The Application of Cobalt-Based Catalysts in Carbonylation Reactions

Zhaoxiong Tian; Kunyao Zhang; Airong Gu; Mengjiao Ding; Daming Sun; Heyuan Song

doi:10.7536/PC20250628

Progress in Chemistry ›› 2026, Vol. 38 ›› Issue (4) : 636-648 DOI: 10.7536/PC20250628

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The Application of Cobalt-Based Catalysts in Carbonylation Reactions

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Abstract

Carbonylation reactions represent an important approach for producing high-value-added chemicals by introducing carbonyl groups （C=O） into molecules. Owing to their high atom economy and compliance with green and sustainable development requirements， these reactions have found widespread applications in fields such as organic synthesis， medicinal chemistry， and materials science. Although numerous catalysts for carbonylation reactions have been developed to date， most fail to meet the requirements for industrial application. In recent years， significant progress has been made in the research of cobalt-based catalysts for carbonylation reactions， which have attracted considerable attention due to their low cost， abundant resources， and environmental friendliness. Through strategies like ligand design and support optimization， the activity， selectivity， and stability of cobalt catalysts have been significantly enhanced. This review systematically summarizes the latest advances in cobalt-based catalysts for reactions including hydroesterification， hydroformylation， aminocarbonylation， and hydrocarboxylation， discusses the impacts of ligand design， reaction mechanisms， and heterogenization strategies on catalytic performance， and prospects their development prospects in green chemistry and industrial applications.

Contents

1 Introduction

2 Hydrogen esterification reaction

3 Hydroformylation reaction

4 Amine carbonylation reaction

5 Hydrocarboxylation reaction

6 Conclusion

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Keywords

cobalt catalyst / carbonylation reaction / homogeneous catalysis / heterogeneous catalysis / green chemistry

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Zhaoxiong Tian, Kunyao Zhang, Airong Gu, Mengjiao Ding, Daming Sun, Heyuan Song. The Application of Cobalt-Based Catalysts in Carbonylation Reactions. Progress in Chemistry, 2026, 38(4): 636-648 DOI:10.7536/PC20250628

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1 Introduction

To address the severe challenges posed by intensifying global climate change, catalytic technologies in the new era focus on renewable energy conversion and environmental protection, striving to advance sustainable technology development and the efficient utilization of renewable resources^[1]. Among these, the heterogenization of homogeneous catalysts stands out as a key research direction in catalysis. Due to its ability to enable catalyst recycling and significantly reduce waste pollution, it demonstrates prominent application value in the current context of green and sustainable development. As a crucial strategy for constructing carbon-carbon and carbon-heteroatom bonds, carbonylation plays an irreplaceable role in the synthesis of fine chemicals, preparation of pharmaceutical intermediates, and the polymer materials sector^[2], serving as a vital synthetic route for producing high-value-added carbonyl-containing compounds. Since the early 20th century, when the German chemist Roelen^[3]first discovered transition metal-catalyzed carbonylation for aldehyde synthesis while studying the Fischer-Tropsch reaction, carbonylation reactions have been widely applied in industry, such as in the large-scale production of carbonylation products like acetic acid and butyraldehyde. Traditionally, noble metal catalysts (e.g., Pd, Rh) have dominated carbonylation catalysis due to their high activity and selectivity; however, their high cost, scarcity, and potential environmental risks limit large-scale industrial applications. With the deepening concepts of green chemistry and sustainable development, developing efficient, economical, and environmentally friendly non-noble metal catalytic systems has become a research hotspot. Transition metal catalysts are an important resource capable of promoting the transformation of organic compounds. By introducing transition metal catalysts, a series of complex organic synthesis reactions can be achieved, which holds significant importance for fields such as materials science, drug synthesis, and agricultural chemistry^[4-7]; as a transition metal with relatively high abundance in the Earth's crust, Co exhibits unique potential in the catalytic field due to its diverse oxidation states (Co⁰, Co⁺, Co²⁺, etc.), flexible coordination capabilities, and tunable electronic structures. In carbonylation reactions, cobalt catalysts demonstrate irreplaceable and unique advantages compared to other non-noble metals like Fe and Ni. In terms of electronic structure, its d⁷configuration endows it with ideal electron transfer capabilities, enabling it to form an optimal σ-π interaction balance with CO and efficiently activate C—O bonds. Regarding coordination modes, the coordination number and patterns are flexible and diverse, allowing for precise binding and activation of substrates while avoiding the formation of highly toxic Ni(CO)₄associated with nickel-based catalysts, thus offering superior safety and stability. In terms of reaction pathways, cobalt catalysis provides precise selectivity control and broad substrate adaptability; compared to iron-based catalysts, it features lower activation energy for the olefin insertion step and faster reaction rates. These advantages make cobalt the preferred choice for non-noble metal carbonylation catalysts, holding a prominent status in industrial applications and organic synthesis^[8-9]. In recent years, significant progress has been made in the application of Co-based catalysts in carbonylation reactions: through ligand engineering, support optimization, and other strategies, the activity, selectivity, and stability of cobalt catalysts have been significantly enhanced. Meanwhile, Co catalysts have demonstrated unique mechanisms distinct from noble metals in emerging directions such as asymmetric carbonylation and the resourceful utilization of CO₂, for instance, by activating inert substrates via radical pathways or synergistic redox cycles, providing new ideas for expanding reaction types^[10].

