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Mechanistic and Kinetic Factors of ortho‐Benzyne Formation in Hexadehydro‐Diels‐Alder (HDDA) Reactions
Zitieren Sie bitte immer diese URN: urn:nbn:de:bvb:20-opus-239006
- With the rapid development of the hexadehydro‐Diels‐Alder reaction (HDDA) from its first discovery in 1997, the question of whether a concerted or stepwise mechanism better describes the thermally activated formation of ortho‐benzyne from a diyne and a diynophile has been debated. Mechanistic and kinetic investigations were able to show that this is not a black or white situation, as minor changes can tip the balance. For that reason, especially, linked yne‐diynes were studied to examine steric, electronic, and radical‐stabilizing effects ofWith the rapid development of the hexadehydro‐Diels‐Alder reaction (HDDA) from its first discovery in 1997, the question of whether a concerted or stepwise mechanism better describes the thermally activated formation of ortho‐benzyne from a diyne and a diynophile has been debated. Mechanistic and kinetic investigations were able to show that this is not a black or white situation, as minor changes can tip the balance. For that reason, especially, linked yne‐diynes were studied to examine steric, electronic, and radical‐stabilizing effects of their terminal substituents on the reaction mechanism and kinetics. Furthermore, the influence of the nature of the linker on the HDDA reaction was explored. The more recently discovered photochemical HDDA reaction also gives ortho‐arynes, which display the same reactivity as the thermally generated ones, but their formation might not proceed by the same mechanism. This minireview summarizes the current state of mechanistic understanding of the HDDA reaction.…
Autor(en): | Jan Maier, Todd B. Marder |
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URN: | urn:nbn:de:bvb:20-opus-239006 |
Dokumentart: | Artikel / Aufsatz in einer Zeitschrift |
Institute der Universität: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Sprache der Veröffentlichung: | Englisch |
Titel des übergeordneten Werkes / der Zeitschrift (Englisch): | Chemistry – A European Journal |
Erscheinungsjahr: | 2021 |
Band / Jahrgang: | 27 |
Heft / Ausgabe: | 30 |
Erste Seite: | 7978 |
Letzte Seite: | 7991 |
Originalveröffentlichung / Quelle: | Chemistry – A European Journal 2021, 27(30):7978–7991. DOI: 10.1002/chem.202100608 |
DOI: | https://doi.org/10.1002/chem.202100608 |
Allgemeine fachliche Zuordnung (DDC-Klassifikation): | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Freie Schlagwort(e): | Alkyne; Benzyne; Cyclization; Hexadehydro-Diels-Alder; reaction mechanism |
Datum der Freischaltung: | 16.12.2021 |
Lizenz (Deutsch): | CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International |