Selective formation of γ-lactams via C–H amidation enabled by tailored iridium catalysts
作者： Seung Youn Hong , Yoonsu Park , Yeongyu Hwang , Yeong Bum Kim , Mu-Hyun Baik
关键词: Intramolecular force 、 Combinatorial chemistry 、 Nitrene 、 Denticity 、 Selectivity 、 Chemistry 、 Density functional theory 、 Catalysis 、 Iridium 、 Isocyanate
摘要: Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form γ-lactam rings has traditionally been hindered by competing isocyanate formation. We report the application theory and mechanism studies optimize a class pentamethylcyclopentadienyl iridium(III) catalysts for suppression this pathway. Modulation stereoelectronic properties auxiliary bidentate ligands be more electron-donating was suggested density functional calculations lower C–H barrier favoring desired reaction. These transform wide range 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, corresponding γ-lactams via sp 3 2 amidation with exceptional selectivity. The power method further demonstrated successful late-stage functionalization amino acid derivatives other bioactive molecules.
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