Pd(0)-Catalyzed Cyclizative Phosphorylation of (Z)-1-Iodo-1,6-diene: Synthesis of Alkylphosphonate and Alkylthionophosphonate

A palladium-catalyzed cyclizative phosphorylation reaction of (Z)-1-iodo-1,6-diene with diethyl H-phosphonate is developed, which provides facile access to unsaturated six-membered heterocycles bearing an alkyl-phosphonate group. The key step of this process is the efficient capture of the involved alkyl-Pd(II) species by H-phosphonate with the help of CsF, followed by reductive elimination of alkyl-Pd(II)-P(O)(OEt)(2). Moreover, this reaction is successfully extended to H-thionophosphonate.