The enantioselective β-selective hydroalkylation exhibited good compatibility with many functional groups and was perfectly compatible for the late-stage functionalization of biorelevant molecules (Figure ). Derivatives of indomethacin (2w), coumarin (2x), and probenecid (2y) were smoothly reacted with alkene 3a to provide the desired products (6aw, 6ax, and 6ay) in good yield (72~89%) and selectivity (93~96% e.e. and 7.9:1~11:1 r.r.). In the modification of natural products L-proline (2v), estrone (2z), and D-galactopyranoside (2A), we obtained diastereoisomers (6av and 7av, 6az and 7az, 6aA and 7aA) using the proper enantiomer of the ligand. The preloaded chiral centres in the natural products hardly affect the coupling efficiency and regio-and enantioselectivity of the reaction. In terms of scalability, the synthesis of product 6aB could be conducted on a gram scale with an 86% yield (Figure ). After hydrolysis of 6aB with HCl in propanol, deprotected primary alkyl amine 8 was obtained in a 70% isolated yield. Reduction of 6aB by LiAlH4 afforded the corresponding secondary amine 9 in a 90% isolated yield. The scale-up reaction and easy removal of the protecting group highlight the practicality of this β-branched alkyl amine synthesis. We applied this reaction to synthesize intermediates of bioactive molecules and their analogues (Figure ). Compound 6lC was prepared as the intermediate of the acesodyne medication Lyrica, a γ-aminobutyric acid (GABA) receptor agonist.