Electrochemical Enabled Cascade Phosphorylation of N−H/O−H/S−H Bonds with P−H Compounds: An Efficient Access to P(O)‐X Bonds

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An electrochemical three component cascade phosphorylation reaction of various heteroatoms‐containing nucleophiles including carbazoles, indoles, phenols, alcohols, and thiols with Ph2PH has been established. Electricity is used as the “traceless” oxidant and water and air are utilized as the “green” oxygen source. All kinds of structurally diverse organophosphorus compounds with P(O)‐N/P(O)‐O/P(O)‐S bonds are assembled in moderate to excellent yields (three categories of phosphorylation products, 50 examples, up to 97 % yield). A tentative free radical course is put forward to rationalize the reaction procedure.