Bending Enamine Patterns of Stabilized Pentalenes into "Polymethine Ylides"
We report the synthesis and structural study of 2-substituted 1,3-bis(dimethylamino)pentalenes. The two electrons donating substituents shift the formally anti-aromatic pattern toward more suitable polarized structures. A subtle steric trade-off can result either in planar cyclopentadienyl vinamidiniums or in distorted structures featuring a pyramidalized ylidic carbon adjacent to a stabilized π-conjugated iminium (polymethine). This latter pattern mimics a postulated activated distorted geometry for key Breslow intermediates in the active site of thiamine-dependent enzymes. It highlights how the energetic drive to avoid anti-aromaticity can be used to access models for unconventional distorted conformations of organic molecules.
Références
- Titre
- Bending Enamine Patterns of Stabilized Pentalenes into "Polymethine Ylides"
- Type de publication
- Article de revue
- Année de publication
- 2023
- Auteurs
- Thery, Valentin, Barra Cyriac, Simeoni Alexandra, Pécaut Jacques, Tomás-Mendivil Eder, and Martin David
- Revue
- Organic Letters
- Volume
- 25
- Pagination
- 560–564
- ISSN
- 1523-7060
Soumis le 3 février 2023