Carboxylation Reaction Research Articles

Recent Advances on the Carboxylations of C(sp3)–H Bonds Using CO2 as the Carbon Source

AbstractCarbon dioxide (CO2) is widely known as being a sustainable C1 synthon for the synthesis of various carboxylic acid derivatives, including essential natural and unnatural amino acids. While it is sustainable, the high thermodynamic stability and kinetic inertness of the CO2 molecule is a major drawback to its wider use in organic synthesis. However, the reduction of this inert and highly stable CO2 molecule has been carried out successfully over the past few years using various stoichiometric as well as catalytic approaches. Initially, chemists employed transition-metal/transition-metal-free thermochemical methods for the incorporation of CO2 into organic compounds, however, gradually, the introduction of greener approaches such as visible-light-induced photoredox catalysis and electrocatalysis became revolutionary for the synthesis of carboxylic acids under mild reaction conditions. In this short review, we discuss the recent advances in carboxylation reactions via functionalization of the (sp3)C–H bonds of various organic molecules with CO2 using thermochemical, photochemical and electrochemical methods.1 Introduction2 Transition-Metal/Transition-Metal-Free Thermochemical Carbox ylations of C(sp3)–H Bonds2.1 C(sp3)–H Bond Carboxylation of Carbonyls2.2 Allylic, Benzylic and Alkyl C(sp3)–H Bond Carboxylation3 Photochemical C(sp3)–H Bond Carboxylation3.1 Allylic C(sp3)–H Bond Carboxylation3.2 Benzylic C(sp3)–H Bond Carboxylation4 Electrochemical Carboxylation of C(sp3)–H Bonds5 Conclusion and Outlook

Molecular transformation of dissolved organic matter in refinery wastewaters: Characterized by FT-ICR MS coupled with electrospray ionization and atmospheric pressure photoionization

Dissolved organic matter (DOM) in refinery wastewater is an extremely complex mixture of various organic compounds. Using mass spectrometry, it is impossible to characterize all of the DOM molecules with only one ionization source. In this study, negative-ion, electrospray ionization (ESI), positive-ion ESI, and positive-ion atmospheric pressure photoionization (APPI) were coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to analyze the molecular composition of DOM in a refinery wastewater stream during the treatment process. There were obvious differences in the heteroatom composition, number of DOM constituents, and chemical properties in refinery wastewater under the three ionization modes. Acidic CHO and CHOS compounds detected by (−)ESI, basic CHN and CHON compounds detected by (+)ESI, and hydrocarbons detected by (+)APPI were analyzed to determine the molecular transformations that occurred during treatment. In an anaerobic biological treatment process, acidic CHO and CHOS compounds with a high oxygen content were preferentially removed, and acidic CHO and CHOS compounds with a low oxygen content were produced. In an aerobic biological process, acidic CHO and CHOS compounds with a low oxygen content were preferentially removed, and acidic CHO and CHOS compounds with a high oxygen content were produced. The whole biological treatment process has a poor removal efficiency for CHN and CHON compounds, and hydrocarbons. An activated carbon (AC) adsorption process removed different heteroatom compounds mainly with a low oxygen content for acidic and basic compounds. The transformation mechanism of CHO and CHOS compounds in the biological treatment process was analyzed by the Kendrick mass defect (KMD) theory and a mass difference network analysis. In the anaerobic process, large amounts of oxygenated CHO and CHOS compounds were degraded by decarboxylation, deoxydation, demethoxylation, and dehydration reactions, and converted to lower oxygen content compounds. In the aerobic processes, these low oxygen CHO and CHOS compounds mainly underwent carboxylation and oxidation reactions. This study determined the transformation characteristics and mechanisms of different types of organic compounds in refinery wastewater during the treatment process. The results provide guidance for the design and optimization of technologies for refinery wastewater treatment. • Molecular composition of DOM in refinery wastewater was characterized by ESI and APPI FT-ICR MS. • Transformation characteristics and mechanism of different types of compound were investigated. • Biological process could remove acidic CHO and CHOS compounds. • AC adsorption process removed various different heteroatom compounds.

Recent progress in reductive carboxylation of C-O bonds with CO2.

