Zhang Chun-Ling, Su Dao, Wang Habuer, Muschin Tegshi, Wu Yun, Bao Yong-Sheng, Zhu Huai-Yong
Inner Mongolia Key Laboratory of Green Catalysis, College of Chemistry and Environmental Science, Inner Mongolia Normal University, Hohhot 010022, China.
School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, 2 George Street, Brisbane 4001, Australia.
Molecules. 2025 May 21;30(10):2232. doi: 10.3390/molecules30102232.
Copper complexes have attracted significant interest for catalyzing oxidative dehydrogenative carboxylation of alkanes to form esters. Here, we report a heterogeneous catalyst, in which copper complexes are immobilized on coal-bearing kaolin for the synthesis of allylic esters via C()-H bond activation through cross-dehydrogenation coupling reactions between cyclic alkanes and aromatic carboxylic acids. Systematic optimization of reaction conditions-including catalyst loading, copper content, oxidant, temperature, and reaction time-resulted in a high yield of 71% of allylic ester, comparable to homogeneous transition metal catalysts. The catalyst is easily recoverable via centrifugation and retains its activity over five consecutive reuse cycles. This system demonstrates broad substrate compatibility with various aromatic carboxylic acids and cyclic alkanes. Beyond offering an efficient and reusable catalytic route for allylic ester synthesis, this work highlights the potential of coal-bearing kaolin as a sustainable support material for transition metal catalysis and provides an environmentally benign method for activating inert C()-H bonds.
铜配合物在催化烷烃氧化脱氢羧化反应以形成酯方面引起了广泛关注。在此，我们报道了一种多相催化剂，其中铜配合物负载于含煤高岭土上，用于通过环烷烃与芳族羧酸之间的交叉脱氢偶联反应，经由C（）-H键活化来合成烯丙基酯。对反应条件（包括催化剂负载量、铜含量、氧化剂、温度和反应时间）进行系统优化后，烯丙基酯的产率高达71%，与均相过渡金属催化剂相当。该催化剂可通过离心轻松回收，并在连续五个重复使用循环中保持其活性。该体系对各种芳族羧酸和环烷烃表现出广泛的底物兼容性。除了为烯丙基酯合成提供一种高效且可重复使用的催化途径外，这项工作还突出了含煤高岭土作为过渡金属催化的可持续载体材料的潜力，并提供了一种环境友好的活化惰性C（）-H键的方法。
