Nickel-Catalyzed Defluorophosphonylation of Aryl Fluorides
Zhensheng You1, Yusuke Masuda2,1, Tomohiro Iwai1
1Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan.
Abstract:
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.
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