title: Radical amination of C(sp3)-H bonds using N-hydroxyphthalimide and dialkyl azodicarboxylate.
abstract: A direct conversion of C(sp(3))-H bonds to C(sp(3))-N bonds has been achieved by utilizing catalytic N-hydroxyphthalimide (NHPI) and stoichiometric dialkyl azodicarboxylate. NHPI functions as a precursor of the electron-deficient phthalimide N-oxyl radical (PINO) to abstract hydrogens, and dialkyl azodicarboxylate acts as a trapping agent of the resultant carbon radical to generate the hydrazine derivatives. This C-H amination proceeds in a highly chemoselective manner with a wide applicability to functionalize benzylic, propargylic, and aliphatic C-H bonds. Furthermore, the obtained hydrazine compounds were readily converted to the corresponding carbamates or amines. Hence, the present protocol for direct introduction of the nitrogen functionality serves as a powerful tool for efficient construction of nitrogen-substituted natural products and pharmaceuticals.
authors.affiliation: Graduate School of Pharmaceutical Sciences,  The University of Tokyo , Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Yuuki
authors.initials: Y
authors.lastname: Amaoka
authors.forename: Shin
authors.initials: S
authors.lastname: Kamijo
authors.forename: Tamaki
authors.initials: T
authors.lastname: Hoshikawa
authors.forename: Masayuki
authors.initials: M
authors.lastname: Inoue
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D000586:Amination; D001391:Azo Compounds / Q000737:chemistry*; D002384:Catalysis; D006860:Hydrogen Bonding; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D010797:Phthalimides / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000473:Alkanes; D001391:Azo Compounds; D010797:Phthalimides; C525414:phthalimide-N-oxyl; C037437:N-hydroxyphthalimide; D009584:Nitrogen