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Porous Organic Frameworks Featured by Distinct Confining Fields for the Selective Hydrogenation of Biomass‐Derived Ketones
Author(s) -
Yang Yajie,
Deng Dan,
Zhang Shenli,
Meng Qinghao,
Li Zhangnan,
Wang Zeyu,
Sha Haoyan,
Faller Roland,
Bian Zheng,
Zou Xiaoqin,
Zhu Guangshan,
Yuan Ye
Publication year - 2020
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.201908243
Subject(s) - materials science , biomass (ecology) , porosity , chemical engineering , porous medium , nanotechnology , composite material , ecology , engineering , biology
The asymmetric hydrogenation of biomass‐derived molecules for the preparation of single enantiomer compounds is an effective method to reduce the rapid consumption of fossil resources. Porous organic frameworks (POFs) with pure organic surfaces may provide unusual confinement effects for organic substrates in chiral catalysis. Here, a series of POF catalysts are designed with chiral active centers decorated into sharply defined one‐dimensional channels with diameters in the range of 1.2–2.9 nm. Due to the synergistic effect originating from the conjugated inner wall, the POF material (aperture size 2.4 nm) concentrates over 90% of aromatic species into the porous architecture, and its affinity is one or two orders of magnitude higher than those of classical porous solids. As determined by PBE+D3 calculation, the phenyl fragment reveals strong π–π interaction for steric hindrance around the metal active site to achieve stronger asymmetric induction. Therefore, this POF catalyst achieves high conversion (>99% yield) and enantioselectivity (>99% ee ) for various substrates. The advantages of using the POF platform as a chiral catalyst can provide new perspectives on POF‐based solid‐state host–guest chemistry and asymmetric heterogeneous catalysis.