Carboxylation Reaction Research Articles

Bifunctional Ionic Deep Eutectic Electrolytes for CO2 Electroreduction.

CO2 is a low-cost monomer capable of promoting industrially scalable carboxylation reactions. Sustainable activation of CO2 through electroreduction process (ECO2R) can be achieved in stable electrolyte media. This study synthesized and characterized novel diethyl ammonium chloride−diethanolamine bifunctional ionic deep eutectic electrolyte (DEACl–DEA), using diethanolamine (DEA) as hydrogen bond donors (HBD) and diethyl ammonium chloride (DEACl) as hydrogen bond acceptors (HBA). The DEACl–DEA has −69.78 °C deep eutectic point and cathodic electrochemical stability limit of −1.7 V versus Ag/AgCl. In the DEACl–DEA (1:3) electrolyte, electroreduction of CO2 to CO2•– was achieved at −1.5 V versus Ag/AgCl, recording a faradaic efficiency (FE) of 94%. After 350 s of continuous CO2 sparging, an asymptotic current response is reached, and DEACl–DEA (1:3) has an ambient CO2 capture capacity of 52.71 mol/L. However, DEACl–DEA has a low faradaic efficiency <94% and behaves like a regular amine during the CO2 electroreduction process when mole ratios of HBA–HBD are greater than 1:3. The electrochemical impedance spectroscopy (EIS) and COSMO-RS analyses confirmed that the bifunctional CO2 sorption by the DEACl–DEA (1:3) electrolyte promote the ECO2R process. According to the EIS, high CO2 coverage on the DEACl–DEA/Ag-electrode surface induces an electrochemical double layer capacitance (EDCL) of 3.15 × 10–9 F, which is lower than the 8.76 × 10–9 F for the ordinary DEACl–DEA/Ag-electrode. COSMO-RS analysis shows that the decrease in EDCL arises due to the interaction of CO2 non-polar sites (0.314, 0.097, and 0.779 e/nm2) with that of DEACl (0.013, 0.567 e/nm2) and DEA (0.115, 0.396 e/nm2). These results establish for the first time that a higher cathodic limit beyond the typical CO2 reduction potential is a criterion for using any deep eutectic electrolytes for sustainable CO2 electroreduction process.

Crystal structure of a type III Rubisco in complex with its product 3-phosphoglycerate.

The crystal structure of the complex of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco; EC 4.1.1.39) from Archaeoglobus fulgidus (afRubisco) with its products 3PGAs has been determined to a resolution of 1.7Å and is of the closed form. Type III Rubiscos such as afRubisco have 18 out of the 19 essential amino acid residues of canonical Rubisco; the 19th is Tyr rather than Phe. Superposition with the structure of a complex of the similar tkRubisco with the six-carbon intermediate analog 2CABP shows the same conformation of the 19 residues except for Glu46 and Thr51. Glu46 adopts a unique conformation different from that in other Rubiscos and makes two H-bonds with the ligand 3PGA. Similar to other closed state Rubiscos, the backbone of Thr51 is rotated and the side chain makes an H-bond with the ligand 3PGA. Two product 3PGA molecules are bound at the active site, overlapping well with the 2CABP of tkRubisco/2CABP. The positions of the P1 and P2 phosphate groups differ by 0.4 and 0.53 Å, respectively, between 2CABP and the two 3PGAs. This afRubisco/3PGA complex mimics an intermediate stage of the carboxylation reaction which occurs after the production of the two 3PGA products but before the reopening of the active site. The stability of this complex suggests that the Rubisco active site will not reopen before both 3PGA products are formed.

Box-Behnken experimental design for optimizing process parameters in carbonate-promoted direct thiophene carboxylation reaction with carbon dioxide

A feasible synthesis route is developed for achieving the direct carboxylation of thiophene and CO 2 in a relatively mild solvent-free carboxylate-assisted carbonate (semi) molten state. The effects of reaction factors on the carboxylate yield are investigated in the preliminary screening experiments, and the phase behavior analysis of the reaction medium is detected through the thermal characterization analysis of in-situ high temperature X-ray diffraction measurement ( in-situ XRD). The application of response surface methodology (RSM) based on the Box-Behnken design (BBD) is conducted to investigate the effect of the reaction parameters, such as reaction temperature, carbonate proportion, CO 2 pressure and thiophene amount, on the product yield. The regressed second-order polynomial model equation well correlates all the independent variables. The analysis of variance (ANOVA) results reveal that the quadratic effect of reaction temperature is the most effective parameter in this carboxylation reaction owing to it’s the highest contribution to the sum of square (30.18%). The optimum reaction conditions for maximum product yield are the reaction temperature of 287 ℃, carbonate proportion of 32.20%, CO 2 pressure of 10 bar and thiophene amount of 9.35 mmol. Operating under these selected experimental conditions, a high product yield (50.98%) can be achieved.

