| Autor: |
Deng T; Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, MC 111, Chicago, Illinois 60607, United States., Mazumdar W; Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, MC 111, Chicago, Illinois 60607, United States., Yoshinaga Y; Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, MC 111, Chicago, Illinois 60607, United States., Patel PB; Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, MC 111, Chicago, Illinois 60607, United States., Malo D; Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, MC 111, Chicago, Illinois 60607, United States.; Hinsdale South High School, 7401 Clarendon Hills Road, Darien, Illinois 60561, United States., Malo T; Hinsdale South High School, 7401 Clarendon Hills Road, Darien, Illinois 60561, United States., Wink DJ; Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, MC 111, Chicago, Illinois 60607, United States., Driver TG; Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, MC 111, Chicago, Illinois 60607, United States. |
| Abstrakt: |
The development of the first intermolecular Rh 2 (II)-catalyzed aziridination of olefins using anilines as nonactivated N atom precursors and an iodine(III) reagent as the stoichiometric oxidant is reported. This reaction requires the transfer of an N -aryl nitrene fragment from the iminoiodinane intermediate to a Rh 2 (II) carboxylate catalyst; in the absence of a catalyst only diaryldiazene formation was observed. This N -aryl aziridination is general and can be successfully realized by using as little as 1 equiv of the olefin. Di-, tri-, and tetrasubstituted cyclic or acylic olefins can be employed as substrates, and a range of aniline and heteroarylamine N atom precursors are tolerated. The Rh 2 (II)-catalyzed N atom transfer to the olefin is stereospecific as well as chemo- and diastereoselective to produce the N -aryl aziridine as the only amination product. Because the chemistry of nonactivated N -aryl aziridines is underexplored, the reactivity of N -aryl aziridines was explored toward a range of nucleophiles to stereoselectively access privileged 1,2-stereodiads unavailable from epoxides, and removal of the N -2,4-dinitrophenyl group was demonstrated to show that functionalized primary amines can be constructed. |
