Reaction of RuO4 with carbon–carbon double bonds. Part 8.1 Reaction of 7,8-didehydrocholesteryl acetate and cholesteryl acetate with RuO4 and OsO4. A comparative view

Albarella, Laura; Lasalvia, Maria; Piccialli, Vincenzo; Sica, Donato

doi:10.1039/a700294g

Cited by 15 publications

(10 citation statements)

References 19 publications

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“…Support for the pathway set out in Scheme 3 is provided by the fact that we have recently proven the existence of a cyclic ruthenium(VI) diester akin to the postulated intermediate II (Scheme 3). [20,22] Furthermore, we have carried out KMnO 4 oxidations of compounds 1, 3, 8, and 12 according to the procedure of Klein and Rojahn. In all cases, the yields of the cis-tetrahydrofuran derivatives were lower than those achieved applying our procedure for RuO 4 oxidation to the same 1,5-dienes.…”

Section: Resultsmentioning

confidence: 99%

Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols

2001

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An improved procedure for the ruthenium tetraoxide catalysed oxidation of 1,5-dienes, employing 0.05 equiv. of the catalyst RuO 2 ·2H 2 O, 2.5 equiv. of NaIO 4 as a stoichiometric oxidant, and a biphasic solvent system of AcOEt/(CH 3 ) 2 CO/ H 2 O (2:1:1, v/v/v), is presented. Reactions of 1,5-dienes 1, 3, and 5 furnished the new cis-tetrahydrofuran products 2, 4, 6, and 7 with total stereospecificity. The structures of the products have been established on the basis of NMR and MS data, as well as chemical evidence. Application of this procedure to geranyl acetate (8) and neryl acetate (12) afforded the cis-tetrahydrofuran derivatives 9, 10, and 13 in high yields, accompanied by small amounts of trans-tetrahydrofu-

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Section: Resultsmentioning

confidence: 99%

Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols

2001

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“…In a successive study, [95] a careful investigation of this process was carried out and further evidence was gained. In particular, it was observed that three distinct species ( 28 – 30 , Scheme 20) were produced during the oxidation of 7-dehydrocholesteryl acetate and that the most abundant one (>95%) was the new compound 29 .…”

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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“…1,2 Though the most popular process mediated by PCC is the oxidation of primary and secondary alcohols to aldehyde and ketones, respectively, many other functional groups undergo PCC oxidation. As a continuation of our interest in oxidative processes mediated by transition metal oxo-species [3][4][5][6][7][8][9][10][11] as well as in the synthesis and derivatization of new THF-containing compounds, [12][13][14][15][16][17][18][19][20][21] we recently focused on oxidation processes mediated by PCC. These studies led to the discovery of new interesting transformations including oxidative spiroketalization, 22 oxidative cleavage of trisubstituted mono-THF compounds 23 and synthesis of bis--acyloxy-1,4-and 1,5-diketones from THF and THP-diols, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…24 During these studies evidence on some similarities about the oxidative behaviour of PCC and RuO4 were also recorded. In particular, we have previously reported 22 that penta-THF 1 17,20 (Scheme 1), when treated with PCC furnishes the new compounds 2-8 four of which (5)(6)(7)(8) representative of a novel class of poly-THF spiroketals displaying antitumor activity on breast and ovarian cancer cell lines. 22 …”

Section: Introductionmentioning

confidence: 99%

Pyridinium chlorochromate chemistry. New insight into oxidation of tetrahydrofurans

Zaccaria¹,

Borbone²,

Oliviero³

et al. 2017

Arkivoc

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A thorough investigation of the minor oxidation products of two penta-tetrahydrofuran compounds with pyridinium chlorochromate has been carried out. Isolation of ring-B oxygenated spiroketal and degradation products, including polycyclic mono-and bis-lactone compounds, supports the previously postulated involvement of cyclic enolether intermediates in the oxidation of THF and poly-THF substances with PCC. Based on the collected evidence, a new mechanistic route for the PCC-mediated oxidative cleavage of -hydroxy-THF compounds to -lactones has been postulated. The proposed mechanism well agrees with the one reported for the oxidative cleavage of 8-hydroxy-neoisocedranol oxide by RuO4, a fact that further supports our previous observation on the similar oxidizing behaviour shown by PPC and RuO4 towards THFcontaining compounds.

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Reaction of RuO4 with carbon–carbon double bonds. Part 8.1 Reaction of 7,8-didehydrocholesteryl acetate and cholesteryl acetate with RuO4 and OsO4. A comparative view

Cited by 15 publications

References 19 publications

Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols

Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols

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

Pyridinium chlorochromate chemistry. New insight into oxidation of tetrahydrofurans

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