Decarboxylation Research Articles

Iron‐Catalyzed, Visible‐Light‐Mediated Decarboxylative Cyclization Reactions: A Viable Approach to 2,3‐Dihydrobenzofuran Derivatives

AbstractThis study reports a visible‐light‐induced photoredox decarboxylative cyclization reaction of enone acids via iron photocatalysis. The protocol provides a facile entry to structurally valuable highly functionalized 2,3‐dihydrobenzofuran scaffolds in good to excellent yields. This method features cheap iron photocatalyst, excellent functional group tolerance, wide substrate scope, and environmentally friendly features.

A Dual Role for the N-Perfluorobutanesulfinamide Auxiliary in an Asymmetric Decarboxylative Mannich Reaction.

Herein, we demonstrate that the enhanced electrophilicity of N-perfluorobutanesulfinamide auxiliary-derived imines enables a highly selective decarboxylative Mannich reaction under mild conditions. The molecular sieves-mediated transformation tolerates a broad substrate scope and produces chiral β-amino thioesters in high yield. Additionally, we demonstrate that the N-perfluoroalkyl sulfinyl group can function as a phase tag for fluorous purification, thus enabling the rapid isolation of the chiral amine products by solid-phase extraction. The synthetic utility of this method is illustrated by the synthesis of sitagliptin, ruspolinone, and the natural product negamycin.

Henkel‐like Decarboxylation Produces Mononuclear Arylalkalis, [4‐(CH3)3N(C6H4)M]+ which Hydrolyse and Undergo Surprising SN2 Reactions Between Alkali Hydroxides and (CH3)3NC6H5+

AbstractBenzoate substituted with a cationic quaternary ammonium group at the para‐position, [4‐(CH3)3N(C6H4)CO2], forms mononuclear alkali metal ion complexes, [4‐(CH3)3N(C6H4)CO2M]+ (M=Li, Na, K, Rb and Cs), which are observed by electrospray‐ionisation mass spectrometry. When mass selected and subjected to collision‐induced dissociation each of these complexes undergoes decarboxylation to produce the mononuclear arylalkali complex cations, [4‐(CH3)3N(C6H4)M]+, which subsequently react with water via hydrolysis to yield the quaternary ammonium cation, (CH3)3NC6H5+. The unexpected product ions, [M((CH3)2NC6H5)]+, [M(CH3OH)]+, and M+, which are associated with the hydrolysis pathway, suggest an unusual reaction occurring within the exit channel ion‐molecule complex, [(CH3)3NC6H5+MOH]+. DFT calculations were used to examine the: decarboxylation reaction of [4‐(CH3)3N(C6H4)CO2M]+, which readily proceeds via a four‐centred transition state; the hydrolysis and SN2 reactions accounting for formation of products in the exit channel, which are connected via a roaming mechanism in which the metal hydroxide moiety migrates from the para‐hydrogen of (CH3)3NC6H5+ to one of the methyl groups.

Modulating Decarboxylative Oxidation Photocatalysis by Ligand Engineering of Atomically Precise Copper Nanoclusters.

Copper nanoclusters (Cu NCs) characterized by their well-defined electronic and optical properties are an ideal platform for organic photocatalysis and exploring atomic-level behaviors. However, their potential as greener, efficient catalysts for challenging reactions like decarboxylative oxygenation under mild conditions remains unexplored. Herein, we present Cu13(Nap)3(PPh3)7H10 (hereafter Cu13Nap), protected by 1-naphthalene thiolate (Nap), which performs well in decarboxylative oxidation (90% yield) under photochemical conditions. In comparison, the isostructural Cu13(DCBT)3(PPh3)7H10 (hereafter Cu13DCBT), stabilized by 2,4-dichlorobenzenethiolate (DCBT), yields only 28%, and other previously reported Cu NCs (Cu28, Cu29, Cu45, Cu57, and Cu61) yield in the range of 6-18%. The introduction of naphthalene thiolate to the surface of Cu13 NCs influences their electronic structure and charge transfer in the ligand shell, enhancing visible light absorption and catalytic performance. Density functional theory (DFT) and experimental evidence suggest that the reaction proceeds primarily through an energy transfer mechanism. The energy transfer pathway is uncommon in the context of previous reports for decarboxylative oxidation reactions. Our findings suggest that strategically manipulating ligands holds significant potential for creating composite active sites on atomically precise copper NCs, resulting in enhanced catalytic efficacy and selectivity across various challenging reactions.