In the past few decades, carbonylation reactions have developed rapidly and made tremendous progress^[11-14], among various types of carbonylation reactions, the carbonylation of unsaturated hydrocarbon compounds has been studied most extensively^[15-26]. However, the industrial application of Co catalysts still faces challenges. For instance, issues such as harsh reaction conditions (high-pressure CO environments), limited substrate generality, and insufficient cycling stability urgently need to be addressed^[27-29]. This article reviews recent innovative achievements of cobalt-based catalysts in carbonylation reactions, focusing on their design strategies, mechanistic understanding, and performance optimization pathways, and prospects their development prospects under the goal of green synthesis.

2 Hydroesterification reaction

Hydroesterification reaction^[10,12,30]Also known as alkoxycarbonylation reaction, it refers to the process of synthesizing carboxylic acid esters and their derivatives by reacting unsaturated hydrocarbons (olefins, alkynes, etc.), epoxides, halogenated hydrocarbons, etc. with alcohols and CO. Early research focused on Co₂(CO)₈as the core catalyst for hydroesterification reactions, but high-pressure conditions (24 MPa) limited its application. In 1961, Eisenmann et al.^[31]first used Co₂(CO)₈as a catalyst to achieve the hydroesterification of propylene oxide; under conditions of 130 °C and CO pressure of 24 MPa for 4 h, the product yield reached 41.9%. In 1992, Drent et al.^[32]reported that under conditions of 110 °C and CO pressure of 2.7 MPa for 14 h, using 3-hydroxypyridine-coordinated Co₂(CO)₈to catalyze the hydroesterification of styrene oxide, the yield could reach 67%, with significantly improved reaction activity. Therefore, researchers began to focus on ligand-modified cobalt carbonyl catalyst systems^[33-34]; using such catalysts can lower reaction conditions and improve yields.

In 2014, Baburajan et al.^[35]developed a microwave-assisted synthesis strategy based on Co₂(CO)₈catalysis, successfully achieving the hydroesterification of aryl halides (bromides, iodides) to synthesize β-keto esters. This study innovatively constructed a multicomponent catalytic system composed of Pd(OAc)₂, 4,5'-bis(diphenylphosphino)-9,9′-dimethylxanthene (xantphos), Co₂(CO)₈, imidazole, MgCl₂, and triethylamine (TEA). Using potassium monoethyl malonate as the carbon nucleophile and tetrahydrofuran (THF) as the solvent, the conversion was completed in 30 min at 90 °C under microwave irradiation. Through a systematic evaluation of the hydroesterification performance of various aryl halides (bromides and iodides), the study found that when the substrate was 4-methoxyphenyl halide, the yield of the target product reached an optimal value of 92%. This scheme employs Co₂(CO)₈as a carbonyl source instead of CO, which not only avoids the risks associated with high-pressure gas operations but also effectively improves reaction selectivity by guiding the direction of carbonyl insertion through coordination at the cobalt carbonyl center.

In 2016, the Lv group^[36]reported a series of polyether-substituted imidazolium carbonylcobalt ionic liquids ([H(OCH₂CH₂)_nbim]Co(CO)₄), and applied them to the hydroesterification of 4-isobutylstyrene (Figure 1); under conditions of 150 °C and a CO pressure of 7.0 MPa for 32 h, the conversion of 4-isobutylstyrene and the selectivity of the product reached 97.2% and 83.9%, respectively. The structure featuring dual ionic bonds and polyether chains renders the tetracarbonylcobalt anion relatively stable; due to its good solubility in water and various other highly polar solvents, this catalyst can be applied in various solution systems. The reaction mechanism of the hydroesterification of 4-isobutylstyrene is as shown inFigure 2. The results indicate that the LnCo(CO)₄(Ln = [H(OCH₂CH₂)_nbim]⁺) complex is the active species for the hydroesterification of 4-isobutylstyrene catalyzed by [H(OCH₂CH₂)_nbim]Co(CO)₄; it adds the olefin to the Ln–Co bond to form a mixture of isomeric alkyltetracarbonylcobalt complexes, which then react with CO to form acyltetracarbonylcobalt^[37-38]; subsequently, the acyltetracarbonylcobalt reacts with methanol to yield branched esters and [H(OCH₂CH₂)_nbim]Co(CO)₄.

