Scope of enantioselective β-selective hydroalkylation. The scoping study results for the production of enantioenriched β-branched alkyl amines through enantioselective β-selective hydroalkylation are summarized in Figure . The reaction was conducted smoothly with various alkyl bromides and iodides and protected allylamines and resulted in the production of the target products in good to excellent yields (45~96%) with high regioisomeric ratios and enantioinduction. Compared to the model reaction with 2a, both the selected alkyl iodides (2k and 2l) that lacked any heteroatoms and the substrates containing sulfur or phosphonate atoms (2r and 2s) were successfully transformed to their corresponding products (6ak, 6al, 6ar, 6as) without significant differences in coupling efficiency or enantioselectivity. This asymmetric hydroalkylation tolerated a wide range of functional groups, including ester (6ad), trifluoromethyl (6am), trifluoromethoxy (6an), cyano (6ao), and aryl chloride (6ah). Heterocycles such as phthalimide (6ap), furan (6ag), and thiophene (6aq) remained unchanged in this hydroalkylation reaction. Although the reaction conditions involve a medium-strength base K3PO4(H2O), compounds with keto carbonyl groups (6at, 6au) were well tolerated and thus demonstrated the excellent compatibility of this reaction with base-sensitive functional groups. Many internal alkenes were proven to be suitable substrates. Excellent enantioselectivities (88~96% e.e.) were obtained in all cases. In general, alkenes with less bulky substituents provided good yields (6ba, 6da), while bulkier substrates resulted in moderate coupling efficiency (6cJ). Notably, the Z/E configuration of the alkene indeed affects the regio-and enantioselectivity (6da). Another limitation of this reaction is that the regioselectivity of the reaction is not satisfying when utilizing substrates with intolerable ester groups in the alkyl chain (6ea, 6fa), which suggests that there is a need to further optimize the reaction conditions. Cinnamylamine derivatives have potentially competitive benzylic active reaction sites. We examined several cinnamylamine derivatives with different electronic properties of the aryl ring. Both electroneutral (6gb), electron-rich (6hb, 6ia), and electron-deficient (6ja, 6ka) compounds gave uniformly good coupling yields and regio-and enantioselectivities.