Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 21, 2025

Carboxylation with CO2 offers an attractive and sustainable access to valuable carboxylic acids. Among these methods, direct C−H carboxylation of terminal alkynes has attracted much attention for one-carbon homologation alkynes, enabling rapid synthesis propiolic In contrast, the multi-carbons construct important non-conjugated alkynyl-containing acids not been reported. Herein, we present alkynylcarboxylation alkenes via photoredox copper dual catalysis. This protocol provides a practical method form alkynyl from readily available CO2. Additionally, this approach also features mild (room temperature, 1 atm CO2) redox-neutral conditions, high atom step economy, good functional group tolerance, selectivities. Moreover, diverse transformations β-alkynyl acid products bioactive molecule (GPR40/FFA1 agonist) further illustrate synthetic utility methodology. The report multi-carbon is rare. authors catalysis, affording

Язык: Английский

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Rational design and fabrication of S-scheme NiTiO3/CdS heterostructures for photocatalytic CO2 reduction

Journal of Material Science and Technology, Год журнала: 2025, Номер unknown

Опубликована: Март 1, 2025

Язык: Английский

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C(sp³)–H Carboxylation via Carbene/Photoredox Cooperative Catalysis

ACS Catalysis, Год журнала: 2025, Номер 15(2), С. 1287 - 1293

Опубликована: Янв. 7, 2025

C(sp3)–H bond functionalization is a powerful strategy for the synthesis of organic compounds due their abundance in simple starting materials. Photoredox catalysis has led to diverse array enabling activation strategies; however, general platform direct carboxylic acid derivatives remains elusive. Disclosed herein development cooperative NHC/photoredox-catalyzed esterification transformation. This method enables access benzylic, α-heteroatom, and formal β-esterification products moderate high yields under mild reaction conditions.

Язык: Английский

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Organo-mediator enabled electrochemical transformations

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review highlights organo-mediators that enable electrochemical reactions via outer-sphere electron transfer (ET), offering advantages such as availability, tunability, and simplified post-processing compared to direct electrolysis.

Язык: Английский

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Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Дек. 13, 2024

ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and power source, chemists are provided with system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds. Indeed, electroreduction offers alternative generating highly active intermediates from electrophiles (e.g., halides, alkenes, etc.) in organic synthesis, which untouchable traditional reduction methods. Meanwhile, reductive coupling extensively utilized both industrial academic settings due their ability swiftly, accurately, effectively construct C–C C–X bonds, present innovative approaches synthesizing complex molecules. Nonetheless, its application is constrained by several inherent limitations: (a) requirement stoichiometric quantities agents, (b) scarce activation strategies inert substrates high potentials, (c) incomplete mechanistic elucidation, (d) challenges isolation intermediates. merging represents attractive approach address above limitations synthesis seen increasing use synthetic community over past few years.Since 2020, our group dedicated developing electroreductive cross-coupling using readily available small molecules, such arenes, CO2, D2O, value-added products. Electroreductive chemistry versatile powerful capacity precise selectivity control, allowed us develop three electrochemical modes lab: (1) An economically advantageous direct (EDR) strategy that emphasizes efficiency, achieves atom utilization, minimizes unnecessary atomic waste. (2) A class organo-mediated (EOMR) methods controlling reaction pathways. This allows modulation processes enhance efficiency selectivity. (3) metal-catalyzed (EMCR) method enables selective functionalization specific bonds functional groups under mild conditions, thereby occurrence side reactions. We commenced studies establishing organic-mediator-promoted carboxylation aryl alkyl halides. was then employed arylcarboxylation simple styrenes halides manner. electrolysis arenes epoxides CO2 carboxyl source achieved. Moreover, through adjustment we successfully accomplished deuteration olefins, unactivated enabling efficient formation D-labeled Finally, building on previous understanding developed series alkylation enable C(sp3)–C(sp3)

Язык: Английский

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Advances in methanol synthesis via MOF-based catalysts: A comprehensive review and critical analysis

Inorganic Chemistry Communications, Год журнала: 2025, Номер unknown, С. 114266 - 114266

Опубликована: Март 1, 2025

Язык: Английский

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Visible-Light Photoredox-Catalyzed Direct Carboxylation of Tertiary C(sp³)–H Bonds with CO₂: Facile Synthesis of All-Carbon Quaternary Carboxylic Acids

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Окт. 7, 2024

Direct carboxylation of C–H bonds with CO2 represents an attractive strategy to synthesize valuable carboxylic acids high atom, step, and redox economy. Although great progress has been achieved in this field, catalytic tertiary C(sp3)–H still remains challenging due their inherent inertness significant steric hindrance. Herein, we report a direct benzylic via visible-light photoredox catalysis. Various all-carbon quaternary acids, which are importance medicinal chemistry, successfully obtained yields. This is characterized by good functional group tolerance, broad substrate scope, mild operational conditions. Furthermore, our methodology enables the efficient rapid synthesis key drug or bioactive molecules, such as carbetapentane, caramiphen, PRE-084 (σ1 receptor agonist), facilitates various functionalizations C(sp2)–H using directing ability target thus highlighting its practical applications. Mechanistic studies indicate that carbanion, serves intermediate react CO2, catalytically generated single electron reduction radical through consecutive photoinduced transfer process.

Язык: Английский

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Transition Metal‐Free Direct Electrochemical Carboxylation of Organic Halides Using a Sacrificial Magnesium Anode: Straightforward Synthesis of Carboxylic Acids

ChemistryOpen, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Abstract The direct electrochemical carboxylation of aryl, benzyl and alkyl halides by CO 2 is described using a magnesium anode nickel foam cathode in an undivided cell. process employs sacrificial does not require the additional use transition metal catalyst or demanding conditions, as reactions are carried out under galvanostatic mode, at −10 °C with commercial DMF. Under these operationally simple important range carboxylic acids affordable. Mechanistic investigation account for situ generation carbanionic species that organomagnesium halide.

Язык: Английский

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Anodic reactions matter for cathodic electrocarboxylation with CO2

Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101263 - 101263

Опубликована: Фев. 1, 2025

Язык: Английский

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A general electrochemical CO2 fixation to aromatic carboxylic acids via the CO2·− intermediate using a non-transition metal electrode

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 28, 2025

Язык: Английский

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