Nitrene-mediated intermolecular N–N coupling for efficient synthesis of hydrazides
| Autor: | Sukbok Chang, Gong Chen, Hao Wang, Shiyang Zhu, Gang He, Hoimin Jung, Fangfang Song, Danye Chen, Ziqian Bai |
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| Rok vydání: | 2021 |
| Předmět: |
Steric effects
chemistry.chemical_classification 010405 organic chemistry Chemistry Hydrogen bond General Chemical Engineering Nitrene Carboxylic acid General Chemistry 010402 general chemistry 01 natural sciences Combinatorial chemistry 0104 chemical sciences Catalysis Nucleophile Electrophile Chemoselectivity |
| Zdroj: | Nature Chemistry. 13:378-385 |
| ISSN: | 1755-4349 1755-4330 |
| Popis: | N-N linkages are found in many natural compounds and endow fascinating structural and functional properties. In comparison to the myriad methods for the construction of C-N bonds, chemistry for N-N coupling, especially in an intermolecular fashion, remains underdeveloped. Here, we report a nitrene-mediated intermolecular N-N coupling of dioxazolones and arylamines under iridium or iron catalysis. These reactions offer a simple and efficient method for the synthesis of various hydrazides from readily available carboxylic acid and amine precursors. Although the Ir-catalysed conditions usually give higher N-N coupling yield than the Fe-catalysed conditions, the reactions of sterically more demanding dioxazolones derived from α-substituted carboxylic acids work much better under the Fe-catalysed conditions. Mechanistic studies revealed that the nitrogen atom of Ir acyl nitrene intermediates has strong electrophilicity and can undergo nucleophilic attack with arylamines with the assistance of Cl···HN hydrogen bonding to form the N-N bond with high efficiency and chemoselectivity. |
| Databáze: | OpenAIRE |
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