Is the reaction sequence in phosphine-catalyzed [8+2] cycloaddition controlled by electrophilicity?

Is the reaction sequence in phosphine-catalyzed [8+2] cycloaddition controlled by electrophilicity?

In the presence of multiple electrophiles, the reaction sequence is a critical mechanistic problem. Here, we report a theoretical study on the mechanism of phosphine-catalyzed [8+2] cycloaddition of heptafulvenes and allenoate. DFT calculations showed that electrophilicity is the barrier for nucleop...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Chemical communications (Cambridge, England) England), 2021-01, Vol.57 (6), p.761-764
Hauptverfasser: Lin, Wen-Xuan, Pei, Zhuolin, Gong, Cunxi, Mo, Huilin, Yang, Kai, Qu, Ling-Bo, Wei, Donghui, Song, Jin-Shuai, Li, Shi-Jun, Lan, Yu
Format: Artikel
Sprache:eng
Schlagworte:
Cycloaddition
Enthalpy
Mathematical analysis
Phosphines
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:In the presence of multiple electrophiles, the reaction sequence is a critical mechanistic problem. Here, we report a theoretical study on the mechanism of phosphine-catalyzed [8+2] cycloaddition of heptafulvenes and allenoate. DFT calculations showed that electrophilicity is the barrier for nucleophilic attack, while it fails in the prediction of priority. The sequence and priority influenced by electrophilicity.
ISSN:1359-7345
1364-548X
DOI:10.1039/d0cc07370a