Kong Lingfang, Tao Zekun, Li Yunjia, Gong Huiwen, Bai Yun, Li Longbin, Zhang Xianjin, Zhou Zhonggao, Chen Yiwang
College of Chemistry and Chemical Engineering/Analysis and Testing Center/Key Laboratory of Jiangxi University for Functional Materials Chemistry, Gannan Normal University Ganzhou 341000 P. R. China
Institute of Chemistry Education, Fujian Institute of Education Fuzhou 350025 P. R. China.
Chem Sci. 2024 Aug 27;15(37):15321-31. doi: 10.1039/d4sc03106g.
The synthesis of high-value chemicals featuring C-C and/or C-heteroatom bonds CO is critically important, yet efficiently converting thermodynamically stable and kinetically inert linear CO and propargylic amine to the heterocyclic compound 2-oxazolidinone with an integrated catalytic system continues to pose a considerable challenge. Herein, we have designed an "all-in-one" (AIO) palladium (Pd) catalyst (Cat1), distinguished by its co-coordination with acetylglucose (AcGlu) and bis(benzimidazolium) units at the Pd center, which promotes the cyclization of CO and propargylic amine achieving a highest turnover frequency (TOF) of up to 3456 h. Moreover, Cat1 demonstrates excellent stability across various temperatures, with its catalytic activity remaining unchanged even after 10 cycles. The catalyst Cat1 simultaneously activates propargylic amine and CO, facilitating the formation of N-heterocyclic carbene (NHC)-CO adducts and AcGlu-CO philes from CO in simulated flue gas, a key factor in reaching unprecedented TOF values. The catalytic mechanism was elucidated through NMR and C-isotope labeling experiments. Notably, this is the first instance of an AIO Pd catalyst that enables the simultaneous capture, activation, and catalytic conversion of activated CO along with propargylic amine. The design strategy of this AIO catalyst introduces a novel approach to overcoming the challenges in the efficient conversion of inert CO.
合成具有C-C和/或C-杂原子键的高价值化学品至关重要，然而，利用集成催化体系将热力学稳定且动力学惰性的线性CO和炔丙胺高效转化为杂环化合物2-恶唑烷酮仍然是一个巨大的挑战。在此，我们设计了一种“一体化”（AIO）钯（Pd）催化剂（Cat1），其特点是在Pd中心与乙酰葡萄糖（AcGlu）和双（苯并咪唑鎓）单元协同配位，该催化剂促进了CO和炔丙胺的环化反应，实现了高达3456 h⁻¹的最高周转频率（TOF）。此外，Cat1在不同温度下均表现出优异的稳定性，即使经过10次循环，其催化活性仍保持不变。催化剂Cat1同时激活炔丙胺和CO，促进了模拟烟道气中N-杂环卡宾（NHC）-CO加合物和AcGlu-CO亲核试剂的形成，这是达到前所未有的TOF值的关键因素。通过¹³C NMR和¹³C同位素标记实验阐明了催化机理。值得注意的是，这是首例能够同时捕获、激活并催化转化活性CO和炔丙胺的AIO Pd催化剂。这种AIO催化剂的设计策略为克服惰性CO高效转化中的挑战引入了一种新方法。
