Gold-amine cooperative catalysis for reductions and reductive aminations using formic acid as hydrogen source

• Published in: Applied catalysis. B, Environmental Vol. 267; p. 118728
• Main Authors: Fiorio, Jhonatan L., Araújo, Thaylan P., Barbosa, Eduardo C.M., Quiroz, Jhon, Camargo, Pedro H.C., Rudolph, Matthias, Hashmi, A. Stephen K., Rossi, Liane M.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 15.06.2020; Elsevier BV
• Subjects: Alkenes; Alkyne; Alkynes; Amination; Amine; Amines; Carbonyl compounds; Carbonyls; Catalysis; Catalysts; Chemical synthesis; Deuterium; Formic acid; Gold; Gold nanoparticles; Hydrogen storage; Reducing agents; Reductive amination; Transfer hydrogenation; Reductive amination; Transfer hydrogenation; Amine; Gold nanoparticles; Formic acid; Alkyne
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2020.118728

Transfer hydrogenation via amine-assisted formate decomposition at the Au NPs interface is a cleaner, safer, more efficient and selective manner to access Z-alkynes and valuables amines. [Display omitted] •A gold catalyst assisted by amine was applied in transfer hydrogenation reactions.•High reaction rate was obtained when using an appropriate amine.•Decomposition of Au-formate species is involved in the rate-determining step of the reaction.•The catalyst could be reused up to five times without any significant loss of activity.•Efficient and selective method to catalyze the semihydrogenation of alkynes and synthesis of valuables amines. Selective hydrogenation of alkynes to alkenes and reductive amination are industrially important reactions to synthesize a variety of fine and bulk chemicals. We report herein on a green and convenient approach for Z-alkenes and secondary amines using gold catalyst and formic acid (FA) as a green reductant. Furthermore, we highlight that the key to successfully obtain high reaction rates is to use an appropriate amine, which acts cooperatively with the gold surface, to activate formic acid. Studies with deuterium-labeled hydrogen donors gave insights that the decomposition of Au-formate species is involved in the rate-determining step. Moreover, various valuable secondary amines could be synthetized from readily available nitro and carbonyl compounds. This new strategy provides a cleaner, safer, more efficient and selective way to catalyze the synthesis of Z-alkenes and valuable amines.