ChemInform Abstract: Functionalization of Saturated Hydrocarbons. Part 4. The Gif System for Selective Oxidation Using Molecular Oxygen.

Barton, Derek H. R.; Boivin, Jean; Gastiger, Michel J.; Morzycki, Jacek W.; Hay-Motherwell, Robyn S.; Motherwell, William B.; Ozbalik, Nubar; Schwartzentruber, Kathy M.

doi:10.1002/chin.198638117

Cited by 4 publications

(7 citation statements)

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“…(until pH ca. 2). and extracted continuously with CH2C1, for 18 h. The extracts were washed successively with 1~ H2S04, sat.…”

Section: Experimental Partmentioning

confidence: 99%

“…C(2) appears at 19.05, C(7) at 44.28, C(1 I ) at 18.52, and C( 12) at 45.07 ppm. Applying the methodology described above, we found the oxidation site Tor 16 to be at C (2). The "C-NMR spectrum of 17 shows that the oxidation has occurred in c ( position to a quaternary C-atom.…”

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confidence: 97%

“…-In the preceding parts of this series [l-61, we reported our findings on the oxidation of saturated hydrocarbons by the 'Gifsystem'. This process, especially in its most elaborate form (catalytic amounts of iron cluster Fe,O(OAc),Pyr, 5, Zn powder, AcOH, pyridine, and air at room temperature) was successfully applied to a variety of simple hydrocarbons [2] [3] and then to more complex molecules such as steroids [4] [5] and terpenoids [l] [6]. As a rule, this oxidising system leads to the formation of ketones as major products, i.e.…”

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confidence: 99%

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Functionalisation of saturated hydrocarbons. Part XI. Oxidation of cedrol, β‐ and γ‐eudesmol, sclareol, manoyl oxide, 1,9‐dideoxyforskolin, methyl trans‐dihydroiasmonate, and tetrahydrolinalool by the ‘Gif system’

Barton

Beloeil

Billion

et al. 1987

Helvetica Chimica Acta

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Dedicated to Professor Tadeus Rrichstrin on the occasion of his 90th birthday (10.V11.87)The oxidation of cedrol (l), p-and y-eudesmol(6 and 7, resp.), sclareol(14), manoyl oxide ( 1 3 , 1,9-didcoxyforskolin (22) (+)-methyl trans-dihydrojasmonate (28), and tetrahydrolinalool(32), nearly all of natural terpenoid origin, by the 'Gifsystem' has afforded a number of novel products (3, 11, and 12, 16/17, 18/19, 26, 29-31, and ketones corresponding to 34-35, resp.). The structures of these compounds were established by spectroscopic techniques including 2D-NMR and, wherc appropriate, by comparison with authentic samples.Introduction. -In the preceding parts of this series [l-61, we reported our findings on the oxidation of saturated hydrocarbons by the 'Gifsystem'. This process, especially in its most elaborate form (catalytic amounts of iron cluster Fe,O(OAc),Pyr, 5, Zn powder, AcOH, pyridine, and air at room temperature) was successfully applied to a variety of simple hydrocarbons [2] [3] and then to more complex molecules such as steroids [4] [5] and terpenoids [l] [6]. As a rule, this oxidising system leads to the formation of ketones as major products, i.e. selective attack on secondary positions. This regioselectivity is rather unusual when compared with other oxidising processes. A noticeable exception was observed in the case of cholestane derivatives where the important side-chain cleavage to give 20-ketones competed with the oxidation of the methylenes of the steroidal nucleus [4]

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“…(until pH ca. 2). and extracted continuously with CH2C1, for 18 h. The extracts were washed successively with 1~ H2S04, sat.…”

Section: Experimental Partmentioning

confidence: 99%

mentioning

confidence: 97%

mentioning

confidence: 99%

See 1 more Smart Citation

Functionalisation of saturated hydrocarbons. Part XI. Oxidation of cedrol, β‐ and γ‐eudesmol, sclareol, manoyl oxide, 1,9‐dideoxyforskolin, methyl trans‐dihydroiasmonate, and tetrahydrolinalool by the ‘Gif system’

