Redox-Active Reagents for Photocatalytic Generation of the OCF 3 Radical and (Hetero)Aryl C-H Trifluoromethoxylation

The trifluoromethoxy (OCF ) radical is of great importance in organic chemistry. Yet, the catalytic and selective generation of this radical at room temperature and pressure remains a longstanding challenge. Herein, the design and development of a redox-active cationic reagent (1) that enables the f...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-10, Vol.57 (42), p.13795-13799
Main Authors: Zheng, Weijia, Lee, Johnny W, Morales-Rivera, Cristian A, Liu, Peng, Ngai, Ming-Yu
Format: Article
Language:English
Subjects:
Catalysis
Chlorofluorocarbons, Methane - chemistry
Indicators and Reagents - chemistry
Oxidation-Reduction
Photochemical Processes
Protons
Structure-Activity Relationship
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Summary:The trifluoromethoxy (OCF ) radical is of great importance in organic chemistry. Yet, the catalytic and selective generation of this radical at room temperature and pressure remains a longstanding challenge. Herein, the design and development of a redox-active cationic reagent (1) that enables the formation of the OCF radical in a controllable, selective, and catalytic fashion under visible-light photocatalytic conditions is reported. More importantly, the reagent allows catalytic, intermolecular C-H trifluoromethoxylation of a broad array of (hetero)arenes and biorelevant compounds. Experimental and computational studies suggest single electron transfer (SET) from excited photoredox catalysts to 1 resulting in exclusive liberation of the OCF radical. Addition of this radical to (hetero)arenes gives trifluoromethoxylated cyclohexadienyl radicals that are oxidized and deprotonated to afford the products of trifluoromethoxylation.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201808495