Nitrogen-containing ligands (such as pyridine, imidazole, etc.), as key promoters, have demonstrated broad applicability in homogeneous carbonylation reaction systems of epoxides^[39]. Recent studies have found that when metal nanoparticles are anchored on the surface of nitrogen-doped carbon (NC) materials, strong metal-nitrogen (M-N) interfacial interactions can be formed. This characteristic enables NC-supported cobalt-based catalysts to exhibit excellent performance in industrially important reactions such as oxidation, reduction, and oxidative carbonylation^[40-42]. Based on this research background, in 2020, Zeng et al.^[43]developed a porous support-loaded nitrogen-doped cobalt nanocatalyst for the ring-opening carbonylation of propylene oxide (PO). The experiments used tetrahydrofuran (THF) as the solvent, reacting at 70 °C under a CO pressure of 6.0 MPa for 40 h, systematically investigating the effect of different supports on catalytic performance. The results showed that the catalyst constructed with a SiO₂/pyrazole composite support exhibited optimal performance, with both PO conversion and β-lactone selectivity reaching 93%; whereas TiO₂, α-Al₂O₃, and γ-Al₂O₃and other supports, although capable of achieving high reaction activity, resulted in significantly reduced product selectivity. This phenomenon was attributed to the presence of abundant Brønsted acid sites on the surface of acidic supports, which significantly promoted the competitive etherification side reaction between PO and methanol^[44].

The hydroesterification products of 1,3-butadiene (such as methyl pentenoate and dimethyl adipate) are key raw materials for nylon synthesis, plasticizer preparation, and pharmaceutical intermediate production. However, the inherent π-π conjugation effect of this olefin substrate leads to sluggish reaction kinetics, compounded by the challenge of controlling regioselectivity arising from minimal differences in double bond activation energies, making it a long-standing challenging system in the field of catalytic conversion. To address this issue, the Wang research team^[45]achieved a breakthrough in 2024; they designed and developed a novel class of carbonyl cobalt-functionalized ionic liquid catalysts, successfully realizing the efficient hydroesterification of 1,3-butadiene to synthesize methyl pentenoate. Studies show (Figure 3) that when using the ionic liquid IL1 with a specific structure as the catalyst, the yield of the target product exceeded 60% after reacting for 16 h at 120 °C under a CO pressure of 8.6 MPa. Notably, ionic liquids with different cationic structures exert a significant regulatory effect on the distribution of product isomers (with selectivity differences exceeding 35%), providing a new strategy for precisely manipulating olefin functionalization sites through catalyst structure design.

In 2022, our research group^[46]achieved a significant breakthrough in the hydroesterification of diisobutylene to synthesize methyl isononanoate, pioneeringly constructing pyridine/imidazole-functionalized porous organic polymers (POLs) supported cobalt-based catalysts (Co/POLs), asshown in Figure 4. Under optimized conditions, the catalyst composition was Co₂(CO)₈/VPy-DVB = 2:1, with a cobalt loading of 4 wt%, an N/Co molar ratio of 2:1, a CO pressure of 8 MPa, and a reaction at 150 °C for 12 h, achieving excellent performance with a diisobutylene conversion of 89.3% and a target product selectivity of 92.2%. The catalytic system demonstrated good cyclic stability; however, activity declined after six consecutive uses. Research indicated that this gradual deactivation might be caused by factors such as pore collapse of the polymer and sintering of Co species. Building on previous work, our research group^[47]further innovatively developed a poly(ionic liquid)/cobalt salt composite catalyst system in 2024 (Figure 5). The study systematically evaluated the impact of different poly(ionic liquid) coordination environments on catalytic performance, among which HVIMI-VPy-DVB (1:1)@Co₂(CO)₈exhibited the best comprehensive performance: under conditions of 8.0 MPa CO pressure and 150 °C, the diisobutylene conversion reached 88.0%, with a methyl isononanoate selectivity of 91.4%. Furthermore, this catalyst system is applicable to the hydroesterification of various terminal olefins and demonstrates high recyclability and thermal stability.

In 2023, our research group^[48]developed a nitrogen-ligand-functionalized ZSM-5 zeolite catalyst anchored via Si—O bonds (Figure 6), which was successfully applied to the hydroesterification of diisobutylene for the synthesis of methyl isononanoate. Researchers grafted different nitrogen-containing ligands onto the surface of ZSM-5 zeolite, synthesizing a series of functionalized ZSM-5@Co₂(CO)₈catalysts with well-defined active sites. Under optimized conditions (Co₂(CO)₈loading of 4 wt.%, methanol-to-diisobutylene molar ratio of 15:1, CO pressure of 6.0 MPa, and 140 °C) for 10 h, the functionalized catalyst ZSM-5iCPdPy@Co₂(CO)₈exhibited the highest activity, achieving a diisobutylene conversion of 88.3% and a methyl isononanoate selectivity as high as 93.4%. This catalyst system is also applicable to the hydroesterification of diisobutylene with various alcohols, providing an important reference for developing efficient and stable olefin carbonylation catalysts.Figure 7explains the reaction mechanism of diisobutylene hydroesterification. In protic solvents, the nitrogen-coordination-modified cobalt catalyst first initiates the disproportionation of Co₂(CO)₈to generate [Co(CO)₄]^-[Co(CO)_5-nL_n]⁺, followed by protonation in the system to form the active intermediate HCo(CO)₄(a), which coordinates with diisobutylene to generate an alkylcobalt intermediate (b). At this stage, CO molecules undergo migratory insertion into the Co—C bond to form an acylcobalt complex (c). In the presence of excess CO, the acylcobalt complex (c) further undergoes a carbonylation reaction to form a highly active acylcobalt complex (d), which is finally treated with methanol to yield the target ester compounds.

