Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles

A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P­(III)-nucleophiles (P­(OR)₃, ArP­(OR)₂, Ar₂P–OR) has been established via Michaelis–Arbuzov-type reaction. A broad range of P­(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP­(OR)₂) as substrates. The control experiments and ³¹P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C­(sp³)–P bonds in Michaelis–Arbuzov-type reactions.