Sustainable route to biomass-based amines: rhodium catalyzed hydroaminomethylation in green solvents

Sustainable route to biomass-based amines: rhodium catalyzed hydroaminomethylation in green solvents

[Display omitted] •The hydroaminomethylation of biomass-based substrates: estragole, limonene, camphene and β-pinene, was developed.•Di-n-butylamine, morpholine, 4-methylpiperidine or 1,2,3,4-tetrahydroisoquinoline were used as condensation counterparts.•Several novel amines with potential bioactivi...

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Bibliographic Details
Published in:Applied catalysis. A, General Vol. 574; pp. 97 - 104
Main Authors: de Oliveira Dias, Adelson, Gutiérrez, María G.P., Villarreal, Jesus A.A., Carmo, Raul L.L., Oliveira, Kelley C.B., Santos, Alexandra G., dos Santos, Eduardo N., Gusevskaya, Elena V.
Format: Journal Article
Language:English
Published: Amsterdam Elsevier B.V 25-03-2019
Elsevier Science SA
Subjects:
Aldehydes
Alkenes
Amines
Anisole
Biorenewables
Camphene
Cascade chemical reactions
Estragole
Ethanol
Hydroaminomethylation
Limonene
Morpholine
Rhodium
Solvents
Substrates
Sustainability
Toluene
β-Pinene
Biorenewables
Limonene
Camphene
Hydroaminomethylation
Estragole
β-Pinene
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Summary:[Display omitted] •The hydroaminomethylation of biomass-based substrates: estragole, limonene, camphene and β-pinene, was developed.•Di-n-butylamine, morpholine, 4-methylpiperidine or 1,2,3,4-tetrahydroisoquinoline were used as condensation counterparts.•Several novel amines with potential bioactivity were obtained in 80–98% yields.•The reactions can be performed in eco-friendly solvents such as p-cymene, anisole and ethanol.•The use of bio-renewable ethanol as a solvent improved the process sustainability and yields of final amines in some cases. The hydroaminomethylation of bio-renewable alkenes, i.e., estragole, limonene, camphene and β-pinene, was studied using di-n-butylamine, morpholine, 4-methylpiperidine or 1,2,3,4-tetrahydroisoquinoline as condensation counterparts. This tandem reaction consists of the alkene hydroformylation step followed by the reductive amination of the resulting aldehydes. A series of novel amines with potential bioactivity was obtained in excellent yields. p-Cymene, anisole and ethanol proved to be excellent greener alternatives for toluene, a solvent conventionally used for hydroaminomethylation in most of the previous studies. The performance of p-cymene and anisole was similar to that of toluene; whereas the use of bio-renewable ethanol as a solvent allowed not only to improve the process sustainability but also to obtain much better yields of final amines in several applications, especially, for estragole and β-pinene, the most challenging substrates in the study.
ISSN:0926-860X
1873-3875
DOI:10.1016/j.apcata.2019.02.003