Eco-friendly acetylcholine-carboxylate bio-ionic liquids for controllable N-methylation and N-formylation using ambient CO2 at low temperatures

• Published in: Green chemistry : an international journal and green chemistry resource : GC Vol. 21; no. 3; pp. 567 - 577
• Main Authors: Zhao, Wenfeng, Chi, Xiaoping, Li, Hu, He, Jian, Long, Jingxuan, Xu, Yufei, Yang, Song
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 2019; Royal Society of Chemistry
• Subjects: Acetonitrile; Acetylcholine; Anions; Biodegradability; Biodegradation; Carbon dioxide; Carbon dioxide fixation; Carbon sequestration; Carbon sources; Catalysis; Cations; Chemistry; Chemistry, Multidisciplinary; Computer applications; Electrostatic properties; Fine chemicals; Green & Sustainable Science & Technology; Green chemistry; Hydrosilylation; Ionic liquids; Ions; Low temperature; Methylamine; Methylation; Organic chemistry; Physical Sciences; Reaction mechanisms; Science & Technology; Science & Technology - Other Topics; Selectivity; Solvents; Substrates; MILD; FUNCTIONALIZATION; CATALYZED HYDROSILYLATION; REDUCTION; SOLVENTS; AMINES; CONVERSION; CHOLINE; SILANES; CARBON-DIOXIDE
• ISSN: 1463-9262; 1463-9270
• DOI: 10.1039/c8gc03549k

Catalytic fixation of CO2 to produce valuable fine chemicals is of great significance to develop a green and sustainable circulation of excessive carbon in the environment. Herein, a series of non-toxic, biodegradable and recyclable acetylcholine-carboxylate bio-ionic liquids with different cations and anions were simply synthesized for producing formamides and methylamines using atmospheric CO2 as a carbon source, and phenylsilane as a hydrogen donor. The selectivity toward products was tuned by altering the reaction temperature under solvent or solvent-free conditions. N-Methylamines (ca. 96% yield) were obtained in acetonitrile at 50 degrees C, while N-formamides (ca. 99% yield) were attained without a solvent at 30 degrees C. The established bio-ionic liquid catalytic system found a wide range of applicability in substrates and possessed a high potentiality in scale-up to gram-grade production. The developed catalytic system was fairly stable, which could be easily reused without an apparent loss of reactivity, possibly due to the strong electrostatic interactions between the cation and anion. The combination of experimental and computational results explicitly elucidated the reaction mechanism: PhSiH3 activated by a bio-IL was favorable for the formation of silyl formate from hydrosilylation of CO2, followed by a reaction with an amine to give an N-formamide, while an N-methylamine was formed by further hydrosilylation of the N-formamide.