A potential novel and general route for bromide replacement in diimine ReI tricarbonyl complexes leading to carboxylates: The effect in luminescence

The reaction of the 3,5-dimethylpyrazolyl-pyridazine-6-carboxylic acid (Me2LCOOH) or pyrazolyl-pyridazine-6-carboxylic acid (LCOOH) with [(THF)(CO)3Re(µ-Br)2Re(CO)3(THF)] in DMF followed by the addition of traces of water leads to a series of dehalided rhenium(I) tricarbonyl carboxylates: [(Me2LCOO)(H2O)Re(CO)3] and [(LCOO)(H2O)Re(CO)3] instead of the normal rhenium(I) tricarbonyl bromide obtained by reaction in chloroform, [(Me2LCOOH)Re(CO)3Br]. The reaction is believed to occur through adventitious amine in the reaction media which leads to the carboxylic acid deprotonation and reaction. To test this idea the diimine-rhenium(I) tricarbonyl bromide [(phen)Re(CO)3Br] and [(bppdz)Re(CO)3Br] (phen: 1,10-phenanthroline; bppdz: 3,6-bis(1H-pyrazol-1-yl)pyridazine) were reacted with glacial acetic acid and triethylamine in dry DMF at room temperature. These reaction lead to the corresponding rhenium(I) acetates [(phen)Re(CO)3(OOCCH3)] and [(bppdz)Re(CO)3(OOCCH3)] in good to high yields using soft reaction conditions and without the use of a silver salt. Thiethylammonium bromide is also obtained from the reaction. Moreover, the fact that this unexpected rhenium(I) tricarbonyl carboxylates were obtained in as N,N and N,O coordination isomers for [(Me2LCOO)(H2O)Re(CO)3] and the comparison of the newly synthetized [(phen)Re(CO)3(OOCCH3)] and [(bppdz)Re(CO)3(OOCCH3)] compounds with their corresponding bromides allow to stablish that the replacement of the halide by a carboxylate hypsochromically shift the energy of the MLCT band while the emission experiences the opposite, it is bathochromically shifted. The emission quantum yields are slightly diminished. Interestingly the [(phen)Re(CO)3(OOCCH3)] and [(bppdz)Re(CO)3(OOCCH3)] acetates are dual emitters.

Unraveling the effects of P and S doping over g-C3N4 in strengthening Lewis basicity for CO2/glycerol conversion: A theoretical and experimental study

Conversion of CO2 to chemicals and fuels has attracted considerable attention as CO2 is a nontoxic, non-flammable, and cheap carbon-oxygen source. However, the kinetics of CO2 conversion into other chemicals remains a challenge due to its thermodynamic stability. Herein, P and S co-doped graphitic-carbon nitride (PSCN) catalyst was synthesized through one-step thermal condensation to improve its Lewis acidity and basicity and investigate carbon dioxide/glycerol (CO2/GLY) conversion. The catalytic GLY conversion at 210 °C reached 60% and 85% using pristine g-C3N4 (CN) and PSCN, respectively, with CO2 as a carbon feedstock and CH3CN as a dehydrating agent. Density-functional theory (DFT) calculations revealed that the efficient charge transfer resulting from P and S doping could increase the catalytic activity for CO2/GLY conversion by lowering the activation barrier. This is the first study to demonstrate the catalytic activity of the PSCN catalyst for the CO2/GLY conversion and the computational work for the GLY carboxylation reaction. Moreover, the interaction site and adsorption energy were investigated for the adsorption of CO2 and GLY on PSCN and CN to elucidate the reaction mechanism. Our results demonstrated that PSCN could serve as a superior catalyst and pave new light for CO2/GLY conversion.

Computational Insights into Malononitrile-Based Carbanions for CO2 Capture.