Transformation of carbon dioxide (CO2) into value-added organic compounds has attracted increasing interest of scientific community in the last few decades, not only because CO2 is the primary greenhouse gas that drives global climate change and ocean acidification, but also because it has been regarded as a plentiful, nontoxic, nonflammable and renewable one-carbon (C1) feedstock. Among the various CO2-conversion processes, carboxylation reactions represent one of the most beautiful and attractive research topics in the field, since it offers the possibility for the construction of synthetically and biologically important carboxylic acids from various easily accessible (pseudo)halides, organosilicon, and organoboron compounds. The purpose of this review is to summarize the available literature on deoxygenative carboxylation of alcohols and their derivatives utilizing CO2 as a carboxylative reagent. Depending on the C-O compounds employed, the paper is divided into five major sections. The direct dehydroxylative carboxylation of free alcohols is discussed first. This is followed by reductive carboxylation of carboxylates, triflates, and tosylates. In the final section, the only reported example on catalytic carboxylation of fluorosulfates will be covered. Notably, special attention has been paid on the mechanistic aspects of the reactions that may provide new insights into catalyst improvement and development, which currently mainly relies on the use of transition metal catalysts.

Base-mediated carboxylation of C-nucleophiles with CO2.

Carbon dioxide (CO2) is an available, abundant, and renewable C1 resource, which could be converted into value-added chemicals. Due to its inherent thermodynamic stability and kinetic inertness, it is difficult to realize its efficient utilization. Nevertheless, many elegant strategies for the utilization of CO2 have been developed using Lewis bases, frustrated Lewis pairs, hydroxyl-containing compounds, amino-group-containing compounds or transition metal catalysis. Among them, base-mediated carboxylation of C-nucleophiles is an environmentally friendly strategy for CO2 conversion, which is operationally simple, using low-toxicity bases and economical available promoters, without the use of complex ligands or cocatalysts. This review summarizes related work on the base-mediated carboxylation of C-nucleophiles with CO2, based on the effects of nucleophiles, promoters, additives, and solvents. The types of pronucleophile are categorized as follows: hydrocarbon with C(sp3)-H, C(sp2)-H or C(sp)-H bonds, organosilanes, organotin, organoboron, and N-tosylhydrazones. Typical mechanisms and applications of these carboxylation reactions are also depicted. Moreover, mechanistic comprehension of CO2 activation and conversion at a molecular level aims to further expand the repertoire of carboxylation transformations mediated by bases.

Nickel-catalyzed divergent formylation and carboxylation of aryl halides with isocyanides.

Herein, we describe a nickel-catalyzed divergent formylation and carboxylation reaction of aryl halides with isocyanides. A rich array of aromatic aldehydes and carboxylic acids can be, respectively, accessed in moderate to good yields. Some sensitive functional groups such as hydroxyl, iodine, cyano, and indolyl are fairly tolerant of nickel catalysis. In the carboxylation reactions, the combination of isocyanide and H2O is first employed as a promising carbonyl surrogate instead of gaseous CO and CO2.

Amphoteric cellulose microspheres for the efficient remediation of anionic and cationic dyeing wastewater

Amphoteric cellulose porous microsphere adsorbents (ACM) with high contents of functional groups were prepared by carboxylation and amination reactions. The obtained ACM possess similar contents of carboxyl groups (1.52 mmol/g) and amino groups (1.51 mmol/g). In addition, the modified microspheres exhibited excellent mechanical properties benefiting from the dense porous structures. The ACM could simultaneously remove the cationic dye methyl orange (MO) as well as the anionic dye methylene blue (MeB) with adsorption capacities as high as 345.32 mg/g and 616.12 mg/g, respectively. Another the microspheres are also with good regeneration that the adsorption capacities still maintained more than 90 % after 8 cycles.

