Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(16), С. 7206 - 7237

Опубликована: Янв. 1, 2022

This review covers the recent progress in electro-/photo-catalytic alkene-derived radical cation chemistry for organic synthesis, including synthetic strategies, plausible mechanisms and further research outlook.

Язык: Английский

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Electrochemical Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11269 - 11335

Опубликована: Сен. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Язык: Английский

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Recent progress in cathodic reduction-enabled organic electrosynthesis: Trends, challenges, and opportunities

eScience, Год журнала: 2022, Номер 2(3), С. 243 - 277

Опубликована: Апрель 23, 2022

Compared with general redox chemistry, electrochemistry using the electron as a potent, controllable, yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis. With its environmentally benign features gradually being uncovered and studied, electrosynthesis is currently undergoing revival becoming rapidly growing area within synthetic community. Among electrochemical transformations, anodically enabled ones have been far extensively exploited than those driven by cathodic reduction, although both approaches are conceptually attractive. To stimulate development of cathodically reactions, this review summarizes recently developed reductive electrosynthetic protocols, discussing highlighting reaction features, substrate scopes, applications, plausible mechanisms reveal recent trends in area. Herein, reduction-enabled preparative transformations categorized into four types: reduction (1) unsaturated hydrocarbons, (2) heteroatom-containing carbon-based systems, (3) saturated C-hetero or C–C polar/strained bonds, (4) hetero-hetero linkages. Apart from net electroreductive few examples photo-electrosynthesis well paired electrolysis also introduced, which offer opportunities overcome certain limitations improve versatility. The electrochemically driven, transition metal-catalyzed cross-couplings that comprehensively discussed several other reviews not included here.

Язык: Английский

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Carbon dioxide cycle via electrocatalysis: Electrochemical carboxylation of CO2 and decarboxylative functionalization of carboxylic acids

Green Synthesis and Catalysis, Год журнала: 2021, Номер 2(1), С. 19 - 26

Опубликована: Фев. 1, 2021

As one of the most important biogeochemical cycles, carbon dioxide (CO2) cycle between atmosphere and biosphere has a profound impact on life earth. Therefore, search for sustainable solutions to normalize currently unbalanced is central research topic many scientific disciplines. The green electrocatalysis offers very promising answer cycle. In this review, recent advances in enabled CO2 including electrochemical carboxylation decarboxylative functionalization carboxylic acids are highlighted.

Язык: Английский

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Nickel-catalyzed electrochemical carboxylation of unactivated aryl and alkyl halides with CO2

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Дек. 6, 2021

Electrochemical catalytic reductive cross couplings are powerful and sustainable methods to construct C-C bonds by using electron as the clean reductant. However, activated substrates used in most cases. Herein, we report a general practical electro-reductive Ni-catalytic system, realizing electrocatalytic carboxylation of unactivated aryl chlorides alkyl bromides with CO2. A variety bromides, iodides sulfonates can also undergo such reaction smoothly. Notably, realize electrochemical (pseudo)halides CO2 avoiding use sacrificial electrodes. Moreover, this economic strategy reductant features mild conditions, inexpensive catalyst, safe cheap electrodes, good functional group tolerance broad substrate scope. Mechanistic investigations indicate that might proceed via oxidative addition halides Ni(0) complex, reduction aryl-Ni(II) adduct Ni(I) species following

Язык: Английский

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Electrochemical Dearomative Dicarboxylation of Heterocycles with Highly Negative Reduction Potentials

