A New Approach for Oxygenation Using Nitric Oxide under the Influence of <i>N</i>-Hydroxyphthalimide

Eikawa, Masahiro; Sakaguchi, Satoshi; Ishii, Yasutaka

doi:10.1021/jo982406o

Cited by 45 publications

(25 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, by simply moving into acetonitrile, they observed the selective oxygenation of phthalane to the corresponding phthalaldehyde in 80% yield [23]. In both cases the reaction proceeds via the formation of a carbocation intermediate (Scheme 7).…”

Section: Reviewmentioning

confidence: 99%

Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review

Melone¹,

Punta²

2013

Beilstein J. Org. Chem.

151

View full text Add to dashboard Cite

SummarySince the beginning of the century, N-hydroxyphthalimide and related compounds have been revealed to be efficient organocatalysts for free-radical processes and have found ample application in promoting the aerobic oxidation of a wide range of organic substrates. When combined with different co-catalysts, they are activated to the corresponding N-oxyl radical species and become able to promote radical chains, involving molecular oxygen, directly or indirectly. Most of the examples reported in the literature describe the use of these N-hydroxy derivatives in the presence of transition-metal complexes. However, eco-friendly standards, including the demand for highly selective transformations, impose the development of metal-free processes, especially for large-scale productions, as in the case of the oxygenation of hydrocarbons. For this reason, many efforts have been devoted in the past decade to the design of new protocols for the activation of N-hydroxy imides in the presence of nonmetal initiators. Herein we provide a concise overview of the most significant and successful examples in this field, with the final aim to furnish a useful instrument for all scientists actively involved in the O2-mediated selective oxidation of organic compounds and looking for environmentally safe alternatives to metal catalysis.

show abstract

Section: Reviewmentioning

confidence: 99%

Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review

Melone¹,

Punta²

2013

Beilstein J. Org. Chem.

151

View full text Add to dashboard Cite

show abstract

“…[160] The reaction of 4-methoxymethyltoluene catalyzed by NHPI (10 mol %) under NO (1 atm) for 5 h led to p-tolualdehyde in 50% yield. tert-Butoxymethyltoluene was transformed into the aldehyde in 72% yield.…”

Section: Reaction Of No With Organic Compoundsmentioning

confidence: 99%

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

2001

Self Cite

View full text Add to dashboard Cite

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

show abstract

“…After the completion of the oxidation, the reaction mixture was diluted with CH 2 Cl 2 (50.0 mL), washed with 10% aqueous Na 2 SO 4 (2 ϫ 30.0 mL), dried with Na 2 SO 4 , filtered, and concentrated to dryness. When suitable, the obtained reaction products were conveniently isolated by standard techniques (Table 2): 4-(methoxymethyl)benzaldehyde (2t, 2.96 g, 79%), [74] methyl 4-formylbenzoate (2v, 3.53 g, 86%), [75] 4-(chloromethyl)benzaldehyde (2x, 3.50 g, 91%), [76] and 4-[(acetyloxy)methyl)]benzaldehyde (2y, 3.56 g, 80%). [77] Reaction between 3,4-Dihydro-1H-isochromene (34) and HNO 3 in CH 2 Cl 2 : A solution of 3,4-dihydro-1H-isochromene (34, 3.35 g, 25.0 mmol) in CH 2 Cl 2 (5.0 mL) was treated as described in the general oxidation procedure (Ͼ 99% conv.…”

Section: General Procedures For the Oxidation Of Benzylic Alcohols Andmentioning

confidence: 99%

Oxidation of Benzylic Alcohols and Ethers to Carbonyl Derivatives by Nitric Acid in Dichloromethane

Strazzolini

Runcio

2003

Eur J Org Chem

View full text Add to dashboard Cite

Nitric acid in dichloromethane may be successfully employed for the oxidation of benzylic alcohols and ethers to the corresponding carbonyl compounds. The proposed method proved to be of general applicability, affording very good yields of aldehydes and ketones and showing interesting chemoselectivity in many instances, allowing competitive aromatic nitration to be avoided, as well as − in the case of aldehydes − any further oxidation to carboxylic acids. The reaction probably proceeds by a radical mechanism, the active species in the oxidation process being NO2. Competitive formation of nitro esters was observed in some cases, whereas poor results were obtained with allylic and non‐benzylic substrates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

show abstract

A New Approach for Oxygenation Using Nitric Oxide under the Influence of N-Hydroxyphthalimide

Cited by 45 publications

References 22 publications

Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review

Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

Oxidation of Benzylic Alcohols and Ethers to Carbonyl Derivatives by Nitric Acid in Dichloromethane

Contact Info

Product

Resources

About