Heterogeneous Iridium-Catalyzed Carbene N-H Bond Insertion with α-Alkyl Diazo Esters

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作   者：

Ping Guo;  Yan Chen;  Lei Tao; 

作者机构：

East China University of Science and Technology;  Feringa Nobel Prize Scientist Joint Research Center;  School of Chemistry and Molecular Engineering;  China;  University of Chinese Academy of Sciences;  Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering;  Shanghai 200237;  Frontiers Science Center for Materiobiology and Dynamic Chemistry;  Beijing 100049; 

关键词：

iridium;  selectivity;  carbene insertion;  catalysis.;  heterogeneous; 

期刊名称：

ACS catalysis

i s s n：

2155-5435

年卷期：

2024 年 14 卷 7 期

页   码：

4690-4698

页   码：

摘   要：

A heterogeneous iridium single-atom site catalyst (Ir-SA) was synthesized and investigated in catalyzing the carbene insertion reaction with challenging α-alkyl diazo ester substrates. With only 0.23 mol % catalyst loading, our Ir-SA demonstrated remarkable performance in heterogeneous carbene N-H bond insertion reactions involving various (hetero) aryl amines coupled with α-alkyl diazo esters. Notably, in the case of using a chiral diamino substrate with two reactive sites, Ir-SA exhibited high selectivity toward single carbene N-H insertion, leading to the generation of a class of unsymmetric chiral diamino ligands. Further mechanism study revealed that the lower activation barrier associated with the single N-H bond insertion step, as compared to either β-hydride elimination or downstream dual N-H bond insertion, accounted for the remarkable selectivity observed in this carbene insertion reaction catalyzed by Ir-SA.