Graphene-Catalyzed Direct Friedel–Crafts Alkylation Reactions: Mechanism, Selectivity, and Synthetic Utility

Hu, Feng; Patel, Mehulkumar; Luo, Feixiang; Flach, Carol R.; Mendelsohn, Richard; Garfunkel, Eric; He, Huixin; Szostak, Michal

doi:10.1021/jacs.5b09636

Cited by 149 publications

(108 citation statements)

References 135 publications

(148 reference statements)

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“…Although the molecular basis of the increased stability of membrane fragments to detergents and trypsin is not clear, it is possible that membrane fragments are chemically cross-linked. GO has been characterized as a potent oxidant for preparative organic chemistry, 42 and treatment of RBL cells may result in the cross-linking of various PM components. However, we are unaware of other examples of such reactivity in biological systems.…”

Section: Resultsmentioning

confidence: 99%

Graphene Oxide Nanosheets Stimulate Ruffling and Shedding of Mammalian Cell Plasma Membranes

Sun

Wakefield

Han

et al. 2016

Chem

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Summary Graphene oxide (GO) has attracted intense interest for use in living systems and environmental applications. GO’s compatibility with mammalian cells is sometimes inferred from its low cytotoxicity, but such conclusions ignore non-lethal effects that will influence GO’s utility. Here we demonstrate, with rat basophilic leukemia (RBL) cells, profound plasma membrane (PM) ruffling and shedding induced by GO using confocal and live cell fluorescence microscopy, as well as scanning electron microscopy. These membrane structures contain immunoglobulin E receptors, are resistant to detergents, and lack detectable fluorescence labeling of F-actin and fibronectin. The formation of these membrane structures correlates with a loss of contact inhibition between RBL cells. We observe similar cellular responses towards GO for NIH-3T3 fibroblast cells and MDA-MB-231 human breast cancer cells. These findings reveal a previously unreported cellular response towards foreign nanomaterials. Membrane ruffling and shedding raise fundamental questions about how GO interacts with the PM, as well as its potential to modulate cellular mechanosensing for tissue engineering, stem cell differentiation, and other biomedical applications.

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Section: Resultsmentioning

confidence: 99%

Graphene Oxide Nanosheets Stimulate Ruffling and Shedding of Mammalian Cell Plasma Membranes

Sun

Wakefield

Han

et al. 2016

Chem

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“…1‐Benzyl‐2,4‐dimethoxybenzene (11) : By the general procedure from 1,3‐dimethoxybenzene (33.7 mg, 31.9 μL) and benzyl chloride (20.6 mg, 18.7 μL), a waxy solid (33.8 mg, 91 %) was obtained. The NMR spectral data were in accord with those reported in literature …”

Section: Methodsmentioning

confidence: 99%

Green, Mild, and Efficient Friedel–Crafts Benzylation of Scarcely Reactive Arenes and Heteroarenes under On‐Water Conditions

et al. 2019

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Metal‐free Friedel–Crafts benzylation (FCB) of scarcely reactive arenes and heteroarenes was performed under on‐water conditions by an environmentally sustainable procedure. The catalytic strategy exploits the hydrophobicity of the resorcinarene macrocycle 1 a. The proposed mechanism is based on the activation of benzyl chloride by H‐bonding interactions with catalyst 1 a. In fact, under on‐water conditions the hydrophobic amplification of the strength of the H‐bonding interactions between the OH groups of the resorcinarene catalyst and the chlorine atom of benzyl chloride leads to polarization of the C−Cl bond, which consequently promotes electrophilic attack of the π nucleophile. Thus, many arenes and heteroarenes were efficiently benzylated under mild on‐water conditions by using resorcinarene 1 a as catalyst. The FCB of benzene is industrially relevant for the synthesis of diphenylmethane, and hence the on‐water procedure was extended to the gram‐scale synthesis of diphenylmethane, starting from benzene and benzyl chloride in the presence of resorcinarene catalyst 1 a.

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“…Therein, the authors activated GO by adding a catalytic amount of NaI, which possibly interacted with the methyl group of acetophenone, resulting in the synthesis of imidazole‐fused pyrimidines via a multicomponent reaction. In 2015, Szostak and co‐workers reported a GO‐catalyzed direct alkylation of arenes (Scheme c) . Therein, they described a direct Fridel–Crafts C−C bond formation owing to polar and aromatic groups on the graphene surface in the absence of transition‐metal catalysts.…”

Section: Methodsmentioning

confidence: 99%

Graphene Oxide as a Carbocatalyst for a Diels–Alder Reaction in an Aqueous Medium

Girish

Pandit

2017

Chemistry An Asian Journal

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The Diels-Alder (DA) reaction, a [4+2] cycloaddition reaction, is highly important in synthetic organic chemistry and is frequently used in the synthesis of natural products containing six-membered rings. Herein, we report an efficient protocol for the DA reaction between 9-hydroxymethylanthracene and N-substituted maleimides using two-dimensional graphene oxide (GO) as a heterogeneous carbocatalyst in an aqueous medium at room temperature. High yields, a wide substrate scope, low temperature, excellent functional group tolerance, atom economy, and water as a green solvent are noteworthy features of this protocol. The heterogeneous GO catalyst can be easily recovered and used multiple times without any significant loss in catalytic activity.

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Graphene-Catalyzed Direct Friedel–Crafts Alkylation Reactions: Mechanism, Selectivity, and Synthetic Utility

Cited by 149 publications

References 135 publications

Graphene Oxide Nanosheets Stimulate Ruffling and Shedding of Mammalian Cell Plasma Membranes

Graphene Oxide Nanosheets Stimulate Ruffling and Shedding of Mammalian Cell Plasma Membranes

Green, Mild, and Efficient Friedel–Crafts Benzylation of Scarcely Reactive Arenes and Heteroarenes under On‐Water Conditions

Graphene Oxide as a Carbocatalyst for a Diels–Alder Reaction in an Aqueous Medium

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