[3,3]-Sigmatropic Rearrangement of Cyclopropenylcarbinyl Cyanates: Access to Alkylidene(aminocyclopropane) Derivatives

Guillaume Ernouf; Jean-Louis Brayer; Benoît Folléas; Jean-Pierre Demoute; Christophe Meyer; Janine Cossy

doi:10.1002/chem.201803231

[3,3]-Sigmatropic Rearrangement of Cyclopropenylcarbinyl Cyanates: Access to Alkylidene(aminocyclopropane) Derivatives

Chemistry. 2018 Oct 9;24(56):15104-15111. doi: 10.1002/chem.201803231. Epub 2018 Sep 10.

Authors

Guillaume Ernouf¹, Jean-Louis Brayer², Benoît Folléas², Jean-Pierre Demoute², Christophe Meyer¹, Janine Cossy¹

Affiliations

¹ Laboratory of Organic Chemistry, Institute of Chemistry, Biology, and Innovation (CBI) ESPCI Paris, CNRS (UMR 8231), PSL Research University, 10 rue Vauquelin, 75231, Paris Cedex 05, France.
² Diverchim, 6 rue du Noyer, ZAC du Moulin, 95734, Roissy CDG, France.

PMID: 30021051
DOI: 10.1002/chem.201803231

Abstract

Cyclopropenylcarbinyl cyanates, generated in situ by dehydration of the corresponding carbamates, underwent an efficient and stereoselective [3,3]-sigmatropic rearrangement leading to the corresponding alkylidene(isocyanatocyclopropanes), which could be converted into various alkylidene(aminocyclopropane) derivatives in a one-pot manner. This transformation complements the repertoire of sigmatropic rearrangements involving cyclopropenylcarbinol derivatives and in particular, the previously reported Overman rearrangement of cyclopropenylcarbinyl trichloroacetimidates.

Keywords: cyanates; isocyanates; sigmatropic rearrangement; strained rings; synthetic methods.