Osmium-Catalyzed Dihydroxylation of Olefins in Acidic Media: Old Process, New Tricks

Advanced Synthesis and Catalysis

Volumn 344, Issue 3-4, 2002, Pages 421-433

  Dupau, Philippe ^a   Epple, Robert ^a   Thomas, Allen A ^a   Fokin, Valery V ^a   Sharpless, K Barry ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

Alkenes; Dihydroxylations; Homogeneous catalysis; Osmium; Oxidations

Indexed keywords

EID: 0000451948     PISSN: 16154150     EISSN: None     Source Type: Journal    
DOI: 10.1002/1615-4169(200206)344:3/4<421::AID-ADSC421>3.0.CO;2-F     Document Type: Article

References (36)

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13. a) A. A. Thomas, R. Epple, D. S. Nirschl, K. B. Sharpless, unpublished results;
14. b) D. S. Nirschl, Ph. D. dissertation, The Scripps Research Institute, 2000; Diss. Abstr. Int. B 2000, 61(6), 3065.
15. The following automation equipment was used in these studies. Solutions of the additives for screening were prepared using Bohdan weighing-dissolution station, capable of preparing 192 solutions with a defined concentration in each run. Gilson 215 liquid handler was used to prepare reaction mixtures and to take aliquots for analysis at predefined time intervals. The yield of the diol 2 was quantitatively analyzed by mass spectrometry. For additional details, see A. A. Thomas, Ph. D. dissertation, The Scripps Research Institute, 2000; Diss. Abstr. Int. B 2000, 61(3), 1421; J. P. Chiang, Ph. D. dissertation, The Scripps Research Institute, 2000; Diss. Abstr. Int. B 2000, 61(3), 1410.
16. The following automation equipment was used in these studies. Solutions of the additives for screening were prepared using Bohdan weighing-dissolution station, capable of preparing 192 solutions with a defined concentration in each run. Gilson 215 liquid handler was used to prepare reaction mixtures and to take aliquots for analysis at predefined time intervals. The yield of the diol 2 was quantitatively analyzed by mass spectrometry. For additional details, see A. A. Thomas, Ph. D. dissertation, The Scripps Research Institute, 2000; Diss. Abstr. Int. B 2000, 61(3), 1421; J. P. Chiang, Ph. D. dissertation, The Scripps Research Institute, 2000; Diss. Abstr. Int. B 2000, 61(3), 1410.
17. Direct diol quantification using electrospray ionization mass spectrometry (ESI-MS) greatly increases analytical throughput, as each run takes as little as 90 seconds. With proper calibration, the accuracy of this method is as good as quantitative LC analysis. See also: A. E. Rubin, Ph. D. Dissertation, The Scripps Research Institute, 1999; Diss. Abstr. Int. B 1999, 60(6), 2705.
18. 4NOAc as turnover-facilitating additive. With the exception of fumarate, the yields were significantly lower compared to the new acidic conditions. Overoxidation byproducts were also always observed.
19. Many other catalytic osmylation procedures often give products tinged from gray to brown or black due to traces of osmium complexes entrained as impurities.
20. a) J. S. M. Wai, I. Marko, J. S. Svendsen, M. G. Finn, E. N. Jacobsen, K. B. Sharpless, Tetrahedron Lett. 1989, 30, 1123;
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22. a) J. S. M. Wai, K. B. Sharpless, unpublished results;
23. b) B. J. Lohray, V. B'husahn, R. K. Kumar, J. Org. Chem. 1994, 59, 1375;
24. c) W. P. Griffith, in Comprehensive Coordination Chemistry, (Ed.: G. Wilkinson), Pergamon Press, New York, 1987, Vol. 4, pp. 519.
25. The neutral bis(glycolate) ii was prepared according to literature methods: a) R. Criegee, B. Marchand, H. Wannowius, Justus Liebigs Ann. Chem. 1942, 550, 99;
26. b) E. D. Korn, J. Cell Biology 1967, 34, 627; it was transformed to the dioxoosmate dianion dipotassium salt iv by treatment with 1 M KOH in MeOH.
27. At very low pH (less than ca. 3), Os(VI) complexes usually disproportionate to Os(VIII) and Os(IV) species. The latter is virtually insoluble, and as a result is entirely excluded from participation in the catalytic cycle.
28. [14a]
29. a) V. V. Fokin, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 3455;
30. b) V. V. Fokin, K. B. Sharpless, unpublished results;
31. c) M. A. Andersson, R. Epple, V. V. Fokin, K. B. Sharpless, Angew. Chem. Int. Ed. 2002, 41, 472.
32. S. U. Hansen, M. Bols, J. Chem. Soc. Perkin Trans. 1 2000, 911.
33. Olefins containing primary and secondary amine groups failed to react under these conditions.
34. Use of TMO was pioneered by Malteson; he found it to be superior to NMO for the dihydroxylation of α-pinene at elevated temperatures and with pyridine as an additive; see: E. Erdik , D. S. Matteson, J. Org. Chem. 1989, 54, 2742.
35. Z. P. Demko, K. B. Sharpless, J. Org. Chem. 2001, 66, 7945.
36. Dihydroxylations at temperatures above 100°C were performed using SmithSynthesizer Workstation made available by Personal Chemistry AB (Uppsala, Sweden) under the Scientific Partnership Program.