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Redox‐Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C−H Di‐ and Trifluoromethoxylation
Author(s) -
Lee Johnny W.,
Lim Sanghyun,
Maienshein Daniel N.,
Liu Peng,
Ngai MingYu
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202009490
Subject(s) - redox , catalysis , aryl , chemistry , photochemistry , inorganic chemistry , organic chemistry , alkyl
Applications of TEMPO . catalysis for the development of redox‐neutral transformations are rare. Reported here is the first TEMPO . ‐catalyzed, redox‐neutral C−H di‐ and trifluoromethoxylation of (hetero)arenes. The reaction exhibits a broad substrate scope, has high functional‐group tolerance, and can be employed for the late‐stage functionalization of complex druglike molecules. Kinetic measurements, isolation and resubjection of catalytic intermediates, UV/Vis studies, and DFT calculations support the proposed oxidative TEMPO . /TEMPO + redox catalytic cycle. Mechanistic studies also suggest that Li 2 CO 3 plays an important role in preventing catalyst deactivation. These findings will provide new insights into the design and development of novel reactions through redox‐neutral TEMPO . catalysis.