The trade-off function of photorespiration in a changing environment

Abstract The photorespiratory pathway in plants comprises metabolic reactions distributed across several cellular compartments. It emerges from the dual catalytic function of Rubisco, i.e. ribulose-1,5-bisphosphate carboxylase/oxygenase. Rubisco either carboxylates or oxygenates ribulose-1,5-bisphosphate. Carboxylation reactions produce 3-phosphoglycerate molecules which are substrates for the central carbohydrate metabolism. However, oxygenation reactions additionally form 2-phosphoglycolate molecules which are (i) substrate for a multicompartmental recovery process, and (ii) inhibit several enzymes of the Calvin–Benson–Bassham cycle. Here, an approach of structural kinetic modelling is presented to investigate the extent of stabilization of the Calvin–Benson–Bassham cycle and carbohydrate metabolism by photorespiration. This method is based on a parametric representation of the Jacobian matrix of a metabolic system which offers a robust strategy for handling uncertainties associated with in vitro kinetic constants. Our findings indicate that oxygenation of ribulose-1,5-bisphosphate by Rubisco significantly stabilizes the Calvin–Benson–Bassham cycle. Hence, a trade-off function of photorespiration is suggested which reduces carbon assimilation rates but simultaneously stabilizes metabolism by increasing plasticity of metabolic regulation within the chloroplast. Furthermore, our analysis indicates that increasing carbon flux towards sucrose biosynthesis has a stabilizing effect. Finally, our findings shed light on the role of a multicompartmental metabolic pathway in stabilizing plant metabolism against perturbation induced by a dynamic environment.

Elucidation of the Roles of Water on the Reactivity of Surface Intermediates in Carboxylic Acid Ketonization on TiO2.

The effects of water on the carboxylic acid ketonization reaction over solid Lewis-acid catalysts were examined by nuclear magnetic resonance (NMR) spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), temperature-programmed desorption (TPD), and kinetic measurements. Acetic acid and propanoic acid were used as model compounds, and P25 TiO2 was used as a model catalyst to represent the anatase TiO2 since the rutile phase only contributes to <2.5% of the overall ketonization activity of P25 TiO2. The kinetic measurement showed that introducing H2O vapor in gaseous feed decreases the ketonization reaction rate by increasing the intrinsic activation barrier of gas-phase acetic acid on anatase TiO2. Quantitative TPD of acetic acid indicated that H2O does not compete with acetic acid for Lewis sites. Instead, as indicated by combined approaches of NMR and DRIFTS, H2O associates with the adsorbed acetate or acetic acid intermediates on the catalyst surface and alters their reactivities for the ketonization reaction. There are multiple species present on the anatase TiO2 surface upon carboxylic acid adsorption, including molecular carboxylic acid, monodentate carboxylate, and chelating/bridging bidentate carboxylates. The presence of H2O vapor increases the coverage of the less reactive bridging bidentate carboxylate associated with adsorbed H2O, leading to lower ketonization activity on hydrated anatase TiO2. Surface hydroxyl groups, which are consumed by interaction with carboxylic acid upon the formation of surface acetate species, do not impact the ketonization reaction.

PH-responsive organic/inorganic hybrid nanocolloids for transcellular delivery of ribonucleolytic payloads toward targeted anti-glioma therapy

Proteins have been appreciated to be a superlative modality of therapeutics in view of their direct roles in regulating diverse sets of biological events, nonetheless, the clinical applications of the proteinic therapeutics have been strictly limited to act on the cell surface receptors owing to their inherent cell-impermeable character of the proteins. To this obstacle, we contrived carboxylation reaction upon the proteins (RNase A) into the overall negatively charged pro-RNase, followed by elaboration of intelligent pH-responsive pro-RNase delivery nanocolloids based on co-precipitation of pro-RNase and Arg-Gly-Asp (RGD)-functionalized poly(ethylene glycol) (PEG)-block-polyanion with aids of inorganic calcium phosphate (CaP). The resulting nanocolloids appeared to actively accumulate into glioma due to the specific binding affinities of RGD and glioma-enriched αVβ3 and αVβ5 integrins. Furthermore, the pH responsiveness to the acidic endolysosomal microenvironment of all compositions of nanocolloids (including: decarboxylation of pro-RNase composition to restore the native RNase A, ionization of CaP composition to elicit osmotic pressure, and charge reversal of PEG-block-polyanion into membrane-disruptive polycation) could stimulate not only efficient endolysosomal escape for translocation into the cytosol but also structural disassembly for ready liberation of the RNase A payloads, eventually exerting non-specific RNA degradation for apoptosis of the affected cells. Systemic dosage of the proposed nanocolloids demonstrated potent anti-tumor efficacies towards xenograft glioma due to massive RNA degradation. Therefore, our proposed RNase A prodrug nanocolloids could represent as a versatile platform for engineering transcellular protein delivery systems, which are expected to spur thriving emergence of a spectrum of proteins in precision intervention of intractable diseases.

