Dicarboxylation of Alkenes with CO2 and Formate via Photoredox Catalysis

Article Chemistry, Multidisciplinary

Photoredox-Catalyzed Defluorinative Functionalizations of Polyfluorinated Aliphatic Amides and Esters

Jian-Heng Ye et al.

Summary: A new catalytic approach for the selective functionalization of strong C-F bonds in polyfluorinated aliphatic esters and amides has been reported, allowing access to important partially fluorinated motifs.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Electrochemical Dearomative Dicarboxylation of Heterocycles with Highly Negative Reduction Potentials

Yong You et al.

Summary: The dearomative dicarboxylation of stable heteroaromatics using CO2 is a challenging yet powerful method for producing useful dicarboxylic acids. This study introduces a new electrochemical protocol that utilizes CO2 radical anion to produce trans-oriented 2,3-dicarboxylic acids, which can be used as intermediates for biologically active compounds.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Chemistry, Organic

Defluorinative Alkylation of Trifluoromethylbenzimidazoles Enabled by Spin-Center Shift: A Synergistic Photocatalysis/Thiol Catalysis Process with CO2•-

Pei Xu et al.

Summary: This article describes a catalytic strategy for the direct alkylation of trifluoromethylbenzimidazoles at the single C(sp(3))-F bond using a photoinduced thiol catalysis process. The CO2 radical anion (CO2 center dot-) has been identified as the most efficient single-electron reductant for achieving this transformation. The spin-center shift of the generated radical anion intermediate plays a key role in the mild and efficient activation of the C-F bond.

ORGANIC LETTERS (2022)

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Article Chemistry, Physical

Visible-light photocatalytic di- and hydro-carboxylation of unactivated alkenes with CO2

Lei Song et al.

Summary: In this study, we report the photocatalytic carboxylation of unactivated alkenes with CO2 using visible-light. Unlike previous reports limited to activated alkenes, we demonstrate the selective carboxylation of diverse unactivated aliphatic alkenes, providing carboxylic acids, dicarboxylic acids, and unnatural alpha-amino acid derivatives in moderate to good yields.

NATURE CATALYSIS (2022)

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Article Chemistry, Multidisciplinary

Recent advances in the electrochemically mediated chemical transformation of carbon dioxide

ZiQi Yu et al.

Summary: This review presents the recent progress in electrocarboxylation methods, including metal-mediated electrocarboxylation, direct electrocarboxylation, and some novel electrocarboxylation approaches.

CHEMICAL COMMUNICATIONS (2022)

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Article Chemistry, Organic

Hydrocarboxylation of Alkenes with Formate Salts via Photocatalysis

Yan Huang et al.

Summary: A transition-metal-free selective hydrocarboxylation of alkenes under mild conditions has been developed using a formate salt as the reductant and carbonyl source. A broad range of alkenes can be efficiently converted into value-added carboxylic acid products. This method is also characterized by low catalyst loading, good functional group tolerance, and easy scalability.

CHINESE JOURNAL OF ORGANIC CHEMISTRY (2022)

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Article Chemistry, Applied

Visible-light photoredox-catalyzed selective carboxylation of C(sp2)-F bonds in polyfluoroarenes with CO2

Zhi-Yu Bo et al.

Summary: In this study, a novel visible light-driven carboxylation of aryl C-F bonds with CO2 has been reported. The method enables selective carboxylation of strong C(sp(2))-F bonds in various polyfluoroarenes using visible-light photoredox catalysis, providing a facile access to important polyfluoroaryl carboxylic acids.

CHINESE JOURNAL OF CATALYSIS (2022)

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Article Chemistry, Multidisciplinary

Visible-light-driven regioselective carbocarboxylation of 1,3-dienes with organic halides and CO2

Chunlin Zhou et al.

Summary: This study reports a method of using light to drive a regioselective carbocarboxylation reaction between CO2 and aryl and alkyl halides. This method allows for the rapid and highly regioselective synthesis of complex β,γ-unsaturated carboxylic acids.

GREEN CHEMISTRY (2022)

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Article Chemistry, Multidisciplinary

A versatile catalyst-free redox system mediated by carbon dioxide radical and dimsyl anions

Yan Huang et al.

Summary: The study demonstrated a redox system mediated by carbon dioxide radical and dimsyl anions, achieving a variety of high efficiency transformations and producing valuable products, showing promising applications in other reactions.

CELL REPORTS PHYSICAL SCIENCE (2022)

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Article Chemistry, Multidisciplinary

Visible-Light-Driven Anti-Markovnikov Hydrocarboxylation of Acrylates and Styrenes with CO2

He Huang et al.

