TY - JOUR
T1 - N-formyl-stabilizing quasi-catalytic species afford rapid and selective solvent-free amination of biomass-derived feedstocks
AU - Li, Hu
AU - Guo, Haixin
AU - Su, Yaqiong
AU - Hiraga, Yuya
AU - Fang, Zhen
AU - Hensen, Emiel J.M.
AU - Watanabe, Masaru
AU - Smith, Richard Lee
N1 - Funding Information:
This work is financially supported by Nanjing Agricultural University (68Q-0603), International Postdoctoral Exchange Fellowship Program of China (20170026), Postdoctoral Science Foundation of China (2016M600422), and Jiangsu Postdoctoral Research Funding Plan (1601029A) for study at Tohoku University. We thank Cheng-jiang Fang (Guizhou University) for recording part of the NMR spectra, and also acknowledge the Research Center of Supercritical Fluid Technology (Director, Prof. Hiroshi Inomata) of Tohoku University for logistics support. Special thanks to Professor Sir Martyn Poliakoff (University of Nottingham) for providing helpful comments on the manuscript.
Publisher Copyright:
© 2019, The Author(s).
PY - 2019/12/1
Y1 - 2019/12/1
N2 - Nitrogen-containing compounds, especially primary amines, are vital building blocks in nature and industry. Herein, a protocol is developed that shows in situ formed N-formyl quasi-catalytic species afford highly selective synthesis of formamides or amines with controllable levels from a variety of aldehyde- and ketone-derived platform chemical substrates under solvent-free conditions. Up to 99% yields of mono-substituted formamides are obtained in 3 min. The C-N bond formation and N-formyl species are prevalent in the cascade reaction sequence. Kinetic and isotope labeling experiments explicitly demonstrate that the C-N bond is activated for subsequent hydrogenation, in which formic acid acts as acid catalyst, hydrogen donor and as N-formyl species source that stabilize amine intermediates elucidated with density functional theory. The protocol provides access to imides from aldehydes, ketones, carboxylic acids, and mixed-substrates, requires no special catalysts, solvents or techniques and provides new avenues for amination chemistry.
AB - Nitrogen-containing compounds, especially primary amines, are vital building blocks in nature and industry. Herein, a protocol is developed that shows in situ formed N-formyl quasi-catalytic species afford highly selective synthesis of formamides or amines with controllable levels from a variety of aldehyde- and ketone-derived platform chemical substrates under solvent-free conditions. Up to 99% yields of mono-substituted formamides are obtained in 3 min. The C-N bond formation and N-formyl species are prevalent in the cascade reaction sequence. Kinetic and isotope labeling experiments explicitly demonstrate that the C-N bond is activated for subsequent hydrogenation, in which formic acid acts as acid catalyst, hydrogen donor and as N-formyl species source that stabilize amine intermediates elucidated with density functional theory. The protocol provides access to imides from aldehydes, ketones, carboxylic acids, and mixed-substrates, requires no special catalysts, solvents or techniques and provides new avenues for amination chemistry.
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U2 - 10.1038/s41467-019-08577-4
DO - 10.1038/s41467-019-08577-4
M3 - Article
C2 - 30741927
AN - SCOPUS:85061290909
VL - 10
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 699
ER -