In 2025, Faculak et al.^[49]successfully developed a light-promoted cobalt-catalyzed hydroesterification system for olefins. This study employed cobalt carbonyl as the catalyst, with 4-dimethylaminopyridine (DMAP) and triethylammonium p-toluenesulfonate ([TEA-H][OTs]) as co-catalytic components. Under 390 nm LED irradiation and mild reaction conditions, the yield of the target product reached up to 95% (Table 1). Experimental results demonstrated that this catalytic system exhibits excellent substrate scope. Further mechanistic studies confirmed that the co-catalyst facilitates the generation of the key active species HCo(CO)₃.

The mechanism of hydroesterification reactions for hydrocarbon compounds can be summarized into three core steps: (1) Coordination activation of the hydrocarbon: The hydrocarbon molecule forms a π-complex intermediate (I) through coordination with the d-orbitals of the cobalt catalytic center; (2) CO migratory insertion: Based on coordination activation, a CO molecule undergoes intramolecular migratory insertion into the Co—C bond to form an acylcobalt intermediate (II); (3) Hydrogen transfer and esterification: Through proton migration or hydrogen transfer, intermediate (II) undergoes oxidative addition/reductive elimination processes to generate aldehyde products, which are ultimately converted into ester compounds under the action of alcoholic nucleophiles. In recent years, research interest in cobalt-based catalysts in the field of hydroesterification has continued to rise; they achieve carbonylation reactions under mild conditions via unique H-Co active centers, demonstrating significant advantages in atom economy and regioselectivity control.

3 Hydroformylation reaction

Hydroformylation, as one of the most representative reactions in modern homogeneous catalysis, is essentially a process where olefins and synthesis gas (CO/H₂) are catalytically converted into linear or branched aliphatic aldehydes with a carbon chain extended by one carbon atom^[2], also known as the "oxo reaction"; it features high atom economy and is one of the most powerful and widely applied chemical processes^[50-52].Figure 8illustrates the reaction mechanism of olefin hydroformylation: first, the olefin inserts into the M—H bond (A) to form an M-alkyl intermediate (B); subsequently, a CO molecule inserts into the M—C bond, and the resulting M-acyl compound, under the action of hydrogen, generates an aldehyde compound (D) while regenerating the M-H active species, thereby sustaining the catalytic cycle.

In 2015, Achonduh et al.^[53]successfully developed an efficient catalytic system based on Cytec bidentate cyclic phosphine ligands (Figure 9). This scheme used toluene as the solvent, with 2-ethylhexanoic acid and KOH/EtOH solution as additives, Co₂(CO)₈as the catalyst. Under optimized conditions (Co/ligand = 1:2 molar ratio), the reaction was conducted at CO/H₂= 1.4/2.8 MPa and 110 °C for 22 h. When using the Lim-10 phosphine ligand, the conversion of 1-decene reached 100%, with a linear product selectivity of 77%. Mechanistic studies indicate that the strong electron-donating properties of the phosphine ligand regulate the electron cloud density of the metal center, promoting the in situ generation of the HCo(CO)₃L active species, thereby significantly enhancing the selectivity for linear products.

In 2022, Delolo et al.^[54]reported a new strategy for the hydroesterification ring-expansion of oxetanes catalyzed by cobalt complexes. This study employed Co₂(CO)₈with phosphine oxides (P1-7) and corresponding phosphines (L1-7) to construct novel coordination catalytic systems (Figure 10). In toluene solvent, by regulating reaction conditions (Co₂(CO)₈/tricyclohexylphosphine oxide (P7), CO/H₂gas mixture (1:1, total pressure 4.0 MPa), 80 °C, reaction for 24 h), efficient conversion of reactants was achieved (product yield up to 94%). Phosphine oxides, especially P7, as key substances promoting the transformation of Co₂(CO)₈into HCo(CO)₄active species under syngas atmosphere, play an important role in activating oxetanes.

In 2022, Zhang et al.^[55]conducted the first systematic verification and confirmation of the long-term stability of unmodified cobalt hydrocarbonyl (HCo(CO)₄)) under low-pressure conditions. This study prepared unmodified cobalt carbonyl catalysts using different cobalt precursors (as shown in Figure 11), achieving efficient catalysis for the hydroformylation of branched internal olefins under mild reaction conditions of 140 °C and syngas (H₂/CO) pressures of 3–5 MPa, with target product yields reaching up to 93%. Notably, this catalytic system requires no phosphine ligands, yet its catalytic activity is comparable to that of phosphine-modified cobalt-based catalysts ^[56], while demonstrating excellent tolerance toward cobalt precursors. Furthermore, by combining kinetic analysis with in situ infrared spectroscopy characterization, the research team further confirmed the structural stability of the active species HCo(CO)₄during the reaction process. This breakthrough lays the foundation for developing low-cost, low-energy hydroformylation processes, holding significant economic and environmental value.

