On the origin of nitrogen-containing promoters in the cobalt-catalyzed methoxycarbonylation of epoxides

Zeng, Bo; Liu, Mengli; He, Julong; Liu, Jianhua; Li, Zhen; Dong, Yuxiang; Fang, Wang; Xia, Chungu

doi:10.1016/j.apcata.2021.118291

Cited by 4 publications

(3 citation statements)

References 42 publications

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“…In fact, proton transfer between cobalt carbonyl and the N-containing compounds was commonly reported by researchers (Kristjansdottir et al, 1991). Zeng et al (2021) also assumed that an acid-base neutralization easily happened between the HCo(CO) 4 with 3hydroxypyridine. It was thus inferred that a positive interaction may exist between the N-donor with rich electron density and the Co center, correlated to the better EO transformation.…”

Section: Carbonylative Transformation Of Ethylene Oxidementioning

confidence: 92%

“…Other research work also confirmed that acidic compound generated from the alcoholysis of carbonyl cobalt salt easily resulted in undesired ethers. Herein, N-donor ligand, especially the 3hydroxypyridine, acted as base additives stabilized the catalyst and partially neutralized the catalyst acidity, inhibiting the etherification by-products (Liu et al, 2006;Gorbunov et al, 2019;Zeng et al, 2021). Under such circumstance, transformation of EO was further optimized by Co 2 (CO) 8 in the presence of 3-hydroxypyridine.…”

Section: Carbonylative Transformation Of Ethylene Oxidementioning

confidence: 99%

“…The selectivity of byproduct 1,2-dimethoxyethane increased to 20.9% at 100 °C. At lower temperature (<60 °C), the nucleophilic reaction was facilitated between EO and MtOH with the increasing temperature (Zeng et al, 2021). However, it is a common sense that the catalytic performance increases until the kinetic equilibrium, only if a stable catalyst, was in use (except for a third-order reaction).…”

Section: Carbonylative Transformation Of Ethylene Oxidementioning

confidence: 99%

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Chemical kinetics and promoted Co-immobilization for efficient catalytic carbonylation of ethylene oxide into methyl 3-hydroxypropionate

et al. 2022

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The carbonylative transformation of ethylene oxide (EO) into methyl 3-hydroxypropionate (3-HPM) is a key process for the production of 1,3-propanediol (1,3-PDO), which is currently viewed as one of the most promising monomers and intermediates in polyester and pharmaceuticals industry. In this work, a homogeneous reaction system using commercial Co2(CO)8 was first studied for the carbonylation of EO to 3-HPM. The catalytic behavior was related to the electronic environment of N on aromatic rings of ligands, where N with rich electron density induced a stronger coordination with Co center and higher EO transformation. A reaction order of 2.1 with respect to EO and 0.3 with respect to CO was unraveled based on the kinetics study. The 3-HPM yield reached 91.2% at only 40°C by Co2(CO)8 coordinated with 3-hydroxypyridine. However, Co-containing colloid was formed during the reaction, causing the tough separation and impossible recycling of samples. Concerning the sustainable utilization, Co particles immobilized on pre-treated carbon nanotubes (Co/CNT-C) were designed via an in situ reduced colloid method. It is remarkable that unlike conventional Co/CNT, Co/CNT-C was highly selective toward the transformation of EO to 3-HPM with a specific rate of 52.2 mmol·gCo-1·h-1, displaying a similar atomic efficiency to that of coordinated Co2(CO)8. After reaction, the supported Co/CNT-C catalyst could be easily separated from the liquid reaction mixture, leading to a convenient cyclic utilization.

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Section: Carbonylative Transformation Of Ethylene Oxidementioning

confidence: 92%

Section: Carbonylative Transformation Of Ethylene Oxidementioning

confidence: 99%

Section: Carbonylative Transformation Of Ethylene Oxidementioning

confidence: 99%

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Chemical kinetics and promoted Co-immobilization for efficient catalytic carbonylation of ethylene oxide into methyl 3-hydroxypropionate

et al. 2022

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Carbonylative Ring Expansion of Epoxides to β‐Lactones Using Inorganic Salt as Catalytic Species Precursor

et al. 2022

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Transition‐metal‐catalyzed carbonylative transformation is a well‐established and indispensable tool in organic chemistry, partially due to that CO is a cheap and readily available C1‐building block. The β‐lactone products via carbonylative ring expansion of epoxide are particularly attractive, because they feature broad utility in organic and polymer chemistry. One of the major challenges for this promising reaction is the usage of toxic, moderately air sensitive, unstable and pyrophoric low‐valent cobalt catalysts. Inorganic salts feature high abundance in nature, and the generation of catalytic species from in situ reduction of divalent cobalt(II) salt has received intense attention, which avoids the unnecessary storage and transport of sensitive low‐valent cobalt compounds. Herein, we have employed this strategy for the selectively carbonylative ring expansion of epoxides under an extremely mild condition, e. g. 40 °C and 1 atm CO pressure. This method eliminates the usage of extremely sensitive cobalt carbonyl catalyst. In addition, this reaction is tolerant to a variety of epoxides, and up to 15 examples of β‐lactones with excellent functionality have been isolated in moderate to excellent yields and selectivity.

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Molybdenum disulfide promoted co-catalyzed alkoxycarbonylation

Zheng,

Zhou,

Deng

et al. 2024

Journal of Catalysis

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On the origin of nitrogen-containing promoters in the cobalt-catalyzed methoxycarbonylation of epoxides

Cited by 4 publications

References 42 publications

Chemical kinetics and promoted Co-immobilization for efficient catalytic carbonylation of ethylene oxide into methyl 3-hydroxypropionate

Chemical kinetics and promoted Co-immobilization for efficient catalytic carbonylation of ethylene oxide into methyl 3-hydroxypropionate

Carbonylative Ring Expansion of Epoxides to β‐Lactones Using Inorganic Salt as Catalytic Species Precursor

Molybdenum disulfide promoted co-catalyzed alkoxycarbonylation

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