Copper-catalyzed cross-dehydrogenative coupling of P(O)−H compounds with O-/S-nucleophiles.

• Mild reaction conditions (room temperature & 12 h). • Oxygen in air is used as the oxidant. • Gram-scale synthesis (1.97 g). • Broad substrate scope, 38 examples (e.g. alcohols, phenols, thiols, thiophenols). The copper-catalyzed cross-dehydrogenative coupling of P(O)−H compounds with O-/S-nucleophiles to construct P−O bonds and P−S bonds for the synthesis of phosphinates and phosphinothioates was developed. A broad range of O- and S-nucleophiles are well tolerated in this transformation, affording the target products with good to excellent yields. This protocol is effective and convenient, which not only employed inexpensive copper iodide as the catalyst, but also avoided the use of hazadous and toxic reagents. Through the step-by-step control experiments and competitive experiments, we proposed a plausible reaction mechanism, and further confirmed that the reaction may follow a radical process. [Display omitted] [ABSTRACT FROM AUTHOR]