In 2024, Jang et al.^[57]first reported the excellent performance of a dinuclear cobalt/bicyclic phosphoramidite (Briphos) synergistic catalytic system in the hydroformylation of long-chain olefins (Figure 12). This system constructs a bimetallic active center through Co₂(CO)₈and an L4-type Briphos ligand (1:1.2 mol rat.) in toluene solvent (CO/H₂=1:3, total pressure 4 MPa), achieving 92% conversion of 1-octene after reacting at 100 °C for 18 h. The unique "bicyclic-helicene" topological structure of the L4 ligand enhances the linear nonanal selectivity to 82% through steric effects and electronic synergy, an improvement of approximately 25% compared to monophosphine ligand systems, providing a new solution for the efficient conversion of industrial-grade C8+ olefins.

Although transition metal catalytic systems (particularly Co- and Rh-based complexes) exhibit excellent homogeneous catalytic performance in hydroformylation reactions, their industrialization has long been constrained by bottlenecks such as difficulties in catalyst-product separation, loss of precious metals, and poor cycling stability. To address this challenge, catalyst immobilization strategies have become a research focus in recent years—by constructing heterogeneous catalysts with active centers, it is possible to retain the high activity advantages of homogeneous systems while achieving convenient catalyst recovery and recycling. In 2016, Ahmed et al.^[58]anchored the Co₂(CO)₈precursor onto the surface of mesoporous SBA-15 molecular sieve via amino coordination (Figure 13), successfully constructing an immobilized catalyst with a well-defined cobalt cluster structure (SBA-15-RCo). This catalyst demonstrated excellent catalytic efficiency in the hydroformylation of 1-octene: under optimized conditions of toluene solvent, 100 °C, CO/H₂=1:1 (total pressure 6.5 MPa), it achieved 97.4% conversion and 91.2% linear nonanal selectivity in only 8 hours, representing an improvement of approximately 15% over traditional homogeneous systems.

In 2018, the Sharma team^[59]developed a rhodium-cobalt bimetallic hydrotalcite catalyst (CoRh-HT) based on the in situ sol-gel method^[60-61], and successfully applied it to the hydroformylation reaction system of 1-octene. After reacting for 6 h under optimized conditions of 100 °C and a syngas pressure of 5 MPa (CO:H₂=1:1), the system exhibited excellent catalytic performance, with olefin conversion and product selectivity reaching 98% and 96%, respectively. It is worth noting that due to their unique layered structure and surface properties, hydrotalcite-based materials have developed into important platform materials in the field of heterogeneous catalysis in recent years. Such materials can not only serve simultaneously as supports for active components and as catalysts themselves, but their good structural stability also demonstrates significant advantages in addressing the key issue of catalyst recovery and reuse, providing important technical support for their scaled application in organic transformation reactions.

Hydroformylation is one of the most important homogeneous processes in industry for producing value-added aldehydes. Significant efforts have been made to heterogenize this process to overcome the drawbacks of homogeneous processes, such as catalyst recovery, product separation, and high pressure.^[62-63]. The history of cobalt-based catalysts in hydroformylation reactions indicates that the stability of the cobalt system provides greater tolerance to impurities in olefin feedstocks. These advantages, combined with the relatively low cost of cobalt, have driven the development of cobalt-based catalysts.

4 Aminocarbonylation reaction

Amides are an important class of natural products and pharmaceutical intermediates, widely used in fine chemicals, new materials, natural rubber, resins, medicine, and other fields. Traditional synthetic strategies mainly rely on two pathways: (1) condensation reactions between amines and carboxylic acid derivatives (acyl chlorides/anhydrides), which require excessive coupling agents and generally involve high reaction temperatures; (2) Staudinger cyclization to construct cyclic amides, which is limited by substrate types. Notably, amine carbonylation has become a cutting-edge strategy for constructing amide bonds due to its near-perfect atom economy (theoretical value 100%) and excellent functional group compatibility (tolerating sensitive groups such as hydroxyl and cyano groups).^[64-66]. In the 1950s, Reppe et al.^[67]first discovered an amine carbonylation reaction system using transition metal Co complexes as catalysts. Subsequently, researchers developed various transition metal-catalyzed amine carbonylation systems, such as Ni, Fe, and Ru. However, drawbacks including harsh reaction conditions (high temperature and pressure), inevitable by-products (formamides), and limited substrate scope have hindered the further application of these methods.

In 2014, the Lei group^[68]in situ prepared NaCo(CO)₄catalyst and reported the reaction of NaCo(CO)₄catalyzing the carbonylation of quaternary ammonium salts to generate tertiary amides. Generally, quaternary ammonium salts are considered a class of very stable compounds due to their high decomposition temperatures; their reactivity is often easily overlooked in transition metal-catalyzed reactions. The experiment selected tetramethylammonium salts with different anions (I^-, Br^-, Cl^-, and OTf^-) as reaction substrates to investigate the reactivity of different tetramethylammonium salts; the results are shown inTable 2. Using N-methylpyrrolidone (NMP) as solvent, with CoCl₂/Zn/Na₂SO₃=1∶1.33∶1 (molar ratio), CO pressure of 3 MPa, at 200 °C for 7 h, the yield and selectivity of N,N-dimethylacetamide (DMAc) reached up to 98.5% and 98.7%, respectively. This result demonstrates that anions have a significant impact on the activity of tetramethylammonium salts, with their reactivity increasing in the order of Cl^-<OTf^-<Br^-<I^-.

