<i>N</i>-Hydroxyphthalimide-Catalyzed Carboxylation of Polycyclic Alkanes with Carbon Monoxide in the Presence of Dioxygen

Kato, Susumu; Iwahama, Takahiro; Sakaguchi, Satoshi; Ishii, Yasutaka

doi:10.1021/jo9718556

Cited by 49 publications

(32 citation statements)

References 29 publications

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“…The ability of such a small amount of PINO • to induce a significant catalytic effect can be attributed to its intrinsically higher reactivity. For instance, PINO • radicals react about 7 times faster with CyH [reaction (18)] than CyOO • radicals, as predicted by the computed energy barriers of 16.0 and 17.6 kcal/mol, respectively [3,33].…”

Section: Performance Of the Heterogeneous Catalystmentioning

confidence: 94%

“…proposed N -hydroxyphthalimide (NHPI, Scheme 1), with or without transition metal ions, as a homogeneous organocatalyst for the liquid-phase oxidation of several substrates [12][13][14][15][16][17][18][19][20][21][22][23]. At present, many accounts can be found on the use of various N -hydroxyimides as efficient catalysts for various oxyfunctionalizations [24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

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Silica-immobilized N-hydroxyphthalimide: An efficient heterogeneous autoxidation catalyst

Hermans

Deun

Houthoofd

et al. 2007

Journal of Catalysis

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Section: Performance Of the Heterogeneous Catalystmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Silica-immobilized N-hydroxyphthalimide: An efficient heterogeneous autoxidation catalyst

Hermans

Deun

Houthoofd

et al. 2007

Journal of Catalysis

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“…Our interest was directed to the trapping of alkyl radicals generated from alkanes under the influence of NHPI catalyst by CO followed by O 2 leading to carboxylic acids (Scheme 15). [143] The carboxylation of adamantane under CO/air (15/1 atm) in the presence of NHPI (10 mol %) in a mixed solvent of acetic acid and 1,2-dichloroethane at 95°C for 4 h afforded 1-adamantanecarboxylic acid, 1,3-adamantanedicarboxylic acid, 2-admantanecarboxylic acid, and several oxygenated products such as 1-adamantanol and 2-adamantanone, but 1-adamantanecarbaldehyde was not formed at all (Equation 35). The selectivity of these products depended markedly on the reaction conditions.…”

Section: Carboxylation Of Alkanes With Co and Omentioning

confidence: 99%

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

2001

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An innovation of the aerobic oxidation of hydrocarbons through catalytic carbon radical generation under mild conditions was achieved by using N‐hydroxyphthalimide (NHPI) as a key compound. Alkanes were successfully oxidized with O2 or air to valuable oxygen‐containing compounds such as alcohols, ketones, and dicarboxylic acids by the combined catalytic system of NHPI and a transition metal such as Co or Mn. The NHPI‐catalyzed oxidation of alkylbenzenes with dioxygen could be performed even under normal temperature and pressure of dioxygen. Xylenes and methylpyridines were also converted into phthalic acids and pyridinecarboxylic acids, respectively, in good yields. The present oxidation method was extended to the selective transformations of alcohols to carbonyl compounds and of alkynes to ynones. The epoxidation of alkenes using hydroperoxides or H2O2 generated in situ from hydrocarbons or alcohols and O 2 under the influence of the NHPI was demonstrated and seems to be a useful strategy for industrial applications. The NHPI method is applicable to a wide variety of organic syntheses via carbon radical intermediates. The catalytic carboxylation of alkanes was accomplished by the use of CO and O2 in the presence of NHPI. In addition, the reactions of alkanes with NO2 and SO2 catalyzed by NHPI provided efficient methods for the synthesis of nitroalkanes and sulfonic acids, respectively. A catalytic carbon‐carbon bond forming reaction was achieved by allowing carbon radicals generated in situ from alkanes or alcohols to react with alkenes under mild conditions. 1 Introduction 2 Discovery of NHPI as Carbon Radical Producing Catalyst from Alkanes 2.1 Historical Background 2.2 Catalysis of NHPI in Aerobic Oxidation 3 NHPI‐Catalyzed Aerobic Oxidation 3.1 Oxidation of Benzylic Compounds 3.2 Alkane Oxidations with Molecular Oxygen 3.3 Oxidation of Alkylbenzenes 3.4 Practical Oxidation of Methylpyridines 3.5 Preparation of Acetylenic Ketones via Alkyne Oxidation 3.6 Oxidation of Alcohols 3.7 Selective Oxidation of Sulfides to Sulfoxides 3.8 Production of Hydrogen Peroxide by Aerobic Oxidation of Alcohols 3.9 Epoxidation of Alkenes using Molecular Oxygen as Terminal Oxidant 4 Carboxylation of Alkanes with CO and O2 5 Utilization of NOx in Organic Synthesis 5.1 First Catalytic Nitration of Alkanes using NO2 5.2 Reaction of NO with Organic Compounds 6 Sulfoxidation of Alkanes Catalyzed by Vanadium 7 Carbon‐Carbon Bond Forming Reaction via Catalytic Carbon Radicals Generated from Various Organic Compounds Assisted by NHPI 7.1 Oxyalkylation of Alkenes with Alkanes and Dioxygen 7.2 Synthesis of α‐Hydroxy‐γ‐lactones by Addition of α‐Hydroxy Carbon Radicals to Unsaturated Esters 7.3 Hydroxyacylation of Alkenes using 1,3‐Dioxolanes and Dioxygen 8 Conclusions

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“…Materials with a high surface density of hydroxyl groups, determined by 29 Si MAS NMR, were found to deactivate very fast [47]. Supports with a low fraction of hydroxyl groups were found to act as truly heterogeneous and recyclable catalysts, although during the first recycle some loss in activity could be observed.…”

Section: Organocatalysis By N-hydroxyphthalimidementioning

confidence: 99%

Autoxidation of Hydrocarbons: From Chemistry to Catalysis

2008

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This contribution summarizes our recent efforts to unravel the radical chemistry of autoxidations. Abstraction of the weakly bonded aH-atom of the primary hydroperoxide product by chain carrying peroxyl radicals is identified as the source of major end products such as alcohol and ketone/aldehyde. In the case of cyclohexane autoxidation, this reaction is even responsible for the majority of ringopened by-products. In a second part, different approaches to autoxidation catalysis are discussed, ranging from transition metal ion catalysis to organocatalysis with immobilized Nhydroxyphthalimide.

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N-Hydroxyphthalimide-Catalyzed Carboxylation of Polycyclic Alkanes with Carbon Monoxide in the Presence of Dioxygen

Cited by 49 publications

References 29 publications

Silica-immobilized N-hydroxyphthalimide: An efficient heterogeneous autoxidation catalyst

Silica-immobilized N-hydroxyphthalimide: An efficient heterogeneous autoxidation catalyst

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

Autoxidation of Hydrocarbons: From Chemistry to Catalysis

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