The Adaptative Modulation of the Phosphinito-Phosphinous Acid Ligand: Computational Illustration Through Palladium-Catalyzed Alcohol Oxidation.

The phosphinito-phosphinous acid ligand (PAP) is a singular bidentate-like self-assembled ligand exhibiting dissymmetric but interchangeable electronic properties. This unusual structure has been used for the generation of active palladium hydride through alcohol oxidation. In this paper, we report the first theoretical highlight of the adaptative modulation ability of this ligand within a direct H-abstraction path for Pd and Pt catalyzed alcohol oxidation.

Platinum-(phosphinito-phosphinous acid) complexes as bi-talented catalysts for oxidative fragmentation of piperidinols: an entry to primary amines.

Platinum-(phosphinito-phosphinous acid) complex catalyzes the oxidative fragmentation of hindered piperidinols according to a hydrogen transfer induced methodology. This catalyst acts successively as both a hydrogen carrier and soft Lewis acid in a one pot - two steps process. This method can be applied to the synthesis of a wide variety of primary amines in a pure form by a simple acid-base extraction without further purification.

Umpolung Reactivity of in Situ Generated Phosphido-Boranes: An Entry to P-Stereogenic Aminophosphine-Boranes.

The synthesis of P-stereogenic aminophosphine-boranes has been developed on the basis of umpolung reactivity of in situ generated alkylarylphosphido-boranes, which are normally configurationally unstable intermediates. In our case, their high configurational stability was due to the slow release of the hydroxyalkyl protecting group, together with the fast formation of the iodophosphanylborane in the presence of N-iodosuccinimide. The subsequent substitution reaction was found to proceed in moderate to good yields and in a very high stereospecifity (es) using a variety of amines as nucleophiles.

Synthesis of chiral supramolecular bisphosphinite palladacycles through hydrogen transfer-promoted self-assembly process.

P-Chiral secondary phosphine oxides react with Pd2(dba)3 in an acidic medium to provide chiral supramolecular bisphosphinite palladacycles through a H-transfer-based self-assembly process prior to SPO-promoted oxidative addition of an acid to a Pd(0) centre. The one-pot methodology allows variations of the X-type ligand as desired. Eight complexes have been characterised by X-ray diffraction.