Boosting Enantioselectivity of Chiral Molecular Catalysts with Supramolecular Metal-Organic Cages (vol 4, pg 1180, 2022)

被引:38
作者
Chu, Dandan
机构
[1] School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai
来源
CCS CHEMISTRY | 2022年 / 4卷 / 04期
基金
中国国家自然科学基金;
关键词
asymmetric catalysis; coordination cage; host-guest chemistry; self-assembly; supramolecular catalysis;
D O I
10.31635/ccschem.021.202100847
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The search for new methodologies to tune and control the enantioselectivities of molecular catalysts is of great importance in the field of asymmetric catalysis. Here, we have illustrated that chiral molecular catalysts can be boosted from very low enantioselectivity to high enantioselectivity when installed in supramolecular metal-organic cages. By deliberately designing two optically active 1,1′-spirobiindane-7,7′-diol (SPINOL)-based dipyridine linkers, we synthesized two chiral Pd3L6 cages featuring chiral dihydroxyl or dimethoxymethyl auxiliaries in the nanosized cavities. After treatment with metal ions, the cage featuring dihydroxyl groups could serve as efficient catalysts for asymmetric conjugate addition of styrylboronic acids to α,β-enones to produce γ,δ-unsaturated ketone and the asymmetric addition of diethylzinc to aldehydes to afford secondary alcohols. While the molecular SPINOL display very low enantioselectivity, restriction of its freedom in the cages led to 91−99.6% and 80−99.9% enantiomeric excess (ee) of products, respectively, which were increased by up to 35% and 78% ee, compared with the molecular control. Thus, our present work paves a way of utilizing supramolecular porous assemblies to manipulate the enantioselectivities of molecular catalysts. © 2022 CCS Chemistry. All rights reserved.
引用
收藏
页码:1452 / 1452
页数:1
相关论文
共 1 条