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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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Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.
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C138: Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.

Mentions: The mechanism of this reaction implies that TMSOTf or SnCl4 promote the heterolytic cleavage of the C–O bond in 478d to form carbocation 481d, which is then attacked by allyltrimethylsilane through a chair-like transition state 482d. The subsequent cyclization of 482d through the stabilized carbocation 483d affords silyl-substituted peroxide, 1,2-dioxane 479d, containing the substituent (–CH2SiMe3) in the equatorial position (Scheme 138).


Rearrangements of organic peroxides and related processes
Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.
© Copyright Policy - Beilstein
Related In: Results  -  Collection

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

C138: Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.
Mentions: The mechanism of this reaction implies that TMSOTf or SnCl4 promote the heterolytic cleavage of the C–O bond in 478d to form carbocation 481d, which is then attacked by allyltrimethylsilane through a chair-like transition state 482d. The subsequent cyclization of 482d through the stabilized carbocation 483d affords silyl-substituted peroxide, 1,2-dioxane 479d, containing the substituent (–CH2SiMe3) in the equatorial position (Scheme 138).

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.


Related in: MedlinePlus