Secondary Phosphine Oxides as Multitalented Preligands En Route to the Chemoselective Palladium‐Catalyzed Oxidation of Alcohols

Secondary phosphine oxides O=PHR2 (SPOs) were identified as multitalented preligands for the chemoselective Pd‐catalyzed oxidation of alcohols by a hydrogen‐ing methodology. SPOs were found to promote the hydrogen‐ion 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. Three talents: The chemoselective PdII‐catalyzed oxidation of a wide range of secondary alcohols is achieved using an ing‐hydrogen methodology. Secondary phosphine oxides promote the hydrogen‐ing step as well as hydrogen transfer to a Michael acceptor through the formation of an active palladium hydride species.