ol8b03702_si_001.pdf (15.21 MB)
Ligand-Free Iron-Catalyzed C–F Amination of Diarylamines: A One-Pot Regioselective Synthesis of Diaryl Dihydrophenazines
journal contribution
posted on 2019-01-10, 16:24 authored by Yuma Aoki, Harry M. O’Brien, Hiroto Kawasaki, Hikaru Takaya, Masaharu NakamuraA 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.