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

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

3
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

10
Visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes to access α, β-unsaturated ketones DOI

Xun Yang,

Yuxuan 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
Aryl Acid-Alcohol Cross-Coupling: C(sp3)–C(sp2) Bond Formation from Nontraditional Precursors DOI

Eva Lin,

Johnny Wang,

Edna Mao

et al.

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

Published: April 23, 2025

Alcohols and aryl carboxylic acids are among the most commercially abundant, synthetically versatile, operationally convenient building blocks in organic chemistry. Despite their widespread availability, direct formation of C(sp3)-C(sp2) bonds from these functional groups remains a challenge. Recently, our group developed robust protocols to harness alcohols as alkyl radical precursors, but activation relatively unexplored. Herein, we describe merger N-heterocyclic carbene (NHC)-mediated deoxygenation nickel-mediated decarbonylation toward bond formation. The utility this method is demonstrated through synthesis diverse range aryl-alkyl cross-coupled products late-stage functionalization complex molecules, including drugs, natural products, biomolecules.

Language: Английский

Citations

0
Metallaphotocatalytic modular synthesis of masked arylaminomethyl trifluoromethyl ketones DOI Creative Commons
Yingde Jiang, Zhongwei Zhang, Chi Wai Cheung

et al.

Cell Reports Physical Science, Journal Year: 2025, Volume and Issue: unknown, P. 102564 - 102564

Published: April 1, 2025

Language: Английский

Citations

0
Recent synthetic methodology advancements towards all-carbon quaternary center formation and applications DOI

Taotao Ling,

Jose M. Garfias,

S. Lawson

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134711 - 134711

Published: May 1, 2025

Language: Английский

Citations

0
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

3