Chiral (ON)Ru-salen catalyzed cyclopropanation: High cis- and enantio-selectivity

Synlett

Volumn , Issue 7, 1999, Pages 1163-1165

  Uchida, Tatsuya ^a   Irie, Ryo ^a   Katsuki, Tsutomu ^a  

^a KYUSHU UNIVERSITY   (Japan)

Author keywords

(ON+)(salen)ruthenium(II) complex; Cis selectivity; Cyclopropanation; Photo activation

Indexed keywords

CYCLOPROPANE; RUTHENIUM COMPLEX;

ARTICLE; CATALYSIS; CATALYST; CHIRALITY; CIS ISOMER; CYCLIZATION; ENANTIOMER; PHOTOACTIVATION; STEREOSPECIFICITY; SUNLIGHT;

EID: 0032775859     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2782     Document Type: Article

References (17)

1. The preceding communications.
2. a) Katsuki, T. J. Mol. Cat. A: Chem. 1996, 113, 87-107.
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4. a) Doyle, M. P. Chem. Rev. 1986, 86, 919-939.
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6. a) Nishiyama, H.; Itoh, Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. J. Am. Chem. Soc. 1994, 116, 2223-2224.
7. b) Nishiyama, H.; Itoh, Y.; Sugawara, Y.; Matsumoto, H.; Aoki, K.; Itoh, K. Bull. Chem. Soc. Jpn. 1995, 68, 1247-1262.
8. (c) Frauenkron, M.; Berkessel, A. Tetrahedron Lett. 1997, 38, 7175-7176.
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10. a) Maxwell, J. L.; O'Malley, S.; Brown, K. C.; Kodadek. T. Organometallics 1992, 11, 645-652.
11. b) It has reported that cyclopropanation using a cyclopentadienyl iron complex as the catalyst shows high cis-selectivity, though in a non-enantioselective manner: Seitz, W. J.; Saha, A. K.; Hossain, M. M. Organometallics 1993, 12, 2604-2608.
12. a) Fukuda, T.; Katsuki, T. Synlett 1995, 825-826.
13. b) Fukuda, T., Katsuki, T. Tetrahedron 1997, 53, 7201-7208.
14. In (salen)cobalt(III) complexes, the lengths of Co-equatorial oxygen atom are in the range of 1.84-1.91 Å. (ON)Ru-salen complex 1 has a longer Ru-oxygen bond: see the following communication.
15. In accord with this observation, the complex bearing the chirality only at the binaphthyl part and ethylenediamine as the diamine unit also showed good cis-trans selectivity (79:21) and high enantioselectivity (91% ee, cis-isomer; 0% ee, trans-isomer). However, due to its very poor solubility to organic solvent, the yield of the cyclopropanation products was low (<5%). In connection to this problem, it is noteworthy that the reactions of styrene and diazoacetate in the presence of chiral Cu, Co, and Rh complexes give trans and cis products, the configurations at Cl of which arc the same (reference 3), while the present reaction provided the trans and cis products isomeric at Cl. The reason for this unusual selectivity is unclear at present.
16. It has been reported that flash photolysis of Ru(TPP)(NO)Cl presumably generates a transient species, Ru(TPP)Cl: Lorkovic, I. M.; Miranda, K. M.; Lee, B.; Bernhard, S.; Schoonover, J. R.; Ford, P. C. J. Am. Chem. Soc. 1998, 120, 11674-11683. However, we can not remove the possibility that the chloro and hydroxo ligands in 2 and 5 dissociate, respectively, under the present reaction conditions to give the same transient species.
17. Absolute configuration of the products has not been determined.