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(8), С. 3685 - 3695

Опубликована: Фев. 22, 2022

The dearomative dicarboxylation of stable heteroaromatics using CO2 is highly challenging but represents a very powerful method for producing synthetically useful dicarboxylic acids, which can potentially be employed as intermediates biologically active molecules such natural products and drug leads. However, these types transformations are still underdeveloped, concise methodologies with high efficiency (e.g., yield selectivity dicarboxylations) have not been reported. We herein describe new electrochemical protocol the radical anion (E1/2 = -2.2 V in DMF -2.3 CH3CN vs SCE) that produces unprecedented trans-oriented 2,3-dicarboxylic acids from N-Ac-, Boc-, Ph-protected indoles exhibit negative reduction potentials (-2.50 to -2.94 V). On basis calculated potentials, N-protected up -3 smoothly undergo desired dicarboxylation. Other heteroaromatics, including benzofuran, benzothiophene, electron-deficient furans, thiophenes, 1,3-diphenylisobenzofuran, N-Boc-pyrazole, also more positive than served effective substrates dicarboxylations. dicarboxylated thus obtained derivatized into synthetic compounds few steps. show how monocarboxylation achieved selectively by choice electrolyte, solvent, protic additive; this strategy was then applied synthesis an octahydroindole-2-carboxylic acid (Oic) derivative, proline analogue.

Язык: Английский

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Electrocatalytic Reactions for Converting CO ₂ to Value‐Added Products

Small Science, Год журнала: 2021, Номер 1(10)

Опубликована: Авг. 8, 2021

Converting CO 2 into valuable chemical products has been intensively explored in recent years. Benefited from the substantial cost reduction of clean electricity, electrochemical methods have emerging as a potential means for conversion and fixation. Direct reaction (CO RR) with H O is achieved continuously improved efficiency, selectivity stability. In contrast, coupled RR small molecules organic substrates, which can allow to form higher chemicals, still hindered by poor selectivity, unclear mechanisms, suboptimal performances electrocatalysts. Herein, development electrocatalysts mechanisms first introduced. Several representative examples are described emphasizing concepts methodologies. The research process then briefly discussed. Finally, challenges perspectives this field addressed further inspire fundamental understanding RR, well optimization electrocatalysts, electrolytes, electrolyzers high activity selectivity.

Язык: Английский

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Electrocarboxylation of Aryl Epoxides with CO₂for the Facile and Selective Synthesis of β‐Hydroxy Acids

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(38)

Опубликована: Июль 30, 2022

Abstract Herein, an efficient and facile approach to valuable β‐hydroxy acid derivatives from readily available aryl epoxides CO 2 with high chemo‐ regioselectivity under mild sustainable electrochemical conditions is described. This showed broad substrate scope good functional‐group compatibility. In addition epoxides, four‐ six‐membered cyclic ethers could all be tolerated in the reaction provide synthetically useful hydroxy acids efficiency. Further late‐stage carboxylation of complex molecules drug demonstrated its potential application pharmaceutical industry. Mechanistic studies disclosed possible pathways.

Язык: Английский

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Recent Advances in Electrocarboxylation with CO₂

Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(17)

Опубликована: Июль 6, 2022

Abstract Carbon dioxide (CO 2 ) is an abundant, inexpensive, renewable C1 resource and the main component of greenhouse gas, thereby research for its sustainable efficient conversion has received notable attention in recent years. Electrochemical organic synthesis, as a green synthetic method, convinced to be ideal approach CO utilization. In this review, advances electrocarboxylation with were summarized through different reaction types, which would disclose great potential synthesis.

Язык: Английский

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Electroreductive Dicarboxylation of Unactivated Skipped Dienes with CO₂

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Апрель 3, 2023

Carboxylation of easily available alkenes with CO2 is highly important to afford value-added carboxylic acids. Although dicarboxylation activated alkenes, especially 1,3-dienes, has been widely investigated, the challenging unactivated 1,n-dienes (n>3) remains unexplored. Herein, we report first skipped dienes via electrochemistry, affording valuable dicarboxylic Control experiments and DFT calculations support single electron transfer (SET) reduction its radical anion, which followed by sluggish addition SET unstabilized alkyl radicals carbanions nucleophilic attack on give desired products. This reaction features mild conditions, broad substrate scope, facile derivations products promising application in polymer chemistry.

Язык: Английский

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