Aza‐MIRC Reactions of Sulfonyl‐Activated Hydroxycarbamates with α,β‐Difunctionalised Acrylates

Abstract

Highly functionalised aziridines are readily obtained in high yields (up to 95%) under mild conditions from the reaction of trisubstituted olefins bearing different groups with nosyloxycarbamates in the presence of calcium oxide. We propose a possible explanation for the different reactivities observed between these olefins and the aminating agents. Reagent‐controlled stereoselective amination reactions led to the expected products with high conversions and purities. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

A Remarkably Efficient Phase-Transfer Catalyzed Amination of α-Bromo-α, β-Unsaturated Ketones in Water

“…Another problem is that aziridine moieties are often introduced after multistep syntheses, and thus, direct aziridination is a goal of considerable importance in organic chemistry [2,7]. Moreover, convenient protocols that afford optically active aziridines are of a high value to the academic, natural product, agrochemical, pharmaceutical, and medicinal chemistry communities [8][9][10].…”

Synthesis of N-Protected Cyano Aziridines

“…It is noteworthy that high chemoselectivity in the amination reaction is induced by CaO even in the presence of the cyano group, that is reported to give also the corresponding oxadiazoles under homogeneous reaction conditions. 12 Aziridines were also obtained starting from a,b-unsaturated 1,1-dinitriles 1k-n (entries [11][12][13][14], showing no differences in reactivity and yields.…”

“…In order to extend the study of the sulfonyl-activated hydroxycarbamate reactivity, reagents with Cbz, 13 Boc, 14 or Fmoc 15 groups rather than ethoxycarbonyl group were tested in the reactions on some a,b-unsaturated nitriles 1. Table 2, different N-protected 2-cyano aziridine-2-carboxylates and 2,2-dicyano aziridines were obtained in high yields and with complete stereoselectivity (entries 1-3 and 5-7).…”

“…In order to extend the study of the sulfonyl-activated hydroxycarbamate reactivity, reagents with Cbz, 13 Boc, 14 or Fmoc 15 groups rather than ethoxycarbonyl group were tested in the reactions on some a,b-unsaturated nitriles 1.…”

“…In summary, a general procedure for the synthesis of highly functionalized aziridines was reported. 4, 14.0, 14.2, 23.3, 38.6, 51.3, 63.4, 64.1, 113.3, 157.2, 162.6 13 C NMR (50 MHz, CDCl 3 ): d = 9.9, 14.0,…”