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Trifluoromethanesulfonyl Azide:  A Powerful Reagent for the Preparation of α-Nitro-α-diazocarbonyl Derivatives

André B. Charette*, Ryan P. Wurz and Thierry Ollevier

*Département de Chimie, Université de Montréal, P.O. Box 6128, Station Downtown, Montréal (Québec) Canada, H3C 3J7, Email: andre.charetteumontreal.ca

A. B. Charette, R. P. Wurz, T. Ollevier, J. Org. Chem., 2000, 65, 9252-9254.

DOI: 10.1021/jo001235w


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Abstract

The reaction of triflyl azide with α-nitrocarbonyl compounds in the presence of pyridine enables a highly efficient preparation of α-nitro-α-diazocarbonyl derivatives.

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Details

The document discusses the development of a highly efficient method for preparing α-nitro-α-diazocarbonyl derivatives using trifluoromethanesulfonyl (triflyl) azide and pyridine. These derivatives are valuable precursors for various transition metal-catalyzed processes, including cyclopropanations and X-H insertion reactions. Traditional methods for synthesizing these compounds were inefficient or involved unstable reagents. The new method involves reacting ethyl nitroacetate with triflyl azide in acetonitrile, yielding ethyl α-nitro-α-diazoacetate in 88% yield. This procedure was successfully applied to various α-nitro-ester and α-nitroketone precursors, producing the desired diazo compounds with high efficiency. The document also provides detailed experimental procedures and safety precautions due to the explosive nature of the compounds involved. The research was supported by NSERC (Canada), Merck Frosst, Boehringer Ingelheim (Canada) Ltd., and the Université de Montréal. The findings contribute to the field of organic synthesis, offering a reliable method for producing structurally diverse α-nitro-α-diazocarbonyl derivatives, which are useful in stereoselective synthesis and other chemical processes.


Key Words

Diazo esters, Diazo ketones


ID: J42-Y2000