LAUSR

Abstract Organophosphorus compounds are fundamental for the chemical industry due to their broad applications across multiple sectors, including pharmaceuticals, agrochemicals, and materials science. Despite their high importance, the sustainable and cost‐effective synthesis of organophoshoryl derivatives remains very challenging. Here, we report the first successful regio‐ and stereoselective hydrophosphorylation of terminal allenamides using an affordable copper catalyst system. This reaction offers an efficient protocol for the synthesis of (E)‐allylic organophosphorus derivatives from various types of P‐nucleophiles, such as H‐phosphonates, H‐phosphinates, and secondary phosphine oxides. Key advantages of this ligand‐free and atom‐economic strategy include low toxicity of the Cu‐based catalyst, cost effectiveness, mild reaction conditions, and experimental simplicity, making it competitive with methods that use toxic and expensive Pd‐based catalysts. In an effort to comprehend this process, we conducted extensive DFT calculations on this system to uncover the mechanistic insights of this process.