Is it possible to perform selective alkylation of amines using known green solvents, a simple cobalt salt, and an available commercial gas mixture? It is shown that it is not only possible but also easy to perform selective production of mono- and bis-alkylated amines without alkyl halides using solvents from biomass instead.

The use of bio-renewable resources as starting materials and reagents in synthetic chemistry is an important area for sustainable development. The use of tetrahydrofuran (THF) and 2-methyltetrahydrofuran (2-MeTHF) is reported, which can be obtained from lignocellulosic biomass, as potential alkylating agents for anilines. The developed N-alkylation process is catalyzed by the readily available cobalt salts and employs industrially available syngas as a reducing agent. The reported approach allows for the green and cost-effective production of N-alkylanilines from readily available feedstocks.