Catalytic diastereo- and positionselective oxidative mono-cyclization of 1,5,9-trienes and polyenes

Göhler, Sabrina; Stark, Christian B. W.

doi:10.1039/b702877f

Cited by 35 publications

(8 citation statements)

References 68 publications

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“…In fact, previous studies from our group had demonstrated that the oxidation of both linear and isoprenoid polyenes constantly furnishes poly-THF compounds possessing threo inter-THF relationships. This is consistent with the syn addition (a [3+2] cycloaddition) of a O=Ru-O portion across each involved C-C double bond, along the all- trans polyene chain ( Scheme 3 ), that also agrees with mechanistic proposals for related oxidative mono-cyclization of 1,5-dienes catalysed by RuO 4 [ 10 , 11 , 12 , 13 , 14 , 15 ] and related oxo-species OsO 4 [ 16 , 17 , 18 ] and MnO 4 - [ 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ], as well as rhenium (VII)-mediated oxidative polycyclization of hydroxypolyenes [ 28 , 29 , 30 , 31 ].…”

Section: Resultssupporting

confidence: 85%

Isolation of a Bis-Iodurated Tetra-THF as a Trace Product from the Oxidation of Squalene with RuO4 and Its Double Ring Expansion to a Novel bis-THF-bis-THP Compound

et al. 2011

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A novel bis-iodurated polyether compound, based on an unprecedented tetra-THF backbone, has been isolated as a trace by-product of the oxidation of squalene with the catalytic system RuO2(cat.)/NaIO4. The double erythro configuration of the central portion of the molecule furnishes the first indirect support of the previously postulated pathway operating in the oxidative pentacyclization of the isoprenoid substrate. A bidirectional double oxidative bis-cyclization is invoked to explain the formation of this compound. The isolated substance was successfully subjected to a double rearrangement-ring expansion to give a novel bis-THF-bis-THP compound.

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Section: Resultssupporting

confidence: 85%

Isolation of a Bis-Iodurated Tetra-THF as a Trace Product from the Oxidation of Squalene with RuO4 and Its Double Ring Expansion to a Novel bis-THF-bis-THP Compound

et al. 2011

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“…As a more recent contribution in this field Stark and co-workers investigated the mono-cyclization of a range of polyenes, namely 1,5,9-trienes, 1,5,9,12-tetraenes and squalene [102]. Selected examples are reported in Scheme 23.…”

Section: Ruthenium Tetroxide Chemistrymentioning

confidence: 99%

“…Oxidative monocyclization of polyenes. Overall yields including overoxidation products are shown in parentheses [102]. …”

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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“…Bisepoxidation of the Δ 7 and Δ 15 double bond in the farnesyl residue (for atom numbering see Scheme 1), followed by regio- and stereoselective nucleophilic addition of water (and methylation) would deliver heronapyrroles A and B. Similarly, regio- and stereoselective nucleophilic addition of water to a tris -epoxy farnesyl intermediate 4 could initiate a cyclization cascade [1,3,8] that would provide the bis -tetrahydrofuran heronapyrrole C (Scheme 1), via a mechanism that closely resembles polyether antibiotic biosynthesis [12–17]. This biosynthetic hypothesis raises the possibility that Streptomyces sp.…”

Section: Resultsmentioning

confidence: 99%

Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

Schmidt

Khalil

Capon

et al. 2014

Beilstein J. Org. Chem.

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SummaryThe heronapyrroles A–C have first been isolated from a marine-derived Streptomyces sp. (CMB-0423) in 2010. Structurally, these natural products feature an unusual nitropyrrole system to which a partially oxidized farnesyl chain is attached. The varying degree of oxidation of the sesquiterpenyl subunit in heronapyrroles A–C provoked the hypothesis that there might exist other hitherto unidentified metabolites. On biosynthetic grounds a mono-tetrahydrofuran-diol named heronapyrrole D appeared a possible candidate. We here describe a short asymmetric synthesis of heronapyrrole D, its detection in cultivations of CMB-0423 and finally the evaluation of its antibacterial activity. We thus demonstrate that biosynthetic considerations and the joint effort of synthetic and natural product chemists can result in the identification of new members of a rare class of natural products.

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Catalytic diastereo- and positionselective oxidative mono-cyclization of 1,5,9-trienes and polyenes

Cited by 35 publications

References 68 publications

Isolation of a Bis-Iodurated Tetra-THF as a Trace Product from the Oxidation of Squalene with RuO4 and Its Double Ring Expansion to a Novel bis-THF-bis-THP Compound

Isolation of a Bis-Iodurated Tetra-THF as a Trace Product from the Oxidation of Squalene with RuO4 and Its Double Ring Expansion to a Novel bis-THF-bis-THP Compound

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

Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

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