A chiral formamide: Design and application to catalytic asymmetric synthesis

Tetrahedron Letters

Volumn 39, Issue 18, 1998, Pages 2767-2770

  Iseki, Katsuhiko ^a   Mizuno, Shin ^a   Kuroki, Yoshichika ^a   Kobayashi, Yoshiro ^a  

^a DAIKIN INDUSTRIES LTD   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE DERIVATIVE; FORMAMIDE;

ARTICLE; CATALYSIS; CHIRALITY; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0032580431     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)00334-7     Document Type: Article

References (26)

1. 1. (a) Kobayashi, S.; Nishio, K. Tetrahedron Lett. 1993, 34, 3453-3456;
2. (b) Kobayashi, S.; Nishio, K. Synthesis 1994, 457-459;
3. (c) Kobayashi, S.; Nishio, K. J. Org. Chem. 1994, 59, 6620-6628;
4. (d) Wang, Z.; Wang, D.; Sui, X. J. Chem. Soc., Chem. Commun. 1996, 2261-2262.
5. 2. For reactions with propargyl- and allenyltrichlorosilanes, see: Kobayashi, S.; Nishio, K. J. Am. Chem. Soc. 1995, 117, 6392-6393.
6. 3. Kobayashi, S.; Yasuda, M.; Hachiya, I. Chem. Lett. 1996, 407-408.
7. 4. For a cleavage of oxiranes with trimethylsilyl azide, see: Saito, S.; Bunya, N.; Inaba, M.; Moriwake, T.; Torii, S. Tetrahedron Lett. 1985, 26, 5309-5312.
8. 5. (S,S)-Bis(-α-methylbenzyl)amine was purchased from AZmax Co. Ltd., Chiba, Japan and formylated with acetic formic anhydride to prepare formamide 1. See: Krimem, L.I. Organic Synthesis; John Wiley: New York, 1988; Collect. Vol. 6, pp 8-9.
9. 6. (a) Denmark, S.E.; Coe, D.M.; Pratt, N.E.; Griedel, B.D. J. Org. Chem. 1994, 59, 6161-6163;
10. (b) Iseki, K.; Kuroki, Y.; Takahashi, M.; Kobayashi, Y. Tetrahedron Lett. 1996, 37, 5149-5150;
11. (c) Iseki, K.; Kuroki, Y.; Takahashi, M.; Kishimoto, S.; Kobayashi, Y. Tetrahedron 1997, 53, 3513-3526.
12. 7. (a) Furuta, K.; Mouri, M.; Yamamoto, H. Synlett 1991, 561-562;
13. (b) Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 11490-11495;
14. (c) Aoki, S.; Mikami, K.; Terada, M.; Nakai, T. Tetrahedron 1993, 49, 1783-1792;
15. (d) Marshall, J. A.; Tang, Y. Synlett 1992, 653-654.
16. 8. The crotylation catalyzed by the BINAP·Ag(I) complex is anti-selective. See: Yanagisawa, A.; Ishiba, A.; Nakashima, H.; Yamamoto, H. Synlett 1997, 88-90.
17. 9. For asymmetric allylations of aldehydes with diallyltin dibromide mediated by chiral diamines, see: Kobayashi, S.; Nishio, K. Tetrahedron Lett. 1995, 36, 6729-6732.
18. 10. Allyltrichlorosilane (3) was purchased from Aldrich Chemical Company, Inc. and distilled before use.
19. 25 -8.94° (c 0.56, ethanol);
20. 3) (80% ee).
21. 12. The reason why HMPA improves the enantioselectivity remains unclear. However, the HMPA-enhanced catalytic activity may be explained by assuming that HMPA dissociates formamide 1 from the reaction product to facilitate regeneration of the chiral catalyst.
22. 13. (E)- and (Z)-Crotyltrichlorosilanes are readily prepared by using literature procedures, see: (a) Kara, M.; Kobayashi, M.; Sakurai, H. Tetrahedron Lett. 1987, 23, 4081-4084.
23. (b) Kira, M.; Hino, T.; Sakurai, H. Tetrahedron Lett. 1989, 30, 1099-1102.
24. 14. Roush, W.R.; Ando, K.; Powers, D.B.; Palkowitz, A.D.; Halterman, R.L. J. Am. Chem. Soc. 1990, 112, 6339-6348.
25. 3).
26. 5CN at -78°C for 3 w gave the corresponding anti (22) and syn homoallylic alcohols in the ratio of 61:39 (19% yield), and the enantiomeric excess of the anti-isomer was 98% [(1S,2R)-22]. The reaction carried out at -20°C for 3 w was syn-selective (syn/anti = 95/5, 34% yield). However, the enantioselectivity was very low [3% ee (the syn-isomer)].