,
25. (b) Denmark, S. E., Ghosh, S. K. Angew. Chem., Int. Ed. 2001, 40, 4759-4762.
26. (c) Denmark, S. E.; Bui, T. Pro. Nat. Acad. Sci. U.S.A. 2004, 101, 5439-5444.
27. (a) Denmark, S. E.; Wynn, T. J. Am. Chem. Soc. 2001, 123, 6199-6200.
28. (b) Denmark, S. E.; Wynn, T.; Beutner, G. L. J. Am. Chem. Soc. 2002, 124, 13405-13407.
29. (c) Denmark, S. E.; Beutner, G. L. J. Am. Chem. Soc. 2003, 125, 7800-7801.
30. (d) Denmark, S. E.; Beutner, G. L.; Wynn, T.; Eastgate, M. D. J. Am. Chem. Soc. 2005, 127, 3774-3789.
31. (a) Denmark, S. E.; Heemstra, J. R. Jr. Org. Lett. 2003, 5, 2303.
32. (b) Denmark, S. E.; Heemstra, J. R., Jr. Synlett. 2004, 2411-2416.
33. (a) Denmark, S. E.; Fan, Y. J. Am. Chem. Soc. 2003, 125, 7825-7827.
34. (b) Denmark, S. E.; Fan, Y. J. Org. Chem. 2005, 70, ASAP; DOI: 10.1021/jo050549m.
35. Mayr, H.; Kempf, B.; Ofial, A. R. Acc. Chem. Res. 2003, 36, 66-77.
36. Other factors include the reaction concentration and catalyst loadings. It was found that the aldol addition can be run at 0.25-0.5 M with 15% mol catalyst to afford aldol products in good yield and selectivity.
37. The second mechanistic scenario implies reversible aldolization, which is very unlikely on the basis of the high enantioselectivity observed in the reaction.
38. There are two problems associated with this class of aldehyde. First is the inherent low reactivity because of the poorer electrophilicity of the aldehyde carbonyl group. Second, the electron-rich nature of the aromatic ring facilitates the ionization of the hydroxyl group of the aldol product under acidic quenching conditions to generate a methanol adduct. Attempts to buffer the methanol during the quench were fruitless.
39. Masamune, S.; Sato, T.; Kim, B. M. Wollmann, T. A. J. Am. Chem. Soc. 1986, 108, 8279-8281.
40. The configuration of other aldol products was assigned by analogy.
41. Although this intermediate has been detected previously in reactions of trichlorosilyl enolates (ref 10), we have independently identified it in these additions as well. Interestingly, i exists as a mixture of diastereomers; see the Supporting Information.
42. The configuration of the α-carbon bearing a hydroxyl group in 7 has not been established. Selective formation of either 6 or 7 under different quenching conditions is being investigated.
43. See the Supporting Information for details. The identity of the lactone was further confirmed by comparison of its spectroscopic data with those previously reported: Casy, G. Tetrahedron Lett. 1992, 33, 8159-8162.