Oxidative Decarboxylation Of Carboxylic Acids Research Articles

Electrochemical contributions: Adolph Wilhelm Hermann Kolbe (1818–1884)

Hermann Kolbe (Figure 1) was a German scientist who greatly contributed to the development of organic chemistry, transforming it to the state as we know it now. Kolbe pioneered organic synthesis from inorganic sources and introduced the term “synthesis” in the meaning how we use it in chemistry now. His name is associated with several synthetic reactions in organic chemistry, e.g., the Kolbe-Schmitt reaction in the preparation of aspirin, the Kolbe nitrile synthesis, etc. His work is particularly remembered in connection to electrolysis of carboxylic acids resulting in the synthesis of various organic compounds, known as the Kolbe reaction. The Kolbe reaction (Figure 2), proceeding as the electrolysis, results in the oxidative decarboxylation of carboxylic acids yielding free radicals, which dimerize producing symmetrical products. For example, the Kolbe electrolysis process can proceed in an aqueous solution of sodium acetate (Figure 2). The acetate ions get decomposed and form methyl radicals. These combine with other free methyl radicals, which leads to the generation of ethane. In general, Kolbe's electrolysis method uses sodium salts of fatty acids to form the corresponding alkanes as products (D. Klüh, W. Waldmüller, M. Gaderer, Clean. Technol. 2021, 3, 1–18). A similar electrochemical synthesis can be used to produce more sophisticated products (Figure 2B). If the initial mixture includes two different acids, the reaction results in three different products from the cross-reaction of two different free radicals. The Kolbe electrolytic decarboxylation of 1,2-dicarboxylic acids results in the formation of double or triple chemical bonds (Figure 3). When carboxylic groups are located at a longer distance in a molecule, the electrolytic decarboxylation may result in the intramolecular radical cyclization of the reaction product. It should be noted that the Kolbe electrolysis reaction may result in the formation of numerous byproducts (Figure 4). The formation of side products depends on the ease of the follow-up oxidation, which leads to carbenium ions, and their subsequent rearrangements. The exact mechanism and kinetics study of the electrochemical Kolbe process have been investigated confirming the complexity of the electrochemical reaction (A.K. Vijh, B.E. Conway, Chem. Rev. 1967, 67, 6, 623-664). The author declares no conflict of interest.

Study on the Effect of Electrolyte pH during Kolbe Electrolysis of Acetic Acid on Pt Anodes

AbstractKolbe already discovered in 1849 that electrochemical oxidative decarboxylation of carboxylic acids is feasible and leads to formation of alkanes and CO2, via alkyl radical intermediates. We now show for Pt electrodes that Kolbe electrolysis of acetic acid is favored in electrolytes with a pH similar to, or larger than the pKa of acetic acid, suppressing the formation of O2. However extended duration of electrolysis of acetate at basic pH results in loss of Faradaic efficiency to ethane, compensated by the formation of methanol. This change in selectivity is likely caused by the dissolution of CO2 near the electrode‐electrolyte interface, resulting in enlarged concentration of bicarbonate/carbonate. On the positively polarized, and oxidized Pt surface, these anions seem to inhibit homocoupling of methyl radicals to ethane. These results demonstrate that reaction selectivity in acetic acid (acetate) oxidation using oxidized Pt electrodes is determined by the pH and the anionic composition of the electrolyte.

Decarboxylative Csp3-N Bond Formation by Electrochemical Oxidation of Amino Acids.

Decarboxylative Csp3-N coupling reactions have been developed through electrochemical oxidation of amino acids. The reaction proceeds via anodic oxidative decarboxylation of carboxylic acids to form stabilized carbocations, which are trapped by azoles or amides to construct C-N bonds. This method avoids the preactivation of carboxylic acids and the use of expensive transition-metals and external chemical oxidants.

Photoinduced Kochi Decarboxylative Elimination for the Synthesis of Enamides and Enecarbamates from N-Acyl Amino Acids.

Decarboxylative elimination of easily accessible N-acyl amino acids to provide enamide and enecarbamate building blocks has been realized through the combination of an organophotoredox catalyst and copper acetate as the terminal oxidant. This operationally simple process utilizes inexpensive and readily available reagents without preactivation of the carboxylic acid. Enamides and enecarbamates are now accessible directly from N-acyl amino acids consequently improving upon the utility of Kochi's oxidative decarboxylation of carboxylic acids.

An Engineered Self-Sufficient Biocatalyst Enables Scalable Production of Linear α-Olefins from Carboxylic Acids

Fusing the decarboxylase OleTJE and the reductase domain of P450BM3 creates a self-sufficient protein, OleT-BM3R, which is able to efficiently catalyze oxidative decarboxylation of carboxylic acids into linear α-olefins (LAOs) under mild aqueous conditions using O2 as the oxidant and NADPH as the electron donor. The compatible electron transfer system installed in the fusion protein not only eliminates the need for auxiliary redox partners, but also results in boosted decarboxylation reactivity and broad substrate scope. Coupled with the phosphite dehydrogenase-based NADPH regeneration system, this enzymatic reaction proceeds with improved product titers of up to 2.51 g L–1 and volumetric productivities of up to 209.2 mg L–1 h–1 at low catalyst loadings (∼0.02 mol %). With its stability and scalability, this self-sufficient biocatalyst offers a nature-friendly approach to deliver LAOs.

