Transition-Metal-Free Anti-Markovnikov Hydroarylation of Alkenes with Aryl Chlorides through Consecutive Photoinduced Electron Transfer DOI
Xu-Dong Mao, Miaomiao Li, Pengfei Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(6), P. 1265 - 1270

Published: Feb. 6, 2024

The hydroarylation of alkenes has emerged as a powerful strategy for arene functionalization. However, aryl chlorides remain large challenge in this type reaction due to the chemical inertness C(sp2)–Cl bond and high negative reduction potential. Herein, we report an anti-Markovnikov radical with via visible-light photoredox catalysis. key reactive radicals can be efficiently achieved from by consecutive photoinduced electron transfer. This transition-metal-free protocol features mild conditions, wide substrate scope, functional group tolerance, producing diverse range linear alkylarenes moderate good yields. is proposed proceed through radical-polar crossover pathway.

Language: Английский

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

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 19, P. 1055 - 1145

Published: July 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.

Language: Английский

Citations

27
Recent Advances in Dearomative Partial Reduction of Benzenoid Arenes DOI

De‐Hai Liu,

Jiajia Ma

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 14, 2024

Abstract Dearomative partial reduction is an extraordinary approach for transforming benzenoid arenes and has been well‐known many decades, as exemplified by the dehydrogenation of Birch hydroarylation Crich addition. Despite its remarkable importance in synthesis, this field experienced slow progress over last half‐century. However, a revival observed with recent introduction electrochemical photochemical methods. In Minireview, we summarize advancements dearomative arenes, including dihydrogenation, hydroalkylation, arylation, alkenylation, amination, borylation others. Further, intriguing utilization synthesis natural products also emphasized. It anticipated that Minireview will stimulate further arene transformations.

Language: Английский

Citations

13
Cyclic Amine Synthesis via Catalytic Radical‐Polar Crossover Cycloadditions DOI
Ying Zhang, Shusheng Chen, Kai‐Dian Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 29, 2024

Abstract The rapid assembly of valuable cyclic amine architectures in a single step from simple precursors has been recognized as an ideal platform term efficiency and sustainability. Although vast number studies regarding synthesis reported, new synthetic disconnection approaches are still high demand. Herein, we report catalytic radical‐polar crossover cycloaddition to triggered primary sulfonamide under photoredox condition. This newly developed disconnection, comparable established approaches, will allow construct β, β‐disubstituted β‐monosubstituted derivatives efficiently. study highlights the unique utility bifunctional reagent, which acts radical precursor nucleophile. open‐shell methodology demonstrates broad tolerance various functional groups, drug natural products economically sustainable fashion.

Language: Английский

Citations

12
Photoinduced Pd-Catalyzed Dearomative 2,5-Difunctionalizition of Furans via Cascade C–C/C–O Bond Formation DOI

Fen Long,

Kai Jiang,

Weiwei Song

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(5), P. 1083 - 1087

Published: Jan. 26, 2024

We report an efficient and mild approach for radical dearomatization via photoinduced palladium-catalyzed reaction of three components (i.e., furans, alcohols, bromoalkanes). In this strategy, various functionalized spiro-heterocycles were prepared from furans in one step cascade C–C/C–O bond formation under redox neutral conditions.

Language: Английский

Citations

9
Photocatalytic Cyclization Cascades by Radical Relay toward Pyrrolo[1,2-a]indoles: Synthesis, Mechanism, and Application DOI

Chen He,

Qi Wang,

Xiaoyang Zhou

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3509 - 3524

Published: Feb. 16, 2024

A photocatalytic annulation cascade of unactivated N-alkene-linked indoles with Langlois' reagent by a radical relay is developed at room temperature under blue LED irradiation. The reaction afforded series tri/difluoromethylated pyrrolo[1,2-a]indoles in moderate to good yields. DFT study suggests that the ascribed rhodamine 6G-induced cyclization involving vinyl addition-radical and hydrogen-atom-abstraction (HAA) processes, interestingly, are applied as fluorescent dyes into fluorescence spectrum live-cell imaging. This paper represents an initial example on cascades HAA process.

