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

Song, Lei; Wang, Wei; Yue, Jun‐Ping; Jiang, Yuan‐Xu; Wei, Ming-Kai; Zhang, Haipeng; Yan, Shusen; Liao, Li‐Li; Yu, Da‐Gang

doi:10.1038/s41929-022-00841-z

Cited by 111 publications

(55 citation statements)

References 54 publications

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“…Nevertheless, the direct attachment of an electron to CO 2 is also challenging, because CO 2 has a large highest-occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap, making the occupation of the LUMO by an electron energetically unfavorable, and the electron affinity (EA) of CO 2 is negative (−0.6 eV) . So the CO 2 •– anion is metastable with a short lifetime of ∼90 ms. , As a result, despite being highly reactive, the direct use of CO 2 •– for further CO 2 fixation has been difficult and scarce . Instead of directly using electrons, another strategy is to use anions or partial negative charges to attack the carbon atom on CO 2 , yielding stable products with carboxylic groups. − …”

Section: Introductionmentioning

confidence: 99%

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO₂

Chen

Wang

et al. 2023

J. Am. Chem. Soc.

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Recent advances in microdroplet chemistry have shown that chemical reactions in water microdroplets can be accelerated by several orders of magnitude compared to the same reactions in bulk water. Among the large plethora of unique properties of microdroplets, an especially intriguing one is the strong reducing power that can be sometimes as high as alkali metals as a result of the spontaneously generated electrons. In this study, we design a catalyst-free strategy that takes advantage of the reducing ability of water microdroplets to reduce a certain molecule, and the reduced form of that molecule can convert CO 2 into value-added products. By spraying the water solution of C 6 F 5 I into microdroplets, an exotic and fragile radical anion, C 6 F 5 I •− , is observed, where the excess electron counter-intuitively locates on the σ* antibonding orbital of the C−I bond as evidenced by anion photoelectron spectroscopy. This electron weakens the C−I bond and causes the formation of C 6 F 5 − , and the latter attacks the carbon atom on CO 2 , forming the pentafluorobenzoate product, C 6 F 5 CO 2 − . This study provides a good example of strategically making use of the spontaneous properties of water microdroplets, and we anticipate that microdroplet chemistry will be a green avenue rich in new opportunities in CO 2 utilization.

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Section: Introductionmentioning

confidence: 99%

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO₂

Chen

Wang

et al. 2023

J. Am. Chem. Soc.

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“…However, Giese radical addition of CO •− to the C�C bond was the initial step to realize the diacids. 7 Considering the essential functions of succinic acids and the difficulties for direct CO 2 reduction, 8 a mild and efficient protocol using alternative C1 source for succinic acid synthesis is urgently required.…”

Section: ■ Introductionmentioning

confidence: 99%

Dicarboxylation of Alkenes with CO₂ and Formate via Photoredox Catalysis

Wang

et al. 2023

ACS Catal.

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Herein, a photocatalytic strategy for the synthesis of succinic acids by alkene dicarboxylation with carbon dioxide (CO2) and formate salt as synergistic carbon sources is described. The formate salt acts as both a C1 source and reductant in the reaction with catalytic amount of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a hydrogen atom transfer reagent. Various mono-, di-, and trisubstituted alkenes, acrylate, acrylamide, and indole derivatives could be converted to the corresponding diacids, which provided potential useful applications in medicinal chemistry and polymer industry.

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“…During the past few decades, tremendous progress has been made in capturing and utilizing CO 2 for the production of high-value chemicals, namely, carboxylic acids, cyclic carbonates, lactones, carbamates, etc. Among them, carboxylation of organic substrates using CO 2 has particularly gained significant interest because of the widespread applicability of carboxylic acids and their derivatives in industrial and pharmaceutical commodities. − A number of methods for the carboxylation of unsaturated compounds with CO 2 using transition metal-based catalysts have been developed so far. − Similar to hydrocarboxylation, difunctionalization of olefins in a single step for introducing −COOH and an additional functional group, for example, thiols, has attracted significant interest as a facile and straightforward approach to producing highly important β-thioacids . The traditional synthesis of β-thioacids involves the reaction of dimethyl sulfoxide, sodium hydride, and sulfides at room temperature followed by the excess suspension of solid CO 2 in ether and subsequent extraction of the crude product with HCl to give the corresponding β-thioacid .…”

Section: Introductionmentioning

confidence: 99%

Visible Light-Driven Metal–Organic Framework-Mediated Activation and Utilization of CO₂ for the Thiocarboxylation of Olefins

Saini

Chakraborty

Erakulan

et al. 2022

ACS Appl. Mater. Interfaces

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Visible light-mediated photoredox catalysis has emerged to be a fascinating approach for the activation of CO2 and its subsequent fixation into valuable chemicals utilizing renewable and inexhaustible solar energy. Although great progress has been made in CO2 photoreduction, visible light-assisted organic synthesis using CO2 as a reactive substrate is rarely explored. Herein, we report an efficient, facile, and economically viable photoredox-mediated approach for the synthesis of important β-thioacids via carboxylation of olefins with CO2 and thiols over a porous functionalized metal–organic framework (MOF), Fe-MIL-101-NH2, as a photocatalyst under ambient conditions. This multicomponent reaction offers wide substrate scope, mild reaction conditions, easy work-up, cost-effective and reusable photocatalysts, and higher product selectivity. Computational studies suggested that CO2 interacts with the thiophenol–styrene adduct to facilitate the synthesis of β-thioacids in almost quantitative yields.

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

Cited by 111 publications

References 54 publications

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO₂

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO₂

Dicarboxylation of Alkenes with CO₂ and Formate via Photoredox Catalysis

Visible Light-Driven Metal–Organic Framework-Mediated Activation and Utilization of CO₂ for the Thiocarboxylation of Olefins

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

Cited by 111 publications

References 54 publications

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO2

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO2

Dicarboxylation of Alkenes with CO2 and Formate via Photoredox Catalysis

Visible Light-Driven Metal–Organic Framework-Mediated Activation and Utilization of CO2 for the Thiocarboxylation of Olefins

Contact Info

Product

Resources

About

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO₂

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO₂

Dicarboxylation of Alkenes with CO₂ and Formate via Photoredox Catalysis

Visible Light-Driven Metal–Organic Framework-Mediated Activation and Utilization of CO₂ for the Thiocarboxylation of Olefins