基于天然樟脑酸构筑的阶梯状手性金属-有机框架及其协同不对称催化★

doi:10.6023/A26010014

摘要/Abstract

框架材料化学的发展为构筑结构可控、功能集成的多孔晶体体系提供了重要平台。手性金属-有机框架材料(CMOFs)因能够在晶态框架中固定并放大分子手性,在不对称催化等领域展现出独特潜力。然而,如何在刚性手性框架内合理组织多种催化位点,并通过框架结构参与反应中间体的稳定与选择性调控,仍面临显著挑战。本文以天然D-樟脑酸为手性源,理性设计并合成了一种新型双功能配体,成功构筑了一例具有阶梯状三维骨架特征的手性铜基金属-有机框架(D-Cam-Cu)。单晶X射线衍射分析表明,该框架由paddle-wheel型双核铜单元逐层连接而成,相邻片层在空间上呈现有序错位,构建出非均匀分布的手性微环境。在此基础上,我们将该CMOF与手性磷酸协同引入,构建了一个非均相协同催化体系,并将其成功应用于β-萘胺与α-重氮酯的不对称N-H键插入反应。结果表明,相较于单一催化剂体系,该协同体系在产率和对映选择性方面均表现出显著提升。结合结构解析与催化行为分析,我们认为阶梯状手性框架在稳定关键反应中间体、促进多活性中心协同及调控反应选择性方面发挥了关键作用。本研究不仅实现了从天然手性分子到功能性手性框架材料的可控构筑,也为发展基于框架材料的多功能协同不对称催化体系提供了新的设计思路。

关键词: 手性金属-有机框架, 天然樟脑酸, 阶梯状结构, 协同不对称催化, N-H键插入反应

The development of framework materials chemistry has provided a powerful platform for constructing porous crystalline systems with precisely controllable structures and integrated functions. Chiral metal-organic frameworks (CMOFs) have attracted considerable interest owing to their ability to immobilize and amplify molecular chirality within crystalline frameworks, offering unique opportunities for asymmetric catalysis. However, the rational organization of multiple catalytic sites within rigid chiral frameworks, as well as the direct involvement of framework structures in stabilizing reaction intermediates and regulating selectivity, remains a significant challenge. Herein, using natural D-camphoric acid as a chiral source, a novel bifunctional ligand was rationally designed and synthesized, enabling the construction of a chiral copper-based metal-organic framework (D-Cam-Cu) featuring a staircase-like three-dimensional architecture. Single-crystal X-ray diffraction analysis reveals that the framework is assembled from paddle-wheel-type dinuclear copper units connected in a layer-by-layer manner, with adjacent layers exhibiting an ordered spatial offset, thereby generating a non-uniform chiral microenvironment. On this basis, the CMOF was integrated with a chiral phosphoric acid to establish a heterogeneous cooperative catalytic system, which was successfully applied to the asymmetric N-H insertion reaction between β-naphthylamine and α-diazocarbonyl esters. Compared with single-catalyst systems, the cooperative system exhibits markedly enhanced reaction yields and enantioselectivities. Combined structural analysis and catalytic investigations suggest that the staircase-like chiral framework plays a crucial role in stabilizing key reaction intermediates, promoting cooperation among multiple active sites, and regulating reaction selectivity. This work not only demonstrates the controllable transformation of natural chiral molecules into functional chiral framework materials but also provides new design principles for developing multifunctional cooperative asymmetric catalytic systems based on framework materials.

Key words: chiral metal-organic frameworks (CMOFs), natural camphoric acid, staircase-like structure, cooperative asymmetric catalysis, N-H bond insertion reaction

引用此文

王赵兴, 王新超, 郑晨阳, 李尚达, 张健. 基于天然樟脑酸构筑的阶梯状手性金属-有机框架及其协同不对称催化^★[J]. 化学学报, doi: 10.6023/A26010014.

Zhaoxing Wang, Xinchao Wang, Chenyang Zheng, Shangda Li, Jian Zhang. A Staircase-Like Chiral Metal-Organic Framework Constructed from Natural Camphoric Acid for Cooperative Asymmetric Catalysis[J]. Acta Chimica Sinica, doi: 10.6023/A26010014.

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