Applications of Organosilanes in Visible Light‐induced Catalytic Asymmetric Reactions

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: March 27, 2024

Abstract Over the past decades, visible light‐mediated photocatalysis has found a mainstream of applications in synthetic chemistry. Organosilanes have been proven to be useful class electron donors generate highly active radical species via photoinduced single transfer oxidation/fragmentation sequence, which may undergo follow‐up coupling or addition process. This minireview highlights comprehensive advances organosilanes photoredox catalyzed asymmetric organic synthesis, with particular emphasis placed on reaction mechanisms. We hope that this review will inspire further design and development new reactions such readily accessible reagents.

Language: Английский

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Enantioselective Desymmetrization of Biaryls via Cooperative Photoredox/Brønsted Acid Catalysis and Its Application to the Total Synthesis of Ancistrobrevolines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 5, 2025

Photoredox catalysis has emerged as a powerful tool for forming and breaking chemical bonds, further taking hold with its integration asymmetric catalysis. While the dual-catalytic approach led to successful examples of control stereogenic centers, axes remained underexplored. In this study, an acylimine intermediate was generated through photoredox catalysis, symmetric substrate, 2-arylresorcinol, desymmetrized aid chiral phosphoric acid Using approach, center axis were successfully controlled provide natural-product-driven compound. The origins enantioselectivity diastereoselectivity investigated density functional theory study four possible enantiodetermining transition states. Consequently, first total syntheses ring-contracted naphthylisoquinoline alkaloid ancistrobrevolines A B accomplished concisely. This provides not only novel methodology strategy synthesize alkaloids but also direction advance catalytic research synthesis studies.

Language: Английский

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Photoinduced Enantioselective Transformations via o-Quinodimethane Intermediates

Tetrahedron Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100131 - 100131

Published: April 1, 2025

Language: Английский

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Enantioselective and Band-Gap Modulation in Photocatalysis of Metal-Free Chiral Carbon Dots

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(15), P. 19379 - 19390

Published: April 3, 2024

Photodriven chiral catalysis is the combination of photocatalysis and considered one cleanest most efficient methods for synthesis compounds or drugs. Furthermore, due to potential metal contamination associated with metal-based catalysts, metal-free photocatalysts are ideal candidates. In this work, we demonstrate that carbon dots (CDs) exhibit size-dependent enantioselective photocatalytic activity. Using serine as raw material, CDs well-defined structures average sizes 2.22, 3.01, 3.70, 4.77, 7.21 nm were synthesized using electrochemical method. These possess band gaps photoresponsive catalytic activity toward oxidation dihydroxyphenylalanine (DOPA). Under light-assisted conditions, (L72, 500 μg/mL) high selectivity (selectivity factor: 2.07) maintain a certain level (1.34 μM/min) even at low temperature 5 °C. The arises from their photoelectrons reducing O2 generate O2-, active oxygen species DOPA oxidation. enantioselectivity attributed differential adsorption capabilities enantiomers. This study provides new approach designing enantioselectivity.

Language: Английский

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Modular Assembly of Acridines by Integrating Photo‐Excitation of o‐Alkyl Nitroarenes with Copper‐Promoted Cascade Annulation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Acridine frameworks stand as pivotal architectural elements in pharmaceuticals and photocatalytic applications, owing to their chemical adaptability, biological activity, unique excited‐state dynamics. Conventional synthetic routes often entail specialized starting materials, anaerobic or moisture‐free conditions, elaborate multi‐stage manipulations for incorporating diverse functionalities. Herein, we present a convergent approach integrating photo‐excitation of readily available ortho ‐alkyl nitroarenes with copper‐promoted cascade annulation. This innovative system enables an aerobic, one‐pot reaction o‐ alkyl arylboronic acids, thereby streamlining the modular construction wide array acridine derivatives various functional groups. encompasses symmetrical, unsymmetrical polysubstituted varieties, some which are otherwise exceptionally difficult synthesize. Furthermore, it significantly improves production structurally varied acridinium salts, featuring enhanced photophysical properties, high excited state potentials ( E * red =2.08–3.15 V), exhibiting superior performance intricate photoredox transformations.

Language: Английский

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Modular Assembly of Acridines by Integrating Photo‐Excitation of o‐Alkyl Nitroarenes with Copper‐Promoted Cascade Annulation

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(42)

Published: July 23, 2024

Abstract Acridine frameworks stand as pivotal architectural elements in pharmaceuticals and photocatalytic applications, owing to their chemical adaptability, biological activity, unique excited‐state dynamics. Conventional synthetic routes often entail specialized starting materials, anaerobic or moisture‐free conditions, elaborate multi‐stage manipulations for incorporating diverse functionalities. Herein, we present a convergent approach integrating photo‐excitation of readily available ortho ‐alkyl nitroarenes with copper‐promoted cascade annulation. This innovative system enables an aerobic, one‐pot reaction o‐ alkyl arylboronic acids, thereby streamlining the modular construction wide array acridine derivatives various functional groups. encompasses symmetrical, unsymmetrical polysubstituted varieties, some which are otherwise exceptionally difficult synthesize. Furthermore, it significantly improves production structurally varied acridinium salts, featuring enhanced photophysical properties, high excited state potentials ( E * red =2.08–3.15 V), exhibiting superior performance intricate photoredox transformations.

Language: Английский

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Proline-based Organocatalyst for the Synthesis of Arylidene Benzofuranone Intermediates Enabling the Construction of Aurone-derived Azadienes

Current Organic Chemistry, Journal Year: 2024, Volume and Issue: 29(2), P. 127 - 134

Published: Aug. 26, 2024

: Organocatalysis has been recognized as a part of chemical research for long time, and it gained significant attention in catalysis recent decades. Amine catalyst is substantial type organocatalysis, successively employed the activation carbonyl compounds. This manuscript delves into exploration proline-based organocatalyst synthesis arylidene benzofuranone intermediates, critical step that facilitates subsequent construction aurone-derived azadienes. In this work, we successfully reported intermediates through Aldol condensation with different aldehydes enabled by proline-derived organic catalysts. To achieve strategy, six examples amine organocatalysts (A1-A6) were evaluated to showcase optimal transformation. Moreover, further interesting azadiene substrates its reaction TsNH2. Notably, using A6 resulted delivery product best yield (94% isolated yield). Under optimized conditions, aromatic heterocyclic containing effectively tolerated generate corresponding which converted products high excellent yield. The claimed structures confirmed spectral analysis.

Language: Английский

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Photo‐induced three‐component reaction for the construction of α‐tertiary amino acid derivatives

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(70)

Published: Sept. 21, 2024

Abstract The synthesis of α‐tertiary amino acids (ATAAs), which are pivotal components in natural metabolism and pharmaceutical innovation, continues to attract significant research interest. Despite substantial advancements, the pursuit a facile, versatile, resource‐efficient methodology remains an area active development. In this work, we introduce visible light‐triggered three‐component reaction involving readily available nitrosoarenes, N ‐acyl pyrazoles, allyl or (bromomethyl)benzenes under mild conditions. This approach enables straightforward assembly wide array ATAA derivatives (42 examples) commendably high yields (up 89 %). Mechanistic investigations elucidate that proceeds through dehydration condensation between nitrosoarenes pyrazoles generate ketimine intermediates. is followed by light‐driven halogen atom transfer (XAT) process radical addition, culminating formation desired products. showcases excellent functional group compatibility late‐stage derivatization potential, offering new insights avenues for analogs.

Language: Английский

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