Inverse‐Electron‐Demand Palladium‐Catalyzed Asymmetric [4+2] Cycloadditions Enabled by Chiral P,S‐Ligand and Hydrogen Bonding

作者:Ya‐Ni Wang; Qin Xiong; Prof. Liang‐Qiu Lu; Qun‐Liang Zhang; Ying Wang; Prof. Yu Lan; Prof. Wen‐Jing Xiao
来源:Angewandte Chemie, 2019, 131(32): 11129-11133.
DOI:10.1002/ange.201905993

摘要

Catalytic asymmetric cycloadditions of ambident Pd‐containing dipolar species with nucleophilic dipolarophiles, namely, inverse‐electron‐demand cycloadditions, are challenging and underdeveloped. Possibly, the inherent linear selectivity of Pd‐catalyzed intermolecular allylations and the lack of efficient chiral ligands are responsible for this limitation. Herein, two cycloadditions of such intermediates with deconjugated butenolides and azlactones were accomplished by using a novel chiral hybrid P,S‐ligand and hydrogen bonding. By doing so, highly functionalized, optically active dihydroquinol‐2‐ones were produced with generally high reaction efficiencies and selectivities. Preliminary DFT calculations were performed to explain the high enantio‐ and diastereoselectivities.