Issue 9, 2024

Orthogonal assisted tandem reactions for the upgrading of bio-based aromatic alcohols using chitin derived mono and bimetallic catalysts

Abstract

The upgrading of a benzyl-type alcohols was explored via an orthogonal tandem sequence comprised of a first oxidative step producing the corresponding aldehydes, and a subsequent reductive amination to achieve both secondary and tertiary amines. To the scope, acetonitrile (ACN) was used as a solvent and a source/precursor of reactant amines, and different heterogeneous catalysts based on Rh and Mo, were designed as mono- and bi-metallic systems in the form of metal nanoparticles dispersed on a chitin-derived N-doped carbons. A parametric analysis carried out separately for the oxidation and the reductive amination allowed to choose the best performant catalyst for both the reactions of the tandem process. A one-pot two-step protocol was implemented accordingly: as an example, benzyl alcohol was quantitatively and selectively oxidised to benzaldehyde (>99%) which in turn, was converted to N-benzylethanamine (66%) or N-benzyl-N-ethylethanamine (60%) in the presence of [Rh(5%)-N/C–Mo(5%)]-N/C or [Rh(3%)-N/C–Mo(5%)]-N/C as catalysts, respectively. The tandem sequence proved successful also for other bio-based benzyl-type alcohols that afforded the corresponding secondary/tertiary amines in yields up to 53–93%. Overall, the study proved the viability of an innovative method aimed not only at process intensification for multistep synthesis, but also at the valorization of substrates (alcohols) and biopolymers (chitin) derived from biomass.

Graphical abstract: Orthogonal assisted tandem reactions for the upgrading of bio-based aromatic alcohols using chitin derived mono and bimetallic catalysts

Supplementary files

Article information

Article type
Paper
Submitted
08 Ker. 2023
Accepted
22 Meur. 2024
First published
26 Meur. 2024

Green Chem., 2024,26, 5221-5238

Orthogonal assisted tandem reactions for the upgrading of bio-based aromatic alcohols using chitin derived mono and bimetallic catalysts

F. Zorzetto, D. Ballesteros-Plata, A. Perosa, E. Rodríguez-Castellón, M. Selva and D. Rodríguez-Padrón, Green Chem., 2024, 26, 5221 DOI: 10.1039/D3GC04848A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements