Scandium trisdodecylsulfate (STDS). A new type of Lewis acid that forms stable dispersion systems with organic substrates in water and accelerates aldol reactions much faster in water than in organic solvents

Tetrahedron Letters

Volumn 39, Issue 30, 1998, Pages 5389-5392

  Kobayashi, Shu ^a,b   Wakabayashi, Takeshi ^b  

^a UNIVERSITY OF TOKYO   (Japan)

^b TOKYO UNIVERSITY OF SCIENCE   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

DODECYL SULFATE; ORGANIC SOLVENT; SCANDIUM TRISDODECYLSULFATE; UNCLASSIFIED DRUG; WATER;

ARTICLE; CATALYSIS; DISPERSION; OXIDATION REDUCTION REACTION; REACTION ANALYSIS;

EID: 0032560708     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01081-8     Document Type: Article

References (38)

1. 1. For leading references, see (a) Organic Synthesis in Water, Grieco, P. Ed.; Chapman & Hall: London, 1997.
2. (b) Anastas, P. T.; Williamson, T. C. Eds. Green Chemistry, ACS Symposium Series 626; American Chemical Society: Washington, DC, 1996.
3. (c) Li, C.-J.; Chan, T.-H. Organic Reactions in Aqueous Media, Wiley: New York, 1997.
4. (d) Reissig, H.-U. in Organic Synthesis Highlights, Waldmann, H. Ed.; VCH: Weinheim, 1991, p 71.
5. (e) Lubineau, A.; Ange, J.; Queneau, Y. Synthesis 1994, 741.
6. (f) Li, C.-J. Chem. Rev. 1993, 93, 2023.
7. (g) Einhorn, C.; Einhorn, J.; Luche, J. Synthesis 1989, 787.
8. 2. (a) Santelli, M.; Pons, J.-M. Lewis Acids and Selectivity in Organic Synthesis, CRC Press: Boca Raton, 1995.
9. (b) Schinzer, D. Ed. Selectivities in Lewis Acid Promoted Reactions, Kluwer Academic Publisheres: Dordrecht, 1989.
10. 3. (a) Kobayashi, S. Synlett 1994, 689.
11. (b) Kobayashi, S. Chem. Lett. 1991, 2187.
12. (c) Kobayashi, S.; Hachiya, I. J. Org. Chem. 1994, 59, 3590.
13. (d) Kobayashi, S.; Hachiya, I.; Yamanoi, Y. Bull. Chem. Soc. Jpn. 1994, 67, 2342.
14. (e) Kobayashi, S.; Ishitani, H. J. Chem. Soc., Chem. Commun. 1995, 1379.
15. (f) Kobayashi, S.; Hachiya, I.; Ishitani, H.; Araki, M. Synlett 1993, 472.
16. (g) Hachiya, I.; Kobayashi, S. J. Org. Chem. 1993, 58, 6958.
17. 4. Mukaiyama, T.; Banno, K.; Narasaka, K. J. Am. Chem. Soc. 1974, 96, 7503.
18. 5. Lubineau et al. reported water-promoted aldol reactions of silyl enol ethers with aldehydes. Lubineau, A.; Meyer, E. Tetrahedron 1988, 44, 6065.
19. 6. Loh, T.-P.; Pei, J.; Cao, G.-Q. J. Chem. Soc., Chem. Commun. 1996, 1819; Loh, T.-P.; Pei, J.; Koh, K. S. V.; Cao, G. Q.; Li, X. R. Tetrahedron Lett. 1997, 38, 3465-3468; 3993-3994 (Corrigendum). See also, Kobayashi, S.; Busujima, T.; Nagayama, S. Tetrahedron Lett. 1998, 1579.
20. 6. Loh, T.-P.; Pei, J.; Cao, G.-Q. J. Chem. Soc., Chem. Commun. 1996, 1819; Loh, T.-P.; Pei, J.; Koh, K. S. V.; Cao, G. Q.; Li, X. R. Tetrahedron Lett. 1997, 38, 3465-3468; 3993-3994 (Corrigendum). See also, Kobayashi, S.; Busujima, T.; Nagayama, S. Tetrahedron Lett. 1998, 1579.
21. 6. Loh, T.-P.; Pei, J.; Cao, G.-Q. J. Chem. Soc., Chem. Commun. 1996, 1819; Loh, T.-P.; Pei, J.; Koh, K. S. V.; Cao, G. Q.; Li, X. R. Tetrahedron Lett. 1997, 38, 3465-3468; 3993-3994 (Corrigendum). See also, Kobayashi, S.; Busujima, T.; Nagayama, S. Tetrahedron Lett. 1998, 1579.
22. 7. (a) Kobayashi, S.; Wakabayashi, T.; Nagayama, S.; Oyamada, H. Tetrahedron Lett. 1997, 38, 4559.
23. (b) Kobayashi, S.; Wakabayashi, T.; Oyamada, H. Chem. Lett. 1997, 831.
24. 8. (a) Tom, K. F. US Patent 3615169, 1971; Chem. Abstr. 1972, 76, 5436a.
25. 8. (a) Tom, K. F. US Patent 3615169, 1971; Chem. Abstr. 1972, 76, 5436a.
26. (b) Kobayashi, S.; Hachiya, I.; Araki, M.; Ishitani, H. Tetrahedron Lett. 1993, 34, 3755.
27. 2O): C, 48.30; H, 9.12; S, 10.74. Found: C, 48.15; H, 9.02; S, 10.53.
28. 3-SDS system makes a kind of micelle (not dispersion), the STDS system makes stable dispersion (probably not micelle but dispersion colloid). See also Ref. 17.
29. 11. Recently, rate enhancement in the presence of Cu(II) dodecylsulfate in Diels-Alder reaction in water was reported. Otto, S.; Bertoncin, F.; Engberts, J. B. F. N. J. Am. Chem. Soc. 1996, 118, 7702.
30. 3 as a catalyst, decomposition of 1 was very fast.
31. 13. Measurement was performed by using Coulter® Sub·micron Particle Analyzer, Model N4MD (Coulter Electronics, Inc.). We are grateful to Dr. Kazuhisa Takahashi, Department of Applied Chemistry, Faculty of Science, Science University of Tokyo (SUT), for measurement of the particle sizes. We also thank Prof. Minoru Ueno, SUT, for his helpful discussion on the dispersion systems.
32. 14. The dispersion system was stable within a few minutes. Quick measurement of this system was indicated that its particle size was 0.4 μm.
33. 15. Cf. (a) Rideout, D.; Breslow, R. J. Am. Chem. Soc. 1980, 102, 7816.
34. (b) Breslow, R. in Structure and Reactivity in Aqueous Solution, Craner, C. J.; Truhlar, D. G. Eds., ACS Symposium Series 568; American Chemical Society: Washington, DC, 1994, p. 291.
35. (c) Blokzijl, W.; Engberts, J. B. F. N. in Structure and Reactivity in Aqueous Solution, Craner, C. J.; Truhlar, D. G. Eds., ACS Symposium Series 568; American Chemical Society: Washington, DC, 1994, p. 303.
36. -4 (1/mol·sec).
37. 3-SDS system, it could be successfully used in the STDS system (Table 3, run 8).
38. 18. A typical experimental procedure for the STDS-catalyzed aldol reactions of silyl enol ethers with aldehydes: To STDS (0.05 mmol, 0.1 eq.) in water (3 ml) was added an aldehyde (0.50 mmol) and a silyl enol ether (0.75 mmol). The mixture was stirred for 4 h at rt. Brine was added and the aqueous layer was extracted with ethyl acetate. The combined organic layer was dried and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to afford the desired aldol adduct.