Selective C–H bond hydroxylation of cyclohexanes in water by supramolecular control

Yang, Bin; Cui, Jian‐Fang; Wong, Man Leung

doi:10.1039/c7ra03930a

Cited by 7 publications

(18 citation statements)

References 70 publications

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“…[86] These findings indicate that b-CD and g-CDc ould act as reaction vessels throughi nclusion complexation of hydrophobic cyclohexanes in water. [86] Moreover,t hese results show that using g-CD as the supramolecular host gave higher yields than using b-CD as the supramolecular host.…”

Section: Site-selective Càhbond Oxyfunctionalization In Total Synthesmentioning

confidence: 88%

“…[84,85] In 2017, the same research group extended this approach to the hydroxylation of cis-a nd trans-substituted cyclohexanes in the presence of CDs by using dioxirane generated in situ from TFP and oxone in aqueous medium. [86] As shown in Scheme 27, trans-1,4-dimethylcyclohexane can be oxidized by dioxirane generated in situ through complexation with g-CD or b-CD in mono-a nd dihydroxylated products, whereas cis-1,2-dimethylcyclohexane gave only monohydroxylation. [86] These findings indicate that b-CD and g-CDc ould act as reaction vessels throughi nclusion complexation of hydrophobic cyclohexanes in water.…”

Section: Site-selective Càhbond Oxyfunctionalization In Total Synthesmentioning

confidence: 99%

“…[86] As shown in Scheme 27, trans-1,4-dimethylcyclohexane can be oxidized by dioxirane generated in situ through complexation with g-CD or b-CD in mono-a nd dihydroxylated products, whereas cis-1,2-dimethylcyclohexane gave only monohydroxylation. [86] These findings indicate that b-CD and g-CDc ould act as reaction vessels throughi nclusion complexation of hydrophobic cyclohexanes in water. [86] Moreover,t hese results show that using g-CD as the supramolecular host gave higher yields than using b-CD as the supramolecular host.…”

Section: Site-selective Càhbond Oxyfunctionalization In Total Synthesmentioning

confidence: 99%

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Continued Progress towards Efficient Functionalization of Natural and Non‐natural Targets under Mild Conditions: Oxygenation by C−H Bond Activation with Dioxirane

D’Accolti

Annese

Fusco

2019

Chemistry A European J

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The successful isolation and characterization of a dioxirane species in 1988 opened up one of the most attractive methods for the efficient oxidation of simple and/or structurally complex molecules. Dioxirane today rank among the most powerful tools in organic chemistry, with numerous applications in commercially important processes. They were quickly recognized as efficient oxygen transfer agents, especially for epoxidations and for a wide range of O‐insertion reactions into C−H bonds. Dioxirane possess catalytic activity and appear as highly (chemo‐, regio‐, and stereo‐) selective oxidants, despite their reactivity under mild and strictly neutral conditions being controlled by a combination of steric and electronic factors. In this review, we discuss some of the most recent and significant developments in the selective homogeneous and heterogeneous oxyfunctionalization of non‐activated C−H bonds in hydrocarbons of natural and non‐natural targets by using isolated dioxirane or, more generally, by using the ketones (i.e., the dioxirane precursors) as organocatalysts.

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Section: Site-selective Càhbond Oxyfunctionalization In Total Synthesmentioning

confidence: 88%

Section: Site-selective Càhbond Oxyfunctionalization In Total Synthesmentioning

confidence: 99%

Section: Site-selective Càhbond Oxyfunctionalization In Total Synthesmentioning

confidence: 99%

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Continued Progress towards Efficient Functionalization of Natural and Non‐natural Targets under Mild Conditions: Oxygenation by C−H Bond Activation with Dioxirane

D’Accolti

Annese

Fusco

2019

Chemistry A European J

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“…Recently,W onga nd co-workersu sed as imilar approachf or the selectiveo xidation of CÀHb onds in water with in-situ-generated dioxiranes in the presence of cyclodextrins. [12] The authors studied the oxidation of esters S1 a-d with two tertiary CÀHb onds, for which electronic factors slightly activatet he terminal position( Scheme 1). [12a] Again, formation of hostguest adducts with cyclodextrins prevents the approach of dioxiranes to the CÀHb onds inside the cavity and leads to pref- erential oxidationo ft he sites outside the CD pocket.…”