Mechanistic studies have revealed the reaction pathway for the carbonylation of quaternary ammonium salts to tertiary amides catalyzed by cobalt carbonyl (Figure 14). This catalytic cycle begins with the in situ generation of the NaCo(CO)₄ active species, and its specific mechanism can be divided into three key stages: (1) C—N bond activation stage: Driven by thermodynamics, the C—N bond in the quaternary ammonium salt first undergoes homolytic dissociation to generate an alkyl halide (R¹X) and a free tertiary amine; this process may involve the coordination and activation of the quaternary ammonium salt by Co(CO)₄^-; (2) Acylation process: The Co(CO)₄^- anion performs a nucleophilic attack on R¹X to form the Co—C bond intermediate B; subsequently, CO migratory insertion occurs to generate the acylcobalt species C; this intermediate further coordinates with CO to form the tetracarbonylcobalt complex D with a stable 18-electron structure, confirming the critical regulatory role of the dynamic equilibrium of the metal center's electronic structure on the reaction progress; (3) Product reconstruction stage: Complex D interacts with the counterion to release the acyl halide (R¹COX), which then undergoes a nucleophilic substitution reaction with the tertiary amine in the system, ultimately generating the target product, the tertiary amide, and regenerating R¹X, thereby completing the catalytic cycle. This mechanistic model not only clarifies the essential nature of the anion effect (reflected in differences in C—N bond dissociation energies and the regulation of intermediate stability) but, more importantly, reveals the multiple catalytic functions of cobalt complexes in the C—N bond activation-acylation-aminolysis process, providing theoretical guidance for designing metal-mediated transformation systems for quaternary ammonium salts.

In 2018, the Li group^[69]innovatively adopted a Co(OAc)₂/phenanthroline complex pyrolysis strategy to successfully construct a cobalt-nitrogen co-doped carbon nanotube composite catalyst (GN-Co-800) on a diatomite support with a porous structure. This catalyst demonstrated excellent catalytic performance in the green carbonylation of amines with CO, with a substrate scope covering various types such as aromatic and aliphatic amines (excluding the phosgene system). Typically, using benzylamine as a model substrate in a 1,4-dioxane solvent system, when the reaction conditions were optimized to a CO pressure of 1.5 MPa, an air pressure of 0.1 MPa, a temperature of 110 °C, and a time of 8 h, the yield of the target formamide reached 94%. The study confirmed that the unique hierarchical pore structure of the diatomite support effectively improved the dispersion of active components and mass transfer efficiency, providing new insights for developing efficient heterogeneous carbonylation catalytic systems.

In subsequent research, the team continuously optimized the material system and reported a Co@N-doped carbon catalyst with a core-shell structure (Co@NC-800) in 2020^[70]. Prepared via an improved template-assisted pyrolysis method, this material features cobalt nanoparticles (~15 nm) uniformly encapsulated within nitrogen-doped graphitic carbon layers. This unique structural design not only prevents metal particle sintering but also enhances the accessibility of active sites. Under milder reaction conditions (CO pressure 1 MPa, 110 °C, 12 h), using DMF as the solvent for the carbonylation of benzylamine, the formamide yield significantly increased to 98%. Notably, Co@NC-800 exhibits excellent cyclic stability (retaining >95% activity after 5 cycles), highlighting the potential industrial application value of this catalytic system.

In 2019, Sargent et al.^[71]developed a catalytic system based on Co₂(CO)₈/TMP. This system utilizes readily available chiral alcohol-derived tosylates to efficiently synthesize chiral amides, carboxylic acids, and ketones, exhibiting excellent chemoselectivity and stereocontrol. Under optimized reaction conditions, the aminocarbonylation of unactivated alkyl tosylates with morpholine achieves an 85% yield and 97% enantiospecificity (es). The stereodirected reaction mechanism is shown inFigure 15: First, amine or TMP mediates the disproportionation of Co₂(CO)₈to generate the Co(CO)₄^-anion; subsequently, the Co(CO)₄^-anion undergoes an SN₂substitution with the tosylate to form an alkylcobalt intermediate, which retains its configuration during CO migratory insertion; finally, the acylcobalt species undergoes nucleophilic substitution with an amine nucleophile to generate chiral non-racemic amide products while regenerating the catalyst.

In 2022, the Zhu research team^[72]innovatively developed a new strategy for cobalt-catalyzed intramolecular carbonyl cyclization, successfully achievingN-(2-vinylphenyl)picolinamide to (NH)-quinolin-2(1H)-one compounds with high efficiency. This strategy demonstrates excellent atom economy and concise steps. (NH)-Quinolin-2(1H)-ones, as a class of privileged heterocyclic scaffolds, are not only widely present in active molecules such as the antimalarial drug mefloquine and the antibacterial natural product cryptolepine^[73], but their unique nitrogen-fused ring structures also make them key synthetic building blocks for constructing complex heterocycles such as indolinones and benzazepines.