Manganese(III) porphyrin supported on multi-wall carbon nanotubes: A highly efficient and reusable biomimetic catalyst for oxidative decarboxylation of α-arylcarboxylic acids and oxidation of alkanes with sodium periodate

In the present work, the highly efficient oxidative decarboxylation of carboxylic acids and also the oxidation of alkanes with sodium periodate catalyzed by tetrakis(p-aminophenyl)porphyrinatomanganese(III) chloride, [Mn(TNH2PP)Cl], supported on functionalized multi-wall carbon nanotubes, MWCNT, is reported. The catalyst, [Mn(TNH2PP)Cl@MWCNT], was used as an efficient and heterogeneous catalyst for hydroxylation of alkenes with NaIO4 at room temperature, in the presence of imidazole as an axial ligand. Also, in this system, carboxylic acids were converted to their corresponding carbonyl compounds. This heterogenized catalyst could be reused several times without significant loss of its catalytic activity.

Polystyrene-bound Mn(T4PyP): A highly efficient and reusable catalyst for biomimetic oxidative decarboxylation of carboxylic acids with sodium periodate

In this report, highly efficient oxidative decarboxylation of carboxylic acids with sodium periodate catalyzed by a supported manganese(III) porphyrin is described. In the presence of manganese(III) tetra(4-pyridyl)porphyrin supported on cross-linked chloromethylated polystyrene, [Mn(T4PyP)-CMP], as catalyst, carboxylic acids were converted to their corresponding carbonyl compounds via oxidative decarboxylation with sodium periodate using imidazole as axial ligand. The oxidation of anti-inflammatory drugs such Indomethacin and Ibuprofen was carried out successfully and the decarboxylated products were obtained. This catalyst can be reused several times without loss of its catalytic activity in the oxidation reactions.

Biomimetic Decarboxylation of Carboxylic Acids with PhI(OAc)2 Catalyzed by Manganese Porphyrin [Mn(TPP)OAc]

Abstract Manganese(III) meso -tetraphenylporphyrin acetate [Mn(TPP)OAc] served as an effective catalyst for the oxidative decarboxylation of carboxylic acids with (diacetoxyiodo)benzene [PhI(OAc) 2 ] in CH 2 Cl 2 -H 2 O(95:5, volume ratio). The aryl substituted acetic acids are more reactive than the less electron rich linear carboxylic acids in the presence of catalyst Mn(TPP)OAc. In the former case, the formation of carbonyl products was complete within just a few minutes with >97% selectivities, and no further oxidation of the produced aldehydes was achieved under these catalytic conditions. This method provides a benign procedure owing to the utilization of low toxic(diacetoxyiodo) benzene, biologically relevant manganese porphyrins, and carboxylic acids.

Oxidative Decarboxylation of Carboxylic Acids with Tetrabutylammonium Periodate Catalyzed by Manganese (III) Meso-Tetraarylporphyrins: Effect of Metals, Meso-Substituents, and Anionic Axial Ligands

Abstract In association with tetrabutylammonium periodate ( n -Bu 4 NIO 4 ) and imidazole (ImH), manganese meso -tetraarylporphyrins have provided an effective catalytic system for the oxidative decarboxylation of carboxylic acids. Meso -tetraarylporphyrins bearing electron-withdrawing and/or bulky aryl groups at meso -positions lowered the catalytic activity of the metalloporphyrins. Although the presence of ImH and the choice of the metal center are crucial for the catalytic properties of the metalloporphyrins, the counter ion plays an important role in this catalytic system. However, the best catalytic activity has been observed for the Mn(TPP)CN/ n- Bu 4 NIO 4 /ImH system. A catalytic cycle is postulated, in which the oxidative decarboxylation of diphenylacetic acid involves the interaction of a high-valent Mn–oxo species with the substrate. Attempts have been made to visualize the possible interactions and electronic changes responsible for the formation of the corresponding carbonyl products.

Rapid and Efficient Oxidative Decarboxylation of Carboxylic Acids with Sodium Periodate Catalyzed by Manganese(III) Schiff Base Complexes.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Rapid and efficient oxidative decarboxylation of carboxylic acids with sodium periodate catalyzed by manganese (III) Schiff base complexes

Rapid and efficient oxidative decarboxylatoin of α-aryl carboxylic acids was observed. In the chemical system containing Mn(III)-salophen complex as catalyst, carboxylic acids are converted efficiently to the corresponding carbonyl derivatives with sodium periodate. The ability of various Schiff base complexes in the oxidative decarboxylation of carboxylic acids was also investigated.

