Recent Advances in Reactions Involving Carbon Dioxide Radical Anion

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 15991 - 16011

Published: Nov. 28, 2023

Carbon dioxide radical anion (CO2•–) is a highly reactive nucleophilic species that has recently emerged in organic chemistry as strong single electron donor (reductant) and reactant for the synthesis of carboxylic acids. In general, CO2•– can be generated by either direct reduction CO2 or HAT formate salts. Achievements reactions involving have been witnessed recent years. This Review summarizes advances highlighting some challenges identifying potential areas improvement, which may offer inspiration future studies.

Language: Английский

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Straightforward synthesis of functionalized γ-Lactams using impure CO2 stream as the carbon source

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 22, 2023

Abstract Direct utilization of CO 2 into organic synthesis finds enormous applications to synthesize pharmaceuticals and fine chemicals. However, pure gas is essential achieve these transformations, the purification highly cost energy intensive. Considering this, we describe a straightforward synthetic route for γ-lactams, pivotal core structure bioactive molecules, by using commercially available starting materials (alkenes amines) impure stream (exhaust collected from car) as carbon source. This blueprint features broad scope, excellent functional group compatibility application late-stage transformation existing natural products functionalized γ-lactams. We believe that our strategy will provide direct access γ-lactams in very sustainable way also enhance Carbon Capture Utilization (CCU) strategy.

Language: Английский

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Challenges and recent advancements in the synthesis of α,α-disubstituted α-amino acids

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 17, 2024

α,α-Disubstituted α-amino acids (α-AAs) have improved properties compared to other types of amino acids. They serve as modifiers peptide conformation and precursors bioactive compounds. Therefore, it has been a long-standing goal construct this highly valuable scaffold efficiently in organic synthesis drug discovery. However, access α,α-disubstituted α-AAs is challenging largely unexplored due their steric constraints. To overcome these, remarkable advances made the last decades. Emerging strategies such synergistic enantioselective catalysis, visible-light-mediated photocatalysis, metal-free methodologies CO

Language: Английский

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Nature-inspired innovation: Alginic-kojic acid material for sustainable antibacterial and carbon dioxide fixation

International Journal of Biological Macromolecules, Journal Year: 2024, Volume and Issue: 277, P. 134514 - 134514

Published: Aug. 5, 2024

The current environmental consciousness of the world's population encourages researchers to work on new materials that are environmentally benign and able display appropriate features for needed application. To develop high-performing, inexpensive eco-materials, scientists have frequently turned nature, attempting mimic its processes' excellent performance at a reasonable price. In this regard, we decided focus alginic acid (AA), polysaccharide widely found in brown algae, kojic (KA), chelating agent fungi produces. This study proposes rapidly synthesizing sustainable, biocompatible material (AK) based AA KA, employing chlorokojic (CKA). has dual function: antibacterial activity both Gram-positive Gram-negative bacteria, without any cytotoxic action human cells vitro, catalytic ability convert CO2 into cyclic carbonates atmospheric pressure, solvents, with high yields, use metals. Furthermore, material's insolubility organic solvents allows it be easily separated from reaction product reused other cycles. Both applications key role medical fields, combating outbreak infections providing an innovative methodology fix specific substrates.

Language: Английский

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Asymmetric Multicomponent Propargylations via Carbon Dioxide Shuttling and Fixation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11646 - 11656

Published: July 22, 2024

Language: Английский

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Nickel-Catalyzed Lactamization Reaction of 2-Arylanilines with CO₂

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3940 - 3944

Published: April 30, 2024

Transition-metal-catalyzed lactamization and lactonization of C–H bonds with CO2 assisted by the chelation amino or hydroxyl groups have been developed but limited to use precious metal catalysts such as palladium rhodium. In this work, we report nonprecious nickel-catalyzed reaction 2-arylanilines under redox-neutral conditions via bond activation. The displayed excellent functional group tolerance, providing various phenanthridinones moderate high yields.

Language: 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, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 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.

Language: Английский

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Recent advances in cycloaddition of CO2 with epoxides: halogen-free catalysis and mechanistic insights

Frontiers of Chemical Science and Engineering, Journal Year: 2023, Volume and Issue: 17(12), P. 1879 - 1894

Published: Aug. 20, 2023

Language: Английский

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Salophen-type Organocatalysts for the Cycloaddition of CO₂ and Epoxides under Solvent, Halide, and Metal-Free Conditions

ACS Omega, Journal Year: 2024, Volume and Issue: 9(17), P. 19385 - 19394

Published: April 15, 2024

8-Formyl-7-hydroxycoumarin (A) and their derived salophen-type organocatalysts L1, L2, L3 were used for the synthesis of cyclic carbonates from carbon dioxide (CO2) epoxides under solvent-, halide-, metal-free conditions. According to previous optimization tests, L1 L2 had best catalytic activity presenting 89 92% conversion toward 3-chloropropylene carbonate (2c) using 8 bar CO2, 100 °C at 9 h. Therefore, they as complete screening with 11 terminal (1a–k) exhibiting highest TOF values 20 22 h–1 1c 1b, respectively. Similarly, tested an internal epoxide, such cyclohexene oxide (1l) 72% conversion, becoming first salophen organocatalyst obtain cis-cyclohexane (2l) in absence a cocatalyst. In addition, reaction mechanism was proposed formation based on experimental data computational techniques; these contributed establishing probable role CO2 pressure along catalysis hydrogen bonds that favor stabilization different intermediates reaction.

Language: Английский

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Recent Progress in Visible Light‐Mediated Synthesis of γ‐lactams

Helvetica Chimica Acta, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

Abstract The integration of sustainable practices, such as employing renewable light sources for synthesizing valuable synthetic scaffolds, has been progressing over the past few decades. Among these noteworthy organic frameworks, lactams, particularly γ‐lactams, have established their prominence due to extensive applications in pharmaceutical, agricultural, and medicinal domains. This growing significance γ‐lactams spurred considerable interest synthesis, especially via milder, more sustainable, environmentally friendly methods. In recent years, numerous innovative reaction mechanisms explored, highlighting how photocatalysis can enable formation from readily accessible precursors through C−N bond cyclization processes. review emphasizes potential photocatalytic strategies not only enhance current methods but also foster development greener chemical processes future.

Language: Английский

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