Substrate scope of migratory hydroalkylation. We sought to examine the generality of this migratory hydroalkylation reaction with suitable reaction conditions by exploring a wide range of alkenes and alkyl iodides (Figure ). An array of alkene substrates with different steric hindrances and chain lengths smoothly underwent alkene isomerization hydroalkylation, convincingly demonstrating the reliability of temperature-regulated regioselectivity. The regioselectivity was precisely controlled by the reaction temperature: high temperature (100 °C) was always α-selective, whereas low temperature (10 °C) was β-selective. In addition, a complete lack of isomerization of the alkyl halides was observed. Both terminal aliphatic alkenes (4aa and 5aa, 4ca and 5ca) and internal alkenes (4ba and 5ba) with different chain lengths performed well. Alkane substrates 1d and 1e have potentially competitive benzylic or α-ester active reaction sites. These substrates delivered prospective α-or βselective migratory hydroalkylation products (4da and 5da, 4ea and 5ea, respectively), indicating that the amide group displays a higher priority directing ability over an aromatic ring or an ester group. However, α-selective migratory hydroalkylation exhibits better regiocontrol capability and applies to a broader range of alkene substrates than β-selective migratory hydroalkylation. Both method A and method B were performed on the 1,1disubstituted alkene 1f. α-Branched product 4fa was obtained smoothly under method A conditions, while method B produced the unexpected linear product 5fa (see Supplementary Figure for DFT calculation results).