Efficient Oxidative Decarboxylation of Carboxylic Acids with Sodium Periodate Catalyzed by Supported Manganese(III) Porphyrin.

Abstract Oxidative decarboxylation of carboxylic acids by a supported manganese (III) porphyrin was investigated. In the chemical system using 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatomanganese (III) chloride supported on crosslinked chloromethylated polystyrene, [Mn(H 2 NTPP)-CMP], as catalyst, carboxylic acids are converted to the corresponding carbonyl compounds via oxidative decarboxylation with sodium periodate.

Efficient oxidative decarboxylation of carboxylic acids with sodium periodate catalyzed by supported manganese (III) porphyrin.

Oxidative decarboxylation of carboxylic acids by a supported manganese (III) porphyrin was investigated. In the chemical system using 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatomanganese (III) chloride supported on crosslinked chloromethylated polystyrene, [Mn(H(2)NTPP)-CMP], as catalyst, carboxylic acids are converted to the corresponding carbonyl compounds via oxidative decarboxylation with sodium periodate.

Application of chemical cytochrome P-450 model systems to studies on drug metabolism—VIII. Novel metabolism of carboxylic acids via oxidative decarboxylation

The oxidative decarboxylation of carboxylic acids by the chemical cytochrome P-450 model and rat liver microsomal systems was investigated. In the chemical system using meso-tetrakis(pentafluorophenyl)porphyrin iron chloride [Fe(TPFPP)Cl] with iodosylbenzene (PhIO), α-arylcarboxylic acids and α,α,α-trisubstituted acetic acids are converted to the corresponding one-carbon-reduced alcohol ( I) and carbonyl derivatives ( II) via oxidative decarboxylation. These products were then used as standards to identify the metabolites in vivo and in vitro. Biliary excretion of I a and II a in bile duct-cannulated rats after oral administration of ketoprofen amounted to 0.22 and 0.03% of the dose, respectively. In the case of indomethacin, I b and II b were detected as metabolites in the rat liver microsomal system, in yields of 2.8 and 0.29%, respectively. Further, the yields of I b and II b were decreased in the presence of SKF-525A. Thus, these metabolites were formed by cytochrome P-450-dependent reactions. Metabolites I a , I b, II a and II b had moderate to strong inhibitory activities on arachidonic acid-induced platelet aggregation and cyclooxygenase activity in vitro, comparable to those of the parent compounds.

ChemInform Abstract: Application of Chemical P‐450 Model Systems to Study on Drug Metabolism. Part 5. Oxidative Decarboxylation of Carboxylic Acids by Iron Porphyrin‐Iodosylbenzene System.

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Oxidative decarboxylation of carboxylic acids by iron porphyrin - iodosylbenzene system

An iodosylbenzene - iron tetraarylporphyrin catalyst system decarboxylated α-aryl carboxylic acids and α,α,α-trisubstituted acetic acids efficiently to give the corresponding alcohol and carbonyl derivatives.

ChemInform Abstract: Iodosobenzene Diacetate, an Efficient Reagent for the Oxidative Decarboxylation of Carboxylic Acids.

AbstractPrimäre und sekundäre Carbonsäuren, z.B. die Steroidcarbonsäuren (I), (IIIa) und (IVa), werden unter den angegebenen Bedingungen oxidativ zu den entsprechenden Iodverbindungen (II), (IIIb) bzw. (IVb) decarboxyliert.

ChemInform Abstract: Silver‐Mediated Oxidative Decarboxylation of Carboxylic Acids by Peroxocompounds.

Chemischer InformationsdienstVolume 17, Issue 12 Preparative Organic Chemistry ChemInform Abstract: Silver-Mediated Oxidative Decarboxylation of Carboxylic Acids by Peroxocompounds. F. MINISCI, F. MINISCISearch for more papers by this authorE. VISMARA, E. VISMARASearch for more papers by this authorU. ROMANO, U. ROMANOSearch for more papers by this author F. MINISCI, F. MINISCISearch for more papers by this authorE. VISMARA, E. VISMARASearch for more papers by this authorU. ROMANO, U. ROMANOSearch for more papers by this author First published: March 25, 1986 https://doi.org/10.1002/chin.198612153AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume17, Issue12March 25, 1986 RelatedInformation

Iodosobenzene diacetate, an efficient reagent for the oxidative decarboxylation of carboxylic acids

Iodosobenzene diacetate, an efficient reagent for the oxidative decarboxylation of carboxylic acids

Silver-mediated oxidative decarboxylation of carboxylic acids by peroxocompounds new sources of carbon-centered radicals for heteroaromatic substitution

The silver catalyzed oxidative decarboxylation of carboxylic acids by aroylperoxides, percarbonates and perborate provides new sources of alkyl radicals useful for selective substitution of lepidine.