Organic Synthesis through Radical Innovation: Frustrated Radical Pairs† DOI
Zhibin Hu, Zengrui Cheng, Ning Jiao

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(10), P. 1157 - 1160

Published: Dec. 26, 2023

Abstract Frustrated Lewis Pairs (FLPs) represent a unique class of interactions in acid‐base chemistry, driven by spatial hindrance or incongruent orbital energy levels that hinder the formation effective coordination bonds. FLPs have received significant attention for their application activating small molecules and facilitating organic synthesis reactions. Recent developments led to emergence Radical (FRPs) as an extension radical family. FRPs are formed from through Single Electron Transfer (SET) exhibit ability activate variety chemical While research on is well‐established, investigations into reactions remain limited. This review highlights current state synthesis, delves mechanistic insights, explores potential, underscores challenges this emerging field.

Language: Английский

NIR-II emissive anionic copper nanoclusters with intrinsic photoredox activity in single-electron transfer DOI Creative Commons
Li‐Juan Liu, Mao‐Mao Zhang, Ziqi Deng

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 1, 2024

Abstract Ultrasmall copper nanoclusters have recently emerged as promising photocatalysts for organic synthesis, owing to their exceptional light absorption ability and large surface areas efficient interactions with substrates. Despite significant advances in cluster-based visible-light photocatalysis, the types of transformations that can catalyze remain limited date. Herein, we report a structurally well-defined anionic Cu 40 nanocluster emits second near-infrared region (NIR-II, 1000−1700 nm) after photoexcitation conduct single-electron transfer fluoroalkyl iodides without need external ligand activation. This photoredox-active efficiently catalyzes three-component radical couplings alkenes, iodides, trimethylsilyl cyanide under blue-LED irradiation at room temperature. A variety fluorine-containing electrophiles nucleophile be added onto an array including styrenes aliphatic olefins. Our current work demonstrates viability using readily accessible metal establish photocatalytic systems high degree practicality reaction complexity.

Language: Английский

Citations

12
Modulating β‐Keto‐enamine‐Based Covalent Organic Frameworks for Photocatalytic Atom‐Transfer Radical Addition Reaction DOI

Yuting Zhao,

Lei Li,

Jiyuan Zang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(24)

Published: Feb. 26, 2024

The atom-transfer radical addition (ATRA) reaction simultaneously forges carbon-carbon and carbon-halogen bonds. However, frequently-used photosensitizers such as precious transition metal complexes, or organic dyes have limitations in terms of their potential toxicity recyclability. Three β-ketoenamine-linked covalent frameworks (COFs) from 1,3,5-triformylphloroglucinol 1,4-phenylenediamines with variable transient photocurrent photocatalytic activity been prepared. A COF bearing electron-deficient Cl atoms displayed the highest toward ATRA polyhalogenated alkanes to give halogenated olefins under visible light at room temperature. This heterogeneous photocatalyst exhibited good functional group tolerance could be recycled without significant loss activity.

Language: Английский

Citations

3
p-Diarylboryl Halothiophenols as Multifunctional Catalysts via Photoactive Intramolecular Frustrated Lewis Pairs DOI

Takeru Kikura,

Y. B. Taura,

Yoshitaka Aramaki

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20425 - 20431

Published: July 8, 2024

p-Diarylboryl halothiophenols are developed and unequivocally characterized. Their photophysical properties catalytic performance unveiled by experimental theoretical investigations. This novel class of triarylboranes behaves as a Brønsted acid to generate the corresponding borylthiophenolate that can absorb visible light undergo intramolecular charge transfer form radical pair consisting boron anion thiyl radical, which acts single-electron reductant while engaging in hydrogen atom regenerate parent borylthiophenol. The synthetic relevance this mode action is demonstrated establishment unique catalysis integrates three different yet tunable functions single cycle, thereby allowing borylthiophenols solely promote assembly sterically congested 1,2-diols 1,2-aminoalcohol derivatives via radical–radical cross-coupling.

