Efficient Diastereoselective and Enantioselective Nitroaldol Reactions from Prochiral Starting Materials: Utilization of La-Li-6,6′-Disubstituted BINOL Complexes as Asymmetric Catalysts

Journal of Organic Chemistry

Volumn 60, Issue 23, 1995, Pages 7388-7389

  Sasai, Hiroaki ^a   Tokunaga, Teruhisa ^a   Watanabe, Shizue ^a   Suzuki, Takeyuki ^a   Itoh, Noriie ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

SPHINGANINE; SPHINGOSINE DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; ENANTIOMER; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0028875444     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00128a005     Document Type: Article

References (17)

1. For representative papers see: Seebach, D.; Colvin, E. W.; Lehr, F.; Weller, T. Chimia 1979, 33, 1-18.
2. Rosini, G. Comprehensive Organic Synthesis; Trost, B. M., Heathcock, C. H., Eds.; Pergamon Press: Oxford, 1991; Vol. 2, p 321 and references therein.
3. Sasai, H.; Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1992, 114, 4418-4420.
4. Sasai, H.; Suzuki, T.; Itoh, N.; Shibasaki, M. Tetrahedron Lett. 1993, 34, 851-854.
5. Sasai, H.; Suzuki, T.; Itoh, N.; Tanaka, K.; Date, T.; Okamura, K.; Shibasaki, M. J. Am. Chem. Soc. 1993, 115, 10372-10373.
6. Sasai, H.; Itoh, N.; Suzuki, T.; Shibasaki, M. Tetrahedron Lett. 1993, 34, 855-858.
7. Sasai, H.; Suzuki, T.; Itoh, N.; Arai, S.; Shibasaki, M. Tetrahedron Lett. 1993, 34, 2657-2660.
8. Sasai, H.; Yamada, Y. M. A.; Suzuki, T.; Shibasaki, M. Tetrahedron 1994, 50, 12313-12318.
9. Sasai, H.; Kim, W.-S.; Suzuki, T.; Shibasaki, M.; Mitsuda, M.; Hasegawa, J.; Ohashi, T. Tetrahedron Lett. 1994, 35, 6123-6126.
10. Henry, L. C. R. Hebd. Seances Acad. Sci. 1895, 120, 1265.
11. Yamamoto, K.; Noda, K.; Okamoto, Y. J. Chem. Soc., Chem. Commun. 1985, 1065-1066.
12. For the use of 6,6'-dibromo-BINOL Terada, M.; Motoyama, Y.; Mikami, K. Tetrahedron Lett. 1994, 35, 6693-6696.
13. It appears that the syn-selectivity in the nitroaldol reaction is best explained by steric hindrance in the bicyclic transition state as can be seen in Newman projections, which suggest that the transition state leading to the syn adduct is most favorable. In the favored transition state, the catalyst is believed to act as a Lewis acid and base at the same time. In contrast, the non-chelation-controlled transition state appears to afford anti-adducts in lower optical purity. In order to confirm the above mechanism, calculation is under investigation. Examples of the other hetero-bimetallic multifunctional catalysts: Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194-6198.
14. Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl., in press.
15. Schwartz, G. K.; Jiang, J.; Kelsen, D.; Albino, A. P. J.Nat. Cancer Inst. 1993, 85, 402-407.
16. Hannun, Y. A.; Bell, R. M. Science 1989, 243, 500-507.
17. Hannun, Y. A.; Loomis, C. R.; Merrill, A. H., Jr.; Bell, R. M. J.Biol. Chem. 1986, 261, 12604-12609.