Zn-Catalyzed Dehydroxylative Phosphorylation of Allylic Alcohols with P(III)-Nucleophiles

A novel
and efficient protocol for the synthesis of diarylallyl-functionalized
phosphonates, phosphinates, and phosphine oxides through the zinc-catalyzed
dehydroxylative phosphorylation of allylic alcohols with P(III)-nucleophiles
via a Michaelis–Arbuzov-type rearrangement is reported. A broad
range of allylic alcohols and P(III)-nucleophiles (P(OR)3, ArP(OR)2, and Ar2P(OR)) are well tolerated
in this reaction, and the expected dehydroxylative phosphorylation
products could be synthesized with good to excellent yields under
the optimal reaction conditions. The reaction can be easily scaled
up at a gram-synthesis level. Furthermore, through the step-by-step
control experiments, kinetic study experiments, and 31P
NMR tracking experiments, we acquired insights into the reaction and
proposed the possible mechanism for this transformation.