Direct synthesis of N‐formamides by integrating reductive amination of ketones and aldehydes with CO2 fixation in a metal‐organic framework

DOI: 10.1002/chem.202303289

Authors: Wenyaun Huang (Manchester University) , Qingqing Mei (Manchester University) , Shaojun Xu (Manchester University) , Bing An (Manchester University) , Meng He (Manchester University) , Jiangnan Li (Manchester University) , Yinlin Chen (Manchester University) , Xue Han (Manchester University) , Tian Luo (Manchester University) , Lixia Guo (Manchester University) , Joseph Hurd (Manchester University) , Daniel Lee (Manchester University) , Evan Tillotson (Manchester University) , Sarah Haigh (Manchester University) , Alex Walton (Manchester University) , Sarah Day (Diamond Light Source) , Louise S. Natrjan (Manchester University) , Martin Schroeder (University of Manchester) , Sihai Yang (Manchester University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry – A European Journal

State: Published (Approved)
Published: October 2023

Abstract: Formamides are important feedstocks for the manufacture of many fine chemicals. State-of-the-art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom-economy. Here, we report the first example of direct synthesis of N-formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass-derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over a metal-organic framework supported ruthenium catalyst, Ru/MFM-300(Cr). Highly selective production of N-formamides has been observed for a wide range of carbonyl compounds. Synchrotron X-ray powder diffraction reveals the presence of strong host-guest binding interactions via hydrogen bonding and parallel-displaced π···π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals.

Journal Keywords: N-formylation; Reductive amination; MFM-300(Cr); SXPD; ssNMR

Subject Areas: Chemistry, Materials, Environment


Instruments: B18-Core EXAFS , I11-High Resolution Powder Diffraction

Added On: 30/10/2023 08:49

Documents:
Chemistry A European J - 2023 - Huang - Direct synthesis of N%E2%80%90formamides by integrating reductive amination of ketones and.pdf

Discipline Tags:

Earth Sciences & Environment Climate Change Physical Chemistry Catalysis Chemistry Materials Science Chemical Engineering Engineering & Technology Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction Spectroscopy X-ray Powder Diffraction X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS) X-ray Absorption Near Edge Structure (XANES)