Photocatalytic carbocarboxylation of styrenes with CO<sub>2</sub>for the synthesis of γ-aminobutyric esters

Hahm, Hyungwoo; Kim, Jiyun; Ryoo, Jeong Yup; Han, Min Su; Hong, Sukwon

doi:10.1039/d1ob00866h

Cited by 14 publications

(3 citation statements)

References 110 publications

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“…In the same year (2021), Hong et al 41 devised a synthetic route for the regioselective carbocarboxylation of different substituted styrenes 24a with CO 2 and amines 24b for the synthesis of a series of γ-aminobutyric esters 24c via visible light-induced photoredox-catalyzed metal-free difunctionalization of styrenes (Scheme 24). However, the method required K 2 HPO 4 as the base, 5 mol% 4CzBnBN as photocatalyst, and DMF as solvent.…”

Section: Czipn-catalyzed Difunctionalizationmentioning

confidence: 99%

Visible light-induced organophotoredox-catalyzed difunctionalization of alkenes and alkynes

Gupta,

Kundu,

Ghosh

et al. 2023

Green Chem.

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Section: Czipn-catalyzed Difunctionalizationmentioning

confidence: 99%

Visible light-induced organophotoredox-catalyzed difunctionalization of alkenes and alkynes

Gupta,

Kundu,

Ghosh

et al. 2023

Green Chem.

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“…79 Previous examples of photoredox catalyzed difunctionalization of aromatic alkenes to generate γ-aminobutyric acid derivatives were limited to N,N-dimethyl anilines that can be intercepted by facile Giese addition with less activated alkenes. [79][80][81] Remarkably, the use of sterically hindered alkyl amines such as N,N-diisopropylethylamine has not been reported in this context. The key feature of our design plan is continuous flow chemistry, incorporating tube-in-tube gas/liquid reactor to enable controlled delivery of carbon dioxide.…”

Section: Alkene -Carbodifunctionalizationmentioning

confidence: 99%

Photocatalytic Generation of Alkyl Carbanions from Alkenes

Czyz,

Horngren,

Kondopoulos

et al. 2023

Preprint

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Organometallic reagents are routinely used as fundamental building blocks in organic chemistry to rapidly diversify molecular fragments via carbanion intermediates. However the catalytic generation of carbanion equivalents particularly from sp3-hybridized alkyl scaffolds, remains an underdeveloped goal in chemical synthesis. To align with the demands of modern synthetic protocols, a general method for the catalytic generation of alkyl carbanions must operate under benign reaction conditions and access commercially available feedstock chemicals. Alkenes constitute an attractive source of latent alkyl carbanion equivalents, however methods for the conversion of carbon-carbon bonds into carbanions is challenged by the need for precious metals and aggressive stoichiometric reductants. Here we disclose an approach for the controlled generation of 2-electron carbon nucleophiles via single electron reduction of aryl alkenes, facilitated by the highly reducing environment of multiphoton photoredox catalysts. We demonstrate that alkene radical anions engage in catalytic, metal free, intermolecular C-C bond-forming reactions with carbonyl derivatives, in a manner analogous to Grignard reagents. Under this reaction manifold, the alkene can be considered a dicarbanion synthon offering new opportunities for orthogonal diversification. This concept was illustrated by the development of four distinct C-C bond forming reactions with aromatic alkenes: hydroalkoxylation, hydroamidation, aminoalkylation and carboxyaminoalkylation, to generate a range of valuable and complex scaffolds.