Section: Càhoxidation Of Stoichiometric Receptor-substrate Adductsmentioning

confidence: 99%

Controlling Selectivity in Aliphatic C−H Oxidation through Supramolecular Recognition

Vìdal

Olivo

Costas

2018

Chemistry A European J

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Aliphatic C-H oxidation is the most straightforward approach to functionalize hydrocarbon skeletons. The main challenge of this reaction is the control of site selectivity, given the multiple C-H bonds present in any organic molecule. Natural enzymes elegantly solve this problem through the interplay of different interactions that geometrically orient the substrate to expose a single C-H bond to the active unit, thus overriding intrinsic reactivity patterns. A combination of molecular catalysts and supramolecular receptors can be a promising way to replicate such control. This strategy indeed unlocks hydroxylation of C-H bonds that are not accessible with conventional methodologies, in which the selectivity is dictated by the geometry of the substrate-receptor adduct. Herein, we review the reports of recognition-driven C-H oxidation reactions and highlight the key design principles that inspired these works.

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“…At present, Pt nanomaterials are conventionally used as anode electrocatalysts for the direct alcohol fuel cells. [1c,d,2a,6] Recently, Au, [7] Ag, [8] Fe, [3c] Ni, [3d] Co, [9] Cu, [10] and Pd [11] nanostructures with relative low cost have been tried to replace expensive Pt as anode electrocatalysts in alkaline media. Among them, only Pd-based electrocatalysts show the comparable activity for the alcohol oxidation reactions relative to Ptbased electrocatalysts.…”

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confidence: 99%

Selective Etching Induced Synthesis of Hollow Rh Nanospheres Electrocatalyst for Alcohol Oxidation Reactions

Kang

Xue

Zhao

et al. 2018

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The hollow noble metal nanostructures have attracted wide attention in catalysis/electrocatalysis. Here a two-step procedure for constructing hollow Rh nanospheres (Rh H-NSs) with clean surface is described. By selectively removing the surfactant and Au core of Au-core@Rh-shell nanostructures (Au@Rh NSs), the surface-cleaned Rh H-NSs are obtained, which contain abundant porous channels and large specific surface area. The as-prepared Rh H-NSs exhibit enhanced inherent activity for the methanol oxidation reaction (MOR) compared to state-of-the-art Pt nanoparticles in alkaline media. Further electrochemical experiments show that Rh H-NSs also have high activity for the electrooxidation of formaldehyde and formate (intermediate species in the course of the MOR) in alkaline media. Unfortunately, Rh H-NSs have low electrocatalytic activity for the ethanol and 1-propanol oxidation reactions in alkaline media. All electrochemical results indicate that the order of electrocatalytic activity of Rh H-NSs for alcohol oxidation reaction is methanol (C ) > ethanol (C ) > 1-propanol (C ). This work highlights the synthesis route of Rh hollow nanostructures, and indicates the promising application of Rh nanostructures in alkaline direct methanol fuel cells.

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Selective C–H bond hydroxylation of cyclohexanes in water by supramolecular control

Abstract: A new approach for selective hydroxylation of non-activated cyclohexanes using dioxirane generated in situ in water through supramolecular control has been developed.

Cited by 7 publications

References 70 publications

Continued Progress towards Efficient Functionalization of Natural and Non‐natural Targets under Mild Conditions: Oxygenation by C−H Bond Activation with Dioxirane

Continued Progress towards Efficient Functionalization of Natural and Non‐natural Targets under Mild Conditions: Oxygenation by C−H Bond Activation with Dioxirane

Controlling Selectivity in Aliphatic C−H Oxidation through Supramolecular Recognition

Selective Etching Induced Synthesis of Hollow Rh Nanospheres Electrocatalyst for Alcohol Oxidation Reactions

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