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Preparation of Cu cluster catalysts by simultaneous cooling–microwave heating: application in radical cascade annulation
Nanoscale Advances ( IF 4.7 ) Pub Date : 2021-1-11 , DOI: 10.1039/d0na00980f
Liangliang Song 1 , Roberta Manno 2, 3 , Prabhat Ranjan 1 , Victor Sebastian 2, 3, 4 , Silvia Irusta 2, 3, 4 , Reyes Mallada 2, 3, 4 , Luc Van Meervelt 5 , Jesús Santamaria 2, 3, 4 , Erik V Van der Eycken 1, 6
Affiliation  

One of the hallmarks of microwave irradiation is its selective heating mechanism. In the past 30 years, alternative designs of chemical reactors have been introduced, where the microwave (MW) absorber occupies a limited reactor volume but the surrounding environment is MW transparent. This advantage results in a different heating profile or even the possibility to quickly cool down the system. Simultaneous cooling–microwave heating has been largely adopted for organic chemical transformations. However, to the best of our knowledge there are no reports of its application in the field of nanocluster synthesis. In this work, we propose an innovative one-pot procedure for the synthesis of Cu nanoclusters. The cluster nucleation was selectively MW-activated inside the pores of a highly ordered mesoporous substrate. Once the nucleation event occurred, the crystallization reaction was instantaneously quenched, precluding the growth events and favoring the production of Cu clusters with a homogenous size distribution. Herein, we demonstrated that Cu nanoclusters could be successfully adopted for radical cascade annulations of N-alkoxybenzamides, resulting in various tricyclic and tetracyclic isoquinolones, which are widely present in lots of natural products and bioactive compounds. Compared to reported homogeneous methods, supported Cu nanoclusters provide a better platform for a green, sustainable and efficient heterogeneous approach for the synthesis of tricyclic and tetracyclic isoquinolones, avoiding a variety of toxic waste/byproducts and metal contamination in the final products.

中文翻译:

同时冷却-微波加热制备铜簇催化剂:在自由基级联环化中的应用

微波辐照的标志之一是其选择性加热机制。在过去的 30 年中,已经引入了化学反应器的替代设计,其中微波 (MW) 吸收器占据了有限的反应器体积,但周围环境是 MW 透明的。这一优势导致不同的加热曲线,甚至可以快速冷却系统。同时冷却-微波加热已被广泛用于有机化学转化。然而,据我们所知,尚无关于其在纳米团簇合成领域应用的报道。在这项工作中,我们提出了一种创新的一锅法合成铜纳米团簇。簇成核在高度有序的介孔基质的孔内被选择性地 MW 激活。一旦成核事件发生,结晶反应瞬间淬火,排除了生长事件并有利于产生具有均匀尺寸分布的铜簇。在这里,我们证明了Cu纳米团簇可以成功地用于自由基级联环化。N-烷氧基苯甲酰胺,产生各种三环和四环异喹诺酮,广泛存在于许多天然产物和生物活性化合物中。与已报道的均相方法相比,负载型铜纳米团簇为绿色、可持续和高效的多相方法提供了一个更好的平台,用于合成三环和四环异喹诺酮类药物,避免了最终产品中的各种有毒废物/副产物和金属污染。
更新日期:2021-01-19
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