A new method for the catalytic aldol reaction to ketones

Journal of the American Chemical Society

Volumn 125, Issue 19, 2003, Pages 5644-5645

  Oisaki, Kounosuke ^a   Suto, Yutaka ^a   Kanai, Motomu ^a,b   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL DERIVATIVE; KETONE DERIVATIVE;

ALDOL REACTION; ALLYLATION; ARTICLE; ASYMMETRIC CATALYSIS; CATALYST; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; DIASTEREOISOMER; ENANTIOSELECTIVITY; GEOMETRY; ISOMER; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION OPTIMIZATION;

EID: 0037620632     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja034993n     Document Type: Article

References (18)

1. Carreira, E. M. In Comprehensive Asymmetric Catalysis: Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Heidelberg, 1999; Vol. III, Chapter 29.1.
2. (a) Kobayashi, S.; Matsui, S.; Mukaiyama, T. Chem. Lett. 1988, 1491.
3. (b) Chen, J.; Sakamoto, K.; Orita, A.; Otera, J. J. Org. Chem. 1998, 63, 9739.
4. Denmark, S. E.; Fan, Y. J. Am. Chem. Soc. 2002, 124, 4233.
5. Yamasaki, S.; Fujii, K.; Wada, R.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2002, 124, 6536.
6. For a copper fluoride-catalyzed asymmetric aldol reaction of a silyl dienolate to aromatic and α,β-unsaturated aldehydes, see: Krüger, J.; Carreira, E. M. J. Am. Chem. Soc. 1998, 120, 837.
7. Pagenkopf, B. L.; Krüger, J.; Stojanovic, A.; Carreira, E. M. Angew. Chem., Int. Ed. 1998, 37, 3124. Aliphatic substrates gave poor yields in those cases.
8. Gulliver, D. J.; Levason, W.; Webster, M. Inorg. Chim. Acta 1981, 52, 153.
9. 3SiF. See the Supporting Information (SI) for details.
10. 3· 2EtOH.
11. 3SiF, a peak at -130 ppm (with a doublet satellite peak, J = 156 Hz) was observed, which supports the assignment of 4.
12. 1H NMR, possibly due to the fast ligand exchange between silicon and copper atoms.
13. 3-6a mixture, suggesting that 5 and 7 were in equilibrium.
14. a was used for the kinetic studies to eliminate the effect of the complex initial ligand exchange process. The fractional order dependency might suggest that the overall reaction contains several rate-determining steps. The ligand-exchange step to generate the active nucleophile, the aldol addition step, and the catalyst turnover step are possible candidates. The inhibitory feature of the ketene silyl acetal (minus order dependency) might be due to the nonproductive fluoride exchange between silicon atoms (inhibition of the active nucleophile generation step).
15. + acts as a Lewis acid cannot be completely excluded.
16. Tsuda, T.; Hashimoto, T.; Saegusa, T. J. Am. Chem. Soc. 1972, 94, 658.
17. The proposed mechanism is distinct from the silyl Lewis acid-catalyzed aldol reaction (Ishihara, K.; Hiraiwa, Y.; Yamamoto, H. Chem. Commun. 2002, 1564) or the tin(II) triflate- and tin fluoride-mediated asymmetric aldol reaction (Kobayashi, S.; Uchiro, H.; Fujishita, Y.; Shiina, I.; Mukaiyama, T. J. Am. Chem. Soc. 1991, 113, 4247).
18. The proposed mechanism is distinct from the silyl Lewis acid-catalyzed aldol reaction (Ishihara, K.; Hiraiwa, Y.; Yamamoto, H. Chem. Commun. 2002, 1564) or the tin(II) triflate- and tin fluoride-mediated asymmetric aldol reaction (Kobayashi, S.; Uchiro, H.; Fujishita, Y.; Shiina, I.; Mukaiyama, T. J. Am. Chem. Soc. 1991, 113, 4247).