Copper-Catalyzed Aerobic Oxidative/Decarboxylative Phosphorylation of Aryl Acrylic Acids with P(III)-Nucleophiles

A copper-catalyzed aerobic oxidative/decarboxylative
phosphorylation
of aryl acrylic acids with P(III)-nucleophiles via the Michaelis–Arbuzov rearrangement for the synthesis of
β-ketophosphine oxides, β-ketophosphinates, and β-ketophosphonates
is reported. The present reaction could be conducted effectively without
the use of a ligand and a base. Various kinds of aryl acrylic acids
and P(III)-nucleophiles are tolerated in the transformation, generating
the desired β-keto-organophosphorus compounds as a valuable
class of phosphorus-containing intermediates with good to excellent
yields. In addition, the possible mechanism and kinetic studies for
the reaction have been explored by step-by-step control experiments
and competitive experiments, and the results proved that this transformation
may follow second-order chemical kinetics as well as involve a radical
process.