Oxidation of 1,2‐Cyclohexanediol to Adipic Acid with Oxygen: A Study Into Selectivity‐Affecting Parameters

Rozhko, Elena; Raabová, Kateřina; Macchia, Francesco; Malmusi, Andrea; Righi, Paolo; Accorinti, P.; Alini, S.; Babini, P.; Cerrato, G.; Manzoli, Maela; Cavani, Fabrizio

doi:10.1002/cctc.201200825

Cited by 30 publications

(32 citation statements)

References 82 publications

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“…As a result of the non‐green nature of such oxidants, catalytic systems in which O 2 is used as an oxidant have been sought. Typical catalysts for oxidative C−C cleavage with O 2 are based on Ru, Mn, Cu, and V . Ru and Mn catalysts can convert aromatic vicinal diol to aldehydes in good yields and they are less effective for aliphatic substrates, especially under neutral or acidic conditions.…”

Section: Introductionmentioning

confidence: 99%

Oxidative C−C Cleavage of Ketols over Vanadium–Carbon Catalysts

et al. 2017

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The oxidation of 2‐hydroxycyclohexanone and carbohydrates to adipic acid and formic acid, respectively, was performed with a combination of a vanadium catalyst, carbon as the cocatalyst, and O2 in water under mild conditions (353 K, 0.1–0.3 MPa). The catalytic activity of aqueous V2O5 was increased significantly by the addition of activated carbon (C), whereas the addition of carbon black, graphene oxide, and carbon nanotubes has a much smaller effect. UV/Vis and inductively coupled plasma optical emission spectroscopy were used to show that most VV species are adsorbed on C at least in a short reaction time. The VIV species (VO2+) was not adsorbed on C. The order of activity of vanadium species was VV on C>dissolved free VV≫dissolved free VIV. To help the oxidation of VIV, the further addition of phosphomolybdate (PMo12O403−; PMo) was also tested, and the activity was improved. The selectivity and yield of adipic acid from 2‐hydroxycyclohexanone was also improved slightly by the addition of PMo. However, in the oxidation of glucose, the addition of PMo did not improve the final formic acid yield. The oxidation of glucose with the V+C system gave a 42 % yield of formic acid, which was comparable to the values reported with a more expensive PVMo polyoxometalate catalyst. A reaction mechanism is proposed in which the reversibly formed “biradical” state of the vanadium ketol complex reacts with O2 and accompanying rearrangement dissociates the C−C bond.

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Section: Introductionmentioning

confidence: 99%

Oxidative C−C Cleavage of Ketols over Vanadium–Carbon Catalysts

et al. 2017

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“…A typical substrate is trans ‐1,2‐cyclohexanediol ( trans ‐1,2‐CHD), and the target product is adipic acid, which is industrially one of the most important dicarboxylic acids . Systems using molecular oxygen as an oxidant for oxidation of 1,2‐CHD to adipic acid are limited (see the Supporting Information, Table S1) . Ru catalysts (e.g., ruthenium pyrochlore oxides, A 2+ x Ru 2− x O 7− y (A=Pb or Bi; 0< x <1; 0< y ≤0.5)) were reported to be effective; however, bases such as NaOH and KOH were necessary for high activity and the product was adipate instead of adipic acid.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Cleavage of Vicinal Diols with the Combination of Platinum and Vanadium Catalysts and Molecular Oxygen

et al. 2016

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The combination of Pt/C and V2O5 catalysts gave good performance for the oxidative cleavage of trans‐1,2‐cyclohexanediol into adipic acid via 2‐hydroxycyclohexanone. The yield of adipic acid reached 90 % in the one‐pot oxidative cleavage of trans‐1,2‐cyclohexanediol. The yield was higher than that obtained in the oxidation of 2‐hydroxycyclohexanone with V catalyst, and the higher yield was due to the low 2‐hydroxycyclohexanone concentration during the one‐pot oxidation of trans‐1,2‐cyclohexanediol. Cyclic vicinal diols having a six‐membered ring and linear vicinal diols having two secondary OH groups were converted into dicarboxylic acids and two carboxylic acids, respectively. The activity of the Pt catalyst decreased during the reaction, and the activity was partially restored by treating the used catalyst with H2 at 573 K. Even without regeneration, the turnover number based on total Pt could reach ≈1000 in a long reaction with an increased amount of trans‐1,2‐cyclohexanediol.

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“…For further validation, a model study was pursued to assess cyclopentenone formation via ring contraction of a 19-OH Gdm progenitor (Scheme 1) reminiscent of the classical cyclohexanone to cyclopentane-1-carboxylate benzilic acid rearrangement. [10] While the corresponding Gdm rearrangement is unprecedented, the analogous Hooker oxidation rearrangement of hydroxynaphthoquinones to indane carboxylic acids served as related precedent. [11] For this study, the synthesis of the Gdm model surrogate 2-hydroxyquinone 21 (Scheme 2) commenced with aryl lithiation–alkylation of benzyl methyl ether 12 .…”

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confidence: 99%

Mccrearamycins A–D, Geldanamycin‐Derived Cyclopentenone Macrolactams from an Eastern Kentucky Abandoned Coal Mine Microbe

et al. 2017

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Four cyclopentenone-containing ansamycin polyketides (mccrearamycins A–D), and six new geldanamycins (Gdms B–G, including new linear and mycothiol conjugates), were characterized as metabolites of Streptomyces sp. AD-23-14 isolated from the Rock Creek underground coal mine acid drainage site. Biomimetic chemical conversion studies using both simple synthetic models and Gdm D confirmed that the mccrearamycin cyclopentenone derives from benzilic acid rearrangement of 19-hydroxy Gdm, and thereby provides a new synthetic derivatization strategy and implicates a potential unique biocatalyst in mccrearamycin cyclopentenone formation. In addition to standard Hsp90α binding and cell line cytotoxicity assays, this study also highlights the first assessment of Hsp90α modulators in a new axolotl embryo tail regeneration (ETR) assay as a potential new whole animal assay for Hsp90 modulator discovery.

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Oxidation of 1,2‐Cyclohexanediol to Adipic Acid with Oxygen: A Study Into Selectivity‐Affecting Parameters

Cited by 30 publications

References 82 publications

Oxidative C−C Cleavage of Ketols over Vanadium–Carbon Catalysts

Oxidative C−C Cleavage of Ketols over Vanadium–Carbon Catalysts

Oxidative Cleavage of Vicinal Diols with the Combination of Platinum and Vanadium Catalysts and Molecular Oxygen

Mccrearamycins A–D, Geldanamycin‐Derived Cyclopentenone Macrolactams from an Eastern Kentucky Abandoned Coal Mine Microbe

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