6533b831fe1ef96bd12990fe

RESEARCH PRODUCT

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

Andreas TrösterTill OpatzPooria FarahaniAndreas DreuwThorsten BachDaniel LefrancoisStefan Pusch

subject

010405 organic chemistryChemistryStereochemistryYield (chemistry)Organic ChemistrySinglet state010402 general chemistrySelectivity01 natural sciencesIsomerizationCis–trans isomerism0104 chemical sciences

description

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.

yearjournalcountryeditionlanguage
2017-12-23The Journal of Organic Chemistry
https://doi.org/10.1021/acs.joc.7b02982