Enantioselective Ring-Opening/Oxidative Phosphorylation and P-Transfer Reaction of Cyclic Diaryliodoniums

Abstract

A Cu-catalyzed enantioselective ring-opening/oxidative phosphorylation reaction of cyclic diaryliodonium salts and diarylphosphine oxides in the presence of TEMPO was reported. 18O-Labeled experiments showed that the reaction proceeded via oxidation, followed by C–O bond formation. Furthermore, atropisomeric phosphine oxides were prepared via a t-BuLi-mediated P-transfer reaction. Computational studies elucidated that the phosphine oxide transfer was through a concerted C–P bond formation and P–O bond-dissociation process.