visitant ::
identificació
|
|||||||||||||||
Cerca | Lliura | Ajuda | Servei de Biblioteques | Sobre el DDD | Català English Español |
Pàgina inicial > Articles > Articles publicats > Iridium-catalyzed isomerization of N-sulfonyl aziridines to allyl amines |
Data: | 2018 |
Resum: | The Crabtree's reagent catalyzes the isomerization of N-sulfonyl 2,2-disubstituted aziridines to allyl amines. The selectivity of allyl amine vs imine is very high (up to 99/1). The unprecedented isomerization takes place in mild conditions without activation of the catalyst by hydrogen. The mechanism has been studied computationally by DFT calculations; instead of the usual hydrogenation of COD, the catalytic species is formed by a loss of the pyridine ligand. Approaching of aziridine to this unsaturated species leads to a carbocation intermediate through a low energy barrier. A metal-mediated tautomerization involving sequentially γ-H elimination and N-H reductive elimination affords selectively the allyl amine. The readiness of the CγH bond to participate in the H elimination step accounts for the selectivity toward the allyl amine product. |
Ajuts: | Ministerio de Economía y Competitividad CTQ2017-87840-P Ministerio de Economía y Competitividad CTQ2017-87889-P |
Drets: | Tots els drets reservats. |
Llengua: | Anglès |
Document: | Article ; recerca ; Versió acceptada per publicar |
Matèria: | Allyl group ; Amines ; Aziridines ; Catalysts ; Isomerization |
Publicat a: | Organic Letters, Vol. 20, issue 18 (Sep. 2018) , p. 5747-5751, ISSN 1523-7052 |
Postprint 6 p, 433.9 KB |