Radical Decyanations of Unactivated Carbon‐CN Bonds: Recent Achievements and Mechanistic Studies DOI
Jiapian Huang, Zhiyuan Chen

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(13), P. 2058 - 2091

Published: May 17, 2023

Abstract Decyanation is an important process in the synthesis of aromatic molecules studies pharmaceutical research, medical and materials sciences. In late‐stage modifications privileged carbo/heterocyclic scaffolds, radical‐type decyanation techniques have been devised to date. As a result, chemistry cyano‐involved conversions, hotly debated subject over past few decades, has advanced significantly. The cyano group (CN), on other hand, rarely acknowledged as good reaction site due its thermodynamic robustness. most recent advancements catalytic radical protocols that CN behaved leaving made are surveyed this article. Following introduction number different modes, reactions used activate C−CN bonds primarily categorized, text herein divided into three groups: (1) photo‐catalyzed transformations, (2) electro‐catalyzed (3) transition‐metal‐catalyzed or metal‐free transformations. With emphasis systems synthetic applications bond activation, review will provide readers with overview reactions.

Language: Английский

Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry DOI
Laura Buglioni, Fabian Raymenants, Aidan Slattery

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2752 - 2906

Published: Aug. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Language: Английский

Citations

540
Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis DOI
Nicholas E. S. Tay, Dan Lehnherr, Tomislav Rovis

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

Citations

357
A general electron donor–acceptor complex for photoactivation of arenes via thianthrenation DOI Creative Commons
Kai Sun,

Anzai Shi,

Yan Liu

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(19), P. 5659 - 5666

Published: Jan. 1, 2022

General photoactivation of EDA complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane was discovered. This practical mode enables the generation aryl radicals for C–H functionalization arenes.

Language: Английский

Citations

126
Red Light-Based Dual Photoredox Strategy Resembling the Z-Scheme of Natural Photosynthesis DOI Creative Commons
Felix Glaser, Oliver S. Wenger

JACS Au, Journal Year: 2022, Volume and Issue: 2(6), P. 1488 - 1503

Published: June 10, 2022

Photoredox catalysis typically relies on the use of single chromophores, whereas strategies, in which two different light absorbers are combined, rare. In photosystems I and II green plants, separate chromophores P680 P700 both absorb independently one another, then their excitation energy is combined so-called Z-scheme, to drive an overall reaction that thermodynamically very demanding. Here, we adapt this concept perform photoredox reactions organic substrates with input red photons instead blue or UV light. Specifically, a CuI bis(α-diimine) complex combination situ formed 9,10-dicyanoanthracenyl radical anion presence excess diisopropylethylamine catalyzes ca. 50 dehalogenation detosylation reactions. This dual approach seems useful because less damaging has greater penetration depth than radiation. UV-vis transient absorption spectroscopy reveals subtle change solvent from acetonitrile acetone induces changeover mechanism, involving either dominant photoinduced electron transfer triplet-triplet pathway. Our study illustrates mechanistic complexity systems operating under multiphotonic conditions, it provides insights into how competition between desirable unwanted steps can become more controllable.

Language: Английский

Citations

74
Photo- and electro-chemical strategies for the activations of strong chemical bonds DOI
Xianhai Tian, Yuliang Liu, Shahboz Yakubov

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 263 - 316

Published: Dec. 7, 2023

The employment of light and/or electricity - alternatively to conventional thermal energy unlocks new reactivity paradigms as tools for chemical substrate activations. This leads the development synthetic reactions and a vast expansion spaces. review summarizes recent developments in photo- electrochemical activation strategies functionalization strong bonds particularly carbon-heteroatom (C-X)

Language: Английский

Citations

42
Radical relay cyclization/C–C bond formation of allyloxy-tethered aryl iodides with quinoxalin-2(1H)-ones via polysulfide anion photocatalysis DOI
Zhongyi Zhang, Yaqin Zhou, Jiehui Wang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(8), P. 1708 - 1713

Published: Jan. 1, 2024

A visible-light-induced radical relay cyclization/C-C bond formation of quinoxalin-2(1

Language: Английский

Citations

26
1,4‐Aminoarylation of Butadienes via Photoinduced Palladium Catalysis DOI Creative Commons
Yuan Cai,

Gaurav Gaurav,

Tobias Ritter

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 9, 2024

Abstract A visible‐light‐induced, three‐component palladium‐catalyzed 1,4‐aminoarylation of butadienes with readily available aryl halides and aliphatic amines has been developed, affording allylamines excellent E ‐selectivity. The reaction exhibits exceptional control over chemo‐, regio‐, stereoselectivity, a broad substrate scope, high functional group compatibility, as demonstrated by the late‐stage functionalization bioactive molecules. Mechanistic investigations are consistent photoinduced radical Pd(0)‐Pd(I)‐Pd(II)‐Pd(0) Heck‐Tsuji–Trost allylation cascade.

Language: Английский

Citations

21
Electro‐mediated PhotoRedox Catalysis for Selective C(sp3)–O Cleavages of Phosphinated Alcohols to Carbanions DOI
Xianhai Tian, Tobias A. Karl, Sebastian Reiter

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(38), P. 20817 - 20825

Published: June 24, 2021

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage C(sp

Language: Английский

Citations

103
Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation DOI Creative Commons
Shun Wang, Hua Wang,

Burkhard König

et al.

Chem, Journal Year: 2021, Volume and Issue: 7(6), P. 1653 - 1665

Published: May 28, 2021

Language: Английский

Citations

80
Light-Induced Single-Electron Transfer Processes involving Sulfur Anions as Catalysts DOI
Shun Wang, Hua Wang,

Burkhard König

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(38), P. 15530 - 15537

Published: Sept. 20, 2021

Photoredox catalysis has evolved as an attractive approach to enable a wide variety of chemical reactions with high selectivity under mild conditions. The development novel photocatalytic systems is key obtaining new reactivity and improving their catalytic performances. In this context, cost-effective organic anion-based photocatalysts have recently attracted increasing interest. particular, sulfur-based anionic catalysts are interest due unique redox properties. This Perspective highlights discusses recent advances in light-induced single-electron-transfer processes directly involving sulfur anions catalysts. content organized along the different photoinduced electron-transfer pathways between substrates.

Language: Английский

Citations

71