Language: Английский

Citations

9
Dearomative 1,4-Difunctionalization of Non-Activated Arenes Enabled by Boryl Radical-Mediated Halogen-Atom Transfer DOI
Chengliang Deng, Hao Wu,

Sheng Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1294 - 1304

Published: Jan. 7, 2025

Given the widespread presence of spirocyclic scaffolds in natural products and pharmacologically relevant synthetic compounds, development efficient methodologies for their construction holds great importance medicinal chemistry pharmaceutical research. In this study, a general photochemical dearomative spirocyclization nonactivated arenes has been established. The key to method lies ability amine-borane radicals activate aryl bromides iodides via halogen-atom transfer, thereby allowing conversion halides into corresponding subsequent chemodivergent transformations. remarkable compatibility versatility 1,4-difunctionalization is showed by rapid assembly structurally diverse 1,4-cyclohexadiene-based spirocycles incorporating oxindole, indoline, or dihydrobenzofuran subunits. Moreover, potential utility protocol exemplified formal total synthesis vasopressin V2 receptor antagonist Satavaptan.

Language: Английский

Citations

1
Visible-Light-Induced Dearomatization via [2+2] Cycloaddition or 1,5-Hydrogen Atom Transfer: Divergent Reaction Pathways of Transient Diradicals DOI
Min Zhu, Xiǎo Zhang, Chao Zheng

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(21), P. 12618 - 12626

Published: Sept. 28, 2020

Visible-light-induced dearomatization reaction via energy-transfer mechanism is an emerging strategy for the synthesis of highly strained polycyclic molecules. Transient, high-energy diradical species are typically involved in this type as key intermediates. Herein, we report visible-light-induced divergent indole-tethered O-methyl oximes, which reactions open-shelled singlet intermediates toward competitive [2 + 2] cycloaddition or 1,5-hydrogen atom transfer can be achieved with exclusive selectivity. The has been well supported by a series experimental and computational investigations. allow facile structurally appealing indoline-fused azetidines related molecules high efficiency.

Language: Английский

Citations

70
Intermolecular Dearomatization of Naphthalene Derivatives by Photoredox‐Catalyzed 1,2‐Hydroalkylation DOI

Yuan‐Zheng Cheng,

Xu‐Lun Huang,

Weihui Zhuang

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(41), P. 18062 - 18067

Published: July 3, 2020

An intermolecular hydroalkylative dearomatization of naphthalenes with commercially available α-amino acids is achieved via visible-light photoredox catalysis. With an organic photocatalyst, a series multi-substituted 1,2-dihydronaphthalenes are obtained in good-to-excellent yields. Intriguingly, by tuning the substituents at C2 position naphthalenes, formal dearomative [3+2] cycloadditions occur exclusively dearomatization-cyclization sequence. This overall redox-neutral method features mild reaction conditions, good tolerance functionalities, and operational simplicity. Diverse downstream elaborations products demonstrated. Preliminary mechanistic studies suggest involvement radical-radical coupling pathway.

Language: Английский

Citations

56
Deacylation-aided C–H alkylative annulation through C–C cleavage of unstrained ketones DOI
Xukai Zhou, Yan Xu, Guangbin Dong

et al.

Nature Catalysis, Journal Year: 2021, Volume and Issue: 4(8), P. 703 - 710

Published: Aug. 2, 2021

Language: Английский

Citations

52
Acridinium Salts and Cyanoarenes as Powerful Photocatalysts: Opportunities in Organic Synthesis DOI
Anis Tlili, Sami Lakhdar

Angewandte Chemie, Journal Year: 2021, Volume and Issue: 133(36), P. 19678 - 19701

Published: April 22, 2021

Abstract The use of organic photocatalysts has revolutionized the field photoredox catalysis, as it allows access to reactivities that were traditionally restricted transition‐metal photocatalysts. This Minireview reports recent developments in acridinium ions and cyanoarene derivatives synthesis. activation inert chemical bonds well late‐stage functionalization biorelevant molecules are discussed, with a special focus on their mechanistic aspects.

Language: Английский

Citations

49