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  Dyotropic Rearrangements and Related σ-σ Exchange Processes

Reetz, M. T. (1977). Dyotropic Rearrangements and Related σ-σ Exchange Processes. In F. G. A. Stone, & R. West (Eds.), Advances in Organometallic Chemistry, Vol. 16: Molecular Rearrangements (pp. 33-65). New York: Academic Press.

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 Urheber:
Reetz, M. T.1, Autor           
Affiliations:
1Philipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein-Straße, Marburg, ou_persistent22              

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 Zusammenfassung: Dyotropic rearrangements have been defined as a new class of pericyclic valence isomerizations in which two σ-bonds migrate intramolecularly. Reactions in which the two migrating groups interchange their positions have been designated as type I. Those of type II involve migration to new bonding sites in a manner that avoids positional exchange. Because the simultaneous cleavage of two bonds—although not rare—is generally considered to be a high-energy process, dyotropic reactions are not expected to occur as generally as sigma tropic shifts. Also, multistep processes must be considered in each case. Reactions are most likely to occur if the R groups are known to have a high migratory aptitude in sigma tropic rearrangements. Because silyl and germyl groups undergo extremely rapid metallotropic shifts, it is reasonable to begin investigations using these functions. To date the most detailed studies have been carried out with organosilicon compounds. The presence of heteroatom appears to be necessary. The σ–σ exchange reactions, irrespective of the mechanism, involve far-reaching molecular transformations and are of potential synthetic interest.

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Sprache(n): eng - English
 Datum: 1977
 Publikationsstatus: Erschienen
 Seiten: 33
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1016/S0065-3055(08)60557-2
 Art des Abschluß: -

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Titel: Advances in Organometallic Chemistry, Vol. 16: Molecular Rearrangements
Genre der Quelle: Reihe
 Urheber:
Stone, F. G. A.1, Herausgeber
West, Robert2, Herausgeber
Affiliations:
1 Department of Inorganic Chemistry, The University, Bristol, England, ou_persistent22            
2 Department of Chemistry, University of Wisconsin, Madison, Wisconsin, ou_persistent22            
Ort, Verlag, Ausgabe: New York : Academic Press
Seiten: - Band / Heft: 16 Artikelnummer: - Start- / Endseite: 33 - 65 Identifikator: ISBN: 978-0-12-031116-3
ISSN: 0065-3055