A green and efficient synthetic methodology towards the synthesis of 1-allyl-6-chloro-4-oxo-1,4-dihydroquinoline-3-carboxamide derivatives.

Quinolone is a privileged scaffold in medicinal chemistry and 4-Quinolone-3-Carboxamides have been reported to harbor vast therapeutic potential. However, conversion of N-1 substituted 4-Quinolone 3-Carboxylate to its corresponding carbamates is highly restrictive. This motivated us to adopt a much simpler, scalable and efficient methodology for the synthesis of highly pure N-1 substituted 4- Quinolone-3-Carboxamides with excellent yields. Our adopted methodology not only provides a robust pathway for the convenient synthesis of N-1 substituted 4- Quinolone-3-Carboxamides which can then be explored for their therapeutic potential, this may also be adaptable for the derivatization of other such less reactive carboxylate species.

Controllable adsorption groups on amine-functionalized carbon nitride for enhanced photocatalytic CO2 reduction

CO2 photoreduction by carbon nitride (CN) is an appealing idea, but its current efficiency remains daunting for practical viability. The amine-functionalized CN with controllable adsorption groups was prepared by carboxylation and acylation reactions. The carboxylation and amine-functionalization process preserved the crystalline structure of CN but exfoliated bulk CN to thin layers avoiding its agglomeration. With the successful graft of EDA, the amounts of –NH2 groups for 24-CN-EDA increased remarkably compared with bulk CN. EDA-functionalization benefited CO2 reduction activity of CN with varying amounts of amino groups. The CO yield of 24-CN-EDA was 5.92 folds to bulk CN. The enhancement was mainly triggered by the enlarged CO2 adsorption capacity and reduced charge transfer resistance, rather than band structure and light absorption. Moreover, DFT calculations suggest that the graft of EDA on CN nanosheets possesses reduced energy barrier for CO2 reduction into CO via enhancing CO* desorption and CO formation.

THE SIMULATION OF INTERMOLECULAR INTERACTIONS OF CARBOXYLIC AND AMINE GROUPS WITH CALCIUM CARBONATE

Surface facilities including tubing and valves at the oilfield have been plagued by mineral scale deposits, which are constitute of calcium carbonate (CaCO3). Penta-potassium diethylenetriaminepentaacetic acid salt (DTPA-K5) has a higher affinity for the metal cations complexes during the chelation process. The eight complexing sites (five carboxylate and three amines) empower the metal ion interactions. This work investigated the molecular dynamics simulations between the DTPA-K5 with the calcium carbonate, CaCO3 scale. The interaction was performed through molecular dynamic (MD) simulation using condensed phase optimised molecular potentials for atomistic simulation studies (COMPASS) force field and the Ewald summation method in Material Studio. The simulation trajectory files examined the intermolecular interactions for radial distribution function (RDF). The simulation shows strong DTPA-K5 with calcium interactions, which revealed the metal ion complexes contributing to the chelation process through the reactive carboxylic and amine functional groups, which were O7 == Ca at radius, r, 2.25 Å with g(r) of 10.09 and N1 -- Ca at radius, r, 2.25 Å with g(r) 2.51.

Study on Reaction Sites of Active Structures in Coal Based on the ReaxFF Reactive Force Field.

To study the reaction paths and reaction mechanisms of the active structures in coal during the oxidation process, the oxygen-free pyrolysis and oxygen-containing combustion were simulated for nine active structures in coal based on the ReaxFF MD method. A separate simulation analysis of the active structure yielded that O2 inhibited the reaction of H1. As the branched chain grows, the reaction paths of C2 and Q2 follow the direction of the reaction of carboxyl and aldehyde groups to CO2 and CO. Considering the reaction rates and reaction process products of A1, B1, and B3 structures, it is obtained that O2 has the greatest contribution to the decomposition reaction of aliphatic hydrocarbon structures. This is due to the strong electron-absorbing property of O2 that attracts H radicals to generate HO2, which in turn affects the reaction path of the active structure. Tracing the reaction process reveals that OH and oxygen-containing radicals under oxygen-free conditions greatly influence the active structural reaction.

Regulation of light energy conversion between linear and cyclic electron flow within photosystem II controlled by the plastoquinone/quinol redox poise.