Although anionic N and O sites have been widely used in chemisorption of CO2, carbanions are much less explored for CO2 capture. Here we employ ab initio calculations and quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations to examine the interaction between CO2 and the malononitrile carbanion, [CH(CN)2]-. We have explored the potential energy surface of CO2 binding by scanning the C-C distance between CO2 and the central C site of the carbanion. We find that CO2 prefers to bind to the nitrile group physically rather than to form a C-C bond via the carboxylation reaction at the sp2 C site. Moreover, the two -CN groups can attract two CO2 molecules at equal strength. The presence of an alkali metal ion enhances both physical and chemical interactions of CO2 with the malononitrile carbanion. QM/MM MD simulations further confirm the preference of physical interaction in the condensed ionic liquid phase with a phosphonium cation. Our findings suggest that ionic liquids based on the malononitrile carbanion may have a high CO2 solubility for carbon capture.

CuNi bimetallic nanocatalyst enables sustainable direct carboxylation reactions

Herein, we combine catalyst synthesis, characterization, catalytic experiments, and theory to investigate the bimetallic CuNi-11 nanocatalyst for direct carboxylation of arenes. Catalytic experiments reveal that the CuNi-11 shows an excellent yield and a higher benzene conversion compared to monometallic Cu and Ni nanocatalysts. The bimetallic CuNi-11 nanocatalyst exhibits a high surface area of 58.993 m2/g with excellent reusability (up to 6 cycles) and the carboxylation reaction is an activator-, additive- and solvent-free taking place under mild conditions. Catalytic experiments are complemented by Density Functional Theory (DFT) calculations demonstrating a plausible mechanistic pathway involving C-H bond activation of benzene and formic acid. The benzoic acid and H2 formation with the benzene C–H activation being the rate-determining step. Overall, our work contributes to introducing sustainable and environmentally friendly carboxylation routes of arenes with a new mechanistic approach.

Cu dispersed ZrO2 catalyst mediated Kolbe- Schmitt carboxylation reaction to 4-hydroxybenzoic acid

The Kolbe-Schmitt reaction is one of the industrially promising route for the production of hydroxybenzoic acids. In the present manuscript, alkali metal hydroxide free, direct carboxylation reaction has been demonstrated over heterogeneous CuO/ZrO2 catalyst. Different basic oxide (ZrO2, TiO2 and Bi2O3) and corresponding Cu dispersed oxides (CuO/ZrO2, CuO/TiO2 and CuO/Bi2O3) were tested for direct carboxylation. The performance of catalysts were elucidated by comparing 4-HBA yield, phenol conversion, TON and TOF. Amongst the tested catalysts, ZrO2 showed highest catalytic activity with TON 0.1022 and TOF 0.0043, hence selected as an efficient catalyst support for Cu dispersion. The lowest value of E-factor (0.12) and PMI (0.39) was obtained for 5 wt% CuO/ZrO2 catalyst. A series of Cu dispersed ZrO2 catalyst were synthesized via simple co-precipitation method with variable Cu precursor loading. Of the tested catalysts 1.25 wt% CuO loaded ZrO2 catalyst showed highest yield (62.57%) and phenol conversion (64.55%) under non-stringent operating condition (60 bar, 170 °C). The in-depth physicochemical characteristion were also conducted by using various analytical tools which dipicted the characterstic properties of CuO/ZrO2 catalyst. The process intensification study was conducted to obtain optimum operating parameters for high yield and conversion. The catalyst recyclability performance study showed the consistency in 4-HBA yield and conversion for four consecutive recycle runs. The plausible reaction mechanism for production of 4-HBA over CuO/ZrO2 catalyst and catalytic cycle has also been proposed. Thus, the present process provides green and efficient route for alkali hydroxide free Kolbe- Schmitt reaction.

Toward Sustainable Photo‐/Electrocatalytic Carboxylation of Organic Substrates with CO2

AbstractHistorically, carbon dioxide found many applications in organic chemistry from reaction medium e. g., super critical carbon dioxide (scCO2) or CO2‐expanded liquid (CXL) system; extraction (natural products), separation (supercritical fluid chromatography); chemo‐, regio‐, and stereoselective transformation via the formation of transient intermediates i. e., carbonate, carbamate etc. Recently, researchers have exploited CO2 as an inexpensive, renewable and non‐toxic C1 feedstock for carboxylation and carbonylation reactions. However, owing to its inherent kinetic and thermodynamic stability, most of the transformations require high temperatures, high pressure, and stoichiometric amounts of organometallic reductants that leads to accidental and environmental hazards. Inspired by the natural processes, photo‐ and electrocatalytic conversion of CO2 into value‐added products has emerged as a benign and practical approach in organic synthesis. Here in this review, we will discuss some recent photo‐ and electrocatalytic methods and their comparison toward sustainable development.