Unprecedented nor-seco-diterpene lactones inhibited osteogenic differentiation of valve interstitial cells

The first examples of ent-atisane and ent-isopimarane diterpene lactones with an unusual 2,3-seco-2-nor-tetrahydro-2H-pyran-2-one nucleus, eufislactones A (1) and B (2), were isolated from the roots of Euphorbia fischeriana, together with a new (3) and fifteen known biosynthetic congeners (4–18). Their structures incorporating absolute configurations were elucidated via the comprehensive spectroscopic analyses, electronic circular dichroism (ECD) calculation, and single-crystal X-ray diffraction analyses. Biogenetically, compounds 1 and 2 were constructed by the plausible monomeric precursors, ent-atis-16-ene-3,14-dione (6) and ent-isopimara-8(14),15-dien-3-one (17), respectively, via key Baeyer-Villiger oxidation, decarboxylation, and semi-acetalization reactions to create a unique 2,3-seco-2-nor-tetrahydro-2H-pyran-2-one core. Our bioassays have revealed that eufislactone A (EFA, 1) displayed significant inhibitory effect on the osteogenic differentiation of human valvular interstitial cells (VICs), highlighting its potential as a preventive agent against the progression of human calcific aortic valve disease (CAVD).

Regioselective Decarboxylative Aromatization of Benzonorcaradienes to Substituted 1‐Acylmethyl‐4‐Arylnaphthalenes

AbstractTf2NH‐mediated decarboxylative dearomatization reaction of benzonorcaradiene γ‐ketoacids, in situ generated by intramolecular alkenylation of alkynylcyclopropane γ‐ketoacids or their tert‐butyl esters, has been described for regioselective synthesis of polyfunctionalized 1‐acylmethyl‐4‐arylnaphthalenes.

Photocatalytic Decarboxylative Alkylation of Cyclic Imine-BF3 Complexes: A Modular Route to Functionalized Azacycles.

Alkyl radicals generated via an acridine photocatalyzed decarboxylation reaction of feedstock carboxylic acids engage with a range of cyclic imine-BF3 complexes to provide α-functionalized azacycles in an operationally simple process. A three-component variant of this transformation incorporating [1.1.1]propellane as an additional reaction partner enables the synthesis of valuable bicyclopentane (BCP)-containing azacycles. Reactions exhibit good functional group compatibility, enabling late-stage modification of complex bioactive molecules.

Photochemical Decarboxylative Radical Alkylation/Cyclization Reaction to Fused Nitrogen Heterocycles by LiI/PPh3 Catalysis

Comprehensive SummaryA visible‐light‐induced decarboxylative radical cascade cyclization reaction between N‐(2‐cyanoaryl)‐acrylamides and alkyl N‐(acyloxy)phthalimide (NHPI esters) for the construction of phenanthridine derivatives has been developed. This approach utilizes lithium iodide (LiI) and triphenylphosphine (PPh3) as the redox catalysts and the alkyl radical is produced through the photoactivation of the electron donor‐acceptor (EDA) complex. A series of primary, secondary, and tertiary alkyl‐substituted phenanthridines are prepared in up to 82% yield without transition‐metal catalysts, chemical oxidants, or metal‐/organic dye‐based photocatalysts.

