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

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 devel-oped. A broad range of O-and S-nucleophiles are well tolerated in this transformation, affording the tar-get products with good to excellent yields. This protocol is effective and convenient, which not only em-ployed 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 re-action mechanism, and further confirmed that the reaction may follow a radical process.(c) 2023 Elsevier B.V. All rights reserved.

Automated summary

A copper-catalyzed cross-dehydrogenative coupling reaction of P(O)-H compounds with O-/S-nucleophiles has been developed for the synthesis of phosphinates and phosphinothioates. The reaction tolerates a wide range of O- and S-nucleophiles, giving good to excellent yields of the target products. The protocol is effective and convenient, using inexpensive copper iodide as the catalyst and avoiding the use of hazardous and toxic reagents. Through control and competitive experiments, a plausible reaction mechanism has been proposed, suggesting a radical process.