Asymmetric sequential hydrogenations of conjugated enynes have been developed using a Ph‐BPE‐CoI catalyst for the precise synthesis of chiral Z‐allylamides in high activity (up to 1000 substrate/catalyst (S/C)) and with excellent enantioselectivity (up to >99 % enantiomeric excess (ee)). Mechanism experiments and theoretical calculations support a cationic CoI/CoIII redox catalytic cycle. The catalytic activity difference between cobalt complexes of Ph‐BPE and QuinoxP* was explained by the process decomposition of rate‐determining step in the second hydrogenation.

Asymmetric sequential hydrogenations of conjugated enynes have been developed using a Ph‐BPE‐CoI catalyst for the precise synthesis of chiral Z‐allylamides in high activity (up to 1000 substrate/catalyst (S/C)) and with excellent enantioselectivity (up to >99 % enantiomeric excess (ee)). Mechanism experiments and theoretical calculations support a cationic CoI/CoIII redox catalytic cycle. The catalytic activity difference between cobalt complexes of Ph‐BPE and QuinoxP* was explained by the process decomposition of rate‐determining step in the second hydrogenation.