Nickel-Catalyzed Three-Component 1,1-Difunctionalization of Unactivated Alkenes with Quinoxaline/Naphthoquinone and Arylboronic Acids via Organometallic-Radical Relay DOI
Lingyu Wan,

S. Guo,

Fei Sun

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

A nickel-catalyzed intermolecular three-component 1,1-difunctionalization of unactivated alkenes with quinoxaline/naphthoquinone and arylboronic acids via organometallic-radical relay is developed. This efficient protocol provides a new method to access variety arylalkanes in moderate good yields broad substrate scope excellent functional group tolerance. The mechanistic studies provide insights into the mechanism origin chemo- regioselectivity as well confirm generation functionalized benzylic radicals.

Language: Английский

Regiodivergent Radical-Relay Alkene Dicarbofunctionalization DOI Creative Commons
Liu Z, Francesco D’Amico, Rubén Martı́n

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 28624 - 28629

Published: Oct. 10, 2024

Herein, we report a regiodivergent 1,n-dicarbofunctionalization of unactivated olefins enabled by Ni-catalyzed radical relay that forges both C(

Language: Английский

Citations

4
Recent progress in the organoselenium-catalyzed difunctionalization of alkenes DOI
Pei Qu, Gong‐Qing Liu

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing their intrinsic advantages, including low cost, toxicity, stability in both air and water, strong compatibility with diverse functional groups. The difunctionalization alkenes-the process incorporating two groups onto carbon-carbon double bond-has garnered particular interest within the chemical community its significant applications synthesis. Recently, organoselenium-catalyzed alkenes has emerged as an ideal powerful route obtain high-value vicinal difunctionalized molecules. This review emphasizes recent advancements this rapidly evolving field, focusing on scope, limitations, mechanisms various reactions.

Language: Английский

Citations

0
Nickel-Catalyzed Branched Hydroalkylation of Alkenes with Diazo Compounds DOI

Nikita Kvasovs,

Valeriia Iziumchenko, Alistair J. Sterling

et al.

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

Published: Feb. 25, 2025

A nickel-catalyzed, branched-selective hydroalkylation of alkenes using diazo compounds has been developed. This protocol enables the functionalization both activated and unactivated alkenes, in directed nondirected manners. Mono-, di-, trisubstituted can be effectively transformed. Highly diastereoselective hydroalkylations have also demonstrated. The method provides a novel approach for introducing an α-carbonyl moiety to which is currently inaccessible by existing methods. Preliminary mechanistic investigations suggest carbene-type mechanism, unusual nickel catalysis.

Language: Английский

Citations

0
Unusual 1,1‐Dicarboxylation Selectivity in the Domino Hydrocarboxylation of Alkynes with Formate and Application in Polyimide Photoresists DOI Open Access
Yaxin Sun, Peng Yang, Jian‐Biao Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

We report for the first time a photoinduced domino 1,1-dicarboxylation of alkynes synthesis malonic acid derivatives using cesium formate solution (80% w/w in water), which is different from previous 1,2-dicarboxylation methods that usually produce succinic acids. Cesium malonate precipitated directly diluted reaction mixture and was collected by filtration without further purification. Interestingly, solid with additional water led to mono-carboxylation product. The solubility alkaline environment are two key factors contributing outcome. A series acids, propionic acids drug intermediates were synthesized good yields. Mechanism experiments DFT calculations indicate formed through α-selective addition CO2 •- cinnamate intermediate. This method enables direct preparation water-soluble carboxylate-functionalized molecules polymers hydrophobic alkyne-containing precursors, showing potential usability photolithography semiconductor manufacturing.

