Rearrangement thermique de cycles a 3 chainons α-ethyleniques α'-acetyleniques trans

Epimerization of Cyclic Vinylphosphirane Complexes: The Intermediacy of Biradicals

“…Thermal isomerizations of vinylaziridines have been shown to yield 3-pyrrolines, but no mechanistic detail was provided in these studies. The same applies to the Cope rearrangements of divinylaziridines and the thermal isomerizations of vinylacetyloxiranes …”

Synthesis and Applications of Vinylaziridines and Ethynylaziridines

“…In a similar manner to vinylaziridines, ethynylaziridines can also be synthesized by the cyclization of 1,2-amino alcohols and related compounds, which can be readily prepared from the corresponding epoxides. In 1977, Manisse and Chuche reported the preparation of 2-ethynyl-3-vinylaziridine 155 via the ring-opening reaction of epoxide 153 and the intramolecular cyclization of erythro - 154 using PPh 3 and CCl 4 (Scheme ). A related synthesis has also been reported involving the construction of ethynylaziridines from epoxides that do not possess a vinyl group .…”

Allenylzinc reagents: new trends and synthetic applications

“…When we started our study, only a few syntheses of acetylenic aziridines had been reported involving the reaction of a nitrene or a nitrene equivalent with an enyne, 84,85, the condensation of a propargylic sulfonium ylide [86][87][88] or of a lithiated cinnamyl chloride with imines, 89 or from acetylenic epoxides in a two-step procedure. 90 As for us, we envisaged the formation of acetylenic aziridines through the reaction of (AE)-Zn-1 with imines followed by the ring closure of the a-chloro amine intermediates. N-Benzyl and N-trimethylsilylimines 25 and 26 were used in this reaction.…”