X-ray crystal and NMR structure of a highly reactive bidentate 1,2-diamine-OsO4 complex, formally a 20-electron outer valence shell species. Mechanistic implications for the 1,2-diamine-accelerated dihydroxylation of olefins by OsO4

Journal of the American Chemical Society

Volumn 118, Issue 33, 1996, Pages 7851-7852

  Corey, E J ^a   Sarshar, Sepehr ^a   Azimioara, Mihai D ^a   Newbold, Ronald C ^a   Noe, Mark C ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

METAL COMPLEX; OSMIUM;

ARTICLE; CATALYSIS; CRYSTALLOGRAPHY; DRUG STRUCTURE; DRUG SYNTHESIS; HYDROXYLATION; NUCLEAR MAGNETIC RESONANCE;

EID: 0029817010     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960536d     Document Type: Article

References (18)

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4. (d) Hirama, H.; Oishi, T.; Itô, S. J. Chem. Soc., Chem. Commun. 1989, 665.
5. (e) Corey, E. J.; Jardine, P. D.; Virgil, S.; Yuen, P.-W.; Connell, R. D. J. Am. Chem. Soc. 1989, 111, 9243.
6. (f) Tomioka, K.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1990, 31, 6421.
7. (g) Hanessian, S.; Meffre, P.; Girard, M.; Beaudoin, S.; Sancéau, J.-Y.; Bennani, Y. J. Org. Chem. 1993, 58, 1991.
8. For a review of catalytic asymmetric dihydroxylation of olefins, see: Kolb, H, C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483:
9. 2, 1.030. Final R indices [I > 2σ(I)],Rl =0.0444, wR2 = 0.1042; R indices (all data), R1 = 0.0534, wR2 = 0.1104; absolute structure parameter 0.04(3). Detailed X-ray crystallographic data are available from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge. CB2 1EZ, U.K.
10. Griffith, W. P.; Skapski, A. C.; Woode, K. A.; Wright, M. J. Inorg. Chem. Acta 1978, 31, L413.
11. ΔG‡ = < 3.5 kcal mol for an equilibrium between two hypothetical interconverting monodentate complexes is calculated by the method of: Bovey, F. A.; Jelinski, L.; Mirau. P. A. Nuclear Magnetic Resonance Spectroscopy, 2nd ed.; Academic Press: New York, 1987; p 300.
12. The reaction was followed by measuring the decrease in the concentration of tetramethylethylene as a function of time.
13. 4 with 1,2-diamines as compared with structurally analogous monoamines must be due at least in part to a more favorable equilibrium for 1,2-diamine complexation, our data do not allow an assessment of the degree to which 1,2-diamine rate enhancement may be due to a greater rate constant for the subsequent reaction with olefin.
14. 13C (125 MHz, 200 K) δ 22.93, 25.28, 23.92, 24.20, 49.52, 56.42, 65.65.
15. Corey. E. J.; Noe, M. C. J. Am. Chem. Soc. 1996, 118, 319.
16. 4 complex, without specifying structural data for the transition state or the basis for enantioselectivity.
17. 4 enantioselective dihydroxylation which would have to involve one of the equatorial oxygens clearly predicts formation of the wrong enantiomer.
18. 4 the osmaoxetane structure "is not a minimum on the potential energy hypersurface."