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Insight into the catalytic properties and applications of metal-organic frameworks in the cyanosilylation of aldehydes

机译：深入了解金属有机骨架在醛的氰基硅烷化反应中的应用

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Here we present a systematic investigation of the cyanosilylation of aldehydes with trimethylsilyl cyanide (TMSCN) by using metal-organic frameworks (MOFs) as catalysts. Four types of thermally stable MOFs (MIL-47 (V), MIL-53 (Al), MIL-101 (Cr), and UiO-66 (Zr)) constructed with the same organic linker, terephthalic acid, were studied, among which MIL-101 (Cr) exhibits the highest catalytic activity. Experimental results revealed that the catalytic activities are in close relation with the types of coordinatively unsaturated metal ions, pore sizes as well as solvents. Using MIL-101 (Cr) as the catalyst, both aliphatic and aromatic aldehydes were efficiently transformed to cyanohydrin trimethylsilyl ether, meanwhile significant size selectivities and electronic effects have also been observed. The solvent-free reaction conditions not only provide a high TON for MOF catalyzed cyanosilylation, but also render the current protocol more attractive to industrial applications.
机译：在这里，我们通过金属有机骨架（MOFs）作为催化剂，对醛类与三甲基甲硅烷基氰化物（TMSCN）的氰基硅烷化进行系统的研究。研究了用相同的有机连接基对苯二甲酸构造的四种类型的热稳定MOF（MIL-47（V），MIL-53（Al），MIL-101（Cr）和UiO-66（Zr））。其中MIL-101（Cr）表现出最高的催化活性。实验结果表明，催化活性与配位不饱和金属离子的类型，孔径以及溶剂密切相关。使用MIL-101（Cr）作为催化剂，脂族和芳族醛均被有效地转化为氰醇三甲基甲硅烷基醚，同时还观察到显着的尺寸选择性和电子效应。无溶剂的反应条件不仅为MOF催化的氰基硅烷化反应提供了较高的TON，而且使当前方案对工业应用更具吸引力。

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