Iron(III)-Catalyzed C-H Functionalization: ortho-Benzoyloxylation of N,N-Dialkylanilines and Its Application to 1,4-Benzoxazepines

• Published in: European journal of organic chemistry Vol. 2014; no. 35; pp. 7839 - 7849
• Main Authors: Chiranjeevi, Barreddi, Vinayak, Botla, Parsharamulu, Thupakula, PhaniBabu, Vemulapalli S., Jagadeesh, Bharatam, Sridhar, Balasubramanian, Chandrasekharam, Malapaka
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.12.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: C-H functionalization; Chemistry; Chemistry, Organic; Cyclization; Hydroxylation; Iron; Physical Sciences; Science & Technology; Synthetic methods; TARGET; DESIGN; Hydroxylation; BOND FORMATION; Iron; C-H functionalization; DISCOVERY; POTENT; AMINATION; Cyclization; PEROXIDES; Synthetic methods; INHIBITORS; DERIVATIVES; ACCESS
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201402751

A C–O bond‐formation reaction that proceeds through C–H functionalization of N,N‐dialkylanilines at the ortho‐position is presented. The iron‐catalyzed selective ortho‐benzoyloxylation follows a polar Friedel–Crafts‐like mechanism and is sensitive to the nucleophilicity of the anilines. The benzoyloxylation of a variety of N,N‐disubstituted anilines and N‐phenyl heterocycles is carried out under extremely mild conditions. Furthermore, the methodology has been successfully employed for the generation of 1,4‐benzoxazepines and o‐aminophenols. An iron‐catalyzed C–O bond‐formation reaction that proceeds through C–H functionalization of N,N‐dialkylanilines at the ortho‐position is presented. The reaction is carried out under extremely mild conditions. The methodology has been successfully employed for the generation of 1,4‐benzoxazepines and o‐aminophenols.