(Salen)ruthenium-catalyzed desymmetrization of meso-diols: Catalytic aerobic asymmetric oxidation under photo-irradiation

Chemistry Letters

Volumn , Issue 11, 2002, Pages 1080-1081

  Shimizu, Hideki ^a   Nakata, Kenya ^a   Katsuki, Tsutomu ^a  

^a KYUSHU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOHEXANE DERIVATIVE; RUTHENIUM DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL REACTION; DESYMMETRIZATION; ENANTIOSELECTIVITY; IRRADIATION; OXIDATION;

EID: 0037027719     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2002.1080     Document Type: Article

References (16)

1. a) G. Fantin and P. Pedrini, in "Asymmetric Oxidation Reactions," ed. by T. Katsuki, Oxford University Press, Oxford (2001 ), pp 200-214.
2. b) J. B. Jones, in "Asymmetric Synthesis," ed. by J. D. Morrison, Academic Press, New York (1984), Vol. 5, pp 309-344.
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4. b) Y. Ishii, K. Osakada, T. Ikariya, and M. Saburi, Chem. Lett., 1982, 1179.
5. Asymmetric Oppenauer oxidation-like desymmetrization of meso-diols (up to 50% ee) has recently been reported: M. Ito, A. Osaku, and T. Ikariya, The 84th Annual Meeting of the Chemical Society of Japan, Tokyo, March 2002, Abstr., No. 3 G4-14.
6. K. Masutani, T. Uchida, R. Irie, and T. Katsuki, Tetrahedron Lett., 41, 5119 (2000).
7. Enantiomer-differentiating aerobic oxidation of racemic alcohols has recently been reported: a) D. R. Jensen, J. S. Pugsley, and M. S. Sigman, J. Am. Chem. Soc., 123, 7475 (2001). (2001).
8. b) E. M. Ferreira and B. M. Stoltz, J. Am. Chem. Soc., 123, 7725 (2001).
9. A. Miyata, M. Murakami, R. Irie, and T. Katsuki, Tetrahedron Lett., 42, 7067 (2001).
10. A. Miyata, M. Furukawa, R. Irie, and T. Katsuki, Tetrahedron Lett., 43, 3481 (2002).
11. (R,R)-1,2-Diamino-1,2-dimethylcyclohexane was prepared according to the reported procedure: W. Zhang and E. N. Jacobsen, Tetrahedron Lett., 32, 1711 (1991).
12. a) I. J. Jakovac, H. B. Goodbrand, K. P. Lok, and J. B. Jones, J. Am. Chem. Soc., 104, 4659 (1982).
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14. c) H.-J. Gais, K. L. Lukas, W. A. Ball, S. Braun, and H. J. Lindner, Liebigs Ann. Chem., 1986, 687.
15. Typical experimental procedure is exemplified by the oxidative desymmetrization of 2a: meso-diol 2a (14.4 mg, 0.1 mmol) and (ON)Ru(salen) 7 (2.0 mg, 2.0 mol%) were dissolved in anhydrous chloroform (0.5 mL). The solution was stirred under irradiation with a halogen lamp in air for 2.7 days at room temperature. The mixture was directly chromatographed on silica gel (hexane/ethyl acetate = 1/1 ) to give lactol 3a (9.2 mg, 65%). To a suspension of lactol 3a and 4 Å molecular sieves (100 mg) in anhydrous dichloromethane (0.5 mL) was added pyridinium dichromate (49 mg, 0.13 mmol). The mixture was stirred for 6h at room temperature, diluted with hexane/ethyl acetate (4/1) and filtered through a pad of silica gel. The filtrate was concentrated under reduced pressure. The enantiomeric excess of the resulting lactone was determined by GLC analysis using optically active column (SUPELCO BETA-DEX-225).
16. All the lactones obtained in these reactions have the corresponding cis-bicyclo ring structures. The configuration of the lactone derived from 2d was proven to be cis by the chemical correlation: LAH reduction of the lactone gave meso-diol 2d.