Enantioenriched α-tertiary ketones are key structural motifs in natural products, pharmaceuticals, and agrochemicals, and serve as versatile intermediates for constructing stereochemically complex molecules (Scheme 1a).[1-5] Despite significant advances in enantioselective enolate alkylation, the stereoselective synthesis of acyclic α-tertiary ketones—particularly those bearing unactivated alkyl substituents—remains a formidable challenge (Scheme 1b).[6-10] A central problem is the propensity...