Leveraging the n→π* Interaction in Alkene Isomerization by Selective Energy Transfer Catalysis.

ABSTRACT: Examples of geometric alkene isomerization in nature are often limited to the net exergonic direction (ΔG°<0), with the antipodal net endergonic processes (ΔG°>0) comparatively under-represented. Inspired by the expansiveness of the maleate to fumarate (Z→E) isomerization in biochemistry, we investigated the inverse E→Z variant to validate n_O →π_C=O * interactions as a driving force for contra-thermodynamic isomerization. A general protocol involving selective energy transfer catalysis with inexpensive thioxanthone as a sensitizer (λ_max =402 nm) is disclosed. Whilst in the enzymatic process n_O →π_C=O * interactions commonly manifest themselves in the substrate, these same interactions are shown to underpin directionality in the antipodal

SUBMITTER: Nevesely T 

PROVIDER: S-EPMC9299456 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature