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Confinement‐Driven Enantioselectivity in 3D Porous Chiral Covalent Organic Frameworks
Author(s) -
Hou Bang,
Yang Shi,
Yang Kuiwei,
Han Xing,
Tang Xianhui,
Liu Yan,
Jiang Jianwen,
Cui Yong
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202013926
Subject(s) - enantiopure drug , enantioselective synthesis , catalysis , covalent bond , covalent organic framework , homogeneous , chemistry , brønsted–lowry acid–base theory , substrate (aquarium) , combinatorial chemistry , diamondoid , porosity , organic chemistry , materials science , molecule , physics , thermodynamics , oceanography , geology
3D covalent organic frameworks (COFs) with well‐defined porous channels are shown to be capable of inducing chiral molecular catalysts from non‐enantioselective to highly enantioselective in catalyzing organic transformations. By condensations of a tetrahedral tetraamine and two linear dialdehydes derived from enantiopure 1,1′‐binaphthol (BINOL), two chiral 3D COFs with a 9‐fold or 11‐fold interpenetrated diamondoid framework are prepared. Enhanced Brønsted acidity was observed for the chiral BINOL units that are uniformly distributed within the tubular channels compared to the non‐immobilized acids. This facilitates the Brønsted acid catalysis of cyclocondensation of aldehydes and anthranilamides to produce 2,3‐dihydroquinazolinones. DFT calculations show the COF catalyst provides preferential secondary interactions between the substrate and framework to induce enantioselectivities that are not achievable in homogeneous systems.