Barton

Beloeil

Billion

et al. 1987

Helvetica Chimica Acta

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“…[32][33][34][35] However, the diradical nature of molecular oxygen means that it can also react with organic substrates via autoxidation pathways. 36,37 As these are not driven by catalysts, autoxidation reactions are difficult to study unambiguously. In addition, when metal oxides, rather than metal complexes or nanoparticles, are used to carry out selective oxidation, 38,39 the reaction is further complicated by the need to identify which oxygen species is responsible for the reaction.…”

Section: Introductionmentioning

confidence: 99%

Catalytic oxygen activation versus autoxidation for industrial applications: a physicochemical approach

Liu

Ryabenkova

Conte

2015

Phys. Chem. Chem. Phys.

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The activation and use of oxygen for the oxidation and functionalization of organic substrates is among the most important reactions in a chemist's toolbox. Nevertheless, despite the vast literature on catalytic oxidation, the phenomenon of autoxidation, an ever-present background reaction that occurs in virtually every oxidation process, is often neglected. In contrast, autoxidation can affect the selectivity to a desired product, to those dictated by pure freeradical chain pathways, thus affecting the activity of any catalyst used to carry out a reaction.This critical review compares catalytic oxidation routes by transition metals versus autoxidation, particularly focusing on the industrial context, where highly selective and "green" processes are needed. Furthermore, the application of useful tests to discriminate between different oxygen activation routes, especially in the area of hydrocarbon oxidation, with the aim of an enhanced catalyst design, is described and discussed. In fact, one of the major targets of selective oxidation is the use of molecular oxygen as ultimate oxidant, combined with the development of catalysts capable to perform the catalytic cycle in a real energy and cost effective manner on a large scale. To achieve this goal, insights from metallo-proteins that could find application in some areas of industrial catalysis are presented, as well as considering the physicochemical principles that are at the fundament of oxidation and autoxidation processes.3

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“…Recently an unusual selectivity in alkane oxidation by dioxygen has been observed in pyridine solution when carboxylic acids were present; this reagent combination is now known as the Gif-system.l. 2 The oxidation is a coupled process involving iron or zinc powder and an iron complex. There exist a few such systems, which differ from each other only in details, e.g., a Hg-cathode is used as a reductant in the Gif-Orsay system.…”

Section: Oxidation Of Saturated Hydrocarbons By Hydrogen Peroxide In ...mentioning

confidence: 99%

Oxidation of saturated hydrocarbons by hydrogen peroxide in pyridine solution catalysed by copper and iron perchlorates

Geletii¹,

Lavrushko²,

Lubimova³

1988

J. Chem. Soc., Chem. Commun.

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ChemInform Abstract: Functionalization of Saturated Hydrocarbons. Part 4. The Gif System for Selective Oxidation Using Molecular Oxygen.

Abstract: Various systems for the selective oxidation of saturated hydrocarbons have been developed.

Cited by 4 publications

References 1 publication

Functionalisation of saturated hydrocarbons. Part XI. Oxidation of cedrol, β‐ and γ‐eudesmol, sclareol, manoyl oxide, 1,9‐dideoxyforskolin, methyl trans‐dihydroiasmonate, and tetrahydrolinalool by the ‘Gif system’

Functionalisation of saturated hydrocarbons. Part XI. Oxidation of cedrol, β‐ and γ‐eudesmol, sclareol, manoyl oxide, 1,9‐dideoxyforskolin, methyl trans‐dihydroiasmonate, and tetrahydrolinalool by the ‘Gif system’

Catalytic oxygen activation versus autoxidation for industrial applications: a physicochemical approach

Oxidation of saturated hydrocarbons by hydrogen peroxide in pyridine solution catalysed by copper and iron perchlorates

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