Functionalized carbons and Pt/C catalysts from biomass using a plasma process

In this paper, plasma conversion of lignocellulosic biomass to high surface area carbons with tunable porosity and their functionalization toward catalyst supports are presented. Specifically, the technique involves mixing biomass with alkali salts and then oxidizing with atmospheric plasma. The biomass conversion process required time scales of less than 2 min compared to hours for the hydrothermal techniques. Furthermore, the resulting high surface area carbons are decorated with ultra-nano particles of platinum using reduction of platinum precursors using hydrogen plasmas. The resulting functionalized carbons loaded with Pt nanoparticles have shown catalytic activity in decarboxylation and further conversion of oleic acid to aromatic and branched hydrocarbons. The catalytic reaction of the resulting Pt nanoparticle loaded high surface area carbon catalyst revealed 100 % conversion of oleic acid with selectivity > 64 % toward C8-C16 hydrocarbons and aromatics, suggesting high catalytic activity of the employed catalyst in decarboxylation reaction of oleic acid.

Catalytic depolymerization of Camellia oleifera shell lignin to phenolic monomers: Insights into the effects of solvent, catalyst and atmosphere

Camellia oleifera shell (COS) is a renewable biomass resource abundant in lignin with significant potential for producing phenolic monomers. However, the dearth of research has led to considerable resource wastage and environmental pollution. Herein, reductive catalytic fractionation (RCF) of COS was performed using noble metal catalysts in different solvents. An 11.1 wt% yield of phenolic monomers was achieved with 91% selectivity toward propylene-substituted monomers in H2O/EtOH (3:7, v/v) cosolvent under N2 atmosphere. Notably, the highest phenolic monomer yield of 17.0 wt% was obtained with impressive selectivity (86.9%) toward propanol-substituted monomers in the presence of H2. The GPC analysis and 2D HSQC NMR spectra indicated the effective depolymerization of lignin oligomers with catalysts. Phenolic monomers with ethyl, propyl, or propanol side chain could be produced from lignin-derived oligomers through hydrogenolysis, hydrogenation, and decarboxylation reactions. Overall, this study has paved the way for the valorization of COS lignin through the RCF strategy.

Hydrothermal carbonization of Chinese medicine residue from licorice: Effects of pore and chemical structures on chromium migration

The Chinese medicine residue (CMR) is composed of wet substances, so using hydrothermal carbonization (HTC) to recover renewable energy from the residue is a suitable treatment method. Chromium (Cr), a kind of heavy metal element, is enriched in hydrochar and severely restricts its effective utilization. An in-depth analysis of the migration path and mechanism of Cr in hydrochar is helpful in promoting energy utilization for CMR. Here, licorice, a significant Chinese medicine, was selected as the example to analyze the evolutions of its pore and chemical structures and their effects on the migration mechanism of Cr during the HTC process. The products obtained under various HTC conditions were analyzed using nitrogen adsorption, FTIR, and 13C NMR. The results show that, considering reaction time and relevant reactions as the primary factors during the HTC process, the migration pathway of Cr in hydrochar undergoes two stages, and they are the accompanying migration stage and the recovery aggregation stage. Active adsorption sites for Cr may exist within the pore structure of hydrochar. In the HTC process, hydrolysis, decarboxylation, and decarbonylation reactions are the direct drivers of Cr migration, while aromatization is the underlying cause of Cr recovery and aggregation. It is hypothesized that Cr catalyzes the acetylene cyclotrimerization reaction, thereby promoting the formation of aromatic structures in hydrochar and integrating into the hydrochar carbon skeleton.

Photocatalytic Decarboxylative Fluorination by Quinone-Based Isoreticular Covalent Organic Frameworks.

The strategic incorporation of fluorine atoms into molecules has become a cornerstone of modern pharmaceuticals, agrochemicals, and materials science. Herein, we have developed a covalent organic framework (COF)-based, robust photocatalyst that enables the photofluorodecarboxylation reaction of diverse carboxylic acids, producing alkyl fluorides with remarkable efficiency. The catalytic activity of an anthraquinone-based COF catalyst TpAQ outperforms other structurally analogous β-ketoenamine COFs. Through comprehensive control experiments, photoluminescence, and electrochemical studies, we have elucidated the unique features of the material and the mechanistic pathway. This in-depth understanding has paved the way for optimizing the reaction conditions and achieving high yields of alkyl fluorides. The versatility of this protocol extends to a broad range of aliphatic acids with diverse functional groups and heterocycles. It also enabled the late-stage diversification of anti-inflammatory drugs and steroid derivatives. This opens up exciting possibilities for synthesizing novel pharmaceuticals and functionalized molecules. The methodology was also generalized to other light-mediated decarboxylative halogenation reactions. Furthermore, our method demonstrates scalability under both batch and continuous flow conditions, offering a promising approach for large-scale production. Additionally, the TpAQ catalyst exhibits exceptional durability and can be reused multiple times without significant activity loss (>80% yield after the eighth cycle), making it a sustainable and cost-effective solution. This work lays the foundation for developing efficient and sustainable light-driven synthesis methods using COFs as photocatalysts with potential applications beyond alkyl halide synthesis.

