23081-74-5Relevant articles and documents
Chelate complexes of phosphorus-nitrogen ligands. 1. Deprotonation, cis-trans isomerism, and anion-catalyzed isomerization in platinum(II) complexes of (o-aminophenyl)diphenylphosphine
Cooper, Mervyn K.,Michael Downes
, p. 880 - 884 (1978)
The new hybrid ligand (o-aminophenyl)diphenylphosphine (PNH2) has been synthesized and bis-ligand chelate complexes of platinum(II) have been prepared. Facile deprotonation of the coordinated amino group has allowed the preparation of both cis and trans isomers of [Pt(PNH2)2]X2, [Pt(PNH-)(PNH2)]X, and [Pt(PNH-)2] (X- is a noncoordinating anion and PNH- is the conjugate base of PNH2). The stereochemistries have been assigned using 31P NMR spectroscopy. The first observation of anion-catalyzed isomerization in square-planar complexes is reported.
Copper-Catalyzed C?P Cross-Coupling of (Cyclo)alkenyl/Aryl Bromides and Secondary Phosphine Oxides with in situ Halogen Exchange
Stankevi?, Marek,Wo?nicki, Pawe?
, p. 3484 - 3491 (2021/07/22)
An efficient protocol for concurrent tandem halogen exchange/C?P cross-coupling of cycloalkenyl bromides and secondary phosphine oxides has been developed. The catalytic system is based on cheap and air-stable copper(I) iodide as the precatalyst, commercially available N,N’-dimethylethylenediamine as the ligand, and Cs2CO3 or K2CO3 as the base. The use of sodium iodide as an additive reduces the excessive use of organic bromides to near-stoichiometric by promoting the in situ transformation to the corresponding iodides. Diarylphosphine oxides undergo cycloalkenylation with 35–99 % yields and dicyclohexylphosphine oxide with 30–53 % yields. In the case of acyclic alkenyl bromides the cross-coupling products undergo conjugate addition of diphenylphosphine oxide and satisfying yields are observed only for internal olefins. In the case of aryl bromides satisfying yields (43–72 %) are observed only for sterically unhindered arenes or arenes possessing an ortho-directing group. Cycloalkenylphosphine oxides prepared in the cross-coupling reaction undergo base-catalyzed and base-promoted conjugate addition to give bis(phosphinoyl)cycloalkanes.
Scalable Rhodium(III)-Catalyzed Aryl C?H Phosphorylation Enabled by Anodic Oxidation Induced Reductive Elimination
Wu, Zheng-Jian,Su, Feng,Lin, Weidong,Song, Jinshuai,Wen, Ting-Bin,Zhang, Hui-Jun,Xu, Hai-Chao
supporting information, p. 16770 - 16774 (2019/11/03)
Transition metal catalyzed C?H phosphorylation remains an unsolved challenge. Reported methods are generally limited in scope and require stoichiometric silver salts as oxidants. Reported here is an electrochemically driven RhIII-catalyzed aryl C?H phosphorylation reaction that proceeds through H2 evolution, obviating the need for stoichiometric metal oxidants. The method is compatible with a variety of aryl C?H and P?H coupling partners and particularly useful for synthesizing triarylphosphine oxides from diarylphosphine oxides, which are often difficult coupling partners for transition metal catalyzed C?H phosphorylation reactions. Experimental results suggest that the mechanism responsible for the C?P bond formation involves an oxidation-induced reductive elimination process.
