Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(21)

Опубликована: Апрель 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Язык: Английский

---

Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp³)−H Alkenylation**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)

Опубликована: Апрель 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Язык: Английский

---

Molecular Photoelectrocatalysis for Radical Reactions

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes capacity to offer novel reactivity selectivity, represents an emerging field in chemistry that addresses growing demands for environmental sustainability synthetic efficiency. This synergistic approach permits access a wider range redox potentials, facilitates transformations under gentler electrode decreases use external harsh reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we others reported first examples modern molecular photoelectrocatalysis. These studies showcased immense hybrid strategy, only inherits strengths its parent fields but also unlocks unprecedented enabling challenging mild conditions while minimizing reliance on stoichiometric oxidants or reductants.In Account, present our efforts develop photoelectrocatalytic strategies leverage homogeneous catalysts facilitate diverse radical reactions. By integrating electrocatalysis with key photoinduced processes such as single electron transfer (SET), ligand-to-metal charge (LMCT), hydrogen atom (HAT), have established methods transform substrates organotrifluoroborates, arenes, carboxylic acids, alkanes into reactive intermediates. intermediates subsequently engage heteroarene C-H functionalization Importantly, photoelectrochemical catalysts, generated bulk solution readily participate efficient reactions without undergoing further overoxidation carbocations, common challenge conventional electrochemical systems.By integration photoelectrocatalysis asymmetric catalysis, developed catalysis (PEAC), proves be enantioselective synthesis chiral nitriles. involves two relay catalytic cycles: initial process engenders benzylic radicals from precursors alkyl aryl alkenes, C-radicals are then subjected cyanation subsequent copper-electrocatalytic cycle.Within realm oxidative transformations, anode serves crucial component recycling generating photocatalyst, cathode promotes proton reduction. dual functionality enables via H

Язык: Английский

---

Electrophotocatalytic tri- or difluoromethylative cyclization of alkenes

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(10), С. 2482 - 2490

Опубликована: Янв. 1, 2023

Photoelectrocatalysis is mild yet potent and this work unlocks the potential of unactivated alkenes for oxidant-free oxidative cyclization alkenes.

Язык: Английский

---

Electrophotochemical Metal‐Catalyzed Enantioselective Decarboxylative Cyanation

Chemistry - A European Journal, Год журнала: 2023, Номер 29(24)

Опубликована: Янв. 13, 2023

Abstract In contrast to the rapid growth of electrophotocatalysis in recent years, enantioselective catalytic reactions powered by this unique methodology remain rare. work, we report an electrophotochemical metal‐catalyzed protocol for direct asymmetric decarboxylative cyanation aliphatic carboxylic acids. The synergistic merging cerium catalysis and electrochemical copper permits mild reaction conditions formation utilization key carbon centered radicals combining power light electrical energy. Electrophotochemical enables radical decarboxylation produce alkyl radicals, which could be effectively intercepted construction C−CN bonds a highly stereoselective fashion. This environmentally benign method smoothly converts diverse array arylacetic acids into corresponding nitriles good yields enantioselectivities without using chemical oxidants or pre‐functionalization acid substrates can readily scaled up.

Язык: Английский

---

Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 26774 - 26782

Опубликована: Ноя. 29, 2023

Direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides for the synthesis alkenes all substitution patterns has been accomplished by means Ce/Ni dual transition metal electrocatalysis. The reactions employ alkyl as limiting reagents and exhibit a broad scope respect to both coupling partners. Notably, simple primary could be readily engaged carbon-centered radical precursors in reaction. This new protocol successfully demonstrated direct modification naturally occurring complex is amenable enantioselective arylacetic acid. Mechanistic studies, including series controlled experiments cyclic voltammetry data, allow us probe key intermediates pathway

Язык: Английский

---

Selective C(sp3)–H arylation/alkylation of alkanes enabled by paired electrocatalysis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Дек. 2, 2023

We report a combination of electrocatalysis and photoredox catalysis to perform selective C(sp3)-H arylation/alkylation alkanes, in which binary catalytic system based on earth-abundant iron nickel is applied. Reaction selectivity between two-component arylation three-component alkylation tuned by modulating the applied current light source. Importantly, an ultra-low anodic potential (~0.23 V vs. Ag/AgCl) this protocol, thus enabling compatibility with variety functional groups (>70 examples). The robustness method further demonstrated preparative scale late-stage diversification natural products pharmaceutical derivatives.

Язык: Английский

---

Unleashing the potentiality of metals: synergistic catalysis with light and electricity

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 4024 - 4040

Опубликована: Янв. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Язык: Английский

---

Photoelectrochemical Fe/Ni cocatalyzed C−C functionalization of alcohols

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 19, 2024

Abstract The simultaneous activation of reactants on the anode and cathode via paired electrocatalysis has not been extensively demonstrated. This report presents a oxidative reductive catalysis based earth-abundant iron/nickel cocatalyzed C–C functionalization ubiquitous alcohols. A variety alcohols (i.e., primary, secondary, tertiary, or unstrained cyclic alcohols) can be activated at very low oxidation potential (~0.30 V vs. Ag/AgCl) photoelectrocatalysis coupled with versatile electrophiles. reactivity yields wide range structurally diverse molecules broad functional group compatibility (more than 50 examples).

Язык: Английский

---

Electrophotocatalysis for Organic Synthesis

Chemical Reviews, Год журнала: 2024, Номер 124(21), С. 12264 - 12304

Опубликована: Окт. 23, 2024

Electrocatalysis and photocatalysis have been the focus of extensive research efforts in organic synthesis recent decades, these powerful strategies provided a wealth new methods to construct complex molecules. Despite intense efforts, only recently has there significant on combined use two modalities. Nevertheless, past five years witnessed rapidly growing interest area electrophotocatalysis. This hybrid strategy capitalizes enormous benefits using photons as reagents while also employing an electric potential convenient tunable source or sink electrons. Research this topic led number for C-H functionalization, reductive cross-coupling, olefin addition among others. field seen broad range catalyst types, including both metal organocatalysts. Of particular note work with open-shell photocatalysts, which tend comparatively large redox potentials. Electrochemistry provides means generate such species, making electrophotocatalysis particularly amenable intriguing class catalyst. review surveys applied synthesis, organized broadly into oxidative, reductive, neutral transformations.

Язык: Английский

---