Ultrapurified Photosystem II complexes crystalize as uniform microcrystals (PSIIX) of unprecedented homogeneity that allow observation of details previously unachievable, including the longest sustained oscillations of flash-induced O2 yield over > 200 flashes and a novel period-4.7 water oxidation cycle. We provide new evidence for a molecular-based mechanism for PSII-cyclic electron flow that accounts for switching from linear to cyclic electron flow within PSII as the downstream PQ/PQH2 pool reduces in response to metabolic needs and environmental input. The model is supported by flash oximetry of PSIIX as the LEF/CEF switch occurs, Fourier analysis of O2 flash yields, and Joliot-Kok modeling. The LEF/CEF switch rebalances the ratio of reductant energy (PQH2) to proton gradient energy (H+o/H+i) created by PSII photochemistry. Central to this model is the requirement for a regulatory site (QC) with two redox states in equilibrium with the dissociable secondary electron carrier site QB. Both sites are controlled by electrons and protons. Our evidence fits historical LEF models wherein light-driven water oxidation delivers electrons (from QA-) and stromal protons through QB to generate plastoquinol, the terminal product of PSII-LEF in vivo. The new insight is the essential regulatory role of QC. This site senses both the proton gradient (H+o/H+i) and the PQ pool redox poise via e-/H+ equilibration with QB. This information directs switching to CEF upon population of the protonated semiquinone in the Qc site (Q-H+)C, while the WOC is in the reducible S2 or S3 states. Subsequent photochemical primary charge separation (P+QA-) forms no (QH2)B, but instead undergoes two-electron backward transition in which the QC protons are pumped into the lumen, while the electrons return to the WOC forming (S1/S2). PSII-CEF enables production of additional ATP needed to power cellular processes including the terminal carboxylation reaction and in some cases PSI-dependent CEF.

Ultrathin origami accordion‐like structure of vacancy‐rich graphitized carbon nitride for enhancing CO2 photoreduction

AbstractRetaining the ultrathin structure of two‐dimensional materials is very important for stabilizing their catalytic performances. However, aggregation and restacking are unavoidable, to some extent, due to the van der Waals interlayer interaction of two‐dimensional materials. Here, we address this challenge by preparing an origami accordion structure of ultrathin two‐dimensional graphitized carbon nitride (oa‐C3N4) with rich vacancies. This novel structured oa‐C3N4 shows exceptional photocatalytic activity for the CO2 reduction reaction, which is 8.1 times that of the pristine C3N4. The unique structure not only prevents restacking but also increases light harvesting and the density of vacancy defects, which leads to modification of the electronic structure, regulation of the CO2 adsorption energy, and a decrease in the energy barrier of the carbon dioxide to carboxylic acid intermediate reaction. This study provides a new avenue for the development of stable high‐performance two‐dimensional catalytic materials.

Nickel‐Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2′‐Bipyridine Ligand

AbstractIn contrast to previous approaches to chiral α‐aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel‐catalyzed general, efficient and highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions using atmospheric CO2 has been developed. A unique chiral 2,2′‐bipyridine ligand named Me‐SBpy featuring compact polycyclic skeleton enabled both high reactivity and stereoselectivity. The utility of this method has been demonstrated by synthesis of various chiral α‐aryl carboxylic acids (30 examples, up to 95 % yield and 99 : 1 er), including profen family anti‐inflammatory drugs and transformations using the acids as key intermediates. Based on mechanistic experimental results, a plausible catalytic cycle involving Ni‐complex/radical equilibrium and Lewis acid‐assisted CO2 activation has been proposed.

Nickel-Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2'-Bipyridine Ligand.

In contrast to previous approaches to chiral α-aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel-catalyzed general, efficient and highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions using atmospheric CO2 has been developed. A unique chiral 2,2'-bipyridine ligand named Me-SBpy featuring compact polycyclic skeleton enabled both high reactivity and stereoselectivity. The utility of this method has been demonstrated by synthesis of various chiral α-aryl carboxylic acids (30 examples, up to 95 % yield and 99 : 1 er), including profen family anti-inflammatory drugs and transformations using the acids as key intermediates. Based on mechanistic experimental results, a plausible catalytic cycle involving Ni-complex/radical equilibrium and Lewis acid-assisted CO2 activation has been proposed.

