An efficient way for the<i>N</i>-formylation of amines by inorganic-ligand supported iron catalysis

Wu, Zhikang; Zhai, Yongyan; Zhao, Wenshu; Wei, Zheyu; Han, Yizhuo; Han, Sheng; Wei, Yongge

doi:10.1039/c9gc03564h

Cited by 50 publications

(14 citation statements)

References 61 publications

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“…Formamides are one of the most important organic molecules due to their wide range of applications in science and industry, including synthetic organic chemistry and large‐scale production. For the synthesis of organic compounds, formamides are an important class of intermediates that have been used as protecting group of amines in the synthesis of peptides [2–4] . There are various drug molecules containing the N ‐formyl group in their scaffolds like benfotiamine, formoterol, vintiamol, and iguratimod (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…For the synthesis of organic compounds, formamides are an important class of intermediates that have been used as protecting group of amines in the synthesis of peptides. [2][3][4] There are various drug molecules containing the Nformyl group in their scaffolds like benfotiamine, formoterol, vintiamol, and iguratimod (Figure 1). [5] Formamides are also frequently used as essential synthetic intermediates in the production of imida-and tetrazole, quinazolinone, quinoline, and quinolone and different heterocyclic substances.…”

Section: Introductionmentioning

confidence: 99%

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Iron‐Catalyzed N, N‐formyl Ethylation of Amines

et al. 2023

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In organic synthesis, formamides are the most abundant class of compounds owing to their importance as the building blocks in synthetic and industrial organic chemistry. Formamides are also one of the most valuable intermediates produced in drug synthesis and act as precursors for the synthesis of therapeutically‐relevant molecules. Here, we developed a simple, practical, and catalytic methodology for the N‐formylation of a wide variety of amines by using iron as a catalyst. This protocol features an inexpensive iron catalyst, short reaction time, mild reaction conditions, good yields, easy workup, and tolerance of a wide variety of functional groups.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Iron‐Catalyzed N, N‐formyl Ethylation of Amines

et al. 2023

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“…To date, metal catalysts, including Fe, Co, Zn, Ni, Cu, Ru, and Pd complexes, − and organocatalysts, such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), N-heterocyclic carbenes (NHCs), ionic liquids (ILs), B(C 6 F 5 ) 3 , tetrabutylammonium fluoride (TBAF), and betaine, − have been proved to be effective for the N-formylation. Despite the encouraging catalytic performance of these systems, most of these approaches still require either harsh reaction conditions or expensive hydrogen source .…”

Section: Introductionmentioning

confidence: 99%

N-Formylation of Amines with Carbon Dioxide and Hydrogen Catalyzed by Ionic Liquid-Assisted Ru Complexes

Fang

Wang

Wei

et al. 2021

ACS Sustainable Chem. Eng.

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The N-formylation reaction of various amines with CO 2 is a promising method to utilize CO 2 for the production of high value-added chemicals. Herein, an efficient Ru catalyst system consisting of Ru complex ([PPN][Ru(CO) 3 Cl 3 ]) and the ionic liquid 1-butyl-3-methylimidazolium hydrogen phosphate ([Bmim] 2 [HPO 4 ]), has been developed for the N-formylation reaction. Activity evaluation demonstrated that the catalyst system exhibited good to excellent yields of formamides under very mild conditions with the assistance of ionic liquids (ILs). Furthermore, the catalyst system could be reused at least five times with a slight loss of activity in N-formylmorpholine production. Further characterization by 1 H nuclear magnetic resonance (NMR), 13 C NMR, and density functional theory (DFT) calculations showed that the ILs ([Bmim] 2 [HPO 4 ]) could facilitate the adsorption of CO 2 by a concerted action of both cations and anions of the ILs to form phosphorus carbonate intermediate, thus effectively promoting the reaction. DFT calculations demonstrated that the formation of Ru−H was the first step, and then the CO 2 absorbed by [Bmim] 2 [HPO 4 ] inserted directly into Ru−H by cooperating with the Ru sites to form HCOO − species. After that, formate species dissociated from Ru catalysts and dehydrated to form formamides by the catalytic action of Ru complex and the basic IL.

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“…Formamide could be synthesized by transformylation or direct amine formylation reactions [3] . The transformylation reaction is generally carried out with amines and formylating agents as substrates and previous researches were majorly focused on the development of various formylating agents, including formic acid and its derivatives, [4] methanol, [5] paraformaldehyde, [6] acetic formic anhydride, N,N‐dimethyl formamide, [7] and in situ generated formylating agents via hydrogenation of carbon dioxide [8] . For the transformylation route, some by‐product, such as water or methanol was produced unavoidably, resulting in energy consumption for separation.…”

Section: Introductionmentioning

confidence: 99%

Catalysis of Positively Charged Ru Species Stabilized by Hydroxyapatite in Amine Formylation

et al. 2021

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Formamide is an important solvent and synthetic intermediate. Herein, we designed a hydroxyapatite (HAP)‐stabilized, positively charged Ru‐based catalysts which can efficiently catalyze the formylation reaction of amines with CO for the synthesis of formamide. The Ru‐HAP showed excellent catalytic performance in N,N‐Dimethylformamide (DMF) synthesis, with about 75 % dimethylamine conversion and >99 % DMF selectivity at 300 h of continuous reaction. The combination of characterization results and control experiments showed that positively charged Ru species, including hydrated RuOx and Ru3+ species, were catalytically active. In particular, the surface RuOx species were more active than the Ru3+ species located within the HAP framework.

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An efficient way for theN-formylation of amines by inorganic-ligand supported iron catalysis

Abstract: A green and highly efficient N-formylation of amines using formic acid as the acylating agent by iron catalysis with excellent selectivity and yields.

Cited by 50 publications

References 61 publications

Iron‐Catalyzed N, N‐formyl Ethylation of Amines

Iron‐Catalyzed N, N‐formyl Ethylation of Amines

N-Formylation of Amines with Carbon Dioxide and Hydrogen Catalyzed by Ionic Liquid-Assisted Ru Complexes

Catalysis of Positively Charged Ru Species Stabilized by Hydroxyapatite in Amine Formylation

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