C(sp3)–F Bond Transformation of Perfluoroalkyl Compounds Mediated by Visible-Light Photocatalysis: Spin-Center Shifts and Radical/Polar Crossover Processes via Anionic Intermediates

Yoshihiro Nishimoto; Naoki Sugihara; Makoto Yasuda

doi:10.1055/a-1755-3476

Synthesis, Table of Contents

Synthesis 2022; 54(12): 2765-2777
DOI: 10.1055/a-1755-3476

short review

C(sp³)–F Bond Transformation of Perfluoroalkyl Compounds Mediated by Visible-Light Photocatalysis: Spin-Center Shifts and Radical/Polar Crossover Processes via Anionic Intermediates

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, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

,

Naoki Sugihara

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

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Abstract

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Abstract

Due to its large bond energy, precisely controllable C–F bond activation is a significant challenge in organic synthesis. A single C(sp³)–F bond transformation of perfluoroalkyl groups is particularly desirable to supply functionalized perfluoroalkyl compounds offering properties that are potentially useful in pharmaceutical and materials chemistry. Recently, the single defluorinative transformation of perfluoroalkyl compounds has been developed via visible-light photocatalysis. Herein, we summarize this field via two main topics. Topic 1 covers the transformations of C(sp³)–F bonds in either perfluoroalkylarenes or perfluoroalkane carbonyl compounds via a defluorinative spin-center shift in the radical anion intermediates. Topic 2 addresses the defluorinative transformations of α-trifluoromethyl alkenes to give gem-difluoroalkenes via a radical/polar crossover process.

1 Introduction

2 C(sp³)–F Transformations via Defluorinative Spin-Center Shifts

3 C(sp³)–F Transformations via a Radical/Polar Crossover Process

4 Conclusions

Key words

photocatalysts - perfluoroalkyl compounds - sp³ C–F bond transformations - single-electron transfer - spin-center shift - radical/polar crossover

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