Li Zhenzhong, Jiang Huating, Zhu Mingxiang, Zhang Fang
Department of Chemistry, Shanghai Normal University, Shanghai 200234, China.
Technical University of Darmstadt, Institute of Inorganic and Physical Chemistry, Darmstadt D-64287, Germany.
ACS Appl Mater Interfaces. 2024 Apr 17;16(15):19003-19013. doi: 10.1021/acsami.4c02215. Epub 2024 Apr 2.
The development of heterogeneous chiral dirhodium catalysts for fabricating important bioactive substances and reducing the loss of noble metals has long been of significant interest. However, there still remains formidable synthetic challenges since it requires multiple steps of the synthetic process, and rhodium is easily leached from solid materials during the reaction. Here, we demonstrated a self-supported strategy based on the Suzuki-Miyaura coupling reaction to construct two chiral dirhodium organic frameworks for heterogeneous asymmetric catalysis. The synthetic approach is simple and efficient since it requires only a small number of preparation steps and does not require any catalyst supporting materials. The obtained chiral dirhodium materials can be highly efficient and recyclable heterogeneous catalysts for asymmetric cyclopropanation between diazooxindole and alkenes. Importantly, Rh-MOCP-2 exhibited almost similar catalytic performance compared to homogeneous catalyst Rh(-Br-NTTL). The afforded catalytic performance (93.9% yield with 80.9% ee) highly surpasses previous heterogeneous dirhodium catalysts reported to date.
长期以来，开发用于制备重要生物活性物质并减少贵金属损失的多相手性铑催化剂一直备受关注。然而，由于合成过程需要多个步骤，并且铑在反应过程中很容易从固体材料中浸出，因此仍然存在巨大的合成挑战。在此，我们展示了一种基于铃木-宫浦偶联反应的自支撑策略，以构建两种用于多相不对称催化的手性铑有机框架。该合成方法简单高效，因为它只需要少量的制备步骤，并且不需要任何催化剂载体材料。所获得的手性铑材料可以成为用于重氮氧化吲哚和烯烃之间不对称环丙烷化的高效且可回收的多相催化剂。重要的是，与均相催化剂Rh(-Br-NTTL)相比，Rh-MOCP-2表现出几乎相似的催化性能。所提供的催化性能（产率93.9%，对映体过量值80.9%）大大超过了迄今为止报道的先前的多相铑催化剂。
