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Rearrangements of organic peroxides and related processes

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ABSTRACT

This 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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The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.
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C161: The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.

Mentions: The Fe(II)-promoted activation of peroxides is believed to be involved in the antimalarial activity of a number of peroxides, including the natural product artemisinin. The understanding of the underlying mechanism of the Fe(II)-promoted cleavage of bicyclic peroxides is critical to the design and preparation of more efficient antimalarial peroxides. From this perspective, metal-catalyzed transformations of peroxides are of special interest. It was shown [502] that the reaction of fluorinated cyclic peroxide 557a with FeBr2 in THF proceeds through an intermediate O-centered radical to form epoxy ketone 558a and 1,4-diol 559a. The reaction of 557b with FeCl2(PPh3)2 in CH2Cl2 proceeds in a different manner through an intermediate O-centered radical to yield diepoxide 560b (Scheme 161) [503].


Rearrangements of organic peroxides and related processes
The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.
© Copyright Policy - Beilstein
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC4979652&req=5

C161: The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.
Mentions: The Fe(II)-promoted activation of peroxides is believed to be involved in the antimalarial activity of a number of peroxides, including the natural product artemisinin. The understanding of the underlying mechanism of the Fe(II)-promoted cleavage of bicyclic peroxides is critical to the design and preparation of more efficient antimalarial peroxides. From this perspective, metal-catalyzed transformations of peroxides are of special interest. It was shown [502] that the reaction of fluorinated cyclic peroxide 557a with FeBr2 in THF proceeds through an intermediate O-centered radical to form epoxy ketone 558a and 1,4-diol 559a. The reaction of 557b with FeCl2(PPh3)2 in CH2Cl2 proceeds in a different manner through an intermediate O-centered radical to yield diepoxide 560b (Scheme 161) [503].

View Article: PubMed Central - HTML - PubMed

ABSTRACT

This 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.

No MeSH data available.