Next, we studied the scope of this two-step one-pot protocol towards 𝛾-chiral enamides (Scheme 3). Firstly, the reaction could be successfully scaled up to 5 mmol (1.4 g) scale with the model substrate (2a), providing high yields and enantiomeric excess with excellent control over the E/Z stereoselectivity and transfer of the chirality (99.5%). The opposite enantiomer ((S)-2a) could also be successfully synthesized. Various substituents at the R 1 -position on the 𝛼-chiral allylic amine (C𝛼) could be tolerated including trifluoromethyl-(2b), bromide-(2c) and m-methoxy-groups (2d). The bulky naphthyl-substituent (2e) A) Ir-catalyzed enantioselective hydroalkenylation of α-olefins (Li) C) This work . . Reaction conditions: i. (R,E)-1a-1y (0.25 mmol, 1 equiv.), TBD (0.013 mmol, 0.05 equiv.), dry toluene (2.5 mL, 0.1 M), 60 °C, 16 h. ii. Acyl chloride (0.5 mmol, 2.0 equiv.), DABCO (0.25 mmol, 1.0 equiv.), 80 °C, 2 h. Isolated yields are reported. E/Z ratio determined by F NMR spectroscopy before purification. Chirality transfer (c.t.): (eeproduct/eeSM) x 100%. a Reaction performed on a 5.0 mmol (1.4 g) scale. b Isomerization at 100 °C. afforded the desired compound with excellent stereoselectivity. Furthermore, the R 2 -position of the 𝛼-chiral allylic amine (C𝛾) was also varied by employing different substituents on the aryl group such as p-methyl (2f), pchloride (2g), and even a thiophene heterocycle (2h) with good compatibility. The methyl-substituent (2i) proved to be more challenging probably due to increasing flexibility, and only moderate yields, Z/E ratios and ee was obtained. The achiral allylic amine 2j was also successful. Limitations were highly electron-donating substituents such as p-and o-methoxy-substituents on the aryl at the R 1 -position, and an electron-withdrawing p-trifluoromethyl-group at the R 2 -position (see Supplementary Information). The R 3 -position on the acyl chloride could also be varied with a diverse class of moieties. An electrondonating p-methyl-(2k), p-halides (2l, 2m) and electronwithdrawing-groups (2n, 2o) were all tolerated. Similarly, heterocycles such as quinoline (2p) and thiophene (2q) delivered the enamides in high yields, high enantiomeric excesses and E/Z ratio. Saturated cyclic (2r, 2s) and acyclic (2t) side-chains were also compatible as well as a bulky adamantyl-group (2u), albeit with lower yield and decrease in E/Z ratio. Comparably, methyl-(2v) and methoxy-groups (2w) led to slight E/Z isomerization, but with good yields and enantiomeric excess. Furthermore, an ester-(2x) and alkyne-functional group (2y) was also tolerated. Interestingly, the acyl chloride of the natural amino acid L-Phenylalanin (2z) could be subjected to the reaction with excellent yields and enantiomeric excess, albeit with lower diastereoselectivity. Control reactions show that this originates from a racemization of the 𝛼carbon stereocenter caused by deprotonation by DABCO. Some limitations include highly electron-donating group as in p-methoxy, cyclic amide, alkene and indole (see Supplementary Information).