Abstract

AbstractThe first solvent‐controlled copper‐catalyzed oxidative decarboxylative coupling of alkenyl acids with P(O)H compounds for alkenyl C(sp2)−P bond formation by a free‐radical process is reported. The reaction enables the highly chemo‐ and stereoselective synthesis of various (E)‐alkenylphosphonates and (E)‐alkenylphosphinate oxides in moderate to good yields. On the basis of this catalytic system, styrenes and β‐nitrostyrene as well as alkenyl acids can also give the corresponding products by cross‐dehydrogenative coupling and denitration, respectively. By altering the oxidant, the oxyphosphorylation of styrenes with P(O)H compounds readily yields β‐ketophosphonates. The reaction described here enables a versatile and practical avenue for the formation of valuable C−P bonds.

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