Synthesis of W‐Phos Ligand and Its Application in the Copper‐Catalyzed Enantioselective Addition of Linear Grignard Reagents to Ketones

Abstract The asymmetric catalytic addition of linear Grignard reagents to ketones has been a long‐standing challenge in organic synthesis. Herein, a novel family of PNP ligands ( W‐Phos ) was designed and applied in copper‐catalyzed asymmetric addition of linear Grignard reagents to aryl alkyl ketones, allowing facile access to versatile chiral tertiary alcohols in good to high yields with excellent enantioselectivities (up to 94 % yield, 96 % ee). The process can also be used to synthesize chiral allylic tertiary alcohols from more challenging α,β‐unsaturated ketones. Notably, the potential utility of this method is demonstrated in the gram‐scale synthesis and modification of various densely functionalized medicinally relevant molecules.