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

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 c...

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Bibliographic Details
Published in:Organic letters 2019-01, Vol.21 (2), p.461-464
Main Authors: Aoki, Yuma, O’Brien, Harry M, Kawasaki, Hiroto, Takaya, Hikaru, Nakamura, Masaharu
Format: Article
Language:English
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Summary: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.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.8b03702