American Chemical Society
ol8b03702_si_001.pdf (15.21 MB)

Ligand-Free Iron-Catalyzed C–F Amination of Diarylamines: A One-Pot Regioselective Synthesis of Diaryl Dihydrophenazines

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journal contribution
posted on 2019-01-10, 16:24 authored by Yuma Aoki, Harry M. O’Brien, Hiroto Kawasaki, Hikaru Takaya, Masaharu Nakamura
A one-pot synthesis of various 5,10-diaryl-5,10-dihydrophenazines (DADHPs) from diarylamines has been achieved by using an iron-catalyzed C–F amination. Homodimerization of magnesium diarylamides, followed by defluorinative intramolecular cyclization (double ortho C–F amination) in the presence of catalytic FeCl2 and stoichiometric 1,2-dibromoethane, affords the corresponding DADHPs with complete regiocontrol. The unique high reactivity of fluorine over other halogens indicates that amination proceeds via an SNAr mechanism facilitated by iron.