Copper‐Catalyzed Enantioselective Dehydro‐Diels–Alder Reaction: Atom‐Economical Synthesis of Axially Chiral Carbazoles

Abstract The dehydro‐Diels–Alder (DDA) reaction is a powerful method for the construction of aromatic compounds. However, the enantioselective DDA reaction has been rarely developed, probably due to the competitive thermal reaction. Herein, we report a copper‐catalyzed enantioselective DDA reaction through vinyl cation pathway. The reaction leads to the atom‐economical synthesis of axially chiral phenyl and indolyl carbazoles in generally excellent yields with good to excellent atroposelectivities. This methodology represents the first example of non‐noble metal‐catalyzed enantioselective DDA reaction. Notably, new chiral ligand and organocatalyst derived from the constructed axially chiral carbazole are demonstrated to be useful in asymmetric catalysis.