A spatially orthogonal hierarchically porous acid-base catalyst for cascade and antagonistic reactions
A spatially orthogonal hierarchically porous acid-base catalyst for cascade and antagonistic reactions
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DOI：
10.1038/s41929-020-00526-5
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发表时间：
2020-10-26
期刊：
影响因子：
37.8
通讯作者：
Lee, Adam F.
中科院分区：
文献类型：
--
作者：
Isaacs, Mark A.;Parlett, Christopher M. A.;Lee, Adam F.
复杂的有机分子在研究和工业化学中具有重要意义，通常是由较小的构件通过多步反应合成的。在一个反应器中进行多次(不同的)转化的能力将大大减少化学制造所需的操作次数，因此开发用于这种一锅反应的多功能催化剂是非常可取的。在这里，我们报道了一种分级多孔骨架的合成，其中大孔被硫酸化的氧化锆固体酸涂层选择性地功能化，而中孔被氧化镁固体碱纳米颗粒选择性地功能化。活性中心区隔和底物通道保护碱催化的三酰甘油酯交换免受游离脂肪酸杂质(即使在50mol%)的毒害，并促进二甲缩醛有效的两步级联脱缩合-Knovenagel缩合成氰酸酯。
Complex organic molecules are of great importance to research and industrial chemistry and typically synthesized from smaller building blocks by multistep reactions. The ability to perform multiple (distinct) transformations in a single reactor would greatly reduce the number of manipulations required for chemical manufacturing, and hence the development of multifunctional catalysts for such one-pot reactions is highly desirable. Here we report the synthesis of a hierarchically porous framework, in which the macropores are selectively functionalized with a sulfated zirconia solid acid coating, while the mesopores are selectively functionalized with MgO solid base nanoparticles. Active site compartmentalization and substrate channelling protects base-catalysed triacylglyceride transesterification from poisoning by free fatty acid impurities (even at 50 mol%), and promotes the efficient two-step cascade deacetalization-Knoevenagel condensation of dimethyl acetals to cyanoates.