title: Iron-catalyzed intramolecular allylic C-H amination.
abstract: A highly selective C-H amination reaction under iron catalysis has been developed. This novel system, which employs an inexpensive, nontoxic [Fe(III)Pc] catalyst (typically used as an industrial ink additive), displays a strong preference for allylic C-H amination over aziridination and all other C-H bond types (i.e., allylic > benzylic > ethereal > 3° > 2° ≫ 1°). Moreover, in polyolefinic substrates, the site selectivity can be controlled by the electronic and steric character of the allylic C-H bond. Although this reaction is shown to proceed via a stepwise mechanism, the stereoretentive nature of C-H amination for 3° aliphatic C-H bonds suggests a very rapid radical rebound step.
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: Shauna M
authors.initials: SM
authors.lastname: Paradine
authors.forename: M Christina
authors.initials: MC
authors.lastname: White
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D000586:Amination; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D005290:Ferric Compounds / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D000498:Allyl Compounds; D000588:Amines; D005290:Ferric Compounds