Photocatalytic amidation and esterification with perfluoroalkyl iodide

Abstract

The successful generation of perfluoroalkyl radicals (R_f˙) through photoredox catalysis has inspired us to investigate the preparation of various organofluorine species. In this work, visible light-induced photocatalytic reactions for the preparation of perfluoroalkyl amides and esters from the corresponding amines and alcohols using different types of triplet emitters as photocatalysts have been studied. The effects of the excited-state characteristics and redox potentials of the photocatalysts have been elucidated. Under optimized reaction conditions, these reactions can be performed successfully with different types of amines or alcohols and perfluoroalkyl iodides. Detailed mechanistic studies based on emission quenching experiments have been performed to study the photocatalytic cycles as well as the role of the different reagents. The proposed mechanism has also been examined by DFT calculations.