Oxidation of cycloalkanes by H2O2 using a copper–hemicryptophane complex as a catalyst

Perraud, Olivier; Sorokin, Alexander B.; Dutasta, Jean‐Pierre; Martinez, Alexandre

doi:10.1039/c2cc37829a

Cited by 70 publications

(50 citation statements)

References 48 publications

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“…Polynuclear metal complexes containing voluminous organic [63,66,118,119,[129][130][131]186,[213][214][215][216][217][218][234][235][236][237][238][239][240][241] or siloxane [221][222][223][224][225][226][227][228] ligands are also very efficient in oxidations of organic compounds including saturated hydrocarbons with peroxides. For example, dinuclear copper complex 11 [221,224] and hexairon complex 15 (for the structure, see Figure 9) affording the products of cyclohexane oxidation in a very high yield of 46% (see Figure 10 [226]) can be considered as "inorganic models of methane monooxygenases."…”

Section: Discussionmentioning

confidence: 99%

“…During the past several decades, many metals have been studied in catalytic activation and functionalization of carbon-hydrogen bonds. The reader is directed to selected recent examples with gold [123], cobalt [124][125][126] chromium [127], copper [128][129][130][131] iron [132][133][134][135], iridium [136], manganese [137][138][139], molybdenum [140], nickel [141], osmium [142][143][144][145][146][147][148], palladium [149][150][151], rhenium [152], rhodium [153,154], ruthenium [155,156], and vanadium [157,158].…”

Section: Metal Ions Most Active In Oxidation Catalysismentioning

confidence: 99%

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New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

170

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This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst). Works of recent years (mainly 2010-2016) devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon-hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.

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Section: Discussionmentioning

confidence: 99%

Section: Metal Ions Most Active In Oxidation Catalysismentioning

confidence: 99%

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

170

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“…In 2013, the first use of a Cu II –hemicryptophane complex 100 (Figure 15) was reported for the oxidation of cyclohexane to cyclohexanol and cyclohexanone 40. The complex catalyzed the oxidation of alkenes in the presence of hydrogen peroxide as the terminal oxidant.…”

Section: Oxidationsmentioning

confidence: 99%

Substrate‐Selective Catalysis

Lindbäck

Dawaigher

Wärnmark

2014

Chemistry A European J

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Substrate selectivity is an important output function for the validation of different enzyme models, catalytic cavity compounds, and reaction mechanisms as demonstrated in this review. In contrast to stereo-, regio-, and chemoselective catalysis, the field of substrate-selective catalysis is under-researched and has to date generated only a few, but important, industrial applications. This review points out the broad spectrum of different reaction types that have been investigated in substrate-selective catalysis. The present review is the first one covering substrate-selective catalysis and deals with reactions in which the substrates involved have the same reacting functionality and the catalysts is used in catalytic or in stoichiometric amounts. The review covers real substrate-selective catalysis, thus only including cases in which substrate-selective catalysis has been observed in competition between substrates.

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“…Moreover, encaged azatrane structures can be formed when a metal or heteroelement is introduced into the tren unit. For instance, the Cu II complex of host 2 (Scheme ) was shown to display remarkable properties in C−H oxidation; an improvement in the yield and substrate selectivity was observed compared with the model molecule, which lacked the cavity . Proazaphosphatrane Verkade superbases were also incorporated into a hemicryptophane core, which strongly affected the thermodynamics and kinetics of proton transfer.…”

Section: Introductionmentioning

confidence: 99%

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

Lefevre

Zhang

Godart

et al. 2016

Chemistry A European J

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A convenient and efficient gram-scale synthesis for enantiopure hemicryptophane-tren (tren=tris(2-aminoethyl)amine) derivatives has been developed. The four-step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.

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Oxidation of cycloalkanes by H2O2 using a copper–hemicryptophane complex as a catalyst

Abstract: Efficient alkane C-H bond oxidation was achieved using a newly designed Cu(II)-hemicryptophane complex. Protection of the copper site in the inner cavity of the host leads to enhanced yields and allows discriminating cyclohexane from cyclooctane or adamantane in competitive experiments.

Cited by 70 publications

References 48 publications

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Substrate‐Selective Catalysis

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

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