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Highly shape- and regio-selective peroxy–trifluoromethylation of styrene by metal–organic framework Cu3(BTC)2
Catalysis Science & Technology ( IF 5 ) Pub Date : 2017-10-26 00:00:00 , DOI: 10.1039/c7cy01892d
Bo Qi 1, 2, 3, 4 , Tiexin Zhang 1, 2, 3, 4 , Mochen Li 1, 2, 3, 4 , Cheng He 1, 2, 3, 4 , Chunying Duan 1, 2, 3, 4, 5
Affiliation  

The peroxy and trifluoromethyl groups play important roles in pharmacy, but it is challenging to introduce both of them selectively into the target molecules in a homogeneous catalytic system. In the presence of the easily available metal–organic framework Cu3(BTC)2 (also well known as HKUST-1), novel peroxy–trifluoromethylation of styrenes was achieved in a heterogeneous mode. The rigid 3D framework of Cu3(BTC)2 is necessary to maintain the structural integrity of the binuclear paddle-wheel Cu(II) catalytic center for the effective electrophilic activation of Togni's reagent and TBHP with a low loading amount of the catalyst and its easy re-use, and the bowl bottom-like confined environment around the copper node is vital for the discrimination of reaction sites with different steric demands. Compared with homogeneous copper salts, the heterogeneous Cu3(BTC)2 showed superior catalytic activity and intrinsic shape- and regio-selectivity for this reaction. The peroxy moieties of the products could be easily converted to carbonyl or hydroxyl groups for further applications.

中文翻译:

金属-有机骨架Cu 3BTC2对苯乙烯的高度定型和区域选择性的过氧-三氟甲基化

过氧和三氟甲基在药房中起着重要的作用,但是在均相催化体系中将它们选择性地引入目标分子是具有挑战性的。在容易获得的金属-有机骨架Cu 3BTC2(也称为HKUST-1)的存在下,苯乙烯以异质方式实现了新型的过氧-三氟甲基化。Cu 3BTC2的刚性3D框架对于维持双核明轮Cu(II)的结构完整性是必不可少的)催化中心,用于Togni试剂和TBHP的有效亲电活化,催化剂的负载量低,并且易于重用,铜节点周围的碗底状密闭环境对于区分不同反应部位至关重要空间需求。与均相铜盐相比,非均相Cu 3BTC2显示出了优异的催化活性以及固有的形状和区域选择性。产物的过氧部分可以容易地转化为羰基或羟基,以用于进一步的应用。
更新日期:2017-11-06
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