Transition Metal Free Catalytic Aerobic Oxidation of Methyl-α-d-Glucopyranoside Under Mild Conditions Using Stable Nitroxyl Free Radicals

Tanielyan, Setrak K.; Augustine, Robert L.; Marin, Norman; Alvez, Gabriela; Stapley, Jonathan A.

doi:10.1007/s11244-012-9827-x

Cited by 8 publications

(3 citation statements)

References 20 publications

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“…Recently, several groups have described metal-free aerobic alcohol oxidation reactions that employ a catalytic nitroxyl species in combination with an inorganic nitrogen oxide cocatalyst. The latter species is proposed to mediate regeneration of an oxoammonium species by O 2 (e.g., Scheme ) . We tested a variety of TEMPO and related nitroxyl derivatives as catalysts, with nitric acid and/or sodium nitrite as the cocatalyst.…”

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confidence: 99%

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin

et al. 2013

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An efficient organocatalytic method for chemoselective aerobic oxidation of secondary benzylic alcohols within lignin model compounds has been identified. Extension to selective oxidation in natural lignins has also been demonstrated. The optimal catalyst system consists of 4-acetamido-TEMPO (5 mol %; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) in combination with HNO3 and HCl (10 mol % each). Preliminary studies highlight the prospect of combining this method with a subsequent oxidation step to achieve C-C bond cleavage.

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confidence: 99%

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin

et al. 2013

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“…As a continuation of their pioneering studies on the use of nitrates as a NO-source, 106 Tanielyan and coworkers reported a very efficient TEMPO-mediated oxidation of glycopyranosides with HNO 3 as a co-catalyst. 112 To this end, the protectinggroup free, selective oxidation of the primary OH-groups in β-methylated glycopyranosides towards the corresponding glucuronic acid derivatives was readily achieved with 4-AcNH-TEMPO as a catalyst under mild conditions in quantitative yield (Scheme 38, top).…”

Section: Transition-metal-free Aerobic Oxidations Of Alcohols Via In ...mentioning

confidence: 99%

Nitroxide-catalyzed transition-metal-free aerobic oxidation processes

2013

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Advances in the field of transition-metal-free nitroxide-catalyzed aerobic oxidation processes are covered in this critical review. Along with the relevant physical properties of nitroxides, their application as oxidation catalysts by using dioxygen as a reagent or terminal oxidant will be discussed. The second part of the review focuses on the use of TEMPO-based nitroxides as catalysts for aerobic alcohol oxidation. Mechanistic studies will also be addressed (130 references).

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“…In a search for new methods for aerobic oxidation, two approaches emergedmetal free catalysis and base metal catalysis, such as iron. Nitrogen oxides, obtained from sodium nitrate or nitric acid, are potent catalysts for aerobic oxidation in conjunction with a cocatalyst such as TEMPO, − bromine, solid acids, carbon-based catalyst and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) . However, they can suffer from formation of an undesired side product N 2 O, which is formed from dimerization of HNO.…”

Section: Introductionmentioning

confidence: 99%

Aerobic Oxidation of Secondary Alcohols with Nitric Acid and Iron(III) Chloride as Catalysts in Fluorinated Alcohol

Možina

Iskra

2019

J. Org. Chem.

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Fluorinated alcohols as solvents strongly influence and direct chemical reaction through donation of strong hydrogen bonds while being weak acceptors. We used 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as the activating solvent for a nitric acid and FeCl 3 -catalyzed aerobic oxidation of secondary alcohols to ketones. Reaction proceeded selectively with excellent yields with no reaction on the primary alcohol group. Oxidation of benzyl alcohols proceeds selectively to aldehydes with only HNO 3 as the catalyst, while reaction on tertiary alcohols proceeds through dehydration and dimerization. A mechanistic study showed in situ formation of NOCl that converts alcohol into alkyl nitrite, which in the presence of Fe 3+ ions and fluorinated alcohol decomposes into ketone. The study indicates that iron(III) acts also as the single-electron transfer catalyst in regeneration of NOCl reactive species.

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Transition Metal Free Catalytic Aerobic Oxidation of Methyl-α-d-Glucopyranoside Under Mild Conditions Using Stable Nitroxyl Free Radicals

Cited by 8 publications

References 20 publications

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin

Nitroxide-catalyzed transition-metal-free aerobic oxidation processes

Aerobic Oxidation of Secondary Alcohols with Nitric Acid and Iron(III) Chloride as Catalysts in Fluorinated Alcohol

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