Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

Multisubstituted arenes such as indanes with attached all‐carbon quaternary centers are unique scaffolds in synthetic functional molecules and sophisticated natural products. A key challenge in preparing such molecules lies in the enantioselective installation of the quaternary carbon centers. Conventional methods in this direction include asymmetric substitution reactions and substrate‐controlled cyclization reactions. These reactions lead to poor stereoselectivities and/or require long and tedious synthetic steps. Disclosed here is a one‐step organic catalytic strategy for enantioselective access to this class of molecules. The reaction involves an N‐heterocyclic carbene catalyzed process for direct benzene construction, indane formation, remote‐carbon desymmetrization, and excellent chirality control. This approach will enable the concise synthesis of arene‐containing molecules, including those with complex structures and challenging chiral centers. Indan‐Bildung: Eine einstufige enantioselektive Synthese von Indanen mit quartären Kohlenstoffzentren verwendet ein N‐heterocyclisches Carben (NHC) als Katalysator für die direkte Arenbildung und beinhaltet eine ferngesteuerte Desymmetrierung mit ausgezeichneter Chiralitätskontrolle. Der Ansatz ermöglicht die präzise Synthese von Arenen mit komplexen Strukturen und anspruchsvollen Chiralitätszentren.