In-situ etching MOF nanoparticles for constructing enhanced interface in hybrid membranes for gas separation

Metal-organic frameworks (MOFs) based hybrid membranes have great potential for energy-efficient gas separation. However, the defective interface structure greatly depresses their separation performance. In this work, a distinctive interfacial design strategy via in-situ etching ZIF-8 nanoparticles is proposed to construct hybrid membranes with nearly defect-free interfaces. The nanoscale etching of ZIF-8 nanoparticles in polymer matrix with acid group (PI-COOHx) is well controlled by the amount of carboxyl group and reaction time. Owing to the strong coordination interaction between Zn2+ ions and –COOH groups, the residual ZIF-8 nanoparticles are tightly wrapped by polymer matrix. Molecular simulation was performed to study the in-situ etching ZIF-8 in PI-COOHx matrix in molecular level. The resulted hybrid membranes (PI-COOHx/E-ZIF-8) exhibit simultaneously enhanced permeability and selectivity with increasing filler loading content. Benefiting from the rational interfacial design, the effective loading content of ZIF-8 nanoparticles is up to 50 wt% for PI-COOH20/E-ZIF-8 membrane. The H2, CO2, and O2 permeability of the membrane are 3058.6, 1429.0, and 459.0 Barrer, increasing by 468.5%, 288.3% and 348.2%, respectively, of pristine PI-COOH20 membrane, and the gas selectivity for H2/N2, H2/CH4, O2/N2, and CO2/CH4 gas pairs are greatly improved from 20.3, 23.4, 3.9 and 16.0 of pristine PI-COOH20 membrane to 30.7, 37.6, 4.6 and 17.6. The comprehensive separation performance for H2/N2, H2/CH4, and O2/N2 gas pairs surpass the 2008 upper bound and approach the 2015 upper bound. Meanwhile, the CO2 plasticization resistance of PI-COOH20/E-ZIF-8 membrane also achieves significant improvement from 6 bar of PI-COOH20 membrane to 27 bar. This work provides an effective and robust strategy to effectively enhance the interfacial compatibility of hybrid membranes.

Femtosecond laser-engineered 3D microfluidic chips: Synthesis system sprouting highly efficient multiphase organic reactions

Recent developments in the utilization of microfluidic chips (MFCs) have shown their potential utility in multiphase organic synthesis by enabling efficient organic reactions in flow chemistry. However, MFCs technology has been wandering in the laboratory of small dose synthetic routes, which is limited to the level of "tiny" fluid flux. To address this issue, we herein report the first case of the chips with high-throughput 3D channels produced by femtosecond laser being used to create a time-saving, cost-effective and risk-free approach suitable for large-scale flow synthesis. Several multiphase reactions have been successfully prepared on demand in our designed flow synthesis system containing 3D MFCs: 1) benzyl alcohol was converted to benzaldehyde in 3 min with a yield of 97.50% by liquid-liquid two-phase transfer catalytic oxidation; 2) organozinc reagents and α-cyano carbonyl carbon compounds were synthesized by solid-liquid two-phase metal insertion reaction in 7 min, and the yield was up to 100%; 3) benzoic acid was synthesized by gas-liquid two-phase carboxylation reaction in 2.8 s with a yield of 96%. Significant gains in production rate result from the effective scaling of flow reactors from microliters per hour in MFCs to intermediate milliliters per minute without affecting mass transport performance. Meanwhile, our 3D MFCs show excellent mass and heat transfer efficiency in large-scale industrial units, breaking through the bottleneck in this field. As a result, it is possible to imagine the creation of a new, streamlined flow synthetic technique via MFCs for green multiphase organic synthesis.

Cover Feature: Toward Sustainable Photo‐/Electrocatalytic Carboxylation of Organic Substrates with CO2 (Asian J. Org. Chem. 11/2022)

Owing to the global environmental policies for decarbonization, conversion of waste CO2 into value-added products is the research focus today. Although CO2 is an excellent C1 source, due to its inherent thermodynamic stability and kinetic inertness most of the carboxylation reactions using CO2 are far from practical as they require high pressure of CO2, harsh conditions, high energy input etc. To circumvent this, photo- and electrocatalysis have emerged as state-of-the-art and promising technique for carboxylation with CO2. In this review, we chronologically present the development of these modern carboxylation reactions aiming towards sustainable development. More information can be found in the Review by Ranjan Jana et al.