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Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal–Organic Frameworks for Batch and Flow Reactions
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-09-14 00:00:00 , DOI: 10.1021/jacs.7b06459 Xu Chen 1 , Hong Jiang 1 , Bang Hou 1 , Wei Gong 1 , Yan Liu 1 , Yong Cui 1, 2
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-09-14 00:00:00 , DOI: 10.1021/jacs.7b06459 Xu Chen 1 , Hong Jiang 1 , Bang Hou 1 , Wei Gong 1 , Yan Liu 1 , Yong Cui 1, 2
Affiliation
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A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal–organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn2L(H2O)2] are prepared from enantiopure phosphono-carboxylate ligands of 1,1′-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3′-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with −CF3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with −F and −Me groups. Under both batch and flow reaction systems, the CF3-containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.
中文翻译：
提高金属有机骨架在间歇和流动反应中的化学稳定性，催化活性和对映选择性
非均相催化的关键挑战是具有高催化活性，选择性和可回收性的非均相催化剂的设计和合成。在这里，我们证明了可以通过使用配体设计策略从金属-有机骨架（MOF）平台设计出高性能的多相不对称催化剂。三种具有骨架式[Mn 2 L（H 2 O）2的多孔手性MOF由1，1′-双酚的对映体纯膦酰基羧酸酯配体制备，所述配体在3，3′-位被3，5-双（三氟甲基）-，双甲基-和双氟-苯基取代基官能化。首次，我们表明不仅可以通过修饰配体结构来调节MOF的化学稳定性，而且可以调节其催化活性和立体选择性。特别地，与具有-F和-Me基团的MOF相比，在孔壁上结合有-CF 3基团的MOF表现出对水，弱酸和碱的增强的耐受性。在间歇和流动反应系统中，CF 3含MOF的化合物具有出色的反应性，选择性和可回收性，可为各种范围的酮酸酯或硝基烯烃与吲哚和吡咯的烷基化提供高收率和对映选择性。相反，相应的均相催化剂在催化测试的反应中给出低的对映选择性。
更新日期：2017-09-15
中文翻译：
提高金属有机骨架在间歇和流动反应中的化学稳定性，催化活性和对映选择性
非均相催化的关键挑战是具有高催化活性，选择性和可回收性的非均相催化剂的设计和合成。在这里，我们证明了可以通过使用配体设计策略从金属-有机骨架（MOF）平台设计出高性能的多相不对称催化剂。三种具有骨架式[Mn 2 L（H 2 O）2的多孔手性MOF由1，1′-双酚的对映体纯膦酰基羧酸酯配体制备，所述配体在3，3′-位被3，5-双（三氟甲基）-，双甲基-和双氟-苯基取代基官能化。首次，我们表明不仅可以通过修饰配体结构来调节MOF的化学稳定性，而且可以调节其催化活性和立体选择性。特别地，与具有-F和-Me基团的MOF相比，在孔壁上结合有-CF 3基团的MOF表现出对水，弱酸和碱的增强的耐受性。在间歇和流动反应系统中，CF 3含MOF的化合物具有出色的反应性，选择性和可回收性，可为各种范围的酮酸酯或硝基烯烃与吲哚和吡咯的烷基化提供高收率和对映选择性。相反，相应的均相催化剂在催化测试的反应中给出低的对映选择性。
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