Copper-Catalyzed Disruption of a Cascade Reaction: Synthesis of γ-Ketoamides from Nitrones and Ynamides DOI Creative Commons

Abdullah S. Alshreimi,

Esther Shim,

Donald J. Wink

et al.

Published: June 19, 2024

A thermal dipolar cycloaddition and rearrangement reaction to form pyrrolines has been redirected towards the synthesis of γ-keto- γ-aldoamides from nitrones ynamides with a Cu(II) catalyst. copper-coordinated iminium intermediate is proposed initiate diastereoselective for C–C bond formation combination catalyst nitrone protecting group balance desired reactivity, diastereoselectivity, sensitivity hydrolysis. Reaction optimization described in addition scope, mechanistic studies, conversion γ-ketoamides 1,4-diones. This catalytic method showcases distinct copper-catalyzed reactivity N-alkenylnitrones 1,4-dicarbonyl compounds.

Language: Английский

Hierarchically Porous Poly(aryl thioether)s Through Dynamic Linker Engineering for Thiyl Radical Photocatalysis DOI Open Access
Sunil Kumar, Doyun Kim, Youngdong Song

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Abstract Hierarchically porous polymers offer large surface areas for enhanced catalytic activity, but incorporating photocatalytic sites into these pore channels remains challenging. Inspired by nature's disulfide bonds, which stabilize proteins and enable redox this study introduces a hierarchically poly(aryl thioether) photocatalyst via dual thioether linkages formed polycondensation. Thiolate intermediates undergo partial oxidation in air, yielding micro/mesoporous polymer with 757 m 2 g⁻¹ area, comparable to its microporous counterpart synthesized N₂. This structure exhibits adsorption capacity, as demonstrated tests volatile organic compounds mercury ions. The disulfide‐functionalized walls thiyl radical formation under visible light, achieving outstanding diphenylacetylene performance. heterogeneous surpasses homogeneous systems, showing >99% conversion efficiency 3.5% apparent quantum yield at 440 nm. pioneers linker engineering strategy integrate hierarchical photoactive generation single photocatalyst.

Language: Английский

Citations

0
Catalyst‐Free Direct Hydrocarbonation of Terminal Alkynes Toward E‐Alkene Substituted Stabilized Sulfoxonium Ylides DOI Creative Commons

Haiting Wu,

Yougen Xu,

Lin An

et al.

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

Amide and alkene moieties are frequently found in natural products privileged structures pharmaceuticals agrochemicals. Moreover, vinyl sulfoxonium ylide can be converted into a broad range of high-value compounds, thus they have been widely employed organic synthesis. However, the synthesis alkene-substituted amide-sulfoxonium ylides via intermolecular hydrocarbonation alkynes remains underexplored. This study describes development high-throughput approach to provide diverse functionalized E-alkene substituted (hetero)amide-sulfoxonium ylides. The reaction occurs under mild metal-free conditions, employing as highly effective nucleophiles, which participate Michael addition reactions with various alkynes, such esters, thioesters, ketones, amides, sulfones. low-cost, operationally simple has substrate scope, high functional group compatibility, excellent regio- stereoselectivity, making it suitable for transformation structurally complex molecules. Furthermore, obtained stabilized directly useful valuable 1,5-dicarbonyl thiabenzene 1-oxide compounds.

Language: Английский

Citations

0
Iodine-Catalyzed Room-Temperature Aerobic Oxidation of C(sp3)–H Bonds and Its Application in the Synthesis of Quinoxaline Derivatives DOI

Hanyu Xiong,

Longxing Wang,

Yuanyang Mu

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

An iodine-catalyzed aerobic oxidation reaction of C(sp3)-H bonds was established at room temperature. In this transformation, iodine acts as a Lewis acid catalyst, and the pyridine moiety in substrate plays crucial role. Under optimum conditions, picolyl ketone substrates were smoothly transformed into corresponding 1,2-dicarbonyl compounds, subsequent introduction 1,2-diaminobenzenes mixture led to formation various quinoxaline derivatives. This synthetic process does not use transition metals also features mild operational simplicity, gram-scale synthesis.

Language: Английский

Citations

0
Transition-Metal- and Photocatalyst-Free Photoinduced Formation of Carbon–Pnictogen (–N, –P) Bonds DOI
Rosalin Bhanja, Shyamal Kanti Bera, Prasenjit Mal

et al.

