Three‐Component Coupling Reaction in Water: A One‐Pot Protocol for the Construction of P–S–C(sp3) and P–Se–C(sp3) Bonds

A one‐pot, three‐component coupling reaction of primary alkyl halides (or tosylates), elemental sulfur/selenium, and P(O)–H compounds in water was developed. This procedure affords valuable phosphorothioates/phosphoroselenoates, including P‐chiral compounds, with broad substrate scope and high efficiency. Moreover, this facile protocol can be applied to gram‐scale preparations.