Synthesis 2013; 45(15): 2079-2087
DOI: 10.1055/s-0033-1339280
practical synthetic procedures
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Synthesis of Amines through Rhodium-Catalyzed C–H Amination with Sulfonimidoylnitrenes

Benjamin Darses
a  Institut de Chimie des Substances Naturelles, UPR 2301 CNRS, Centre de Recherche de Gif, Avenue de la Terrasse, 91198 Gif-sur-Yvette, France   Fax: +33(1)69077247   Email: philippe.dauban@cnrs.fr
,
Amanda G. Jarvis
a  Institut de Chimie des Substances Naturelles, UPR 2301 CNRS, Centre de Recherche de Gif, Avenue de la Terrasse, 91198 Gif-sur-Yvette, France   Fax: +33(1)69077247   Email: philippe.dauban@cnrs.fr
,
Abdel-Kader Mafroud
a  Institut de Chimie des Substances Naturelles, UPR 2301 CNRS, Centre de Recherche de Gif, Avenue de la Terrasse, 91198 Gif-sur-Yvette, France   Fax: +33(1)69077247   Email: philippe.dauban@cnrs.fr
b  Sanofi-Aventis Recherche et Développement, Unité Exploratoire, 1 Avenue Pierre Brossolette, 91385 Chilly-Mazarin, France
,
Geneviève Estenne-Bouhtou
b  Sanofi-Aventis Recherche et Développement, Unité Exploratoire, 1 Avenue Pierre Brossolette, 91385 Chilly-Mazarin, France
,
Gihad Dargazanli
b  Sanofi-Aventis Recherche et Développement, Unité Exploratoire, 1 Avenue Pierre Brossolette, 91385 Chilly-Mazarin, France
,
Philippe Dauban*
a  Institut de Chimie des Substances Naturelles, UPR 2301 CNRS, Centre de Recherche de Gif, Avenue de la Terrasse, 91198 Gif-sur-Yvette, France   Fax: +33(1)69077247   Email: philippe.dauban@cnrs.fr
› Author Affiliations
Further Information

Publication History

Received: 05 April 2013

Accepted after revision: 27 May 2013

Publication Date:
27 June 2013 (online)

Abstract

An efficient asymmetric C–H amination of benzylic and allylic substrates, as well as of adamantane derivatives, through catalytic C–H insertion of a chiral nitrene is reported. The reaction involves a chiral rhodium(II) complex, an iodine(III) oxidant, and a sulfonimid­amide as a nitrene precursor. Experimental protocols for the preparation of the reagents and the catalytic nitrene are provided. The C–H amination can provide the corresponding amino derivatives on a gram scale. Various methods for the cleavage of the sulfonimidoyl group to give the corresponding tert-butoxycarbonyl- or acetyl-protected optically pure amines are also described.

Supporting Information

 
  • References

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