Isomérisation thermique de vinyl-2 aziridines N-substituées

Abstract

The thermal isomerization of 2-vinylaziridines, variously substituted on the ring and the double bond, has been studied. The nature of the products formed depends on the nature of the substituents in positions 1 and 3. If the ring carbon-3 carries a phenyl substituent, the thermolysis yields, in most cases, a Δ-2-pyrroline. With unsubstituted or 3-alkylaziridines the reaction proceeds, depending on the nature of the substituent on the nitrogen, either to an ethylene imine or to a mixture of Δ-2- and Δ-3-pyrrolines. Mechanisms to interpret the experimental results are proposed. [Journal translation]

Synthesis and Applications of Vinylaziridines and Ethynylaziridines

“…Thermal rearrangement of 2-vinylaziridine 380 bearing an electron-withdrawing group on its nitrogen atom in refluxing decalin afforded 2-pyrroline 381 as the major product, along with a small amount of 3-pyrroline derivative 382 (Scheme ) . A similar reaction has also been reported involving N -alkyl-2-phenyl-3-vinylaziridines 383 . On the basis of these reports, it is clear that the nature of products formed from these reactions is dependent on the nature of substituents on the aziridine ring as well as reaction conditions.…”

Synthesis and Aza-[2,3]-Wittig Rearrangements of Vinylaziridines: Scope and Limitations

“…Included in this study are also derivatives 35 and 36 the preparation of which has been previously described . Since it was noted that several of these trans - 2,3-trisubstituted vinylaziridines were prone to undergo thermal [1,5]-hydrogen shifts, these compounds were prepared and processed as quickly as possible, avoiding any prolonged storage or handling at or above room temperature …”

One‐Pot Synthesis of Tri‐ and Tetrasubstituted Pyridines by Sequential Ring‐Opening/Cyclization/Oxidation of N‐Arylmethyl 3‐Aziridinylpropiolate Esters

“…It is known that N-benzyl vinylaziridine causes a [1,5] hydrogen shift under heating to afford the allyl imines. [10] We expected that similar reactions could occur in the case of 1. When N-benzyl 3-aziridinylpropiolate ester (1 a), having a cyclohexyl group on the aziridine ring, was heated in toluene at 100 8C for 9 hours, the desired reaction formed the allenyl imine 2 a in quantitative yield ( Table 1, entry 1).…”