Mechanistic Insights and Rational Design of Ca-Doped CeO2 Catalyst for Acetic Acid Ketonization

Carboxylic acid ketonization has recently gained significant attention to produce biomass-derived hydrocarbon fuels as it not only removes the highly reactive carboxylic functional group but also increases the size of the carbon chain. In this study, Ca-doped CeO2-based catalysts were investigated for acetic acid ketonization using a combined experimental and computational approach. Acetic acid conversion was performed across a range of temperatures including higher temperatures relevant to catalytic hot gas filtration (450 °C). Ca addition slightly decreases overall acetic acid ketonization reactivity yet stabilizes the catalyst at the higher temperatures necessary for catalytic hot gas filtration. From density functional theory calculations of the ketonization reaction mechanism, the C–C coupling and water formation steps are identified as two of the most energy-consuming steps on a CeO2 surface with a proximal oxygen vacancy and the presence of a Ca dopant stabilizes the key intermediates. Calculations predict an optimal structure comprising three Ca ensembles to minimize the reaction free energies for C–C coupling and water formation steps. These findings provide a priori information to guide future experiments for ketonization catalyst design and development.

Carboxylation reactions for integrating CO2 capture with the production of renewable monomers

AbstractResearch advances in carboxylation reactions using CO2 and light organic molecules of renewable origin are reviewed in this work, especially considering chemical catalytic approaches. Carboxylation, one of the most promising carbon capture and utilization (CCU) technologies, has a double environmental benefit, reducing greenhouse gas emissions by developing sustainable processes for commodity synthesis. The industrial interest is based on its potential use in the synthesis of biopolymer precursors from bioplatform molecules such as ethanol or furfural. Acrylic acid is obtained from ethylene (after ethanol dehydration), by a liquid phase reaction activated by organometallic catalysts. Promising yields are reported for different ligands and solvents, but a practical and sustainable implementation of these reactions is still challenging. On the other hand, the furoic acid carboxylation (furoic acid obtained by oxidation of furfural) is a solid‐gas reaction that produces 2,5furandicarboxylic acid in presence of alkaline carbonates. In this case, the economic feasibility is the main bottleneck to solve for scaling‐up, and efforts should be focused on substituting the most active alkaline carbonate (Cs) by more available alternatives. © 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley &amp; Sons Ltd.

Carboxylic Acid-Directed Manganese(I)-Catalyzed Regioselective Hydroarylation of Unactivated Alkenes

A carboxylic acid-directed regioselective hydroarylation reaction of unactivated alkenes with aryl boronic acids was reported. This transformation was enabled by homogeneous manganese catalyst MnBr(CO)5 in the presence of KOH and H2O in the m-xylene reaction medium. Both internal and terminal alkenes worked well in this transformation, and a series of functional groups were tolerated. This reaction not only provided an expeditious method to prepare γ-aryl carboxylic acids from simple starting materials but also would inspire further studies in employing homogeneous manganese catalysis in organic synthesis.

Reaction Mechanism of Human PAICS Elucidated by Quantum Chemical Calculations.

Human PAICS is a bifunctional enzyme that is involved in the de novo purine biosynthesis, catalyzing the conversion of aminoimidazole ribonucleotide (AIR) into N-succinylcarboxamide-5-aminoimidazole ribonucleotide (SAICAR). It comprises two distinct active sites, AIR carboxylase (AIRc) where the AIR is initially converted to carboxyaminoimidazole ribonucleotide (CAIR) by reaction with CO2 and SAICAR synthetase (SAICARs) in which CAIR then reacts with an aspartate to form SAICAR, in an ATP-dependent reaction. Human PAICS is a promising target for the treatment of various types of cancer, and it is therefore of high interest to develop a detailed understanding of its reaction mechanism. In the present work, density functional theory calculations are employed to investigate the PAICS reaction mechanism. Starting from the available crystal structures, two large models of the AIRc and SAICARs active sites are built and different mechanistic proposals for the carboxylation and phosphorylation–condensation mechanisms are examined. For the carboxylation reaction, it is demonstrated that it takes place in a two-step mechanism, involving a C–C bond formation followed by a deprotonation of the formed tetrahedral intermediate (known as isoCAIR) assisted by an active site histidine residue. For the phosphorylation–condensation reaction, it is shown that the phosphorylation of CAIR takes place before the condensation reaction with the aspartate. It is further demonstrated that the three active site magnesium ions are involved in binding the substrates and stabilizing the transition states and intermediates of the reaction. The calculated barriers are in good agreement with available experimental data.

