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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...

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Bibliographic Details
Main Authors: Pusch, Stefan (Author) , Lefrancois, Daniel (Author) , Dreuw, Andreas (Author)
Format: Article (Journal)
Language:English
Published: 2018
In: The journal of organic chemistry
Year: 2017, Volume: 83, Issue: 2, Pages: 964-972
ISSN:1520-6904
DOI:10.1021/acs.joc.7b02982
Online Access:Verlag, Volltext: https://doi.org/10.1021/acs.joc.7b02982
Verlag: https://doi.org/10.1021/acs.joc.7b02982
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Author Notes:Stefan Pusch, Andreas Tröster, Daniel Lefrancois, Pooria Farahani, Andreas Dreuw, Thorsten Bach, and Till Opatz
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Summary: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.
Item Description:Published: December 22, 2017
Gesehen am 15.05.2020
Physical Description:Online Resource
ISSN:1520-6904
DOI:10.1021/acs.joc.7b02982

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