Photocatalyzed C–F Bond Heteroarylation of Trifluoromethyl­arenes with Heteroarenes: Two Roles of Bu3SnI as Fluoride Ion Scavenger and Activator for Photocatalyst

Naoki Sugihara; Masayuki Abe; Yoshihiro Nishimoto; Makoto Yasuda

doi:10.1055/a-2235-1380

Synthesis, Table of Contents

Synthesis 2024; 56(21): 3297-3306
DOI: 10.1055/a-2235-1380

paper

Special Issue PSRC-10 (10th Pacific Symposium on Radical Chemistry)

Photocatalyzed C–F Bond Heteroarylation of Trifluoromethylarenes with Heteroarenes: Two Roles of Bu₃SnI as Fluoride Ion Scavenger and Activator for Photocatalyst

Authors

Naoki Sugihara

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
Masayuki Abe

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
Yoshihiro Nishimoto ∗

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan
Makoto Yasuda ∗

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan

Abstract

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Abstract

We report the C–F bond heteroarylation of trifluoromethylarenes with heteroarenes by using Ir(ppy)₃ catalyst and Bu₃SnI under visible-light irradiation. Various heteroarenes such as pyrrole, furan, and thiophene derivatives were applied to the present reaction. The present heteroarylation enables the transformation of various functionalized trifluoromethylarenes because of the mild reaction conditions. Notably, the late-stage transformation of a drug molecule, bicalutamide, was demonstrated. Mechanistic studies including a light on–off interval experiment, Stern–Volmer luminescence-quenching measurements, and DFT calculations clarified two critical roles of Bu₃SnI for the successful progress of the heteroarylation. Bu₃SnI functions as a fluoride ion scavenger to suppress the undesired C–F bond re-formation. Bu₃SnI also acts as a single-electron source for the reduction of photoexcited Ir(ppy)₃* to generate Ir(II) species to effectively reduce ArCF₃.

Key words

C–F bond transformation - diaryldifluoromethanes - heteroarylation - photocatalysis - organostannanes - pyrroles - furans - thiophenes

Full Text

References

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Supplementary Material

Supporting Information (PDF) (opens in new window)

Photocatalyzed C–F Bond Heteroarylation of Trifluoromethyl­arenes with Heteroarenes: Two Roles of Bu3SnI as Fluoride Ion Scavenger and Activator for Photocatalyst

Authors

Photocatalyzed C–F Bond Heteroarylation of Trifluoromethylarenes with Heteroarenes: Two Roles of Bu₃SnI as Fluoride Ion Scavenger and Activator for Photocatalyst