Oxidation by Oxochromium(VI) Compounds

Freeman, Fillmore

doi:10.1007/978-1-4613-2109-5_2

Cited by 14 publications

(6 citation statements)

References 316 publications

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“…It could be excluded that they were generated in the matrix by isomerization of epoxide complexes and on permethylation of the olefinic bond (i.e., employment of TME) their formation route was completely suppressed. Moreover, first representatives for OCrCl 2 ···epoxide complexes, often proposed as intermediates in the literature, − ,,, have been isolated and characterized. Both types of complexes should be considered as respectable intermediates also under thermal conditions.…”

Section: Discussionmentioning

confidence: 99%

“…For quite some time the olefin oxidation with chromyl chloride (CrO 2 Cl 2 ) seemed to proceed completely unspecifically, and reports with the most different product palettes accumulated. − The first selective oxidation was reported in 1969 by F. Freeman et al claiming that reductive workup of the reaction mixtures in the presence of zinc enables the isolation of carbonyl compounds in good yields . However, mainly disubstituted, electron-rich olefins had been employed in this investigation. − In 1973 K. B. Sharpless et al found that chloroketones are formed selectively if the reactions are carried out in acetone at −78 °C, and they related the findings made on reductive workup 7-11 to the reduction of these oxychlorides by zinc.…”

Section: Introductionmentioning

confidence: 93%

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Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Limberg

Köppe

1999

Inorg. Chem.

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After photolytic induction (411 nm) of the reaction between chromyl chloride and olefins in low-temperature matrixes, for the first time primary products of this system have been isolated and identified: the reaction of propylene yields O=CrCl(2).O=CHCH(2)CH(3) and while in the case of trans- and cis-2-butylene, OCrCl(2).O=C(CH(3))(CH(2)CH(3)) as well as OCrCl(2).(trans-2,3-butylene oxide) and OCrCl(2).(cis-2,3-butylene oxide) are obtained, respectively. Epoxide formation proceeds under complete retention of stereochemistry, and the regioselective reaction route leading to the carbonyl products can be suppressed if all hydrogen atoms at the olefinic bond are substituted: tetramethylethylene is selectively oxidized to tetramethylethylene oxide, which forms a complex with OCrCl(2). All products were characterized by IR spectroscopy, which was further supported by DFT calculations in certain cases. The mechanism leading to the formation of these products, their electronic states, and the implications of the matrix results on the thermal reactions of chromyl chloride are discussed.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 93%

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Limberg

Köppe

1999

Inorg. Chem.

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“…Permanganate [168] and references therein] and oxochromium (VI) reagents such as chromyl acetate and chromyl chloride [169,170,171,172] are well-known to oxidize alkanes. The above examples and literature data indicate that the RuO 4 -catalyzed process has the greatest synthetic potential both for regioselectivity and effectiveness reasons.…”

Section: Ruthenium Tetroxide Chemistrymentioning

confidence: 99%

Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species

Piccialli

2014

Molecules

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Abstract:In the last years ruthenium tetroxide is increasingly being used in organic synthesis. Thanks to the fine tuning of the reaction conditions, including pH control of the medium and the use of a wider range of co-oxidants, this species has proven to be a reagent able to catalyse useful synthetic transformations which are either a valuable alternative to established methods or even, in some cases, the method of choice. Protocols for oxidation of hydrocarbons, oxidative cleavage of C-C double bonds, even stopping the process at the aldehyde stage, oxidative cleavage of terminal and internal alkynes, oxidation of alcohols to carboxylic acids, dihydroxylation of alkenes, oxidative degradation of phenyl and other heteroaromatic nuclei, oxidative cyclization of dienes, have now reached a good level of improvement and are more and more included into complex synthetic sequences. The perruthenate ion is a ruthenium (VII) oxo-species. Since its introduction in the mid-eighties, tetrapropylammonium perruthenate (TPAP) has reached a great popularity among organic chemists and it is mostly employed in catalytic amounts in conjunction with N-methylmorpholine N-oxide (NMO) for the mild oxidation of primary and secondary alcohols to carbonyl compounds. Its use in the oxidation of other functionalities is known and recently, its utility in new synthetic transformations has been demonstrated. New processes, synthetic applications, theoretical studies and unusual transformations, published in the last eight years (2006)(2007)(2008)(2009)(2010)(2011)(2012)(2013), in the chemistry of these two oxo-species, will be covered in this review with the aim of offering a clear picture of their reactivity. When appropriate, related oxidative transformations mediated by other metal oxo-species will be presented to highlight similarities and differences. An historical overview of some aspects of the ruthenium tetroxide chemistry will be presented as well.

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“…Diols seem not to be a product in the reaction of chromyl chloride and olefins; instead, an often complex mixture is produced, with epoxide and cis -chlorohydrin as the main products, and, sometimes, vicinal dichloride 282a. The mechanism by which these products are formed has been the subject of extensive studies since as early as 1893; however, it was not revealed until 1998. , …”

Section: Epoxidationmentioning

confidence: 99%

Theoretical Studies of Some Transition-Metal-Mediated Reactions of Industrial and Synthetic Importance

2000

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Oxidation by Oxochromium(VI) Compounds

Cited by 14 publications

References 316 publications

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species

Theoretical Studies of Some Transition-Metal-Mediated Reactions of Industrial and Synthetic Importance

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Oxidation by Oxochromium(VI) Compounds

Cited by 14 publications

References 316 publications

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl2−Epoxide Complexes

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl2−Epoxide Complexes

Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species

Theoretical Studies of Some Transition-Metal-Mediated Reactions of Industrial and Synthetic Importance

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Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes