Iridium-Catalyzed Isomerization of N-Sulfonyl Aziridines to Allyl Amines

Albert Cabré, Giuseppe Sciortino, Gregori Ujaque, Xavier Verdaguer, Agustí Lledós, Antoni Riera

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12 Citations (Scopus)

Abstract

Copyright © 2018 American Chemical Society. 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.
Original languageEnglish
Pages (from-to)5747-5751
JournalOrganic Letters
Volume20
DOIs
Publication statusPublished - 21 Sep 2018

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