Oxygen Atom Transfer into C−H Bond in Biological and Model Chemical Systems. Mechanistic Aspects

Шилов, А. Е.; Shteinman, A. A.

doi:10.1021/ar980009u

Cited by 94 publications

(58 citation statements)

References 41 publications

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“…This is carried out by means of a catalytic reaction mediated by a transition metal, 116 and can be applied to the difficult activation and functionalization of C-H bonds in hydrocarbons like alkanes. 117 The oxygen donor can be either organic or inorganic. The most common organic donors are: H 2 O 2 , TBPH, O 3 , N 2 O and peracids (RCO 3 H); whereas inorganic donors include: HNO 3 , NaClO, NaClO 2 and KHSO 5 .…”

Section: Oxygen Donors For Catalytic Oxygen Transfermentioning

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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Section: Oxygen Donors For Catalytic Oxygen Transfermentioning

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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“…Although at the current, laboratory stage of their development, the oxidations with H 2 O 2 have not yet been reported to generate technically useful amounts of required oxygenated materials [94], the authors believe that Mn based "green" C-H oxidation systems will go beyond the laboratory scale in the near future.…”

Section: Discussionmentioning

confidence: 99%

“…To date, the catalysts for C-H oxidation on the basis of Mn porphyrin complexes have been very rare (focusing on complex 2 or its modifications); the catalytic reactions have some characteristics of metal-mediated (non-radical) process (presumably driven by high-valent Mn=O species [21]). However, the mechanism of Mn-porphyrin-catalyzed C-H hydroxylations with H 2 O 2 has not yet been reliably established.…”

Section: C-h Oxidations With H 2 O 2 In the Presence Of Mn Porphyrinsmentioning

confidence: 99%

“…The milestone in the area had been the communication of Shul'pin and Lindsay Smith [59,60] 2 , where L = 1,4,7-trimethyl-1,4,7-triazacyclononane, Me 3 tacn [61], Figure 3) catalyzed the oxidation of alkanes (hexane, cyclohexane, cycloheptane) with H 2 O 2 . In acetonitrile, catalyst 6 was very efficient, performing up to 1350 turnovers ( Table 2).…”

Section: C-h Oxidations With H 2 O 2 In the Presence Of Mn Complexes mentioning

confidence: 99%

“…In the last years, selective catalytic oxidations of unactivated C-H bonds have attracted great attention: this approach, if implemented on preparative scale, could provide easy and efficient methodologies for the directed introduction of oxygen atom into complex organic molecules at late stages of multistep syntheses, on the basis of novel synthetic strategies [1][2][3][4][5][6][7][8][9][10][11]. Selective C-H oxidation reactions may lead to formation of new C-C and C-X (e.g., C-O, C-N, C-S, C-halogen, etc.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Direct Selective Oxidative Functionalization of C–H Bonds with H2O2: Mn-Aminopyridine Complexes Challenge the Dominance of Non-Heme Fe Catalysts

2016

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Non-heme iron(II) complexes are widespread synthetic enzyme models, capable of conducting selective C-H oxidation with H 2 O 2 in the presence of carboxylic acid additives. In the last years, structurally similar manganese(II) complexes have been shown to catalyze C-H oxidation with similarly high selectivity, and with much higher efficiency. In this mini-review, recent catalytic and mechanistic data on the selective C-H oxygenations with H 2 O 2 in the presence of manganese complexes are overviewed. A distinctive feature of catalyst systems of the type Mn complex/H 2 O 2 /carboxylic is the existence of two alternative reaction pathways (as found for the oxidation of cumenes), one leading to the formation of alcohol, and the other to ester. The mechanisms of formation of the alcohol and the ester are briefly discussed.

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Hoch regioselektive Oxygenierung von CHBindungen: Diamidmangankomplexe mit angebundenem Substrat als Katalysatormodelle

2000

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Oxygen Atom Transfer into C−H Bond in Biological and Model Chemical Systems. Mechanistic Aspects

Cited by 94 publications

References 41 publications

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

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

Direct Selective Oxidative Functionalization of C–H Bonds with H2O2: Mn-Aminopyridine Complexes Challenge the Dominance of Non-Heme Fe Catalysts

Hoch regioselektive Oxygenierung von CHBindungen: Diamidmangankomplexe mit angebundenem Substrat als Katalysatormodelle

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