A homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis.

A homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis.
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发表时间:
2005
影响因子:
15
通讯作者:
Chuande Wu;A. Hu;Lin Zhang;Wenbin Lin
Chuande Wu;A. Hu;Lin Zhang;Wenbin Lin
中科院分区:
化学1区
文献类型:
--
作者:
Chuande Wu;A. Hu;Lin Zhang;Wenbin Lin

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通过将无限一维[Cd(mu-Cl)2]n锯齿形链与含有正交二级官能团的轴向手性联吡啶桥配体连接,构建了同手性多孔非互穿金属有机框架(MOF) 1。通过1中的大开放通道可接触的仲手性二羟基被用来生成非均相不对称催化剂,用于将二乙锌加成到芳香醛上,以提供高达93%对映体过量(ee)的手性仲醇。不同尺寸的树枝状芳香醛的对照实验表明,由于在多孔 MOF 内部创建了易于接近、均匀的活性催化剂位点,衍生自 1 的多相不对称催化剂具有高活性和对映选择性。
A homochiral porous noninterpenetrating metal-organic framework (MOF), 1, was constructed by linking infinite 1D [Cd(mu-Cl)2]n zigzag chains with axially chiral bipyridine bridging ligands containing orthogonal secondary functional groups. The secondary chiral dihydroxy groups accessible via the large open channels in 1 were utilized to generate a heterogeneous asymmetric catalyst for the addition of diethyzinc to aromatic aldehydes to afford chiral secondary alcohols at up to 93% enantiomeric excess (ee). Control experiments with dendritic aromatic aldehydes of different sizes indicate that the heterogeneous asymmetric catalyst derived from 1 is both highly active and enantioselective as a result of the creation of readily accessible, uniform active catalyst sites inside the porous MOF.