Kessler, Vadim
- Institutionen för molekylära vetenskaper, Sveriges lantbruksuniversitet
Sammanfattning
A previously unrecognized base-mediated rearrangement of a benzylic 1,5-hexadipyridynyl moiety is reported. Upon exposure to base, this structural motif rearranges into a constrained vinyl-pyridine substituted cyclobutene. Computational modeling indicates that the rearrangement takes place following a route involving stepwise deprotonation, shifted reprotonation, and 4 pi-electrocyclization. The reaction rate and the stereochemical outcome is consistent with the experimental observations. Furthermore, nonbase mediates rearrangements, through well-known Cope-like [3,3]-sigmatropic shifts, are found to be high in energy, and therefore, take a backseat to the base-mediated pathway. This rearrangement may provide a novel reactivity pathway of conjugated systems for synthetic methodology development.
Nyckelord
density functional theory; mechanism; reactivity; rearrangement
Publicerad i
Chempluschem
2025
Utgivare: WILEY-V C H VERLAG GMBH
SLU författare
UKÄ forskningsämne
Annan kemi
Publikationens identifierare
- DOI: https://doi.org/10.1002/cplu.202500252
Permanent länk till denna sida (URI)
https://res.slu.se/id/publ/143277