Davis Oxidation

17 October, 2015 / by SK / in Reactions

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General Characteristics

Ketones and esters can be hydroxylated at the α-position when their enolates are treated with 2-sulfonyloxaziridine (N-sulfonyloxaziridine, the Davis reagent).

Asymmetric α-hydroxylation is also possible using the chiral oxaziridine derived from camphor sulfonic acid.

History

In 1978, Professor Franklin Davis and his coworkers at Drexel University (currently at Temple University) reported the synthesis of 2-sulfonyloxaziridine, which is the most widely used oxaziridine reagent today.

General References

Davis, F. A.; Jenkins, R., Jr.; Yocklovich, S. G. Tetrahedron Lett. 1978, 19, 5171. doi:10.1016/S0040-4039(01)85841-X
Davis, F. A.; Vishwakarma, L. C.; Billmers, J. G.; Finn, J. J. Org. Chem. 1984, 49, 3241. DOI: 10.1021/jo00191a048
Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Serajul Haque, M. J. Am. Chem. Soc. 1990, 112, 6679. DOI: 10.1021/ja00174a035
Davis, F. A.; Chen, B. C. Tetrahedron Lett. 1990, 31, 6823. doi:10.1016/S0040-4039(00)97181-8
Davis, F. A.; Kumar, A.; Chen, B. C. Tetrahedron Lett. 1991, 32, 867. doi:10.1016/S0040-4039(00)92107-5

Davis, F. A.; Chen, B. C.Chem. Rev. 1992, 92, 919. DOI: 10.1021/cr00013a008
Edupuganti, R.; Davis, F. Org. Biomol. Chem. 2012. 10, 5021. DOI: 10.1039/C2OB25345C

Reaction Mechanism

Examples

Example 1.^[1]

A diastereoselective example in the synthesis of (+)-jiadifenin.^[2]

Another example in the synthesis of taxol.^[3]

Experimental Procedure

Preparation of the Davis oxaziridine reagents.^[4,5]

Experimental Tips
References

[1] Smith, A. B., III et al. J. Am. Chem. Soc. 1992, 114, 9419. DOI: 10.1021/ja00050a023
[2] Carcache, D. A.; Cho, Y. S.; Hua, Z.; Tian, Y.; Li, Y.-M.; Danishefsky, S. J. J. Am. Chem. Soc. 2006, 128, 1016. DOI: 10.1021/ja056980a
[3] Wender, P. A. et al. J. Am. Chem. Soc. 1997, 119, 2755 & 2757. DOI: 10.1021/ja9635387 DOI: 10.1021/ja963539z
[4] Vishwakarma, L. C.; Stringer, O. D.; Davis, F. A. Org. Synth. 1988, 66, 203. [PDF] [5] Towson , J. C.; Weismiller, M. C.; Lal, G. S.; Sheppard, A. C.; Kumar, A.; Davis, F. A. Org. Synth. 1990, 69, 158. [PDF]