RESUMEN
Transition metal-catalyzed cleavage and reconstruction of the C-P bond provides a highly efficient and rapid method for the transformation of organophosphine compounds. In this study, a novel and general protocol for the palladium-catalyzed C(sp3)-P(V) bond cleavage of free α-aminophosphonates and subsequent functionalization via C-P bond recombination has been developed. The reaction exhibits high reactivity between the C(sp3)-P bond and halides, accommodating a wide range of substrates and enabling the rapid synthesis of aryl, alkenyl, and alkyl organophosphine molecules. Additionally, the synthetic utility is validated by gram-scale synthesis, and the reaction process is corroborated by mechanistic experiments.
RESUMEN
In this report, we present the dual activation models for transient directing group-directed and amino-self-directed Pd-catalyzed α-aminophosphonate side-chain C(sp3)-H arylation. Both strategies showed facile, efficient, and single regioselectivity in the reaction between free α-aminophosphonates and aryl iodides. Furthermore, the modification of amino and late-stage functionalization of the C(sp3)-P bond from products indicates potential applications for α-aminophosphonates.