硝基苯
化学
光化学
胺化
键裂
反应中间体
光解
催化循环
卡宾
催化作用
药物化学
有机化学
作者
Gerard P. Van Trieste,Kaleb A. Reid,Madeline H. Hicks,Anuvab Das,Matthew T. Figgins,Nattamai Bhuvanesh,Andrew Ozarowski,Joshua Telser,Dennis A. Powers
标识
DOI:10.1002/anie.202108304
摘要
Manganese complexes supported by macrocyclic tetrapyrrole ligands represent an important platform for nitrene transfer catalysis and have been applied to both C-H amination and olefin aziridination catalysis. The reactivity of the transient high-valent Mn nitrenoids that mediate these processes renders characterization of these species challenging. Here we report the synthesis and nitrene transfer photochemistry of a family of MnIII N-haloamide complexes. The S=2 N-haloamide complexes are characterized by 1 H NMR, UV-vis, IR, high-frequency and -field EPR (HFEPR) spectroscopies, and single-crystal X-ray diffraction. Photolysis of these complexes results in the formal transfer of a nitrene equivalent to both C-H bonds, such as the α-C-H bonds of tetrahydrofuran, and olefinic substrates, such as styrene, to afford aminated and aziridinated products, respectively. Low-temperature spectroscopy and analysis of kinetic isotope effects for C-H amination indicate halogen-dependent photoreactivity: Photolysis of N-chloroamides proceeds via initial cleavage of the Mn-N bond to generate MnII and amidyl radical intermediates; in contrast, photolysis of N-iodoamides proceeds via N-I cleavage to generate a MnIV nitrenoid (i.e., {MnNR}7 species). These results establish N-haloamide ligands as viable precursors in the photosynthesis of metal nitrenes and highlight the power of ligand design to provide access to reactive intermediates in group-transfer catalysis.
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