Visible-Light Photoredox Decarboxylation of Perfluoroarene Iodine(III) Trifluoroacetates for C–H Trifluoromethylation of (Hetero)arenes

Abstract

A scalable and operationally simple decarboxylative trifluoromethylation of (hetero)arenes with easily accessible C 6 F 5 I(OCOCF 3 ) 2 under photoredox catalysis has been developed. This method is tolerant of various (hetero)arenes and functional groups. Notably, C 6 F 5 I is recycled from the decarboxylation reaction and further used for the preparation of C 6 F 5 I(OCOCF 3 ) 2 . The combination of photoredox catalysis and hypervalent iodine reagent provides a practical approach for the application of trifluoroacetic acid in trifluoromethylation reactions.

Recent Synthetic Applications of the Hypervalent Iodine(III) Reagents in Visible-Light-Induced Photoredox Catalysis

“…In 2018, Qing and coworkers reported the decarboxylative trifluoromethylation of (hetero)arenes using ArI(OCOCF 3 ) 2 as CF 3 source by ruthenium photoredox catalysis (Yang et al, 2018 ) ( Figure 3A ). A series of fluorinated ArI(OCOCF 3 ) 2 were examined and C 6 F 5 I(OCOCF 3 ) 2 (FPIFA) was proved to be the best option.…”

Rhenium‐Catalyzed Decarboxylative Tri‐/Difluoromethylation of Styrenes with Fluorinated Carboxylic Acid‐Derived Hypervalent Iodine Reagents

“…Notably, Maruoka and Qing have elegantly reported photo-promoted introduction of CF 2 H and CF 3 into (hetero)arenes through decarboxylation of fluorine-containing hypervalent iodine(III) reagents, respectively (Scheme 1a). [8] Recently, we have reported an intermolecular decarboxylative oxyalkylation of alkenes enabled by the combination of rhenium catalysis with hypervalent iodine(III) reagents derived from simple aliphatic carboxylic acids.…”

“…[10] As far as we are aware, the application of fluorine-containing hypervalent iodine(III) reagents for trifluoromethylation of alkenes, instead of (hetero)arenes, is still unprecedented. [8,11] As our continuous interests in Re-catalysis, [12] we herein described the first rhenium-catalyzed oxytrifluoromethylation and Z-stereoselective Heck-type trifluoromethylation of styrenes by using PIFA as a trifluoromethylation reagent via decarboxylation (Scheme 1b). Also, the oxydifluoromethylation of styrenes was showcased by employing difluoromethylated carboxylic acid-derived HIRs, which cannot be achieved by the protocol similar to those of oxytrifluoromethylation using Togni reagents.…”

Initiator‐Free Natural Light‐Driven Vapor Phase Synthesis of a Porous Network of 3D Polystyrene Branched Carbon Nanofiber Grafted Polyurethane for Hexane /Water Separation

“…The natural light harvesting is the major focus of the 21 st century to move towards green energy and extraordinary efforts are being put in this regard . For a couple of years, the visible light mediated organic transformation gaining tremendous attention . The photocatalytic based reactions considered a powerful tool to gain a more pure product due to less involvement of the chemical catalysts.…”

“…[30] For a couple of years, the visible light mediated organic transformation gaining tremendous attention. [31] The photocatalytic based reactions considered a powerful tool to gain a more pure product due to less involvement of the chemical catalysts. The visible light driven electrochemical reactions are highly desired and preferable due to environmentally friendly, cost-effective, facile availability and safety.…”