Chemo-, regio-, and stereoselective silver-catalyzed aziridination of dienes: Scope, mechanistic studies, and ring-opening reactions

Josep Llaveria, Álvaro Beltrán, W. M.C. Sameera, Abel Locati, M. Mar Díaz-Requejo, M. Isabel Matheu, Sergio Castillón, Feliu Maseras, Pedro J. Pérez

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51 Citations (Scopus)

Abstract

Silver complexes bearing trispyrazolylborate ligands (Tpx) catalyze the aziridination of 2,4-diene-1-ols in a chemo-, regio-, and stereoselective manner to give vinylaziridines in high yields by means of the metal-mediated transfer of NTs (Ts = p-toluensulfonyl) units from PhI=NTs. The preferential aziridination occurs at the double bond neighboring to the hydroxyl end in ca. 9:1 ratios that assessed a very high degree of regioselectivity. The reaction with the silver-based catalysts proceeds in a stereospecific manner, i.e., the initial configuration of the C=C bond is maintained in the aziridine product (cis or trans). The degree of regioselectivity was explained with the aid of DFT studies, where the directing effect of the OH group of 2,4-diene-1-ols plays a key role. Effective strategies for ring-opening of the new aziridines, deprotection of the Ts group, and subsequent formation of β-amino alcohols have also been developed. © 2014 American Chemical Society.
Original languageEnglish
Pages (from-to)5342-5350
JournalJournal of the American Chemical Society
Volume136
Issue number14
DOIs
Publication statusPublished - 9 Apr 2014

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    Llaveria, J., Beltrán, Á., Sameera, W. M. C., Locati, A., Díaz-Requejo, M. M., Matheu, M. I., Castillón, S., Maseras, F., & Pérez, P. J. (2014). Chemo-, regio-, and stereoselective silver-catalyzed aziridination of dienes: Scope, mechanistic studies, and ring-opening reactions. Journal of the American Chemical Society, 136(14), 5342-5350. https://doi.org/10.1021/ja412547r