Mander’s Reagent

20 May, 2016 / by SK / in Reactions

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General Characteristics

Methyl cyanoformate, also known as Mander’s reagent, is used to introduce a methoxycarbonyl group to metal enolates for the synthesis of β-ketoesters.

Compared with chloroformate esters, which tend to react with enolates to give a mixture of C– and O-carboxylated products, Mander’s reagent is more C-selective.

It serves as a source of cyanide as well, such as for the addition of cyanide to carbonyls in the presence of nucleophilic or Lewis acidic catalysts.

General References

Mander, L. N.; Sethi, S. P. Tetrahedron Lett. 1983, 24, 5425. doi:10.1016/S0040-4039(00)87886-7
Crabtree, S. R.; Chu, W. L. A.; Mander, L. N. Synlett 1990, 169. DOI: 10.1055/s-1990-21025
Bissember, A. C. Synlett 2009, 681. DOI: 10.1055/s-0028-1087716

Reaction Mechanism

Examples

An appearance in the synthesis of strychnine.^[1]

An application to the synthesis of ingenol.^[2]

Experimental Tips
References

[1] Knight, S. D.; Overman, L. E.; Pairaudeau, G. J. Am. Chem. Soc. 1993, 115, 9293. doi:10.1021/ja00073a057
[2] Winkler, J. D.; Rouse, M. B.; Greaney, M. F.; Harison, S. J.; Jeon, Y. T. J. Am. Chem. Soc. 2002, 124, 9726. DOI: 10.1021/ja026600a