Issue 12, 2011

Chemoselective intramolecular allylic C–H aminationversus C[double bond, length as m-dash]C aziridination through Co(ii)-based metalloradical catalysis

Abstract

Excellent chemoselectivity for intramolecular allylic C–H aminationversus C[double bond, length as m-dash]C aziridination was achieved through Co(II)-based metalloradical catalysis. Metalloradical catalyst [Co(P1)], the cobalt(II) complex of D2h-symmetric porphyrin 3,5-DitBu-IbuPhyrin, was shown to be highly effective for selective intramolecular allylic C–H amination of both N-bishomoallylic and N-allylic sulfamoyl azides. The Co(II)-catalyzed intramolecular 1,6-C–H amination of these azides provides a general and efficient method to access the synthetically useful allylic 1,3-diamines under neutral and non-oxidative conditions, without complication from the competitive olefin aziridination. The origin of this remarkable chemoselectivity has direct relevance to the radical mechanism of Co(II)-based metalloradical amination.

Graphical abstract: Chemoselective intramolecular allylic C–H aminationversus C [[double bond, length as m-dash]] C aziridination through Co(ii)-based metalloradical catalysis

Supplementary files

Article information

Article type
Edge Article
Submitted
15 Jun 2011
Accepted
30 Aug 2011
First published
22 Sep 2011

Chem. Sci., 2011,2, 2361-2366

Chemoselective intramolecular allylic C–H aminationversus C[double bond, length as m-dash]C aziridination through Co(II)-based metalloradical catalysis

H. Lu, H. Jiang, Y. Hu, L. Wojtas and X. P. Zhang, Chem. Sci., 2011, 2, 2361 DOI: 10.1039/C1SC00366F

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