Diamidocarbenes as versatile and reversible [2 + 1] cycloaddition reagents

Abstract

We describe the synthesis of a variety of cyclopropanes and epoxides by combining a readily accessible and isolable N,N′-diamidocarbene with a range of structurally and electronically diverse olefins and aldehydes, including electron-rich derivatives. Surprisingly, the cyclopropanation and epoxidation reactions were discovered to be rapid and thermally reversible at relatively low temperatures, two features often desired for applications that utilize dynamic covalent chemistry. In addition, a diamidocyclopropane derivative prepared via this method was hydrolysed successfully to form the corresponding linear carboxylic acid in a metal- and carbon monoxide-free hydrocarboxylation reaction. As such, diamidocarbenes are expected to find utility in the synthesis of cyclopropanes, epoxides and their derivatives, as well as in dynamic covalent chemistry applications. An isolable diamidocarbene is shown to participate in reversible [2+1] cycloadditions with a variety of both electron-deficient and electron-rich olefins and aldehydes. Subsequent hydrolysis of a N,N′-diamidocyclopropane derived from styrene afforded the corresponding linear carboxylic acid, effectively establishing a metal- and carbon monoxide-free, anti-Markovnikov olefin hydrocarboxylation reaction.

Cite this article

Moerdyk, J., Bielawski, C. Diamidocarbenes as versatile and reversible [2 + 1] cycloaddition reagents. Nature Chem 4, 275–280 (2012). https://doi.org/10.1038/nchem.1267

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