Alkaline-Earth Chalcogenide Nanocrystals: Solution-Phase Synthesis, Surface Chemistry, and Stability.

Increasing demand for effective energy conversion materials and devices has renewed interest in semiconductors comprised of earth-abundant and biocompatible elements. Alkaline-earth sulfides doped with rare earth ions are versatile optical materials. However, relatively little is known about controlling the dimensionality, surface chemistry, and inherent optical properties of the undoped versions of alkaline-earth mono- and polychalcogenides. We describe the colloidal synthesis of alkaline-earth chalcogenide nanocrystals through the reaction of metal carboxylates with carbon disulfide or selenourea. Systematic exploration of the synthetic phase space allows us to tune particle sizes over a wide range using a mixture of commercially available carboxylate precursors. Solid-state NMR spectroscopy confirms the phase purity of the selenide compositions. Surface characterization reveals that bridging carboxylates and amines preferentially terminate the surface of the nanocrystals. While these materials are colloidally stable in the mother solution, the selenides are susceptible to oxidation over time, eventually degrading to selenium metal through polyselenide intermediates. As part of these investigations, we have developed the colloidal syntheses of barium di- and triselenides, two among few reported nanocrystalline alkaline-earth polychalcogenides. Electronic structure calculations reveal that both materials are indirect band gap semiconductors. The colloidal chemistry presented here may enable the synthesis of more complex, multinary chalcogenide materials containing alkaline-earth elements.

Simultaneously reinforcing and toughening of shape-memory epoxy resin with carboxylated lignosulfonate: Facile preparation and effect mechanism

To improve the compatibility and reactivity of lignosulfonate (LS) with epoxy oligomers, the LS was firstly functionalized with anhydride via the carboxylation reaction. The carboxylated lignosulfonate (CLS) reinforced epoxy resin with excellent mechanical and shape memory performance was prepared facilely via distributing the CLS into the combined epoxy monomers of DGEBA and PEGDGE with the aid of water, rather than using the normal organic solvents. The incorporated CLS promoted the curing reaction of epoxy resin. A typical sea-island structure was formed in the cured sample at the CLS content of 5 phr, exhibiting the highest increases in tensile strength, modulus, elongation at break and toughness by 23.8 %, 18.2 %, 217 % and 113 %, respectively, relative to neat epoxy. Interestingly, the incorporation of CLS at a proper amount led to the simultaneous strengthening and toughing effects on cured epoxy resin, which could be attributed to the rigid structure of CLS covalently introduced in the epoxy resin network and the heterogeneous structure formed in the epoxy matrix. The rigid CLS component also restrained the movement of chain segments, consequently, the mechanical stability was enhanced and the fast shape recovery rate of epoxy resin network was slowed down to some extent.

A robust [11C]acetate synthesis on a TRACERLab FX C pro module

Carbon-11 labelled acetate ([11C]acetate) is a radiotracer of importance in clinical practice as well as in preclinical research. The TRACERLab FX C Pro Synthesizer can be used this sensitive carboxylation reaction. Starting from 11 GBq [11C]CO2, we were able to isolate about 3 GBq [11C]acetate after only 20 min reaction time (yield 56 ± 7%, n = 10).