Language: Английский

Citations

3
Frustrated Lewis Pair-Promoted Organocatalytic Transformation of Hydrosilanes into Silanols with Water Oxidant DOI

Fuyu Xie,

Sutao Zhang,

Mo Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29373 - 29382

Published: Oct. 16, 2024

Owing to their unique properties, the silanols have attracted intense attention but remain challenging prepare from organocatalytic oxidation of hydrosilanes using H

Language: Английский

Citations

2
TBHP‐Mediated Hydroxyperfluoroalkylation of Alkenes with Perfluoroalkyl Iodides to Construct β‐Perfluoroalkyl Alcohols DOI
Jiantao Zhang, Weiming Zhu,

Renhua Su

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3572 - 3577

Published: April 10, 2024

Abstract A three‐component strategy for the synthesis of β‐perfluoroalkyl allyl alcohols from 1,3‐dienes is developed. diverse range synthetically valuable are obtained in moderate to high yields. Broad substrate scope and good functional group tolerance observed. This method also applicable mono‐olefins 1,3‐enynes. The control experiment results demonstrate that hydroxyl OH product comes TBHP. In addition, practicality mild reaction conditions make these synthetic transformations attractive organic synthesis.

Language: Английский

Citations

1
Frustrated Radical Pair‐Initiated Hydrodehalogenation of Alkyl and Aryl Halides Under Visible Light DOI Creative Commons

Fuyu Xie,

Jianghua He, Yuetao Zhang

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(18)

Published: May 6, 2024

Abstract Here we employed Al(C 6 F 5 ) 3 /Mes P frustrated radical pair (FRP) to catalyze hydrodehalogenation reaction. Through the initiation of FRP, stannane radicals were generated facilitate halogen‐atom transfer (XAT) process and proceed a wide range alkyl aryl halides under visible light at room temperature. Electron paramagnetic resonance (EPR) experiment, clock reaction coupled with control experiments provide solid evidence support mechanism. Moreover, this strategy can be applied synthesis pharmaceutical compounds, such as indoles quinolines well deuterated compounds.

Language: Английский

Citations

1
Synthetic Utilization of 2H-Heptafluoropropane: Ionic 1,4-Addition to Electron-Deficient Carbon–Carbon Unsaturated Bonds DOI Creative Commons
Y. Higashi,

Kotono Shima,

Mikiya Suzuki

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 3962 - 3969

Published: March 5, 2024

We have found a novel method for introducing heptafluoro-2-propyl CF(CF3)2 groups into carbon–carbon unsaturated bonds via nucleophilic reaction using 2H-heptafluoropropane as the source of groups. The involves addition anion, generated by treating with fluoride ion, to various electron-deficient compounds. This allows easy synthesis aliphatic compounds containing

Language: Английский

Citations

0
Lewis Acid-catalyzed Regioselective Addition of Allenoates to Indoles for Synthesis of Bisindolylesters DOI

Fuyu Xie,

Jianghua He, Yuetao Zhang

et al.

Chemical Research in Chinese Universities, Journal Year: 2024, Volume and Issue: unknown

Published: July 17, 2024

Language: Английский

Citations

0
Organic Synthesis through Radical Innovation: Frustrated Radical Pairs† DOI
Zhibin Hu, Zengrui Cheng, Ning Jiao

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(10), P. 1157 - 1160

Published: Dec. 26, 2023

Abstract Frustrated Lewis Pairs (FLPs) represent a unique class of interactions in acid‐base chemistry, driven by spatial hindrance or incongruent orbital energy levels that hinder the formation effective coordination bonds. FLPs have received significant attention for their application activating small molecules and facilitating organic synthesis reactions. Recent developments led to emergence Radical (FRPs) as an extension radical family. FRPs are formed from through Single Electron Transfer (SET) exhibit ability activate variety chemical While research on is well‐established, investigations into reactions remain limited. This review highlights current state synthesis, delves mechanistic insights, explores potential, underscores challenges this emerging field.

Language: Английский

Citations

0