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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.

No MeSH data available.


Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme–catechol system.
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C188: Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme–catechol system.

Mentions: A key step in the cleavage of the aromatic ring is the oxygen-atom insertion into the C–C-double bond as the result of a Criegee-like or Hock-like intermediate rearrangement [582–583]. It was demonstrated that, despite the different mechanisms of the initial step of the substrate/molecular oxygen activation, both reactions produce hydroperoxide 675 as the intermediate. This hydroperoxide undergoes Criegee-like or Hock-like rearrangement through different pathways. Intradiol dioxygenase catalyzes the 1,2-acyl migration (path B) and the formation of an intermediate anhydride 677. On the other hand, extradiol dioxygenase catalyzes the 1,2-migration of the alkenyl moiety (path A) through the intermediate formation of lactone 676 (Scheme 188) [584].


Rearrangements of organic peroxides and related processes
Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme–catechol system.
© Copyright Policy - Beilstein
Related In: Results  -  Collection

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

C188: Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme–catechol system.
Mentions: A key step in the cleavage of the aromatic ring is the oxygen-atom insertion into the C–C-double bond as the result of a Criegee-like or Hock-like intermediate rearrangement [582–583]. It was demonstrated that, despite the different mechanisms of the initial step of the substrate/molecular oxygen activation, both reactions produce hydroperoxide 675 as the intermediate. This hydroperoxide undergoes Criegee-like or Hock-like rearrangement through different pathways. Intradiol dioxygenase catalyzes the 1,2-acyl migration (path B) and the formation of an intermediate anhydride 677. On the other hand, extradiol dioxygenase catalyzes the 1,2-migration of the alkenyl moiety (path A) through the intermediate formation of lactone 676 (Scheme 188) [584].

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.