Synthesis, Journal Year: 2024, Volume and Issue: 56(17), P. 2627 - 2637

Published: April 2, 2024

Abstract Pnictogens, classified within group 15 elements, play a pivotal role in the constitution of diverse array drug molecules, natural products, and functional materials. Recent research has increasingly prioritized exploration mild conditions for synthesizing C–Pnictogen (C–N C–P) bonds, highlighting growing emphasis on efficient sustainable synthetic methodologies. This Short Review explores fundamental mechanisms, addresses constraints, assesses methodologies, underscoring potential photocatalyst- transition-metal-free photochemical reactions advancing sustainability. Divided into two segments, it encompasses recent advancements facilitating C–N C–P bond formation. 1 Introduction 2 Carbon–Nitrogen (C–N) Bond Formation 3 Carbon–Phosphorus (C–P) 4 Summary Outlook

Language: Английский

Citations

1
Regioselective Syntheses of 1,4- and 1,6-Dicarbonyl Compounds via Photoredox-Based Oxidative Heterocoupling of Enolsilanes with Oxygen as an Oxidant DOI

Xinyu Tan,

Zhilin Song,

Xin‐Ting Liang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(26), P. 5403 - 5408

Published: April 18, 2024

A photoredox-based oxidative heterocoupling of enolsilanes to the corresponding 1,4- and 1,6-dicarbonyl compounds was developed by using Mes-Acr+BF4– as photocatalyst, oxygen used oxidant. This newly chemistry adheres principles atom economy, step redox making it a concise efficient method.

Language: Английский

Citations

1
N‐Halosuccinimide‐CeCl3 Transient Charge‐Transfer Complexes as Semi Heterogeneous Photocatalyst in Cyclization of N‐Propargylamides DOI
Sathi Sahoo, Tarun Kumar Dinda, Prasenjit Mal

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(57)

Published: Aug. 1, 2024

In this work, we used photoinert anhydrous cerium(III) chloride, to form a transient charge-transfer (CT) complex with NXS (N-bromosuccinimide or NBS and N-iodosuccinimide NIS) in acetonitrile. These CT complexes acted as semi-heterogeneous photocatalyst. allowed the Ce(III) ions absorb light, turning them into strong electron donors that transferred electrons NXS. This created halide radicals from radical anions, helping turn N-propargylamides oxazole aldehydes. Experiments DMPO spin-trapping showed radical-based mechanism followed single transfer (SET) pathway. Notably, CeCl

Language: Английский

Citations

1
λ3-Iodane-Mediated Umpolung of Ketone and Enolate to Enolonium DOI
Keshaba Nanda Parida

Current Organic Chemistry, Journal Year: 2024, Volume and Issue: 28(8), P. 573 - 575

Published: April 1, 2024

Language: Английский

Citations

0
Copper-Catalyzed Disruption of a Cascade Reaction: Synthesis of γ-Ketoamides from Nitrones and Ynamides DOI Creative Commons

Abdullah S. Alshreimi,

Esther Shim,

Donald J. Wink

et al.

Published: April 30, 2024

A thermal dipolar cycloaddition and rearrangement reaction to form pyrrolines has been redirected towards the synthesis of γ-ketoamides from nitrones ynamides with a Cu(II) catalyst. An iminium N,O-dialkenylhydroxylamine intermediate is proposed initiate diastereoselective C–C bond formation combination copper catalyst nitrone protecting group balance desired reactivity, diastereoselectivity, sensitivity hydrolysis. Reaction optimization described in addition scope, mechanistic studies, conversion 1,4-diones. This catalytic method controls central 1,4-dicarbonyl compounds showcases unique reactivity N-alkenylnitrones for accessing these molecules.

Language: Английский

Citations

0
Copper-Catalyzed Disruption of a Cascade Reaction: Synthesis of γ-Ketoamides from Nitrones and Ynamides DOI Creative Commons

Abdullah S. Alshreimi,

Esther Shim,

Donald J. Wink

et al.

Published: June 19, 2024

A thermal dipolar cycloaddition and rearrangement reaction to form pyrrolines has been redirected towards the synthesis of γ-keto- γ-aldoamides from nitrones ynamides with a Cu(II) catalyst. copper-coordinated iminium intermediate is proposed initiate diastereoselective for C–C bond formation combination catalyst nitrone protecting group balance desired reactivity, diastereoselectivity, sensitivity hydrolysis. Reaction optimization described in addition scope, mechanistic studies, conversion γ-ketoamides 1,4-diones. This catalytic method showcases distinct copper-catalyzed reactivity N-alkenylnitrones 1,4-dicarbonyl compounds.

Language: Английский

Citations

0