Visible Light-Driven, Copper-Catalyzed Aerobic Oxidative Cleavage of Cycloalkanones

Abstract

A visible light-driven, copper-catalyzed aerobic oxidative cleavage of cycloalkanones has been presented. A variety of cycloalkanones with varying ring sizes and various α-substituents reacted well to give the distal keto acids or dicarboxylic acids with moderate to good yields.

Two in one: A Brønsted acid grafted photoactive covalent organic framework as metal-free dual photocatalyst for aerobic oxidative C-C cleavage

“…The peaks of N 1s at 397.8 and 398.8 eV were clearly observed in both COF-367 and COF-367-SO3H, and attributed to the C=N and C-N bonds [47][48], derived from imine-linkage and porphyrin building blocks (Figure 1d, Figure S3). Unsurprisingly, the peak at 399.8 eV in the COF-367-SO3H sample was clearly observed, which originated from the quinolyl N atom [15,[48][49]. This observation further confirmed the formation of a quinoline linkage.…”

“…Visible-light-driven organic transformations would give a green and sustainable alternative to these transformations. Guo et al presented a homogeneous photocatalytic system composed of rosolic acid in concentrated H2SO4 or alternatively Copper(II) trifluoromethanesulfonate to perform the aerobic oxidative cleavage of cycloalkanones driven by visible light [14][15]. Both systems showed a high selectivity and were the first examples of a successful photocatalyst for this reaction.…”

Photoactive Copper Complexes: Properties and Applications

“…In situ generated photoactivatable copper complexes resulting from coordination of a substrate have also been shown to be efficient to promote other reactions in which C–O bonds are formed, such as the oxidative cleavage of cycloalkanones to keto-acids (involving the formation of a photoactivatable cycloalkanone–copper complex) or the dioxygenation of alkynes. In this perspective, the Hwang group reported in 2018 a novel procedure for the dioxygenation of terminal arylalkynes 38 to the corresponding α-ketoesters 242 with molecular oxygen and alcohols 54 using copper­(I) iodide and picolinic acid 241 , involving the in situ formation of photoactivatable copper acetylides (Scheme , middle) .…”

Selective C–C Bond Cleavage of Cycloalkanones by NaNO2/HCl

“…Recently, Kobayashi and Takemoto developed an azolium/hydroquinone cocatalytic system that worked only for two-substituted cyclohexanones . During the preparation of our manuscript, Guo and coworkers disclosed a copper-catalyzed C–C bond cleavage of cycloalkanones under visible-light irradiation …”