Homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis
Homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis
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DOI：
10.1021/ja052431t
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发表时间：
2005-06-29
影响因子：
15
通讯作者：
Lin, WB
中科院分区：
文献类型：
--
作者：
Wu, CD;Hu, A;Lin, WB
通过将无限大的一维[Cd(−-Cl)2]nz型链与含有正交二次官能团的轴向手性联吡啶桥联配体连接起来，构建了一种同手性多孔非互穿金属μ有机骨架1。利用文献[1]中可通过大开路连接的二次手性二羟基生成了一种非均相不对称催化剂，用于二乙基锌与芳香醛的加成反应，得到了对映体过量(Ee)高达93%的手性仲醇。用不同大小的树枝状芳香醛进行的对照实验表明，1衍生的非均相不对称催化剂具有高活性和对映体选择性，这是因为在多孔MOF内创建了易于访问的、均匀的活性中心。
A homochiral porous noninterpenetrating metal−organic framework (MOF),1, was constructed by linking infinite 1D [Cd(μ-Cl)2]nzigzag chains with axially chiral bipyridine bridging ligands containing orthogonal secondary functional groups. The secondary chiral dihydroxy groups accessible via the large open channels in1were 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 from1is both highly active and enantioselective as a result of the creation of readily accessible, uniform active catalyst sites inside the porous MOF.