Decarboxylation in Natural Products Biosynthesis.

Decarboxylation reactions are frequently found in the biosynthesis of primary and secondary metabolites. Decarboxylase enzymes responsible for these transformations operate via diverse mechanisms and act on a large variety of substrates, making them appealing in terms of biotechnological applications. This Perspective focuses on the occurrence of decarboxylation reactions in natural product biosynthesis and provides a perspective on their applications in biocatalysis for fine chemicals and pharmaceuticals.

Organocatalysis for Enantioselective Decarboxylative Nucleophilic Addition Reactions

AbstractThe catalytic decarboxylation of malonic acid half oxy‐ and thioesters, β‐ketocarboxylic acids, and their related compounds is a straightforward, powerful, and atom‐economical strategy for the in‐situ formation of enolates, which are important and well‐studied synthons for various functional materials and natural products. This strategy, inspired by the biosynthesis of polyketides and fatty acids, is an attractive method for synthesizing enols from carboxyl compounds with less reactive α‐hydrogen atoms under mild conditions. In addition, these reactions are environmentally friendly and are of great interest to chemists because the use of a stoichiometric amount of base can be avoided, and the only byproduct is CO2. Thus far, remarkable progress has been made, especially in the field of organocatalytic enantioselective decarboxylation reactions, allowing for the stereocontrolled formation of new C−H, C−C, C−heteroatom, and C−X bonds. This review provides a comprehensive overview of organocatalytic enantioselective decarboxylation reactions and highlights the significant progress made since 2020. In particular, it focuses on chiral catalyst systems and transition states as key parameters for decarboxylation reactions.

Electrochemical Decarboxylative Cross-Coupling with Nucleophiles.

Decarboxylative cross-coupling reactions are powerful tools for carbon-heteroatom bonds formation, but typically require pre-activated carboxylic acids as substrates or heteroelectrophiles as functional groups. Herein, we present an electrochemical decarboxylative cross-coupling of carboxylic acids with structurally diverse fluorine, alcohol, H2O, acid, and amine as nucleophiles. This strategy takes advantage of the ready availability of these building blocks from commercial libraries, as well as the mild and oxidant-free conditions provided by electrochemical system. This reaction demonstrates good functional-group tolerance and its utility in late-stage functionalization.

Effects of atmosphere and stepwise pyrolysis on the pyrolysis behavior, product characteristics, and N/S migration mechanism of vancomycin fermentation residue

Vancomycin fermentation residue (VFR) urgently needs proper treatment due to its complex and hazardous nature. Pyrolysis is a promising treatment method, while the product characteristics of VFR pyrolysis remain unclear. Therefore, the influence of different atmospheres and stepwise pyrolysis (including one-stage reaction in N2 or CO2 and two-stage reaction in N2) on pyrolysis behavior, product characteristics, and N/S migration mechanism during VFR pyrolysis were investigated for the first time in this work. The results showed that VFR mainly decomposed at 180–600 °C, forming non-condensable gas, bio-oil, and biochar. The main released gases included CO2, H2O, NH3, HCN, SO2, and H2S, whereas the N-containing pollutant gas, notably NH3, should be focused due to its high emission (>10 %). Bio-oil was rich in N-containing compounds with a content exceeding 46 %, mainly consisting of Indolizne (9.2–11.5 %), 5H-1-Pyrindine (5.0–9.9 %), and Indole (8.4–9.0 %), and 9-Octadecenamide, (Z)- (1.8–10.1 %). Moreover, the effects of different conditions on the product characteristics were as follows: For the one-stage reaction, compared to N2, the CO2 atmosphere promoted the formation of alcohols (intended product, increasing 2.2–14.6 %), whereas the two-stage reaction in N2 inhibited alcohol production (decreasing 1.1–2.5 %). At CO2 condition, the harmless temperature of VFR reduced from 600 °C (pyrolysis in N2) to 400 °C. Both CO2 (increasing 0.6–1.5 %) and the two-stage reaction in N2 (increasing 0.4–1.0 %) retained more N in the solid. Kinetics showed that the pyrolysis process of VFR conformed to diffusion models and reaction order models (F2/D1/F3/D1 for N2 and F2/D2/F3/D1 for CO2). The VFR transformed to the chemicals and fuels mainly through the deamination, desulfurization, dehydration, decarboxylation, and dehydrogenation reactions. This work provides guidance for harmless disposal and resource utilization during VFR pyrolysis.

