Synthetic Methods Driven by the Photoactivity of Electron Donor–Acceptor Complexes

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(12), P. 5461 - 5476

Published: March 5, 2020

The association of an electron-rich substrate with electron-accepting molecule can generate a new molecular aggregate in the ground state, called electron donor-acceptor (EDA) complex. Even when two precursors do not absorb visible light, resulting EDA complex often does. In 1952, Mulliken proposed quantum-mechanical theory to rationalize formation such colored complexes. However, and besides few pioneering studies 20th century, it is only past years that photochemistry has been recognized as powerful strategy for expanding potential visible-light-driven radical synthetic chemistry. Here, we explain why this photochemical approach was overlooked so long. We critically discuss historical context, scientific reasons, serendipitous observations, landmark discoveries were essential progress field. also outline future directions identify key advances are needed fully exploit photochemistry.

Language: Английский

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Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(2), P. 766 - 897

Published: Dec. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Language: Английский

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Rare‐Earth Incorporated Alloy Catalysts: Synthesis, Properties, and Applications

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(16)

Published: March 12, 2021

Abstract To improve the performance of metallic catalysts, alloying provides an efficient methodology to design state‐of‐the‐art materials. As emerging functional materials, rare‐earth metal compounds can integrate unique orbital structure and catalytic behavior rare earth elements into Such containing alloy catalysts proffer opportunity tailor electronic properties, tune charged carrier transport, synergize surface reactivity, which are expected significantly stability catalysis. Despite its significance, there only few reviews on alloys or related topics. This review summarizes composition, synthesis, applications in field Subsequent comprehensively summarizing constructively discussing existing work, challenges possibilities future research compound materials evaluated.

Language: Английский

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Recent Advances in the Construction of Spiro Compounds via Radical Dearomatization

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(21), P. 4446 - 4461

Published: July 15, 2020

Abstract The field in dearomatization of aromatic compounds for the construction spirocycle has been developed rapidly over last two decades and it provides alternative synthetic method without using extra stoichiometric amounts chemical oxidants or reductants. In addition, radical cascade reactions alkenes alkynes that produce multiple bonds one‐step are significant direct efficient building complex molecules. By combining these concepts, opens a new powerful avenue accessing These have well explored past decade. As result, we summarize recent eventful advances this growing area as review, which typical examples listed mechanism also discussed. magnified image

Language: Английский

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Carbon–sulfur bond formation via photochemical strategies: An efficient method for the synthesis of sulfur-containing compounds

Chinese Chemical Letters, Journal Year: 2021, Volume and Issue: 33(4), P. 1798 - 1816

Published: Sept. 27, 2021

Language: Английский

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Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

Beilstein Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 17, P. 771 - 799

Published: April 6, 2021

The reversible, weak ground-state aggregate formed by dipole–dipole interactions between an electron donor and acceptor is referred to as electron-donor–acceptor (EDA) complex. Generally, upon light irradiation, the EDA complex turns into excited state, causing transfer give radicals initiate subsequent reactions. Besides external energy source, reactions involving participation of complexes are mild, obviating transition metal catalysts or photosensitizers in majority cases line with theme green chemistry. This review discusses synthetic concerned well mechanisms that have been shown over past five years.

Language: Английский

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Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 10(4), P. 711 - 748

Published: Feb. 11, 2021

Abstract Photocatalyzed organic synthesis transformation is a remarkable green synthetic strategy because of the advantages operational simplicity, high chemoselectivities, cheap, and environmental benignancy, along with extensive applications in fields organic, pharmaceutical functional material chemistry. Generally, photoredox catalysts or photosensitizers are necessary for generation their excited states to perform successive oxidative reductive reactions through single electron transfer (SET) energy (ET) process. Furthermore, exploration colored donor‐acceptor (EDA) complex charge (CT) between an electron‐rich electron‐poor substrate provides chance deliver intermediate under irradiation light, resulting formation radical activate species induce various reactions. These were performed without need any external photocatalysts mild reaction conditions. Herein, this review focuses on recent progress photoinduced addition reactions, borylations, radical‐radical cross‐coupling degradation cascade cyclization via EDA complexes. We highlight these novel methodologies applications, as well mechanisms. This will help provide references medicinal chemists who charmed by photochemical transformations based

Language: Английский

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Visible-Light Photoredox-Catalyzed Intermolecular α-Aminomethyl/Carboxylative Dearomatization of Indoles with CO₂ and α-Aminoalkyl Radical Precursors

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 467 - 472

Published: Jan. 5, 2024

Disclosed here is a visible-light photoredox-catalyzed intermolecular sequential α-aminomethyl/carboxylative dearomatization of indoles with CO2 and α-aminoalkyl radical precursors, affording series functionalized indoline-3-carboxylic acids lactams in good yields high regioselectivity. This multicomponent reaction provides green facile method for the synthesis diverse indolines by using as carboxylic carbonyl source.

Language: Английский

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Functionalization of Pyridinium Derivatives with 1,4-Dihydropyridines Enabled by Photoinduced Charge Transfer

Organic Letters, Journal Year: 2020, Volume and Issue: 22(21), P. 8730 - 8734

Published: Oct. 26, 2020

By exploiting electron donor–acceptor (EDA) complexes between 1,4-dihydropyridines and N-amidopyridinium salts under visible light irradiation, we discovered that photoinduced intermolecular charge transfer induces a single-electron event without requiring photocatalyst for the facile functionalization of pyridines. The generality this method is amenable to various types radical precursors generate structurally different radicals such as alkyl, acyl, carbamoyl radicals, ultimately providing access synthetically valuable C4-functionalized A broad range functional groups are well accommodated mild metal-free conditions, synthetic utility present showcased by late-stage variety biologically relevant pyridine-based compounds, pharmaceuticals, peptide feedstocks.

Language: Английский

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Electrochemical Trifluoromethylthiolation and Spirocyclization of Alkynes with AgSCF₃: Access to SCF₃-Containing Spiro[5,5]trienones

Organic Letters, Journal Year: 2021, Volume and Issue: 23(17), P. 6691 - 6696

Published: Aug. 16, 2021

A novel and efficient strategy for trifluoromethylthiolation dearomatization of activated alkynes with stable readily available AgSCF3 has been developed. Reported herein is the unprecedented electrochemical generation SCF3 radical in absence persulfate synthesis SCF3-containing spiro[5,5]trienones good yields via a 6-exo-trig cyclization.

Language: Английский

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