Visible-Light Photoredox-Catalyzed Carboxylation of Benzylic C(sp3)–O Bonds in Ethers with CO2 DOI
Jingwei Yang,

Chuan‐Kun Ran,

Wenjing Zhu

и другие.

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Июнь 5, 2025

Although significant progress has been made in achieving site-selective C-O bond functionalization specific substrates, the selective cleavage and of C(sp3)-O bonds ethers remain a fundamental challenge synthetic chemistry. Herein, we present an efficient carboxylation method via photoredox-catalyzed benzylic with carbon dioxide (CO2). Diverse primary, secondary, tertiary benzyl undergo CO2 to generate valuable aryl acetic acids, including several drug molecules. This photocatalyzed reaction is operationally simple implement versatile for various ethers, exhibiting favorable compatibility diverse functional groups. Mechanistic studies indicate that single electron transfer (SET) reduction might be key generating highly reactive radical anion intermediate, which could another SET process carbanions CO2.

Язык: Английский

Arylcarboxylation of unactivated alkenes with CO2 via visible-light photoredox catalysis DOI Creative Commons
Wei Zhang, Zhen Chen, Yuan‐Xu Jiang

и другие.

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

Опубликована: Июнь 14, 2023

Photocatalytic carboxylation of alkenes with CO2 is a promising and sustainable strategy to synthesize high value-added carboxylic acids. However, it challenging rarely investigated for unactivated due their low reactivities. Herein, we report visible-light photoredox-catalyzed arylcarboxylation CO2, delivering variety tetrahydronaphthalen-1-ylacetic acids, indan-1-ylacetic indolin-3-ylacetic chroman-4-ylacetic acids thiochroman-4-ylacetic in moderate-to-good yields. This reaction features chemo- regio-selectivities, mild conditions (1 atm, room temperature), broad substrate scope, good functional group compatibility, easy scalability facile derivatization products. Mechanistic studies indicate that situ generation carbon dioxide radical anion following addition might be involved the process.

Язык: Английский

Процитировано

52
Alkyl radicals from diacyl peroxides: metal-/base-/additive-free photocatalytic alkylation of N-heteroaromatics DOI

Fukun Cheng,

Lulu Fan, Qi‐Yan Lv

и другие.

Green Chemistry, Год журнала: 2023, Номер 25(20), С. 7971 - 7977

Опубликована: Янв. 1, 2023

Alkyl diacyl peroxides were demonstrated to be efficient alkylating reagents for the visible-light-induced 4CzIPN-catalyzed direct C–H alkylation of N -heteroaromatics.

Язык: Английский

Процитировано

51
Synthesis of 1-(Halo)alkyl-3-heteroaryl Bicyclo[1.1.1]pentanes Enabled by a Photocatalytic Minisci-type Multicomponent Reaction DOI

Jiashun Zhu,

Yu Hong,

Yuxin Wang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 6247 - 6258

Опубликована: Апрель 10, 2024

Aryl-substituted bicyclo[1.1.1]pentane (BCP-aryl) derivatives represent the most important bioisosteres of biaryl scaffolds and widely exist in numerous complex pharmaceutical molecules. The current synthetic method limitations using only tertiary radical precursors, prefunctionalized heteroarenes, toxic transition metals, expensive photocatalysts make it urgent to develop a more simple practical protocol. To confront enrich Minisci-type chemistry, herein, we disclose photocatalytic multicomponent reaction for synthesis various (halo)alkyl BCP-aryls [1.1.1]propellane, alkyl halides, unfunctionalized heteroarenes as starting materials. Diverse kinds radicals (primary, secondary, carbons) derived from chlorides, bromides, fluoroalkyl iodides are very compatible this transformation. practicability is additionally boosted by product derivatizations late-stage functionalization pharmaceutically relevant mechanistic studies demonstrate that relay mechanism initiated consecutive photoinduced electron transfer (ConPET) process operation. We anticipate methodology would act useful tool biaryl-type drug derivatives, ultimately resulting great utility discovery program.

