title: Direct stereospecific synthesis of unprotected N-H and N-Me aziridines from olefins.
abstract: Despite the prevalence of the N-H aziridine motif in bioactive natural products and the clear advantages of this unprotected parent structure over N-protected derivatives as a synthetic building block, no practical methods have emerged for direct synthesis of this compound class from unfunctionalized olefins. Here, we present a mild, versatile method for the direct stereospecific conversion of structurally diverse mono-, di-, tri-, and tetrasubstituted olefins to N-H aziridines using O-(2,4-dinitrophenyl)hydroxylamine (DPH) via homogeneous rhodium catalysis with no external oxidants. This method is operationally simple (i.e., one-pot), scalable, and fast at ambient temperature, furnishing N-H aziridines in good-to-excellent yields. Likewise, N-alkyl aziridines are prepared from N-alkylated DPH derivatives. Quantum-mechanical calculations suggest a plausible Rh-nitrene pathway.
authors.affiliation: Division of Chemistry, Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, TX 75390, USA.
authors.forename: Jawahar L
authors.initials: JL
authors.lastname: Jat
authors.forename: Mahesh P
authors.initials: MP
authors.lastname: Paudyal
authors.forename: Hongyin
authors.initials: H
authors.lastname: Gao
authors.forename: Qing-Long
authors.initials: QL
authors.lastname: Xu
authors.forename: Muhammed
authors.initials: M
authors.lastname: Yousufuddin
authors.forename: Deepa
authors.initials: D
authors.lastname: Devarajan
authors.forename: Daniel H
authors.initials: DH
authors.lastname: Ess
authors.forename: László
authors.initials: L
authors.lastname: Kürti
authors.forename: John R
authors.initials: JR
authors.lastname: Falck
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001388:Aziridines / Q000138:chemical synthesis*; D001688:Biological Products / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry; D006898:Hydroxylamines / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry
chemical_list: D000475:Alkenes; D001388:Aziridines; D001688:Biological Products; D006898:Hydroxylamines; D006859:Hydrogen; C050904:O-(2,4-dinitrophenyl)hydroxylamine; D009584:Nitrogen