Photocatalytic Reductive C–O Bond Cleavage of Alkyl Aryl Ethers by Using Carbazole Catalysts with Cesium Carbonate

Methods to activate the relatively stable ether C–O bonds and convert them to other functional groups are desirable. One-electron reduction of ethers is a potentially promising route to cleave the C–O bond. However, owing to the highly negative redox potential of alkyl aryl ethers (Ered < −2.6 V vs SCE), this mode of ether C–O bond activation is challenging. Herein, we report the visible-light-induced photocatalytic cleavage of the alkyl aryl ether C–O bond using a carbazole-based organic photocatalyst (PC). Both benzylic and non-benzylic aryl ethers underwent C–O bond cleavage to form the corresponding phenol products. Addition of Cs2CO3 was beneficial, especially in reactions using a N–H carbazole PC. The reaction was proposed to occur via single-electron transfer (SET) from the excited-state carbazole to the substrate ether. Interaction of the N–H carbazole PC with Cs2CO3 via hydrogen bonding exists, which enables a deprotonation-assisted electron-transfer mechanism to operate. In addition, the Lewis acidic Cs cation interacts with the substrate alkyl aryl ether to activate it as an electron acceptor. The high reducing ability of the carbazole combined with the beneficial effects of Cs2CO3 made this otherwise formidable SET event possible.