Photocatalytic C-H Activation with Alcohol as a Hydrogen Atom Transfer Agent in a 9-Fluorenone Based Metal-Organic Framework.

Hydrogen atom transfer (HAT) has become an attractive strategy for the activation of hydrocarbon feedstocks. Alcohols, as inexpensive and efficient hydrogen transfer reagents, have limited application in C-H functionalization due to the difficulty in the alkoxy radical acquisition. 9-Fluorenone moieties were incorporated into the metal-organic framework (MOF) as a photocatalyst; through the formation of hydrogen bonds between the carbonyl group of a ligand and alcohol, alkoxy radicals could be obtained by the visible-light-driven oxidation of 2,2,2-trichloroethanol via proton-coupled electron transfer (PCET). Effectively photocatalyzed intermolecular coupling reactions between phenyl vinyl sulfone and aldehyde or cyclic ether were realized through the HAT pathway. Compared to homogeneous catalysts, the heterogeneous MOF photocatalyst improved the catalytic efficiency and could be recycled at least five times. The microenvironment of the Zn-OFDC channel was beneficial for the formation of hydrogen bonds and stability of alkoxy radicals.