Copper-catalysed oxidative C–H/C–H coupling between olefins and simple ethers

Liu, Dong; Liu, Chao; Li, Heng; Lei, Aiwen

doi:10.1039/c4cc00867g

Cited by 181 publications

(72 citation statements)

References 61 publications

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“…Without PPh 3 work up at room temperature, β-peroxylsulfone could be readily isolated in an excellent yield. 18 O isotope labeling experiments revealed that oxygen atom in the product came from dioxygen (eq 9).…”

Section: Model III In Radical Oxidativementioning

confidence: 99%

Recent Advances of Transition-Metal Catalyzed Radical Oxidative Cross-Couplings

2014

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CONSPECTUS: Oxidative cross-coupling reactions between two nucleophiles are a powerful synthetic strategy to synthesize various kinds of functional molecules. Along with the development of transition-metal-catalyzed oxidative cross-coupling reactions, chemists are applying more and more first-row transition metal salts (Fe, Co, etc.) as catalysts. Since first-row transition metals often can go through multiple chemical valence changes, those oxidative cross-couplings can involve single electron transfer processes. In the meantime, chemists have developed diverse mechanistic hypotheses of these types of reactions. However, none of these hypotheses have led to conclusive reaction pathways until now. From studying both our own work and that of others in this field, we believe that radical oxidative cross-coupling reactions can be classified into four models based on the final bond formations. In this Account, we categorize and summarize these models. In model I, one of the starting nucleophiles initially loses one electron to generate its corresponding radical under oxidative conditions. Then, bond formations between this radical and another nucleophile create a new radical, [Nu(1)-Nu(2)](•), followed by a further radical oxidation step to generate the cross-coupling product. The radical oxidative alkenylation with olefin, radical oxidative arylative-annulation, and radical oxidative amidation are examples of this model. In model II, one of the starting nucleophiles loses its two electrons via two steps of single-electron-transfer to generate an electrophilic intermediate, followed by a direct bond formation with the other nucleophile. For example, the oxidative C-O coupling of benzylic sp(3) C-H bonds with carboxylic acids and oxidative C-N coupling of aldehydes with amides are members of this model group. For model III, both nucleophiles are oxidized to their corresponding radicals. Then, the radicals combine to form the final coupling product. The dioxygen-involved radical oxidative cross-couplings between sulfinic acids and olefins or alkynes belong to this bond formation model. Lastly, in model IV, one nucleophile loses two electrons to generate an electrophilic intermediate, while the other nucleophile loses one electron to generate a radical. Then, a bond forms between the cation and the radical to generate a cationic radical, followed by a one-electron reduction to afford the final coupling product. The oxidative coupling between arylboronic acids and simple ethers was classified in this model. At the current stage, there are only a few examples presented for models III and IV, but they represent two types of potentially important transformations. More and more examples of these two models will be developed in the future.

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Section: Model III In Radical Oxidativementioning

confidence: 99%

Recent Advances of Transition-Metal Catalyzed Radical Oxidative Cross-Couplings

2014

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“…However, satisfactory monolithic columns were not successfully synthesized. Based on Zou's report [22], we chose 1-propanol/DEGDE as porogenic systems. As a result, available monolithic columns were obtained.…”

Section: Optimization Of Preparation Conditions Of Imidazolium-based mentioning

confidence: 99%

Facile one‐pot preparation of a novel imidazolium‐based monolith by thiol–ene click chemistry for capillary liquid chromatography

et al. 2016

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In this work, a novel imidazolium-based monolith was fabricated through a simple route. With 1-vinyl-3-octadecylimidazolium bromide and ethylene dimethacrylate as monomers, pentaerythritol tetra-(3-mercaptopropionate) as crosslinker, AIBN as thermal initiator, the monolith was facilely fabricated by one-pot thiol-ene click chemistry. The influences of both the content of monomer/crosslinker and porogenic systems on the morphology, and permeability of the monolith were studied. The optimal reaction conditions were used to prepare a homogeneous and permeable monolith. The optimal preparation of monolithic column was characterized by scanning electron microscopy, Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis. High efficiency and quick separation of alkylbenzenes, styrene and ethylbenzene, polycyclic aromatic hydrocarbon, phenols, anilines, and aromatic acids were achieved. The minimum plate height of this monolith were determined as 11.42 μm for thiourea and 13.26 μm for benzene. All results indicated that thiol-ene click chemistry provides a quick way for the fabrication of imidazolium-based monolith.

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“…Polyhedral oligomeric silsesquioxane (POSS) based monoliths have recently been proposed as a new hybrid monolith family in RP chromatography applications carried out in nano/micro-liquid chromatography systems [6][7][8][9][10][11][12][13][14][15][16][17]. These monoliths with high cross-linking density mostly exhibit retention-independent chromatographic separation efficiency and also high mechanical and chemical resistance.…”

Section: Introductionmentioning

confidence: 99%

“…These monoliths with high cross-linking density mostly exhibit retention-independent chromatographic separation efficiency and also high mechanical and chemical resistance. In addition to all these features, POSS-based monoliths are compatible with thiol-en chemistry, a novel approach in the literature, which allows the functionalization of a monolith by a one-pot process involving hydrophilic or hydrophobic ligands having single or multiple thiol groups [15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Alkanethiol‐functionalized organosilicon monoliths for nano‐reversed‐phase liquid chromatography

2018

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Organosilicon monoliths carrying chromatographic ligands with different alkyl chain lengths were obtained by thiol-methacrylate photopolymerization. The use of thiol-ene chemistry in the presence of a main monomer with a series of methacrylate functionality (i.e., methacrylate substituted polyhedral oligomeric silsesquioxane) allowed the synthesis of organosilicon monoliths with high cross-linking density and carrying hydrophobic alkyl-chain ligands by a one-pot process. In the synthesis runs, 1-butanethiol, 1-octanethiol, and 1-octadecanethiol were used as the hydrophobic thiol ligands with the number of methylene units between 4 and 18. The selectivity analysis performed using cytosine/uracil retention ratio showed that alkanethiol-attached organosilicon monoliths exhibited hydrophobicity close to octadecyl-attached silica-based RP columns. In the RP, chromatographic runs performed in nano-liquid chromatography, phenols, alkylbenzenes, and PAHs were used as the analytes. Among the synthesized monoliths, retention-independent plate height behavior and the smallest plate heights were obtained with 1-octadecanethiol-attached organosilicon monolith for the analytes in a wide polarity range. With this monolith, the mobile phases prepared with ACN contents ranging between 35 and 85% v/v could be used for satisfactory separation of analytes in a wide polarity range.

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Copper-catalysed oxidative C–H/C–H coupling between olefins and simple ethers

Cited by 181 publications

References 61 publications

Recent Advances of Transition-Metal Catalyzed Radical Oxidative Cross-Couplings

Recent Advances of Transition-Metal Catalyzed Radical Oxidative Cross-Couplings

Facile one‐pot preparation of a novel imidazolium‐based monolith by thiol–ene click chemistry for capillary liquid chromatography

Alkanethiol‐functionalized organosilicon monoliths for nano‐reversed‐phase liquid chromatography

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