Language: Английский

Citations

0
Metal‐catalyzed reductive alkylation of alkenes: From copper to alternative catalysts DOI

Deyuan Meng,

Jaesook Yun

Bulletin of the Korean Chemical Society, Journal Year: 2025, Volume and Issue: 46(4), P. 413 - 421

Published: April 1, 2025

Abstract In recent years, transition metal‐catalyzed reductive alkylation of alkenes has gained attention due to its ability circumvent the use unstable organometallic reagents by generating reactive intermediates in situ from stable precursors with enhanced reaction safety and efficiency. This review provides an overview advancements copper‐catalyzed alkenes, a particular focus on hydrosilanes diborons as stoichiometric reducing agents. Key topics include mechanistic insights, strategies for controlling regio‐ stereoselectivity both intra‐ intermolecular reactions, innovative catalyst designs selective product synthesis. Emerging trends such radical‐mediated transformations contributions alternative first‐row metals including nickel iron are also discussed.

Language: Английский

Citations

0
Direct Synthesis of 2-Hydroxytrifluoroethylacetophenones via Organophotoredox-Mediated Net-Neutral Radical/Polar Crossover DOI Creative Commons
Albert Gallego‐Gamo, Pau Sarró, Yingmin Ji

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11682 - 11692

Published: Aug. 1, 2024

Alkene difunctionalization is a very attractive tool in synthetic organic chemistry. Herein, we disclose an operationally and practically simple method to access 2-hydroxytrifluoroethylacetophenones from styrene derivatives via photoredox catalysis. This light-mediated transformation promotes the generation of 1-hydroxy-2,2,2-trifluoroethyl carbon-centered radical as key synthon, which undergoes Giese addition with styrenes followed by Kornblum oxidation process. The presented not only mild cost-effective, but also utilizes photocatalyst DMSO oxidant. Experimental investigations support operative mechanism net-neutral radical/polar crossover.

Language: Английский

Citations

3
Ni-catalysed remote C(sp3)–H functionalization using chain-walking strategies DOI
Ciro Romano, Rubén Martı́n

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

Citations

3
Organocatalytic radical aminoacylation of alkenes for β-aminoketone synthesis DOI

Ayisenbati Jialingbieke,

Xinying Hu,

Z. Liu

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 14, 2024

Language: Английский

Citations

2
Electrochemically Enabled Hydroxyphosphorylation of 1,3-Enynes to Access Phosphinyl-Substituted Propargyl Alcohols DOI
Li Zhu,

Peng-Wei Zhu,

Li‐Yan Hu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10796 - 10804

Published: July 19, 2024

Catalytic difunctionalization with the direct activation of (O)P-H bonds has been recently established as a potentially robust platform to generate valuable organophosphorus compounds. In terms 1,3-enynes, despite various catalytic methods developed for hydrophosphorylation, radical-mediated hetero-functionalization two different atoms less explored. this study, we disclosed an electrochemically induced hydroxyphosphorylation 1,3-enynes construction phosphinyl-substituted propargyl alcohols. The system involves both arylphosphine oxides and oxygen in ambient air no external metal or additive needed. use electrochemistry ensures regioselective, atom-economic eco-friendly process. This strategy highlights advantages mild reaction conditions, readily available starting materials broad substrate scope, showing its practical synthetic value organic synthesis.

Language: Английский

Citations

1
Nickel-Catalyzed Synthesis of Silaindanes via Sequential C–H Activating 1,5-Nickel Migration and C–Si Activating 1,4-Nickel Migration DOI
Donghyeon Lee,

Ikuya Fujii,

Ryo Shintani

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 907 - 916

Published: Dec. 30, 2024

Catalytic reactions involving 1,n-metal migration provide a powerful approach for the synthesis of complex molecular skeletons from simple precursors through activation unreactive bonds. In this work, nickel-catalyzed 3,3-disubstituted 1-silaindanes, silicon analogues valuable indanes, was developed by reaction 1,5-nickel via C–H bond and 1,4-nickel C–Si activation. It found that not only enabled at remote position but also controlled regioselectivity subsequent alkene insertion. The detailed mechanism investigated conducting deuterium labeling experiments DFT calculations. results obtained here demonstrate high potential catalytic nickel migrations activations useful cyclic organosilicon compounds.

Language: Английский

Citations

1