Summary: In this study, a novel visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO2 was developed, which could selectively generate organic compounds, providing a new strategy for CO2 utilization.

CCS CHEMISTRY (2021)

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Article Chemistry, Physical

Photocatalyzed, β-Selective Hydrocarboxylation of α,β-Unsaturated Esters with CO2 under Flow for β-Lactone Synthesis

Guowei Kang et al.

Summary: A photochemical, beta-selective hydrogenation of alpha, beta-unsaturated esters using CO2 radical anion under flow conditions was developed. The reaction tolerated various substrates with different functional groups and resulted in a series of quaternary carboxylic acids. Mechanistic studies suggest a Giese-type CO2 radical anion conjugate addition followed by hydrogen atom transfer as the main reaction pathway, and a telescoped process for beta-lactone synthesis.

ACS CATALYSIS (2021)

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Article Chemistry, Multidisciplinary

Photochemical C-F Activation Enables Defluorinative Alkylation of Trifluoroacetates and -Acetamides

Mark W. Campbell et al.

Summary: A photochemically mediated method has been successfully developed for the defluorinative alkylation of ethyl trifluoroacetate, providing an efficient pathway for the synthesis of novel gem-difluoro analogs. This method can also be used for the hydroalkylation of a diverse suite of alkenes, expanding the range of substrates for the reaction.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Physical

Photoredox Activation of Formate Salts: Hydrocarboxylation of Alkenes via Carboxyl Group Transfer

Yan Huang et al.

Summary: A photoredox activation mode using formate salts was developed for carboxylation, allowing a wide range of alkenes to be converted into acid products through a carboxyl group transfer strategy. Key intermediates in the transformation were identified as radical anion species. High catalytic efficiency and a simple catalytic system make this method promising for industrial applications.

ACS CATALYSIS (2021)

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Review Chemistry, Multidisciplinary

Radical Carboxylative Cyclizations and Carboxylations with CO2

Jian-Heng Ye et al.

Summary: Carbon dioxide is a valuable carbon resource in organic synthesis, but its utilization is challenging due to stability and inertness. Researchers have developed radical-type carboxylations and cyclizations using visible-light photoredox catalysis and copper catalysis. These strategies have expanded the scope of CO2 transformations and provided new methods for selective organic synthesis.

ACCOUNTS OF CHEMICAL RESEARCH (2021)

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Article Chemistry, Physical

Dicarboxylation of alkenes, allenes and (hetero)arenes with CO2 via visible-light photoredox catalysis

Tao Ju et al.

Summary: The use of visible-light photoredox catalysis in incorporating two CO2 molecules into organic compounds to form multiple C-C bonds represents a simple, rapid, and sustainable approach. The method exhibits high selectivity, mild conditions, and low catalyst loading, making it suitable for drug and material molecule synthesis.

NATURE CATALYSIS (2021)

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Article Chemistry, Multidisciplinary

Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides

Jinhui Xu et al.

Summary: This article discusses the unprecedented discovery that a family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts can activate reductively recalcitrant aryl chlorides under mild conditions, producing valuable organic synthesis products.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Photoinduced Hydrocarboxylation via Thiol-Catalyzed Delivery of Formate Across Activated Alkenes

Sara N. Alektiar et al.

Summary: This new photochemical process efficiently prepares carboxylic acids from formate salts and alkenes with high yields and excellent regioselectivity. It is operationally simple and easily scalable, with the potential to enable the direct synthesis of isotopically labeled carboxylic acids using commercially available formate carbon isotologues. Mechanistic studies support a thiol-catalyzed radical chain process involving the delivery of atoms from formate across the alkene substrate via CO2 center dot-.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Radical Chain Reduction via Carbon Dioxide Radical Anion (CO2•-)

Cecilia M. Hendy et al.

Summary: An effective method using the radical anion of carbon dioxide as a reductant was developed, allowing for reductive activation of various substrate classes through a radical chain reaction. Different reactions such as hydroarylation, deamination, radical formation, and cleavage were successfully demonstrated, showcasing the versatility of this approach in predicting reaction outcomes based on substrate reduction potentials.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Visible-light photoredox-catalyzed selective carboxylation of C(sp3)-F bonds with CO2

Si-Shun Yan et al.

Summary: This study demonstrates the dual role of CO2 as both an electron carrier and an electrophile, enabling selective carboxylation of C(sp(3))-F bonds to construct various alpha-fluorocarboxylic acids via visible-light photoredox catalysis. The fluorinated substrates undergo reduction by CO2 radical anions generated from sequential hydride-transfer reduction and hydrogen-atom transfer processes. This methodology shows promise for the late-stage functionalization of complex molecules.

CHEM (2021)

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Article Chemistry, Multidisciplinary