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.

Atroposelective transformation of axially chiral (hetero)biaryls. From desymmetrization to modern resolution strategies

“…Aiming to introduce a phosphine functionality into the biaryl atropisomeric skeletons, Gu and co-workers reported also a Cucatalysed ring-opening/oxidative phosphorylation reaction of cyclic diaryliodonium salts and diarylphosphine oxides (Scheme 10F). 26 During preliminary experiments designed to obtain axially chiral phosphine oxides, an unexpected overoxidized phosphinate was also observed. The addition of TEMPO resulted in higher chemoselectivity toward the later, allowing for the preparation of a large variety of phosphinates in very good overall yields and excellent enantioselectivities.…”

Palladium Catalyzed Asymmetric Hydrophosphination of Internal Alkynes: Access to Phosphine-Functionalized Axially Chiral Olefins

“…[70][71][72][73][74][75] In addition to unsaturated substrates, carbon and hetero electrophiles also effectively coupled with P(III)-H and P(V)-H reagents. [76][77][78][79][80][81][82][83][84][85] In all these reports, the reactions are limited to generation of C-or P-chiral centers. Of note, synthesis of the large family of axially chiral phosphines remains largely untouched via hydrophosphination.…”

Cu-Catalyzed Site-Selective and Enantioselective Ring Opening of Cyclic Diaryliodoniums with 1,2,3-Triazoles

“…With Cu­(I)/( R , R )-Bn-PyBox as the catalyst, we realized a high enantioselectivity amination/ring-opening reaction of cyclic diaryliodoniums (Scheme , B). Subsequently, by taking advantage of the remarkably high reactivity of diaryliodoniums, asymmetric ring-opening reactions with various nucleophiles were developed, wherein generally excellent enantioselectivities were obtained (Scheme , C–D). , …”