The research team systematically optimized reaction parameters to construct a synergistic catalytic system using Co(OAc)₂·4H₂O as the catalyst, benzene-1,3,5-tricarboxylate (TFBen) as the tricarbonyl donor, and Ag₂CO₃as the oxidant, with Et₃N as the base assistant. Under conditions of 130 °C for 20 h, the yield of the target quinolinone derivatives reached up to 88%. Mechanistic studies indicate that the cobalt catalyst achieves precise C—C bond construction and stereo-electronic control of the cyclization process by selectively activating the olefin units and amide groups in the substrate. This method not only avoids the tedious amine protection/deprotection steps common in traditional synthesis but also aligns better with the principles of green chemistry by utilizing TFBen as a solid carbonyl source.

Based on theoretical foundations and experimental data, the authors constructed a cobalt-catalyzed redox cycle mechanism model asFigure 14shows, the core steps of which can be analyzed into five key stages: (1) Catalyst activation: The Co(II) precursor is converted into highly active Co(III) species under the oxidation of Ag₂CO₃, followed by coordination with the nitrogen atom of pyridine amide1ato form metal complex A, completing the construction of the catalytic active center; (2) C—H bond activation: Complex A achieves selective cleavage of the olefin β-C—H bond via a metal-directed concerted deprotonation mechanism, generating intermediate B containing a Co(III)-C σ bond; (3) CO migratory insertion: CO molecules released from TFBen insert into the Co—C bond after coordination, forming acylcobalt(III) intermediate C; (4) Reductive elimination and cyclization: Intermediate C undergoes an intramolecular reductive elimination process to produce Co(I) complex D with a 16-electron configuration, simultaneously completing the stereoselective construction of the quinolinone ring system; (5) Catalyst regeneration: After the Co(I) species hydrolyzes to release the product2a, it is re-oxidized to the Co(II) active center via Ag(I)-mediated oxidative electron transfer, closing the catalytic cycle.

In 2024, Faculak et al.^[74]reported a new strategy for light-promoted cobalt-catalyzed olefin aminocarbonylation. This strategy uses unmodified Co₂(CO)₈as the catalyst. Driven by light irradiation, it efficiently constructs amide compounds under mild reaction conditions. Relevant mechanistic studies (Figure 17) reveal that light plays a key role in the reaction: it promotes the dissociation of carbonyl ligands in the catalyst, thereby generating HCo(CO)₃active species; this active species subsequently undergoes key steps including olefin coordination, CO insertion, and nucleophilic attack by amines to generate the target amide, with the photolysis process driving the catalytic system through multiple cycles. Among these, the HCo(CO)₃active species generated via photolysis is the core factor ensuring high catalytic activity of the system under mild conditions. This method demonstrates significant technical advantages: first, it successfully solves the industry challenge of catalyst poisoning easily caused by alkylamine substrates; second, it possesses excellent substrate generality, being applicable not only to polysubstituted olefins but also compatible with structurally complex natural product derivatives and pharmaceutical molecule amine substrates; third, the reaction achieves 100% atom economy and supports solvent-free reaction modes, fully aligning with the development concept of green chemistry.

Due to the widespread application of amides in medicinal chemistry, their synthesis is undoubtedly one of the most important reactions in organic chemistry. Approximately one-quarter of marketed drugs and two-thirds of candidate drugs contain at least one amide bond. Therefore, numerous reports and improvements regarding amide synthesis have been published.^[75-76].

5 Hydrocarboxylation reaction

Under the action of a catalyst, olefins can not only react with CO and H₂, but also react with nucleophilic reagents containing active hydrogen such as water, alcohols, acids, and amines to obtain carboxylic acids and their derivatives; this reaction is called hydrocarboxylation. The most commonly used hydrocarboxylation catalysts are divided into two major categories: metal carbonyls and proton acid or Lewis acid catalysts. In industry and organic synthesis, hydrocarboxylation reactions are widely used to prepare carboxylic acid compounds.^[2]Transition metals such as Fe, Co, and Ni can all be converted into metal carbonyls to participate in the reaction; they are inexpensive and versatile, and have successfully replaced precious metals as the main catalysts for hydrocarboxylation reactions. Among them, cobalt-catalyzed C—H bond activation processes have attracted widespread attention from researchers due to their economic efficiency, low toxicity, and simple operation. As early as the 1960s, the German company BASF developed the first commercialized cobalt iodide-based catalyst for the hydrocarboxylation of methanol to produce acetic acid. However, liquid-phase carbonylation reactions require the timely addition of iodide co-catalysts, which cause severe corrosion to equipment, making them unsuitable for industrial promotion and application.

In 2013, She et al.^[77]reported a protocol for synthesizing phenylacetic acid derivatives via benzyl chloride hydrocarboxylation. Phenylacetic acid derivatives are fundamental components of various pharmaceutical compounds (e.g., diclofenac, carbenicillin, vancomycin, or ibuprofen) and exhibit significant biological activity. To date, carbonylation reactions are considered the optimal method for preparing phenylacetic acid derivatives. Using benzimidazole as a ligand and a cobalt salt as a catalyst under CO₂ at a pressure of 0.2 MPa and 60 °C for 22 h; when CoCl₂·6H₂O was used as the catalyst and 2-(1H-benzimidazol-2-yl)benzoic acid as the ligand, the reaction achieved optimal results with a yield of up to 60%. During the experiment, the catalytically active species Co(L1)₂(H₂O)₂ was obtained, with its crystal structure asshown in Figure 18.

