Direct Catalytic Enantioselective C(sp ² )–H Allylation of Acrylic Acids: Modular Access to Chiral 1,4-Skipped Dienes

The direct enantioselective C–H functionalization of carboxylic acids represents a formidable yet highly appealing goal in synthesis, offering efficient access to chiral molecules from abundant feedstocks. Herein, we disclose a chiral Cp x Rh(III)-catalyzed strategy for the enantioselective alkenyl C–H allylation of acrylic acids. This transformation achieves a unique asymmetric C(sp 2 )–C(sp 3 ) cross-coupling between two olefin coupling partners─acrylic acids and allyl acetates─delivering valuable enantioenriched 1,4-dienes with high efficiency and excellent enantioselectivity. This transformation exhibits a broad substrate scope and high functional group tolerance, with its synthetic utility demonstrated through scalable synthesis and diverse downstream derivatizations. This strategy establishes a versatile and practical approach to asymmetric alkenyl C–H functionalization for the convenient synthesis of valuable enantioenriched architectures.