Язык: Английский

Процитировано

42
Recent Advances in Photochemical/Electrochemical Carboxylation of Olefins with CO2 DOI
Qian Wang, Yanwei Wang, Min Liu

и другие.

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(18), С. 2249 - 2266

Опубликована: Май 15, 2024

Comprehensive Summary CO 2 is an abundant, nontoxic, and renewable C1 feedstock in synthetic chemistry. Direct carboxylation of readily available olefins incorporating regarded as a promising strategy to access high value‐added carboxylic acids well fixation. However, due the thermodynamic stability kinetic inertness difficulty controlling regioselectivity, with still remains challenging. Radical‐type functionalization represented powerful protocol enabled development novel transformations this realm. More recently, advance new technology, such photoredox catalysis renaissance electrochemistry organic synthesis, offered unique chemical reactivities radical precursors provided solutions olefins. This review presents recent advances radical‐type olefins, which has mainly been achieved through photocatalysis electrocatalysis last decade. In article, we provide comprehensive introduction progress, summarize advantages limitations current research, discuss potential outlook for further development. Key Scientists

Язык: Английский

Процитировано

19
Excited Organic Radicals in Photoredox Catalysis DOI Creative Commons
Björn Pfund, Oliver S. Wenger

JACS Au, Год журнала: 2025, Номер 5(2), С. 426 - 447

Опубликована: Янв. 29, 2025

Many important synthetic-oriented works have proposed excited organic radicals as photoactive species, yet mechanistic studies raised doubts about whether they can truly function photocatalysts. This skepticism originates from the formation of (photo)redox-active degradation products and picosecond decay electronically radicals, which is considered too short for diffusion-based photoinduced electron transfer reactions. From this perspective, we analyze synthetic transformations where been photocatalysts, comparing their theoretical maximum state potentials with required observed photocatalytic reactivity. We summarize structurally similar photocatalysts indicating different reaction pathways some catalytic systems, addressing cases radical exceed Additionally, perform a kinetic analysis to explain in on subpicosecond time scales. further rationalize potential anti-Kasha reactivity higher states femtosecond lifetimes, highlighting how future photocatalysis advancements could unlock new photochemical pathways.

Язык: Английский

Процитировано

6
Shining Fresh Light on Complex Photoredox Mechanisms through Isolation of Intermediate Radical Anions DOI Creative Commons
Samuel J. Horsewill, Gabriele Hierlmeier,

Zahra Farasat

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(14), С. 9392 - 9403

Опубликована: Июнь 30, 2023

Photoredox catalysis (PRC) has gained enormous and wide-ranging interest in recent years but also been subject to significant mechanistic uncertainty, even controversy. To provide a method by which the missing understanding can begin be filled in, we demonstrate herein that it is possible isolate as authentic materials one-electron reduction products of representative PRC catalysts (PCs). Specifically, KC8 both 9,10-dicyanoanthracene naphthalene monoamide derivative presence cryptand provides convenient access corresponding [K(crypt)+][PC·-] salts clean fully characterized techniques including EPR XRD. Because PC·- states are key intermediates reactions, such isolation allows for highly controlled study these anions' specific reactivity hence their roles. As demonstration this principle, show used conveniently interrogate mechanisms recent, high-profile "conPET" "e-PRC" currently acute Using very simple experiments, able striking insights into reactions' underlying observe surprising levels hidden complexity would otherwise have challenging identify emphasize care control needed when interrogating interpreting mechanisms. These studies foundation far broader range questions around conPET, e-PRC, other reaction future, using same strategy isolation.

Язык: Английский

Процитировано

35
Photoredox catalysis harvesting multiple photon or electrochemical energies DOI Creative Commons
Mattia Lepori, Simon Schmid, Joshua P. Barham

и другие.

Beilstein Journal of Organic Chemistry, Год журнала: 2023, Номер 19, С. 1055 - 1145

Опубликована: Июль 28, 2023

Photoredox catalysis (PRC) is a cutting-edge frontier for single electron-transfer (SET) reactions, enabling the generation of reactive intermediates both oxidative and reductive processes via photon activation catalyst. Although this represents significant step towards chemoselective and, more generally, sustainable chemistry, its efficacy limited by energy visible light photons. Nowadays, excellent alternative conditions are available to overcome these limitations, harvesting two different but correlated concepts: use multi-photon such as consecutive photoinduced electron transfer (conPET) combination photo- electrochemistry in synthetic photoelectrochemistry (PEC). Herein, we review most recent contributions fields activations organic functional groups. New opportunities chemists captured, selective reactions employing super-oxidants super-reductants engage unactivated chemical feedstocks, scalability up gram scales continuous flow. This provides comparisons between techniques (multi-photon photoredox PEC) help reader fully understand their similarities, differences potential applications therefore choose which method appropriate given reaction, scale purpose project.

Язык: Английский

Процитировано

28
Electrophotocatalytic hydrogenation of imines and reductive functionalization of aryl halides DOI Creative Commons
Wenjie Kang, Yanbin Zhang, Bo Li

и другие.

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

Опубликована: Янв. 22, 2024

Abstract The open-shell catalytically active species, like radical cations or anions, generated by one-electron transfer of precatalysts are widely used in energy-consuming redox reactions, but their excited-state lifetimes usually short. Here, a closed-shell thioxanthone-hydrogen anion species ( 3 ), which can be photochemically converted to potent and long-lived reductant, is under electrochemical conditions, enabling the electrophotocatalytic hydrogenation. Notably, TfOH regulate potential this system. In presence TfOH, precatalyst 1 ) reduction occur at low potential, so that competitive H 2 evolution inhibited, thus effectively promoting hydrogenation imines. absence reducing ability system reach potency even comparable Na 0 Li , thereby allowing hydrogenation, borylation, stannylation (hetero)arylation aryl halides construct C−H, C−B, C−Sn, C−C bonds.

Язык: Английский

Процитировано

18
Catalytic Asymmetric Redox‐Neutral [3+2] Photocycloadditions of Cyclopropyl Ketones with Vinylazaarenes Enabled by Consecutive Photoinduced Electron Transfer DOI

Wenhui Wei,

Chunyang Li, Yifan Fan

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(30)

Опубликована: Апрель 30, 2024

Abstract Consecutive photoinduced electron transfer (ConPET) is a powerful and atom‐economical protocol to overcome the limitations of intrinsic redox potential visible light‐absorbing photosensitizers, thereby considerably improving substrate reaction types. Likely because such an exothermic single‐electron (SET) process usually does not require aid chiral catalysts, resulting in inevitable racemic background reaction, notably, no enantioselective manifolds have been reported. Herein, we report on viability cooperative ConPET hydrogen‐bonding catalysis for [3+2] photocycloaddition cyclopropyl ketones with vinylazaarenes. In addition enabling first use olefins that preferentially interact this platform paves way efficient synthesis pharmaceutically synthetically important cyclopentyl functionalized by azaarenes high yields, ees dr. The robust capacity method can be further highlighted low loading catalyst (1.0 mol %), good compatibility both 2‐azaarene 3‐pyridine‐based olefins, successful concurrent construction three stereocenters cyclopentane rings involving elusive but all‐carbon quaternary.

Язык: Английский

Процитировано

11
Catalytic asymmetric photocycloaddition reactions mediated by enantioselective radical approaches DOI
Yanli Yin,

Mengdi You,

Xiangtao Li

и другие.

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The use of olefins in the construction cyclic compounds represents a powerful strategy for advancing pharmaceutical industry.

Язык: Английский

Процитировано

2