Nickel-Catalyzed Defluorophosphonylation of Aryl Fluorides

J Org Chem. 2022 Nov 4;87(21):14731-14737. doi: 10.1021/acs.joc.2c02048. Epub 2022 Oct 18.


A Ni-catalyzed cross-coupling reaction between aryl fluorides and dialkyl phosphonates [HP(O)(OR)2] (R = secondary alkyl groups) in the presence of potassium tert-butoxide as a base is reported. The reaction converted various aryl fluorides into the corresponding aryl phosphonates even when electron-donating substituents were present on the aromatic ring. The combined experimental and computational studies suggested Ni-K+ cooperative action of a Ni(0) complex chelated with a strongly electron-donating ion-bridged dimeric phosphite ligand system [P(OR)2O-K+]2 that facilitates turnover-limiting C-F bond oxidative addition of aryl fluorides.