Coupling N–H Deprotonation, C–H Activation, and Oxidation: Metal-Free C(sp3)–H Aminations with Unprotected Anilines

• Published in: Journal of the American Chemical Society Vol. 139; no. 45; pp. 16210 - 16221
• Main Authors: Evoniuk, Christopher J, Gomes, Gabriel dos Passos, Hill, Sean P, Fujita, Satoshi, Hanson, Kenneth, Alabugin, Igor V
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 15.11.2017; Amer Chemical Soc
• Subjects: acidity; amination; aromatic compounds; carbon-hydrogen bond activation; chemical bonding; Chemistry; Chemistry, Multidisciplinary; dimethylformamide; heterocyclic nitrogen compounds; oxidants; oxidation; oxygen; Physical Sciences; Science & Technology; transition elements; AROMATIC-HYDROCARBONS; DENSITY FUNCTIONALS; CHEMICAL-SHIFTS NICS; RADICAL STABILITY; SOMO-HOMO CONVERSION; EFFICIENT SYNTHESIS; CONNECTOR GROUPS; SINGLET OXYGEN; SYNTHETIC APPROACH; INTRAMOLECULAR ADDITION

An intramolecular oxidative C­(sp3)–H amination from unprotected anilines and C­(sp3)–H bonds readily occurs under mild conditions using t-BuOK, molecular oxygen and N,N-dimethylformamide (DMF). Success of this process, which requires mildly acidic N–H bonds and an activated C­(sp3)–H bond (BDE <...