Development of new synthetic strategies exploiting an unexpected rearrangement of vinylcyclopropanes
(2023)
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- Authors
- Supervisors
- Robiette, Raphaël
- Abstract
- Vinylcyclopropanes are key intermediates in organic chemistry which undergo several important rearrangements. The group of Prof. Robiette recently discovered a new rearrangement of vinylcyclopropanes into skipped dienes proceeding at room temperature and with a high selectivity. Based on this transformation, we developed new synthetic methods targeting important but synthetically challenging scaffolds in organic synthesis: skipped dienes, β,γ-unsaturated aldehydes, primary homoallylic alcohols, α-aryl α,β-unsaturated aldehydes and, via the development of a new (4+3) annulation methodology, cycloheptadienes. We also developed a new one-carbon homologation of olefins enabling the insertion of a CHR group. All these methodologies are atom economic, easy to use and are performed under mild transition metal free reaction conditions from cheap or easily obtained reagents. The substituent effects in the key 1,2-migration process shared by almost all our methodologies was investigated by a combination of experimental and computational methods. This allowed us to improve our understanding of the mechanisms at play and the factors controlling reactivity and selectivity in these processes. These combined studies provide a better insights into the Lewis acid triggered rearrangement of donor-acceptor vinylcyclopropanes, vinylexpoxides and DACPs.
- Affiliations
Citations
Delbrassinne, A. (2023). Development of new synthetic strategies exploiting an unexpected rearrangement of vinylcyclopropanes. https://hdl.handle.net/2078.5/105469