Effect of the Fe0/PMS advanced oxidation system on the removal of aromatic organic compounds

The aromatic organic compounds present in groundwater environments have low contents, high toxicity, long half-lives and stable chemical properties, which increase the difficulty of degradation under natural conditions. In this study, an zero-valent iron activated peroxymonosulfate system (Fe0/PMS) was constructed to remove common aromatic organic compounds in groundwater. The results showed that at an initial pH of 7.0, Fe0=0.3 g/L, PMS= 0.5 mM, and initial concentration of organic matter (C0) =0.1 mM, the removal efficiency of the seven aromatic organic compounds by the Fe0/PMS system reached more than 70 %, which shows good removal ability. Alcohol quenching tests and liquid chromatography time-of-flight mass spectrometry tests showed that the main active oxygen species in the system were SO4•─ and OH•, which could efficiently degrade aromatic organic compounds through electrophilic substitution, hydroxylation, carbonylation and decarboxylation reactions and reduce the biological toxicity of organic compounds in wastewater to a certain extent. In the long-term dynamic reaction process, the removal rate of aromatic organic compounds in actual groundwater by the Fe0/PMS system can be maintained above 75 %, and the complex structure can be effectively destroyed. This research can provide a theoretical basis for the efficient treatment of aromatic organic compounds in groundwater.

Constructing p-n heterojunctions of Cl-Cu2O and PANI on three-dimensional nanofiber networks for enhanced photocatalytic degradation of oxytetracycline

A p-n heterojunction was constructed on a bacterial cellulose (BC) film by combining n-type semiconductor chlorine-doped Cu2O (Cl-Cu2O) and p-type semiconductor polyaniline (PANI), creating a ternary composite flexible film of Cl-Cu2O/PANI/BC. The chemical structure, microscopic morphology, and photoelectrochemical properties of Cl-Cu2O/PANI/BC were characterized and analyzed. Compared with pure Cl-Cu2O, the Cl-Cu2O/PANI/BC composite flexible film exhibited a broader response range to visible and near-infrared light, higher carrier concentration, lower impedance value, and substantial reduction in the recombination probability of photogenerated carriers. The process conditions for the photocatalytic degradation of oxytetracycline (OTC) were optimized using the response surface method, and the degradation rate of OTC caused by the Cl-Cu2O/PANI/BC was 96.3 %. In the degradation process of OTC, superoxide radical is the main active species. It was found that OTC molecules degraded via demethylation, secondary alcohol oxidation, decarboxylation, and deamination reactions, finally being degraded into H2O, CO2, and other small organic molecules. Thirteen major intermediates and possible degradation pathways were speculated. The photocatalytic performance of the Cl-Cu2O/PANI/BC was improved owing to the successful construction of the p-n heterojunction. The built-in electric field generated at the interface between the two semiconductors promoted the diffusion of photogenerated holes from the n-type Cl-Cu2O particles to the PANI coating layer on the BC chain, whereas the photogenerated electrons from PANI diffused toward Cl-Cu2O, accelerating the separation efficiency of photoinduced electrons and holes in the two semiconductors and thereby improving the efficiency of photocatalytic degradation. In addition, the three-dimensional network structure of a composite flexible film can help recover the photocatalyst. After performing seven experiments for recovery and reuse, the photocatalytic degradation rate of OTC still remained above 90 %.

