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A facile and efficient protocol for P(O)–O bond formation was discovered through NaIO4/air-initiated phosphorylation of alcohols with H-phosphine oxides in water. This reaction showed good functional group tolerance and a broad substrate scope, providing an alternative method for constructing P(O)–O bonds. Mechanistic studies suggested that a phosphoryl radical-involving process from H-phosphine oxides facilitated the phosphorylation of alcohols under air.

Graphical abstract: NaIO4/air-initiated phosphorylation of alcohols with H-phosphine oxides for the construction of P(O)–O bonds in water

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