Buchumschlag

Mechanism and cis/trans Selectivity of Vinylogous Nazarov-type [6π] Photocyclizations

Vinylogous Nazarov-type cyclizations yield seven-membered rings from butadienyl vinyl ketones via a photochemical [6π] photocyclization followed by subsequent isomerization steps. The mechanism of this recently developed method was investigated using unrestricted DFT, SF-TDDFT, and CASSCF/NEVPT2 cal...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Hauptverfasser: Pusch, Stefan (VerfasserIn) , Lefrancois, Daniel (VerfasserIn) , Dreuw, Andreas (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 2018
In: The journal of organic chemistry
Year: 2017, Jahrgang: 83, Heft: 2, Pages: 964-972
ISSN:1520-6904
DOI:10.1021/acs.joc.7b02982
Online-Zugang:Verlag, Volltext: https://doi.org/10.1021/acs.joc.7b02982
Verlag: https://doi.org/10.1021/acs.joc.7b02982
Volltext
Verfasserangaben:Stefan Pusch, Andreas Tröster, Daniel Lefrancois, Pooria Farahani, Andreas Dreuw, Thorsten Bach, and Till Opatz
Beschreibung
Zusammenfassung:Vinylogous Nazarov-type cyclizations yield seven-membered rings from butadienyl vinyl ketones via a photochemical [6π] photocyclization followed by subsequent isomerization steps. The mechanism of this recently developed method was investigated using unrestricted DFT, SF-TDDFT, and CASSCF/NEVPT2 calculations, suggesting three different pathways that lead either to pure trans, pure cis, or mixed cis/trans configured products. Singlet biradicals or zwitterions occur as intermediates. The computational results are supported by deuterium-labeling experiments.
Beschreibung:Published: December 22, 2017
Gesehen am 15.05.2020
Beschreibung:Online Resource
ISSN:1520-6904
DOI:10.1021/acs.joc.7b02982

Ähnliche Einträge