Overlooked Roles and Transformation of Carbon-Centered Radicals Produced from Natural Organic Matter in a Thermally Activated Persulfate System.

The presence and induced secondary reactions of natural organic matter (NOM) significantly affect the remediation efficacy of in situ chemical oxidation (ISCO) systems. However, it remains unclear how this process relates to organic radicals generated from reactions between the NOM and oxidants. The study, for the first time, reported the vital roles and transformation pathways of carbon-centered radicals (CCR•) derived from NOM in activated persulfate (PS) systems. Results showed that both typical terrestrial/aquatic NOM isolates and collected NOM samples produced CCR• by scavenging activated PS and greatly enhanced the dehalogenation performance under anoxic conditions. Under oxic conditions, newly formed CCR• could be oxidized by O2 and generate organic peroxide intermediates (ROO•) to catalytically yield additional •OH without the involvement of PS. Nuclear magnetic resonance (NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) results indicated that CCR• predominantly formed from carboxyl and aliphatic structures instead of aromatics within NOM through hydrogen abstraction and decarboxylation reactions by SO4•- or •OH. Specific anoxic reactions (i.e., dehalogenation and intramolecular cross-coupling reactions) further promoted the transformation of CCR• to more unsaturated and polymerized/condensed compounds. In contrast, oxic propagation of ROO• enhanced bond breakage/ring cleavage and degradation of CCR• due to the presence of additional •OH and self-decomposition. This study provides novel insights into the role of NOM and O2 in ISCO and the development of engineered strategies for creating organic radicals capable of enhancing the remediation of specific contaminants and recovering organic carbon.

Co-pyrolysis of pretreated cotton stalk and low-density polyethylene: Evolved products and pyrolysis mechanism analysis

The preparation of bio-oil from cotton stalks and agricultural residue films using co-pyrolysis technology can achieve resource recovery and energy conversion, which has important research value and significance. In this study, cotton stalks were subjected to different chemical pretreatments using NaOH, HCl, and H2O solutions to understand their structural changes and pyrolysis characteristics. In addition, the lower H/C ratio of cotton stalks resulted in higher oxygen content in the pyrolysis oil, which limited its efficient and clean utilization. Therefore, the characteristics and pyrolysis kinetics of the pyrolysis products of pretreated cotton stalks and LDPE (low-density polyethylene) were studied. The results showed that the ash content of alkali pretreatment cotton stalks decreased by 1.24 %, and the dense structure of cotton stalks significantly relaxed. NaOH pretreatment effectively removed hemicellulose sugars and cracked them. During the co-pyrolysis process, when the ratio of NaOH-CS/LDPE was 50/50, the synergistic effect was more pronounced, and the oil yield increased by 2 % compared to the theoretical value. The oxygen content of CO and CO2 in the pyrolysis gas was higher than the theoretical value, at 10.4 % and 14.1 % respectively. The synergistic effect of bio-oil on hydrocarbons was the most significant, reaching 18.9 %. More hydrogen and less oxygen migrated into the co-pyrolysis oil, resulting in an increase in hydrocarbons and a decrease in oxygen-containing compounds, and improving the quality of bio-oil. Results from electron paramagnetic resonance (EPR) indicated that adding LDPE might raise the quantity of stable free radicals. The evolution mechanism of functional groups of NaOH-CS and LDPE co-pyrolysis behavior was analyzed by Fourier in-situ infrared spectrometry (FTIR), and it was found that C–O–C, C=O, and O–H decreased due to dehydroxylation, decarboxylation, decarbonylation, and demethoxy reactions with the increase of temperature, indicating that there was a synergistic effect between NaOH-CS and LDPE co-pyrolysis. The pyrolysis kinetics of NaOH-CS, LDPE and their blends were determined by the model-free method. The introduction of LDPE can reduce the activation energy of NaOH -CS pyrolysis alone, and the 3D diffusion (D3) model is suitable for their blends.