Iron(II)-promoted rearrangement of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]oct-5-enes: a mechanism distinct from that postulated previously

Kamata, Masaki; Satoh, Chika; Kim, Hye‐Sook; Wataya, Yusuke

doi:10.1016/s0040-4039(02)02024-5

Cited by 13 publications

(5 citation statements)

References 23 publications

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“…Modification in the cycloheptane ring, with complete saturation of C7-C8, was expected to improve antimalarial activity by obviating possible peroxide-diepoxidation rearrangement. 39 However, saturation in the cycloheptane ring was found to be unfavorable for antimalarial activity in the thaperoxide series. Saturated analogues (25,(28)(29)(30)(31) were less active than the corresponding unsaturated analogues (3,(20)(21)(22)(23).…”

Section: Resultsmentioning

confidence: 99%

Design, Synthesis, and Development of Novel Guaianolide-Endoperoxides as Potential Antimalarial Agents

et al. 2010

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Design and synthesis of a guaianolide-endoperoxide (thaperoxide) 3 was pursued as a new antimalarial lead which was found to be noncytotoxic as compared to the natural product lead thapsigargin 2. Several analogues of 3 were successfully synthesized and found to be comparable to derivatives of artemisinin 1 in in vitro antimalarial assay. Among the synthesized compounds, 22 showed excellent in vitro potency against the cultured parasites (W2 IC(50) = 13 nM) without apparent cytotoxicity. Furthermore, SAR trends in thaperoxide analogues are presented and explained with the help of docking studies in the homology model of PfSERCA(PfATP6).

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Section: Resultsmentioning

confidence: 99%

Design, Synthesis, and Development of Novel Guaianolide-Endoperoxides as Potential Antimalarial Agents

et al. 2010

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“…In a related study investigating the reaction of 557а–с with FeBr 2 , bis-epoxides 560а–с and epoxy ketones 561а–с were obtained as the major products ( Table 29 ) [ 504 ] and the proposed mechanism of the rearrangement of 557a–c is presented in Scheme 162 .…”

Section: Reviewmentioning

confidence: 99%

Rearrangements of organic peroxides and related processes

Yaremenko¹,

Vil²,

Demchuk³

et al. 2016

Beilstein J. Org. Chem.

194

136

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SummaryThis review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

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“…A similar type of fragmentation was induced within endoperoxide 34 by an iron(II) species, leading to bis-epoxide 38 , as shown in Scheme b . This rearrangement is presumed to proceed through the sequential one-electron transfers involving transient species 35 – 37 . , Photochemically-induced homolytic rupture of endoperoxides is also possible as demonstrated in Scheme c . Specifically, endoperoxide 40 , generated from naphthalene derivative 39 , formed bis-epoxide 42 , presumably via diradical 41 .…”

Section: Resultsmentioning

confidence: 96%

“…29k This rearrangement is presumed to proceed through the sequential one-electron transfers involving transient species 35 – 37 . 30 , 31 Photochemically-induced homolytic rupture of endoperoxides is also possible as demonstrated in Scheme 3 c. 29c Specifically, endoperoxide 40 , generated from naphthalene derivative 39 , formed bis-epoxide 42 , presumably via diradical 41 . Further elaboration of 42 led first to syn diol 43 and thence dihydroxy quinone 44 , demonstrating the accessibility and versatility of the endoperoxide moiety.…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of Viridicatumtoxin B and Analogues Thereof: Strategy Evolution, Structural Revision, and Biological Evaluation

et al. 2014

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The details of the total synthesis of viridicatumtoxin B (1) are described. Initial synthetic strategies toward this intriguing tetracycline antibiotic resulted in the development of key alkylation and Lewis acid-mediated spirocyclization reactions to form the hindered EF spirojunction, as well as Michael–Dieckmann reactions to set the A and C rings. The use of an aromatic A-ring substrate, however, was found to be unsuitable for the introduction of the requisite hydroxyl groups at carbons 4a and 12a. Applying these previous tactics, we developed stepwise approaches to oxidize carbons 12a and 4a based on enol- and enolate-based oxidations, respectively, the latter of which was accomplished after systematic investigations that revealed critical reactivity patterns. The herein described synthetic strategy resulted in the total synthesis of viridicatumtoxin B (1), which, in turn, formed the basis for the revision of its originally assigned structure. The developed chemistry facilitated the synthesis of a series of viridicatumtoxin analogues, which were evaluated against Gram-positive and Gram-negative bacterial strains, including drug-resistant pathogens, revealing the first structure–activity relationships within this structural type.

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Iron(II)-promoted rearrangement of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]oct-5-enes: a mechanism distinct from that postulated previously

Cited by 13 publications

References 23 publications

Design, Synthesis, and Development of Novel Guaianolide-Endoperoxides as Potential Antimalarial Agents

Design, Synthesis, and Development of Novel Guaianolide-Endoperoxides as Potential Antimalarial Agents

Rearrangements of organic peroxides and related processes

Total Synthesis of Viridicatumtoxin B and Analogues Thereof: Strategy Evolution, Structural Revision, and Biological Evaluation

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