Carboxylated cellulose nanocrystals as environmental-friendly and multi-functional additives for bentonite water-based drilling fluids under high-temperature conditions

During the oil and gas drilling engineering, the selection of drilling fluids must take account of the technical and environmental factors. This study investigated the effectiveness of carboxylated cellulose nanocrystals (denoted as CNCs) as environmentally friendly additives for improving the rheological, filtration, and inhibitive properties of water-based drilling fluids (WBDFs). CNCs used in this study were modified by carboxylation reaction, displaying small size, negative surface charge, good colloidal stability, and prominent shear-thinning behavior. Experimental results indicated that BT/CNC suspensions had superior rheological properties, low fluid loss volumes, and effective inhibition, even at 140 °C. Microstructure analysis demonstrated that CNCs could attach to the surface of BT via hydrogen bond and ionic bond. CNCs, BT, and vicinal water molecules could form a stiff gel network, which had a strong resistance to flow under shear force, leading to a significant improvement in the rheological properties. Moreover, under the differential pressure, BT/CNC suspensions formed thin and less hydrophilic filter cakes with compact layered structure, thereby efficiently decreasing the fluid loss volume. Finally, due to the gel network and filtration ability, BT/CNC suspensions performed low water activity, which was beneficial for preventing the penetration of free water into the shales and borehole well. Thus, CNCs also exerted satisfactory inhibition on hydration and dispersion of BT and shales. As a result, CNCs showed great potential to be used as efficient, multi-functional, and environmentally friendly additives in WBDFs.

Recent Advances in Copper‐Catalyzed Carboxylation Reactions with CO2

AbstractAs an ideal one‐carbon synthon, CO2has been successfully utilized in diverse carboxylation reactions to construct a series of value‐added products. Among various transition‐metal catalysts, the inexpensive copper complexes exhibit unique catalytic activity in carboxylation reactions. This review summarizes the recent developments in copper‐catalyzed carboxylation reactions with CO2, the contents of which are divided into five parts based on the type of the substrates or products: organic halides and their surrogates, C−C double bonds, C−C triple bonds, C−H bonds and the synthesis of heterocycles.

Injectable thermosensitive chitosan/gelatin hydrogel for dental pulp stem cells proliferation and differentiation.

Introduction: Biocompatible and biodegradable scaffolds based on natural polymers such as gelatin and chitosan (CS) provide suitable microenvironments in dental tissue engineering. In the present study, we report on the synthesis of injectable thermosensitive hydrogel (PNIPAAm-g-CS copolymer/gelatin hybrid hydrogel) for osteogenic differentiation of human dental pulp stem cells (hDPSCs). Methods: The CS-g-PNIPAAm was synthesized using the reaction of carboxyl terminated PNIPAAm with CS, which was then mixed with various amounts of gelatin solution in the presence of genipin as a chemical crosslinker to gain a homogenous solution. The chemical composition and microstructures of the fabricated hydrogels were confirmed by FT-IR and SEM analysis, respectively. To evaluate the mechanical properties (e.g., storage and loss modulus of the gels), the rheological analysis was considered. Calcium deposition and ALP activity of DPSCs were carried out using alizarin red staining and ALP test. While the live/dead assay was performed to study its toxicity, the real-time PCR was conducted to investigate the osteogenic differentiation of hDPSCs cultured on prepared hydrogels. Results: The hydrogels with higher gelatin incorporation showed a slightly looser network compared to the other ones. The hydrogel with less gelatin indicates a rather higher value of G', indicating a higher elasticity due to more crosslinking reaction of amine groups of CS via a covalent bond with genipin. All the hydrogels contained viable cells with negligible dead cells, indicating the high biocompatibility of the prepared hydrogels for hDPSCs. The quantitative results of alizarin red staining displayed a significant rise in calcium deposition in hDPSCs cultured on prepared hydrogels after 21 days. Further, hDPSCs cultured on hydrogel with more gelatin displayed the most ALP activity. The expression of late osteogenic genes such as OCN and BMP-2 were respectively 6 and 4 times higher on the hydrogel with more gelatin than the control group after 21 days. Conclusion: The prepared PNIPAAm-g-CS copolymer/gelatin hybrid hydrogel presented great features (e.g., porous structure, suitable rheological behavior, and improved cell viability), and resulted in osteogenic differentiation necessary for dental tissue engineering.

Recent Advances in Light‐Induced Carboxylation of Organic (Pseudo)Halides with CO2

AbstractCarbon dioxide is an ideal C1 source in organic synthesis as a precursor for the carboxyl group. With the development of photocatalysis, the carboxylation reactions with CO2 incorporation could be carried out in a more environmental and sustainable manner without the addition of stoichiometric metallic reductants. This minireview summarizes the recent development in light‐induced carboxylation of organic (pseudo)halides and analogues with CO2 via C−X (X=Br, Cl, O, N, etc.) bond cleavage.