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“…为缺电子的底物的反应效果, 随后, Hong 课题组 [9] 报道了富电子和缺电子烯烃都适用的 N,N-二取代的芳胺和二氧化碳的烯烃双官能团化反应. 立足上述领域, 在尝试对应烯烃的羧基化反应过程中, 发现了脂肪胺和二氧化碳参与的活化烯烃的碳羧化反应后经不常见的 C-C 断裂过程, 从而获得了一系列芳基乙酸和 β-酸酯化合物 (Scheme 1c).…”

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Visible Light-Induced Decarbon-Carboxylation of Activated Alkenes by Carbon Dioxide

Duan,

Ma,

Liu

et al. 2024

Chinese Journal of Organic Chemistry

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An efficient visible light-facilitated decarbon-carboxylation of activated alkenes has been successfully developed. Compared with traditional alkene carboxylation, this method features mild conditions, up to 96% yield and good compatibility with a variety of functional groups. It provides a new method for the synthesis of phenylacetic acid and its derivatives. The mechanism study shows that the reaction realizes the synthesis of the corresponding carboxylic acid with constant apparent carbon number by substituting the carbon-carbon double bond of alkene. Keywords visible light induction; carbon dioxide; activated alkene; carboxylation 二氧化碳(CO 2 )作为丰富的可再生的 C1 合成子在合成羧酸及其衍生物中备受关注 [1] , 其中, 芳基乙酸类化合物有着显著的生物活性, 且部分已被开发为药物应用于生活中(图 1) [2] . 为此, 利用二氧化碳实现芳基苄位羧化有着重要应用价值. 在众多现有转化中, 存在底物复杂、使用昂贵的过渡金属、反应条件苛刻、反应规模小、反应废弃物多等不足, 所以, 发展绿色环保、反应条件温和且无过渡金属参与的利用二氧化碳实现反应底物的羧基化有着广阔的应用前景. 以往的合成策略通常为以下几种(Scheme 1a): (1)芳环苄位预留官能团后与二氧化碳羧化获得目标产物 [3] . 该类方法底物难直接获得, 原子经济性不高. (2)芳环苄位被攫氢或拔氢后与二氧化碳反应 [4] . 该策略往往因为攫氢效率低, C-H 选择性差而未得到实际应用. (3)利用芳基烯烃与二氧化碳的氢羧化 [5] 或者双官能团化反应 [6] 可以得到芳基乙酸类化合物. 此类方法因其高效被化学家所青睐, 目前已发展出众多方法, 包括烯烃的氢羧基化, 碳羧基化, 硫、硅、膦等杂原子的羧基化. 其中, 2020 年, Xi 等 [7] 报道了光催化的二氧化碳和 N,N-二取代的芳胺参与的芳基烯烃的碳羧化反应(Scheme 1b). 该反应中, 三级胺既可以作为光氧化还原反应中良好的还原剂, 同时也是氨基 α 位的碳自由基前体试剂 [8] . 在反应中本身被氧化成氨基自由基阳离子, 经脱质子可以生成氨基 α 位的碳自由基物种.

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Photocatalytic carbocarboxylation of styrenes with CO₂for the synthesis of γ-aminobutyric esters

Abstract: The metal-free photoredox-catalyzed carbocarboxylation of various styrenes with carbon dioxide (CO2) and amines to give γ-aminobutyric ester derivatives has been developed (up to 91%, 36 examples). The radical anion of...

Cited by 14 publications

References 110 publications

Visible light-induced organophotoredox-catalyzed difunctionalization of alkenes and alkynes

Visible light-induced organophotoredox-catalyzed difunctionalization of alkenes and alkynes

Photocatalytic Generation of Alkyl Carbanions from Alkenes

Visible Light-Induced Decarbon-Carboxylation of Activated Alkenes by Carbon Dioxide

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Photocatalytic carbocarboxylation of styrenes with CO2for the synthesis of γ-aminobutyric esters

Abstract: The metal-free photoredox-catalyzed carbocarboxylation of various styrenes with carbon dioxide (CO2) and amines to give γ-aminobutyric ester derivatives has been developed (up to 91%, 36 examples). The radical anion of...

Cited by 14 publications

References 110 publications

Visible light-induced organophotoredox-catalyzed difunctionalization of alkenes and alkynes

Visible light-induced organophotoredox-catalyzed difunctionalization of alkenes and alkynes

Photocatalytic Generation of Alkyl Carbanions from Alkenes

Visible Light-Induced Decarbon-Carboxylation of Activated Alkenes by Carbon Dioxide

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Product

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Photocatalytic carbocarboxylation of styrenes with CO₂for the synthesis of γ-aminobutyric esters