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Graphical Abstract Enantioenriched P-stereogenic alkenylphosphonamidates can be accessed in high yield and stereoselectivity through a chemo- and diastereodivergent Ni-catalyzed C−P coupling of readily available BINOL-based phosphoramidites and alkenyl halides. The reaction showed a broad scope and the chiral alkenylphosphonamidates proved to be versatile synthetic handles for the divergent synthesis of functionalized chiral-at-P organophosphorus compounds.
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