Copper‐Catalyzed Enantioselective Dehydro‐Diels–Alder Reaction: Atom‐Economical Synthesis of Axially Chiral Carbazoles
Hua-Hong Chen, Yang‐Bo Chen, Jun-Zhe Gao, Long‐Wu Ye, Bo Zhou
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.