Iridium-catalyzed isomerization of N-sulfonyl aziridines to allyl amines
Cabré, Albert (Institut de Recerca Biomèdica)
Sciortino, Giuseppe (Universitat Autònoma de Barcelona. Departament de Química)
Ujaque Pérez, Gregori (Universitat Autònoma de Barcelona. Departament de Química)
Verdaguer, Xavier (Universitat de Barcelona. Departament de Química Inorgànica i Orgànica)
Lledós, Agustí (Universitat Autònoma de Barcelona. Departament de Química)
Riera, Antoni (Universitat de Barcelona. Departament de Química Inorgànica i Orgànica)

Date:	2018
Abstract:	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.
Grants:	Ministerio de Economía y Competitividad CTQ2017-87840-P Ministerio de Economía y Competitividad CTQ2017-87889-P
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Subject:	Allyl group ; Amines ; Aziridines ; Catalysts ; Isomerization
Published in:	Organic Letters, Vol. 20, issue 18 (Sep. 2018) , p. 5747-5751, ISSN 1523-7052

DOI: 10.1021/acs.orglett.8b02450
PMID: 30188732

Postprint 6 p, 433.9 KB

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