A Greatly Improved Procedure for Ruthenium Tetraoxide Catalyzed Oxidations of Organic Compounds

Journal of Organic Chemistry

Volumn 46, Issue 19, 1981, Pages 3936-3938

  Carlsen, Per H J ^a   Katsuki, Tsutomu ^a   Martin, Victor S ^a   Sharpless, K Barry ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 2542433188     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00332a045     Document Type: Article

References (22)

1. Djerassi, C.; Engle, R. R. J. Am. Chem. Soc. 1953, 75, 3838.
2. Lee, D. G.; van den Engh, M. In “Oxidation in Organic Chemistry”; Trahanovsky, W. S., Ed.; Academic Press: New York, 1973; Part B. Chapter 4.
3. Dark-colored, ruthenium containing precipitates can usually be observed in inactive systems.
4. Spencer, A.; Wilkinson, G. J. Chem. Soc., Dalton Trans. 1972, 1570.
5. In a related type of experiment, addition of acetonitrile to reaction mixtures in which catalysis had ceased (due to precipitation of the ruthenium catalyst in the course of an oxidation) resulted in dissolution of the precipitate and restoration of full catalytic activity.
6. Acetonitrile was the first cosolvent tried, but in the end it remained the most effective of many solvents which were examined. It should be noted that acetonitrile and water alone are not effective; the third solvent component, CCI4, plays an important role.
7. Dehand, J.; Rose, J. J. Chem. Res. 1979, 155.
8. This is the optimum solvent ratio, and deviations from it led, for some substrates, to slower reactions and poorer yields.
9. For an example of a sensitive case where it succeeded when other oxidative cleavage methods failed, see Rossiter, B. E.; Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 464.
10. Potassium metaperiodate is also satisfactory. Sodium hypochlorite is unfortunately much less effective. “Oxone” (Du Pont) works but is slower and is required in large excess.
11. Calculations based on n = 1 [RuCl3(H20)n]. Ruthenium dioxide hydrate is equally effective.
12. This ether treatment precipitates any remaining ruthenium species.
13. Furans 3 and 6 were identified by comparison with authentic samples. 14 Furans 4, 5, and 7 are new compounds; for proof of their structures, see supplementary material (the structures were proved by chemical correlations which, incidentally, involve four uses of the new ruthenium-catalyzed oxidation procedure).
14. Klein, E.; Rojahn, W. Tetrahedron 1965, 21, 2353.
15. Powell, K. A.; Hughes, A L.; Katchian, H.; Jerauld, J. F.; Sable, H. Z. Tetrahedron 1972, 28, 2019.
16. Walba, D. M.; Wand, M. D.; Wilkes, M. C. J. Am. Chem. Soc. 1979, 101, 4396.
17. Walba, D. M.; Edwards, P. D. Tetrahedron Lett. 1980, 21, 3531.
18. Baldwin, J. E.; Crossley, M. J.; Lehtonen, E.-M. M. J. Chem. Soc., Chem. Commun. 1979, 918.
19. The cleavage of olefins to acids (Tables I and II) also proceeds via the aldehyde. The aldehyde is formed rapidly and then, in a slower step, it is oxidized to the acid. However, the rate differences have so far not been large enough to allow one to stop crisply at the aldehyde stage.
20. Carlsen, P. H. J.; Sharpless, K. B., unpublished results, Stanford University.
21. Smith, A. B.; Scarborough, R. M. Synth. Commun. 1980, 10, 205.
22. Address correspondence to Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139.