Dynamic control of ligand conformation: Asymmetric epoxidation using achiral (salen)manganese(III) complex

Synlett

Volumn , Issue 6, 1999, Pages 783-785

  Miura, Keishi ^a   Katsuki, Tsutomu ^a  

^a KYUSHU UNIVERSITY   (Japan)

Author keywords

(salen)manganese(III) complex; Asymmetric epoxidation; Dynamic stereocontrol

Indexed keywords

2,2 DIMETHYLCHROMENE DERIVATIVE; BIPYRIDINE; MANGANESE DERIVATIVE; OXIDE;

ARTICLE; CHEMICAL REACTION; COMPLEX FORMATION; CONFORMATION; ENANTIOMER; EPOXIDATION;

EID: 0032997344     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2732     Document Type: Article

References (13)

1. Katsuki, T. J. Mol, Cat. A, Chem. 1996, 113, 87-107.
2. a) Hamada, T.; Fukuda, T.; Imanishi, H.; Katsuki, T. Tetrahedron 1996, 52, 515-530.
3. b) Noguchi, Y.; Irie, R., Fukuda, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4533-4536.
4. c) Ito, Y.N.; Katsuki, T. Tetrahedron Lett. 1998, 39, 4325-4328.
5. d) Irie, R.; Hashihayata, T.; Katsuki,T.; Akita, M.; Moro-oka, Y. Chem. Lett. 1998, 1041-1042.
6. a) Hashihayata, T.; Ito, Y.; Katsuki, T. Synlett 1996, 1079-1081.
7. b) Hashihayata, T.; Ito, Y.; Katsuki, T. Tetrahedron 1997, 53, 9541-9552.
8. Irie, R.; Ito, Y.; Katsuki, T. Synlett 1991, 265-266.
9. a) Nakajima, M.; Sasaki, Y.; Shiro, M.; Hashimoto, S. Tetrahedron: Asymmetry 1997, 8, 341-344.
10. b) Nakajima, M.; Sasaki, Y.; Iwamoto, H.; Hashimoto, S. Tetrahedron Lett. 1998, 39, 87-88.
11. c) Nakajima, M.; Saito, M.; Shiro, M.; Hashimoto, S. J. Am. Chem. Soc. 1998, 120, 6419-6420.
12. Our preliminary results and proposal (reference 3) were criticized by speculation due to the low chemical yield of the epoxide: Palucki, M.; Finney, N.S.; Pospisil, P.J.; Güler, M.L.; Ishida, T.; Jacobsen, E.N. J. Am. Chem. Soc. 1998, 120, 948-954. They pointed out the possibility of kinetic resolution of the resulting epoxide. We exposed racemic 6-acetamido-2,2-dimethyl-7-nitrochromene oxide to the present reaction conditions for 48 h but no decomposition of the epoxide was observed. The enantiomeric excess of the recovered epoxide was 0% within the limits of detection by HPLC analysis.
13. Kanno et al. have indicated that (+)-N,N'-dioxide has S-configuration by CD spectroscopic study: Kanno, H.; Kashiwabara, K.; Fujita, J. Bull. Chem. Soc. Jpn. 1979, 52, 1408-1412. However, this is not the conclusive determination of the configuration of the N,N'-dioxide (a private communication from Dr. Kanno).