Figure 19reveals the mechanism of the reaction. First, the position occupied by water molecules is easily replaced by CO to form complex 1; in the presence of CO, the addition of PTC (phase transfer catalyst) and NaOH promotes the reduction of Co(II) to Co(I), generating complex 2, which readily transforms into resonance structure 3; subsequently, insertion of benzyl halide into complex 3 forms possible intermediate 4; coordination and introduction of CO leads to the formation of complex 5. Then, the OH carried by PTC^-attacks 5, accompanied by the elimination of the desired phenylacetate ester, along with the regeneration of active cobalt complex 2, completing the catalytic cycle.

The application of cobalt catalysts in hydrocarboxylation reactions has undergone a profound transformation from traditional homogeneous systems to green heterogeneous catalysis, with mechanistic studies advancing from macroscopic kinetics to atomic-level electronic structure analysis. Future efforts need to further integrate machine learning-assisted catalyst design, in situ characterization techniques, and process intensification engineering to promote the scaled application of this technology in the pharmaceutical, polymer material, and carbon neutrality fields.

6 Conclusion and Outlook

In recent years, significant progress has been made in the research and application of cobalt-based catalysts in the field of carbonylation reactions. Compared with traditional synthetic methods, these catalysts demonstrate unique advantages: they enable the precise construction of structurally complex organic compounds with important application values (such as pharmaceutical intermediates, fine chemicals, and precursors for functional materials) through relatively simple, efficient, and highly atom-economical approaches. This not only effectively circumvents common issues in traditional synthetic routes, such as lengthy steps, harsh conditions, numerous by-products, and potential environmental pollution, but also aligns with the core strategic demands of developing green chemistry and achieving sustainable development in the 21st century, providing a highly promising technical pathway for designing environmentally friendly synthetic processes.

However, despite the fruitful achievements of cobalt-catalyzed carbonylation reactions at the laboratory scale, their translation to large-scale industrial production still faces key challenges. The current main bottleneck lies in the recyclability and separation recovery of the catalysts. Specifically, many highly efficient cobalt catalysts (especially homogeneous systems) are difficult to separate efficiently from the product mixture after the reaction, and the recovery process is complex and costly; some catalysts are prone to deactivation or decomposition under reaction conditions, rendering them unable to be reused. These deficiencies significantly increase the operational difficulty and economic cost of industrial applications, constraining their practical promotion.

Therefore, future research on cobalt-catalyzed carbonylation reactions should focus on addressing the aforementioned industrialization barriers and continuously optimizing performance, with key directions including:

(1) Industrial process optimization and scale-up: Building on existing laboratory results, conduct in-depth engineering research dedicated to developing more efficient, low-energy-consumption, and low-pollution large-scale production processes. This includes optimizing reaction conditions (temperature, pressure, concentration), designing high-efficiency reactors (such as continuous flow reactors), improving process economics and environmental benefits, and establishing a rigorous quality control system.

(2) Development of mild condition processes: Focus on breaking through the dependence of certain existing reactions on high-pressure carbon monoxide, and further research and refine efficient carbonylation processes for cobalt catalytic systems under ambient temperature and pressure (or near-ambient pressure). This will not only significantly reduce equipment investment and safety risks but also broaden the scope of applicable substrates and enhance process safety.

(3) Catalyst Immobilization and Novel Material Design: Actively explore and develop novel, efficient ligands or support materials (such as functionalized polymers, magnetic nanoparticles, metal-organic frameworks (MOFs), covalent organic frameworks (COFs), dendrimers, etc.). The core objective is to achieve the heterogenization (immobilization) of homogeneous catalysts, constructing new catalytic systems that combine the high activity/selectivity of homogeneous catalysis with the easy separation and recovery characteristics of heterogeneous catalysts, thereby significantly enhancing catalytic efficiency and recyclability.

(4) Research on Efficient Separation and Recovery Technologies: Targeted research and development of simple, economical, and environmentally friendly methods for catalyst recovery. This involves the application and optimization of various technologies such as membrane separation, extraction, adsorption, and precipitation (e.g., temperature/solvent-induced phase separation), aiming to achieve efficient and non-destructive separation of catalysts from products while maximizing the retention of catalyst activity to facilitate recycling.

Through systematic in-depth research in the aforementioned directions, it is expected to overcome the bottlenecks hindering the industrial application of current cobalt-catalyzed carbonylation technologies, promote their transition from the laboratory to actual production, and contribute significantly to the development of green chemical synthesis and a sustainable chemical industry.

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Funding

Key Research and Development Program of Gansu Province-Industrial Project(23YFGA0041)

“Innovation Star” Project for Outstanding Postgraduate Students of Gansu Provincial Department of Education(2025CXZX-691)

Gansu Provincial Youth Science and Technology Fund Projects(22JR11RA147)

Department of Education of Gansu Province： University Teachers’ Innovation Fund Project(2026B-074)

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1 Introduction

2 Hydroesterification reaction

3 Hydroformylation reaction

4 Aminocarbonylation reaction

5 Hydrocarboxylation reaction

6 Conclusion and Outlook

References

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