氯化膦与羟基化合物参与的 P(III)→P(V)重排反应研究进展

Pentavalent organophosphorus compounds are widely used in synthesis, materials, biology, medicine, agriculture, etc, and their synthetic methods have attracted a long-term interest from organic chemists. The P(III)→P(V) rearrangement from trivalent organophosphorus compounds is an important strategy for the synthesis of pentavalent organophosphorus compounds. The classical Michaelis-Arbuzov reaction, which involves a P(III)→P(V) rearrangement reaction between nucleophilic phosphite (P(OR)3) and alkyl halides, provides an important method for the synthesis of phosphonates. In contrast, the reaction between electrophilic phosphine chlorides (ClPR¹R²) and hydroxyl containing compounds (RA—OH) generaes a RA—O—PR¹R² intermediate in situ, followed by A—O bond cleavage and A—P bond formation thus to realize P(III)→P(V) rearrangement, also provides an effective synthetic method for pentavalent organophosphorus compounds. Two types of the P(III)→P(V) rearrangement reactions are both driven by the oxophilicity of phosphorus, bearing the advantages of high atom economy and readily available substrates. The P(III)→P(V) rearrangement reactions of phosphine chlorides with different types of hydroxyl containing compounds, such as alcohols, carboxylic acids, oximes, hydroxylamines, etc, for the synthesis of phosphine oxides, phosphonates, and phosphoric amides are mainly reviewed, respectively.