Rh 2 (II)-Catalyzed Intermolecular N -Aryl Aziridination of Olefins Using Nonactivated N Atom Precursors

• Published in: Journal of the American Chemical Society Vol. 143; no. 45; pp. 19149 - 19159
• Main Authors: Deng, Tianning, Mazumdar, Wrickban, Yoshinaga, Yuki, Patel, Pooja B, Malo, Dana, Malo, Tala, Wink, Donald J, Driver, Tom G
• Format: Journal Article
• Language: English
• Published: United States 17.11.2021
• Subjects: Alkenes - chemistry; Aniline Compounds - chemistry; Aziridines - chemical synthesis; Catalysis; Cyclization; Oxidation-Reduction; Rhodium - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.1c09229

The development of the first intermolecular Rh (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 -aryl nitrene fragment from the iminoiodinane intermediate to a Rh (II) carboxylate catalyst; in the absence of a catalyst only diaryldiazene formation was observed. This -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 (II)-catalyzed N atom transfer to the olefin is stereospecific as well as chemo- and diastereoselective to produce the -aryl aziridine as the only amination product. Because the chemistry of nonactivated -aryl aziridines is underexplored, the reactivity of -aryl aziridines was explored toward a range of nucleophiles to stereoselectively access privileged 1,2-stereodiads unavailable from epoxides, and removal of the -2,4-dinitrophenyl group was demonstrated to show that functionalized primary amines can be constructed.