Secondary phosphine oxides O=PHR2 (SPOs) were identified as multitalented preligands for the chemoselective Pd‐catalyzed oxidation of alcohols by a hydrogen‐abstracting methodology. SPOs were found to promote the hydrogen‐abstraction step as well as hydrogen transfer to a Michael acceptor by generating a putative active H−Pd species. The catalytic system operates under neutral conditions and was proven to be compatible with various electrophilic and nucleophilic functionalities within the substrates as well as water‐ and air‐sensitive functional groups.

Secondary phosphine oxides proved to be effective preligands to stabilise a hydroxy‐platinum based catalyst that allows the aerobic/anaerobic oxidation of challenging substrates. Kinetic comparisons showed that this system is more efficient and stable than previously reported similar palladium‐based catalysts. A neutral platinum dimer bearing bridging hydroxy ligands has been isolated and fully characterised by X‐ray diffraction and its involvement in the mechanism has been evidenced by mechanistic studies.

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.

A convenient method to access a broad variety of N-alkyl-(2,2,6,6)-tetramethylpiperidin-4-ol compounds is reported. The thermal treatment of a mixture of (2,2,6,6)-tetramethylpiperidin-4-ol and allyl or benzyl bromide derivatives gave the corresponding N-alkylated compounds in good yields while leaving the hydroxyl functional group intact. Whereas 40 h were needed to reach complete conversion, microwave irradiation allowed the reaction time to be reduced (20 min) and improved the yields in most cases.