Stereoselective Control of Iminium Catalysis at Elevated Temperatures

A significant challenge in the field of organocatalysis is limited scope of substrate applicability, particularly in facilitating efficient reactions involving low‐reactivity substrates. Stereoselective control at elevated temperatures stands out as one of the most effective strategies for mitigating the challenge. We herein report the stereoselective control achieved through iminium catalysis at elevated temperatures utilizing secondary amine‐strong acid catalytic systems. According to the construction of a hydrocarbazole polycyclic skeleton containing continuous chiral centers and all‐carbon quaternary stereocenters, this strategy has demonstrated significant advantages in promoting reactions with low‐reactivity substrates.