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. A convenient and efficient one‐pot protocol for the construction of P–S–C and P–Se–C bonds from elemental sulfur and selenium is developed in water. Valuable phosphorothioates and phosphoroselenoates including P‐chiral compounds are produced in good to excellent yields.