Reactions of nitric oxide and nitrogen dioxide with functionalised alkenes and dienes †

Park, Jonathan S. B.; Walton, John C.

doi:10.1039/a702295f

Cited by 47 publications

(32 citation statements)

References 9 publications

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“…While this observation, first confirmed by Brown in 1957, 78 holds true for reactions conducted in the absence of higher nitrogen oxides, such as NO 2 , this common impurity in NO catalyzes the addition process and leads to the formation of β-nitro-nitroso compounds (pseudonitrosites) 79 and/or their dimers. 80 …”

Section: Binary Nitrogen Oxides and Related Reagentsmentioning

confidence: 99%

Methods for direct alkene diamination, new & old

2012

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The 1,2-diamine moiety is a ubiquitous structural motif present in a wealth of natural products, including non-proteinogenic amino acids and numerous alkaloids, as well as in pharmaceutical agents, chiral ligands and organic reagents. The biological activity associated with many of these systems and their chemical utility in general has ensured that the development of methods for their preparation is of critical importance. While a wide range of strategies for the preparation of 1,2-diamines have been established, the diamination of alkenes offers a particularly direct and efficient means of accessing these systems. The purpose of this review is to provide an overview of all methods of direct alkene diamination, metal-mediated or otherwise.

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Section: Binary Nitrogen Oxides and Related Reagentsmentioning

confidence: 99%

Methods for direct alkene diamination, new & old

2012

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“…Recently, Yamada et al have reported that NO can be used as a nitrogen source for the synthesis of nitrogen-containing compounds such as 2-nitrosocarboxamides [154] and nitroalkenes. [155] In addition, it has been shown that amines, [156] phenothiazines, [157] and dienes [158] react with NO in the presence or absence of dioxygen. We have now found a novel utilization of NO in organic synthesis.…”

Section: Reaction Of No With Organic Compoundsmentioning

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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“…35 The resulting radical can either react again with nitrogen dioxide to give access to 1,4-dinitro compounds or be trapped by nitric oxide 36,37 to generate diallylaminoxyl radicals (eq 11). 35 Aminohydroxylation.…”

Section: No 2 1-4-additionmentioning

confidence: 99%

2,5-Dimethylhexa-2,4-diene

Beaumard

2011

Encyclopedia of Reagents for Organic Synthesis

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Reactions of nitric oxide and nitrogen dioxide with functionalised alkenes and dienes †

Cited by 47 publications

References 9 publications

Methods for direct alkene diamination, new & old

Methods for direct alkene diamination, new & old

Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions

2,5-Dimethylhexa-2,4-diene

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