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7424732 
Journal Article 
Direct α-alkylation of primary aliphatic amines enabled by CO2 and electrostatics 
Ye, J; Kalvet, I; Schoenebeck, F; Rovis, T; , 
2018 
1 
Nature Chemistry
ISSN: 1755-4330
EISSN: 1755-4349 
Nature Publishing Group 
10 
10 
1037-1041 
English 
30061617 
WOS:000445129300010 
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. 
amine; carbon; carbon dioxide; coordination compound; hydrogen; iridium; alkylation; catalysis; chemistry; light; oxidation reduction reaction; static electricity; Alkylation; Amines; Carbon; Carbon Dioxide; Catalysis; Coordination Complexes; Hydrogen; Iridium; Light; Oxidation-Reduction; Static Electricity 
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