Nickel-catalyzed transamidation of aliphatic amide derivatives
| Autor: | Jacob E. Dander, Neil K. Garg, Emma L. Baker |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Primary (chemistry)
010405 organic chemistry chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences 0104 chemical sciences Catalysis Stereocenter Nickel chemistry.chemical_compound Chemistry chemistry Amide Chemical Sciences Organic chemistry Amine gas treating Organic synthesis Selectivity |
| Zdroj: | Chemical Science Chemical science, vol 8, iss 9 |
| ISSN: | 2041-6520 |
| Popis: | We report a two-step approach to achieve the transamidation of secondary aliphatic amides using non-precious metal catalysis. Transamidation, or the conversion of one amide to another, is a long-standing challenge in organic synthesis. Although notable progress has been made in the transamidation of primary amides, the transamidation of secondary amides has remained underdeveloped, especially when considering aliphatic substrates. Herein, we report a two-step approach to achieve the transamidation of secondary aliphatic amides, which relies on non-precious metal catalysis. The method involves initial Boc-functionalization of secondary amide substrates to weaken the amide C–N bond. Subsequent treatment with a nickel catalyst, in the presence of an appropriate amine coupling partner, then delivers the net transamidated products. The transformation proceeds in synthetically useful yields across a range of substrates. A series of competition experiments delineate selectivity patterns that should influence future synthetic design. Moreover, the transamidation of Boc-activated secondary amide derivatives bearing epimerizable stereocenters underscores the mildness and synthetic utility of this methodology. This study provides the most general solution to the classic problem of secondary amide transamidation reported to date. |
| Databáze: | OpenAIRE |
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