Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized Olefins Using Fluoride Ion

• Published in: Journal of the American Chemical Society Vol. 138; no. 35; pp. 11360 - 11367
• Main Authors: Lu, Deng-Fu, Zhu, Cheng-Liang, Sears, Jeffrey D, Xu, Hao
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 07.09.2016; Amer Chemical Soc
• Subjects: Alkenes - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Fluorides - chemistry; Halogenation; Iron - chemistry; Physical Sciences; Science & Technology; Stereoisomerism; STYRENES; DEOXYFLUORINATION; FUNCTIONALIZED HYDROXYLAMINES; BETA-FLUOROAMINES; HYDROFLUORINATION; FLUORINATION; AZIRIDINES; METAL-FREE; UNACTIVATED ALKENES; DIFLUORINATION
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.6b07221

We herein report a new catalytic method for intermolecular olefin aminofluorination using earth-abundant iron catalysts and nucleophilic fluoride ion. This method tolerates a broad range of unfunctionalized olefins, especially nonstyrenyl olefins that are incompatible with existing olefin aminofluorination methods. This new iron-catalyzed process directly converts readily available olefins to internal vicinal fluoro carbamates with high regioselectivity (N vs F), many of which are difficult to prepare using known methods. Preliminary mechanistic studies demonstrate that it is possible to exert asymmetric induction using chiral iron catalysts and that both an iron-nitrenoid and carbocation species may be reactive intermediates.