Selective Ni(I)/Ni(III) Process for Consecutive Geminal C(sp3)–C(sp2) Bond Formation DOI Creative Commons
Xuejiao Li, Yu Gan, Yiyang Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

Ni-catalyzed multicomponent cross-couplings have emerged as a powerful strategy for efficiently constructing complex molecular architectures from diverse array of organic halides. Despite its potential, selectively forming multiple chemical bonds in single operation, particularly the realm cross-electrophile coupling catalysis, remains significant challenge. In this study, we developed consecutive open-shell reductive Ni enabling formation two geminal C(sp

Language: Английский

Alcohols as Alkyl Synthons Enabled by Photoredox-Catalyzed Deoxygenative Activation DOI

Tanumoy Mandal,

Samrat Mallick,

Malekul Islam

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13451 - 13496

Published: Aug. 26, 2024

Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.

Language: Английский

Citations

8
Aminoalkylation of Alkenes Enabled by Triple Radical Sorting DOI
William L. Lyon, Johnny Wang, Jesús Alcázar

et al.

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

Published: Jan. 9, 2025

The direct synthesis of C(sp3)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there strong impetus to develop new methods by which access sp3-rich from commercial feedstocks, such as alkenes. Herein, we report three-component aminoalkylation reaction utilizes the principles triple radical sorting regioselectively add N-centered and C-centered radicals across This process relies upon photoredox catalysis transform alkyl bromides reductively activated precursors into high-energy species redox-neutral fashion. A broad scope coupling partners demonstrated, multiple applications, including facile syntheses pharmacophoric substituted N-heterocycles.

Language: Английский

Citations

1
Visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes to access α, β-unsaturated ketones DOI

Xun Yang,

Yu‐Xuan Xiao, Ying Yin

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A general method for accessing α,β-unsaturated ketones through visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes has been developed.

Language: Английский

Citations

0
Non-enzymatic methylcyclization of alkenes DOI Creative Commons
Immanuel Plangger,

Elias Schmidhammer,

Sebastian Schaar

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Methyltransferases are a broad class of enzymes that catalyse the transfer methyl groups onto wide variety substrates and functionalities. In their most striking variant, bifunctional methyltransferase-cyclases both group alkenes induce cyclization (methylcyclization). Although recent years have seen substantial advances in methylation alkenes, especially hydromethylation, reactivity demonstrated by nature has yet to be developed into synthetically viable method. Here we report silver(I)-mediated electrophilic methylcyclization rivals selectivities found while not being limited inherent substrate specificity. Our method benefits from use commercial reagents, is applicable range substrates, including heterocycles, affords unique structures difficult access via conventional synthetic methods. Furthermore, computational studies been utilized unravel underlying mechanism ultimately support stepwise cationic reaction pathway with rate-limiting methyltransfer.

Language: Английский

Citations

0
Radical dehydroxylative C-glycosylation of 1-hydroxycarbohydrates enabled by photoredox catalysis DOI Creative Commons
Wenyan Shi,

Xingxiu Yan,

Wuyin Wang

et al.

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

Citations

0
Synergistic LMCT and Ni Catalysis for Methylative Cross-Coupling Using tert-Butanol: Modulating Radical Pathways via Selective Bond Homolysis DOI
Lingfei Duan, Yunzhi Lin, Qing An

et al.

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

Published: April 18, 2025

Ligand-to-metal charge transfer (LMCT) excitation has emerged as a potent strategy for the selective generation of heteroatom-centered radicals, yet its full potential in modulating open-shell radical pathways remains underexplored. Here, we present photocatalytic methylative cross-coupling reaction that capitalizes on synergistic interplay between LMCT and Ni catalysis, enabling use tert-butanol an efficient benign methylating reagent. The electron-deficient ligand 2,6-ditrifluoromethyl benzoate facilitates Ce(IV)-mediated bond scission tert-butanol, generating methyl is subsequently captured by catalytic cycle to form C-CH3 bonds. Under mild conditions, this affords methylation sp3 carbons adjacent carbonyls sp2 centers, demonstrating broad functional group tolerance applicability late-stage functionalization bioactive molecules. Additionally, trideuteromethylative coupling can be facilely achieved using commercial tert-butanol-d10. This approach circumvents need traditional tert-butoxy precursors, such peroxides, while strategically pathway favor β-scission suppress unwanted formation solution. Mechanistic studies reveal plays crucial role facilitating generation, supporting concerted Ce-OR β-C-C homolysis mechanism, further evidenced modulation regioselectivity alkoxy radical-mediated β-scission.

Language: Английский

Citations

0
Cobalt/Photoredox Dual-Catalyzed Cross-Radical Coupling of Alkenes via Hydrogen Atom Transfer and Homolytic Substitution DOI

Yuto Yamaguchi,

Yuuki Hirata, Kosuke Higashida

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4893 - 4897

Published: June 5, 2024

Cobalt-catalyzed metal hydride hydrogen atom transfer (MHAT) in combination with photoredox catalysis has emerged as a powerful synthetic method, owing to its redox nature and applicability various radical precursors. Herein, we describe cross-radical coupling reaction under cobalt/photoredox dual catalysis. MHAT homolytic substitution (SH2) processes enabled Markovnikov-selective hydrobenzylation of di/trisubstituted alkenes, affording products quaternary carbon center redox-neutral manner.

Language: Английский

Citations

2
Cross-Double Deoxygenative Carbon–Carbon Bond Formation between Benzyl Benzoates and Allylic Alcohols DOI
Zhongxian Li, Liwei Wang,

Tianlong Zeng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9496 - 9504

Published: June 10, 2024

Language: Английский

Citations

2
Metal-Hydride C–C Cross-Coupling of Alkenes Through a Double Outer-Sphere Mechanism DOI

Nathan Dao,

Xu-cheng Gan, Ryan A. Shenvi

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16106 - 16113

Published: June 26, 2024

This Synopsis covers recent reports of metal-catalyzed alkene functionalizations that likely involve iterative outer-sphere reactions in which the substrate reacts directly with a metal ligand instead center itself. Traditional hydride-catalyzed this latter pathway whereby forms part sphere (i.e. an inner-sphere reaction). In contrast, alkenes do not ligate so-called and react ligand. These transformations have proved crucial for synthesis high fraction sp3 (Fsp3) targets, especially hindered fragment couplings relevance to natural product space.

Language: Английский

Citations

1
Photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated olefins with aryl bromides DOI Creative Commons
Hongchao Liu, Xinyu Xu, Siyuan Tang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14865 - 14871

Published: Jan. 1, 2024

A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.

Language: Английский

Citations

1