Homogeneous cobalt catalyzed reductive formylation of N-heteroarenes with formic acid

Zhu, Meiling; Tian, Haitao; Chen, Sanxia; Xue, Wenxuan; Wang, Yanhong; Lu, Hongcheng; Li, Ting; Chen, Feng; Tang, Conghui

doi:10.1016/j.jcat.2022.11.006

Cited by 14 publications

(3 citation statements)

References 37 publications

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“…Many methods have been used to prepare these compounds. For example, a variety of hydrogen sources such as hydrogen, [3][4][5] alcohols, [6] formates, [7] silanes, [8] and Hantzsch esters [9] have been used for the chemoselective reduction of quinoline derivatives (Scheme 1a). Among them, direct hydrogenation of nitrogen-containing heteroarenes is an efficient route.…”

Section: Introductionmentioning

confidence: 99%

Development of a Cobalt Catalyst from ZIF‐67 and Application in the Hydrogenation of N‐Heteroarenes

Yuan,

Zhou,

Zhou

et al. 2024

Eur J Org Chem

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Hydrogenation of N‐heteroarenes to saturated N‐heterocycles is an important reaction in organic synthesis. Hydrogen is a green‐reducing reagent and has been widely applied in industrial production. The development of an appropriate catalyst to realize hydrogenation under low pressure and temperature is desired. In this study, we developed a cobalt‐based catalyst derived from ZIF‐67, and it exhibits high activity for N‐heteroarene hydrogenation under 5‐20 bar hydrogen, which is relatively low compared to reported catalytic systems. This nano‐cobalt catalyst shows a broad substrate scope and can be reused without obvious activity loss.

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Section: Introductionmentioning

confidence: 99%

Development of a Cobalt Catalyst from ZIF‐67 and Application in the Hydrogenation of N‐Heteroarenes

Yuan,

Zhou,

Zhou

et al. 2024

Eur J Org Chem

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“…For instance, in 2020, Wu et al used an iron catalyst supported by inorganic ligands (NH 4 ) 3 [FeMo 6 O 18 (OH) 6 ] to catalyze the coupling of formic acid and amine for the synthesis of formamide. Recently, Zhu et al established a homogeneous cobalt-catalyzed reductive N-formylation of amines using formic acid. Moreover, catalysts based on metallic oxide, Co@C–N, Pd/In 2 O 3 , and ionic liquids − have been developed for this reaction.…”

mentioning

confidence: 99%

“…Based on the results of controlled experiments and previous research, − a possible reaction mechanism has been proposed (Scheme ). Initially, the lone pair on the N atoms of aniline attacks the activated C atom of HCOOH, producing formate, which then dehydrates to yield the corresponding formamide.…”

mentioning

confidence: 99%

Catalyst-Free N-Formylation of Amines Using Formic Acid as a Sustainable C1 Source

Liang,

Zhao,

et al. 2023

ACS Sustainable Chem. Eng.

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Formic acid, as an easily available C1 source, can be obtained through CO2 hydrogenation or biomass smelting. For this perspective, N-formylation of amines with formic acid as the C1 synthon can be considered as indirect utilization of CO2 or biomass, thus providing an alternative synthetic strategy. In this work, we present a sustainable protocol for the N-formylation of amines using formic acid as the carbonyl source under catalyst-free conditions. This procedure yields medium to excellent results for various formamides. Furthermore, we successfully extended this protocol to include the reduction coupling of formic acid, primary amines, and aldehydes, demonstrating broad substrate applicability.

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Ruthenium Catalysed Transfer Deuteration of Heteroaromatics in D₂O

Gonzalo‐Navarro,

Ruiz‐Castañeda,

Fidalgo

et al. 2024

Asian J Org Chem

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There is a growing interest in deuterated derivatives in various fields, including the pharmaceutical industry. In this industry, partially hydrogenated heterocycles are also a target. Combining these two concepts, it was studied the reduction of heterocycles with simultaneous deuterium incorporation by transfer deuteration, a process of introducing two deuterium atoms into an organic molecule using non‐D2 sources, avoiding the use of a gas or harmful reagents. Formic acid/sodium formate and D2O as the sole deuterium source were used under mild conditions. The precatalyst was [RuCl(p‐cym)(dmbpy)]BF4, (p‐cym = p‐cymene, dmbpy = 4,4’‐dimethyl‐2,2’‐bipyridine), which is able to generate the “Ru‐D” fragment from D+ by a polarity inversion process (“umpolung”). A wide range of heterocycles were tested. Selective reduction in the nitrogen‐containing ring with deuterium incorporation into the same ring was achieved. The experiments were carried out in a biphasic D2O/toluene medium, which allowed excellent catalyst recycling with a simple work‐up. Through detailed studies for 3‐methylquinoline using DCOOD/DCOONa, the reaction mechanism that involves D+ incorporation at the nitrogen atom and an initial 1,2‐type addition was elucidated. In single‐phase D2O experiments, a distinct selectivity with deuterium incorporation in the non‐hydrogenated ring was observed thus enabling to modulate it by the choice of the medium.

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Homogeneous cobalt catalyzed reductive formylation of N-heteroarenes with formic acid

Cited by 14 publications

References 37 publications

Development of a Cobalt Catalyst from ZIF‐67 and Application in the Hydrogenation of N‐Heteroarenes

Development of a Cobalt Catalyst from ZIF‐67 and Application in the Hydrogenation of N‐Heteroarenes

Catalyst-Free N-Formylation of Amines Using Formic Acid as a Sustainable C1 Source

Ruthenium Catalysed Transfer Deuteration of Heteroaromatics in D₂O

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Homogeneous cobalt catalyzed reductive formylation of N-heteroarenes with formic acid

Cited by 14 publications

References 37 publications

Development of a Cobalt Catalyst from ZIF‐67 and Application in the Hydrogenation of N‐Heteroarenes

Development of a Cobalt Catalyst from ZIF‐67 and Application in the Hydrogenation of N‐Heteroarenes

Catalyst-Free N-Formylation of Amines Using Formic Acid as a Sustainable C1 Source

Ruthenium Catalysed Transfer Deuteration of Heteroaromatics in D2O

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Ruthenium Catalysed Transfer Deuteration of Heteroaromatics in D₂O