Yoshihiro Nishimoto; Naoki Sugihara; Makoto Yasuda
Synthesis, 2022, 54(12), 2765-2777
https://doi.org/10.1055/a-1755-3476

Abstract

Precisely controllable C–F bond activation is a significant challenge in organic synthesis due to its large bond energy. A single C(sp3)–F bond transformation of perfluoroalkyl groups is particularly desirable to supply functionalized perfluoroalkyl compounds offering properties that could be significantly useful in pharmaceutical and materials chemistry. Recently, the single defluoronative transformation of perfluoroalkyl compounds was developed via visible-light photocatalysis. Herein, we summarize this field via two main topics. Topic 1 involves the transformation 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 transformation of α-trifluoromethyl alkenes to gem-difluoroalkenes via a radical/polar crossover process.