Chiral Cages With Asymmetric π‐Clefts Enable Catalytic Enantioconvergent S <sub>N</sub> 1 Transformation via Synergistic Cation–π and Anion–π Interactions
Abstract
ABSTRACT Understanding and exploiting noncovalent interactions are essential for advancing chemical transformations and catalysis. While both cation–π and anion–π interactions have attracted growing attention, their deliberate use as a dominant design element remains elusive. Here, we present an ion–π catalysis strategy employing both π interactions as the key driving force to steer challenging stereoselective carbocation transformation, enabling catalytic enantioconvergent S N 1 reactions. Through straightforward one‐pot synthesis, we efficiently constructed a series of chiral cages composed solely of aromatic units, featuring electron‐rich asymmetric π clefts and electron‐deficient π exterior surfaces. This all‐π system leverages strong cation–π interactions to trap and stabilize carbocation intermediates within its chiral V‐cleft, while simultaneously engaging the counteranion via anion–π interactions on its exterior surface. This synergistic π network drives a highly enantioconvergent S N 1 process, enabling asymmetric allylation of propargyl acetates to form congested quaternary stereocenters. This system shows considerable sensitivity to subtle electronic and steric changes, resembling enzymatic behavior. This work provides a strategic approach for harnessing noncovalent π interactions to address challenging transformations.
Article Details
Authors (11)
Huan Zhang
School of Agriculture and Biology
Yi‐Meng Zhang
Beijing National Laboratory For Molecular Sciences CAS Key Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing China
Teng‐Yu Huang
Beijing National Laboratory For Molecular Sciences CAS Key Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing China
Fei‐Yun Yan
Beijing National Laboratory For Molecular Sciences CAS Key Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing China
Xu‐Dong Wang
Beijing National Laboratory for Molecular Sciences Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing China
Li‐Xia Wang
Huairou Research Center of Institute of Chemistry Chinese Academy of Sciences Beijing China
Jie Cui
Shanghai Sci-Tech Inno Center for Infection and Immunity, National Medical Center for Infectious Diseases, Huashan Hospital, Institute of Infection and Health, Fudan University
Jun‐Feng Xiang
University of Chinese Academy of Sciences Beijing China
Yu‐Fei Ao
Beijing National Laboratory for Molecular Sciences Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing China
De‐Xian Wang
Beijing National Laboratory for Molecular Sciences Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing China
Qi‐Qiang Wang
Beijing National Laboratory for Molecular Sciences Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing China