Merging Paired Electrolysis and Copper Catalysis Enables Electrochemical Arylation of Aziridine for the Synthesis of 1,2-Amino Tertiary Alcohols DOI

Zhong-Shan Teng,

Yu‐Rong Yang,

Xin-Yu Zhang

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 26, 2025

1,2-Amino alcohols are omnipresent in bioactive molecules. Conventional approaches to this motif require multistep reactions. Herein, we develop an electrochemical strategy for copper-catalyzed convergent paired electrolysis. By selectively cleaving the C-N bond of 2-aryl-1-tosylaziridines with electron-deficient aromatics as aryl source, 1,2-amino tertiary alcohol scaffold is rapidly constructed. This method features mild reaction conditions, large-scale preparation, and a lack sacrificial electrodes. Experimental studies DFT calculations indicate that tends toward radical cross-coupling.

Язык: Английский

Electrochemical radical-polar crossover: a radical approach to polar chemistry DOI

Zhoumei Tan,

Haonan Zhang, Kun Xu

и другие.

Science China Chemistry, Год журнала: 2023, Номер 67(2), С. 450 - 470

Опубликована: Ноя. 3, 2023

Язык: Английский

Процитировано

50
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

8
Photoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons DOI Creative Commons
Ping‐Fu Zhong, Jia‐Lin Tu,

Yating Zhao

и другие.

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

Опубликована: Окт. 16, 2023

Organoboron compounds are of high significance in organic synthesis due to the unique versatility boryl substituents access further modifications. The demand for incorporation moieties into molecular structures has witnessed significant progress, particularly C(sp3)-H borylation hydrocarbons. Taking advantage special characteristics photo/electrochemistry, we herein describe development an oxidative reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy. exhibits broad substrate scope (>57 examples), includes use simple alkanes, halides, silanes, ketones, esters nitriles as viable substrates. Notably, unconventional regioselectivity is achieved, with coupling site selectively located distal methyl group. Our method operationally easily scalable, offers a feasible approach one-step high-value organoboron building blocks from hydrocarbons, which would provide ample opportunities drug discovery.

Язык: Английский

Процитировано

38
Electrophotocatalytic tri- or difluoromethylative cyclization of alkenes DOI
Danna Chen,

Xuege Yang,

Dongyin Wang

и другие.

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

Процитировано

35
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

30
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
Photoredox streamlines electrocatalysis: photoelectrosynthesis of polycyclic pyrimidin-4-ones through carbocyclization of unactivated alkenes with malonates DOI

Minglin Tao,

Feng Qin,

Kaixing Gong

и другие.

Green Chemistry, Год журнала: 2024, Номер 26(7), С. 4199 - 4208

Опубликована: Янв. 1, 2024

A new photoelectrocatalytic mode permits the synthesis of polycyclic pyrimidin-4-ones through dehydrogenative cyclization malonates with unactivated alkenes.

Язык: Английский

Процитировано

15
Electrophotocatalysis for Organic Synthesis DOI

Matthew C. Lamb,

Keri A. Steiniger, Leslie Trigoura

и другие.

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

Процитировано

11
Self‐ or Acridinium‐Catalyzed Electrophotosynthesis of Thiocyanato Heterocycles from Activated Alkenes DOI

Kaixing Gong,

Yingchun Ma,

Ping Yu

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(10), С. 2352 - 2362

Опубликована: Апрель 5, 2024

Abstract While the emergence of electrophotochemistry provides opportunities, such a chemistry at this stage suffers from limited reaction types and high photocatalyst loadings. A self‐catalyzed electrophotosynthesis as well one with low loading is presented. These external‐oxidant‐free cyclizations are enabling applicable to range activated alkenes, affording diverse array thiocyanato heterocycles including 4‐pyrrolin‐2‐ones, isoquinoline‐1,3‐diones, indolo[2,1‐ ]isoquinolin‐6(5 H )‐ones, benzoimidazo[2,1‐ )‐ones indolin‐2‐ones, protocols amenable late‐stage diversification complex molecular architectures gram‐scale syntheses. Sunlight could serve light source, be conducted in an all‐solar‐driven mode using commercially available photovoltaic panel produce electricity.

Язык: Английский

Процитировано

10