Direct α-alkylation of primary aliphatic amines enabled by CO2 and electrostatics
| Autor: | Franziska Schoenebeck, Indrek Kalvet, Juntao Ye, Tomislav Rovis |
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| Rok vydání: | 2018 |
| Předmět: |
010405 organic chemistry
Chemistry General Chemical Engineering Intermolecular force General Chemistry Hydrogen atom Alkylation 010402 general chemistry 01 natural sciences Combinatorial chemistry 0104 chemical sciences Catalysis chemistry.chemical_compound Static electricity Amine gas treating Organic synthesis Selectivity |
| Zdroj: | Nature Chemistry. 10:1037-1041 |
| ISSN: | 1755-4349 1755-4330 |
| DOI: | 10.1038/s41557-018-0085-9 |
| Popis: | Primary aliphatic amines are important building blocks in organic synthesis due to the presence of a synthetically versatile NH2 group. N-functionalization of primary amines is well established, but selective C-functionalization of unprotected primary amines remains challenging. Here, we report the use of CO2 as an activator for the direct transformation of abundant primary aliphatic amines into valuable γ-lactams under photoredox and hydrogen atom transfer (HAT) catalysis. Experimental and computational studies suggest that CO2 not only inhibits undesired N-alkylation of primary amines, but also promotes selective intermolecular HAT by an electrostatically accelerated interaction between the in situ-generated negatively charged carbamate and the positively charged quinuclidinium radical. This electrostatic attraction overwhelms the inherent bond dissociation energies which suggest that HAT should occur unselectively. We anticipate that our findings will open up new avenues for amine functionalizations as well as selectivity control in HAT reactions. |
| Databáze: | OpenAIRE |
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