Ethanol-mediated N-formylation of amines with CO2/H2 over cobalt catalysts

Zhenghui Liu; Zhenzhen Yang; Zhengang Ke; Xiaoxiao Yu; Hongye Zhang; Bo Yu; Yanfei Zhao; Zhimin Liu

doi:10.1039/c8nj03047b

Ethanol-mediated N-formylation of amines with CO₂/H₂ over cobalt catalysts

Zhenghui Liu, Zhenzhen Yang, Zhengang Ke, Xiaoxiao Yu, Hongye Zhang, Bo Yu, Yanfei Zhao, Zhimin Liu

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

The CO₂-involved synthesis of chemicals is of great significance from a green and sustainable point of view. Herein, we present an efficient Co-based catalytic system composed of a commercially available Co salt, the tetradentate phosphine ligand P-(CH₂CH₂PPh₂)₃, and a base, denoted as [Co]/PP₃/base, for the synthesis of formamides via the formylation of amines with CO₂/H₂. It was indicated that the selectivity of products (i.e., formamide or methylamine) could be tuned to some extent via changing the solvent and the base. Using ethanol as the solvent, the Co(ClO₄)₂·6H₂O/PP₃/K₂CO₃ system showed high activity for the production of formamides, affording product yields of 82-95%, together with its broad substrate scope. Exploration of the reaction mechanism indicated that formamide was formed with HCOOH as the intermediate, while the methylamine byproduct was produced with HCHO as the intermediate via the hydrogenolysis of dialkylaminomethane.

Original language	English
Pages (from-to)	13933-13937
Number of pages	5
Journal	New Journal of Chemistry
Volume	42
Issue number	16
DOIs	https://doi.org/10.1039/c8nj03047b
State	Published - 2018
Externally published	Yes

Funding

We thank the National Natural Science Foundation of China (No. 21673256, 21533011) and the Chinese Academy of Sciences (QYZDY-SSW-SLH013-2).

Funders	Funder number
National Natural Science Foundation of China	21673256, 21533011
Chinese Academy of Sciences	QYZDY-SSW-SLH013-2

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title = "Ethanol-mediated N-formylation of amines with CO2/H2 over cobalt catalysts",

abstract = "The CO2-involved synthesis of chemicals is of great significance from a green and sustainable point of view. Herein, we present an efficient Co-based catalytic system composed of a commercially available Co salt, the tetradentate phosphine ligand P-(CH2CH2PPh2)3, and a base, denoted as [Co]/PP3/base, for the synthesis of formamides via the formylation of amines with CO2/H2. It was indicated that the selectivity of products (i.e., formamide or methylamine) could be tuned to some extent via changing the solvent and the base. Using ethanol as the solvent, the Co(ClO4)2·6H2O/PP3/K2CO3 system showed high activity for the production of formamides, affording product yields of 82-95%, together with its broad substrate scope. Exploration of the reaction mechanism indicated that formamide was formed with HCOOH as the intermediate, while the methylamine byproduct was produced with HCHO as the intermediate via the hydrogenolysis of dialkylaminomethane.",

author = "Zhenghui Liu and Zhenzhen Yang and Zhengang Ke and Xiaoxiao Yu and Hongye Zhang and Bo Yu and Yanfei Zhao and Zhimin Liu",

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T1 - Ethanol-mediated N-formylation of amines with CO2/H2 over cobalt catalysts

AU - Liu, Zhenghui

AU - Yang, Zhenzhen

AU - Ke, Zhengang

AU - Yu, Xiaoxiao

AU - Zhang, Hongye

AU - Yu, Bo

AU - Zhao, Yanfei

AU - Liu, Zhimin

PY - 2018

Y1 - 2018

N2 - The CO2-involved synthesis of chemicals is of great significance from a green and sustainable point of view. Herein, we present an efficient Co-based catalytic system composed of a commercially available Co salt, the tetradentate phosphine ligand P-(CH2CH2PPh2)3, and a base, denoted as [Co]/PP3/base, for the synthesis of formamides via the formylation of amines with CO2/H2. It was indicated that the selectivity of products (i.e., formamide or methylamine) could be tuned to some extent via changing the solvent and the base. Using ethanol as the solvent, the Co(ClO4)2·6H2O/PP3/K2CO3 system showed high activity for the production of formamides, affording product yields of 82-95%, together with its broad substrate scope. Exploration of the reaction mechanism indicated that formamide was formed with HCOOH as the intermediate, while the methylamine byproduct was produced with HCHO as the intermediate via the hydrogenolysis of dialkylaminomethane.

AB - The CO2-involved synthesis of chemicals is of great significance from a green and sustainable point of view. Herein, we present an efficient Co-based catalytic system composed of a commercially available Co salt, the tetradentate phosphine ligand P-(CH2CH2PPh2)3, and a base, denoted as [Co]/PP3/base, for the synthesis of formamides via the formylation of amines with CO2/H2. It was indicated that the selectivity of products (i.e., formamide or methylamine) could be tuned to some extent via changing the solvent and the base. Using ethanol as the solvent, the Co(ClO4)2·6H2O/PP3/K2CO3 system showed high activity for the production of formamides, affording product yields of 82-95%, together with its broad substrate scope. Exploration of the reaction mechanism indicated that formamide was formed with HCOOH as the intermediate, while the methylamine byproduct was produced with HCHO as the intermediate via the hydrogenolysis of dialkylaminomethane.

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EP - 13937

JO - New Journal of Chemistry

JF - New Journal of Chemistry

IS - 16

ER -

Ethanol-mediated N-formylation of amines with CO₂/H₂ over cobalt catalysts

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