Phosphine oxide

Phosphine oxides are phosphorus compounds with the formula OPX3. When X = alkyl or aryl, these are organophosphine oxides. Triphenylphosphine oxide is an example. An inorganic phosphine oxide is phosphoryl chloride (POCl3). Parent compound The parent compound phosphine oxide (H3PO) is unstable. It has been detected with mass spectrometry as a reaction product of oxygen and phosphine, by means of FT-IR in a phosphine-ozone reaction and in matrix isolation with a reaction of phosphine, vanadium oxytrichloride and chromyl chloride. It has also been reported relatively stable in a water-ethanol solution by electrochemical oxidation of white phosphorus, where it slowly disproportionates into phosphine and hypophosphorous acid. Secondary phosphine oxides (R2P(O)H) are tautomers of phosphinous acids (R2POH). Phosphine oxide is reported as an intermediate in the room-temperature polymerization of phosphine and nitric oxide to solid PxHy. Structure and bonding Terti

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Yun-Suk Jang

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EPFL2019

Cooperative Effects between Chiral Cp-x-Iridium(III) Catalysts and Chiral Carboxylic Acids in Enantioselective C-H Amidations of Phosphine Oxides

Nicolai Cramer, Michael Christian Dieckmann, Yun-Suk Jang

An enantioselective C-H amidation of phosphine oxides by using an iridium(III) catalyst bearing an atropchiral cyclopentadienyl (Cp-x) ligand is reported. A very strong cooperative effect between the chiral Cp-x ligand and a phthaloyl tert-leucine enabled the transformation. Matched-mismatched cases of the different acid enantiomers are shown. The amidated P-chiral arylphosphine oxides are formed in yields of up to 95% and with excellent enantioselectivities of up to 99:1 er. Enantiospecific reduction provides access to valuable P-chiral phosphorus(III) compounds.

Wiley-Blackwell2017

Access to P- and Axially Chiral Biaryl Phosphine Oxides by Enantioselective (CpIrIII)-Ir-x-Catalyzed C-H Arylations

Nicolai Cramer, Yun-Suk Jang, Julia Pedroni, Lukasz Piotr Wozniak

An enantioselective C-H arylation of phosphine oxides with o-quinone diazides catalyzed by an iridium(III) complex bearing an atropchiral cyclopentadienyl (Cp-x) ligand and phthaloyl tert-leucine as co-catalyst is reported. The method allows access to a) P-chiral biaryl phosphine oxides, b) atropo-enantioselective construction of sterically demanding biaryl backbones, and also c) selective assembly of axial and P-chiral compounds in excellent yields and diastereo- and enantioselectivities. Enantiospecific reductions provide monodentate chiral phosphorus(III) compounds having structures and biaryl backbones with proven importance as ligands in asymmetric catalysis.

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