Thermal Dearomative Rearrangement of α-(Prop-2-enyl)-α′-(pyridin-2-yl) Malonate Derivatives toward 4 <i>H</i> -Dihydroquinolizines
Reported herein is a thermally induced dearomative rearrangement of α-(aza-heteroaryl)-α'-prop-2-enyl malonate derivatives, affording 4<i>H</i>-dihydroquinolizine derivatives (21 examples, 26-89%). The rearrangement, assisted by microwave heating, afforded diastereoselective quinolizidine scaffolds, known for their broad biological activities. Experimental results and DFT calculations converge to support a stepwise mechanism initiated by intramolecular [1,4]-addition of pyridine nitrogen to the activated acrylate moiety followed by selective ester transfer.
Authors
- Delphine Hatey
- Emmanuel Riguet (ORCID: https://orcid.org/0000-0002-8926-113X)
- Fabienne Grellepois (ORCID: https://orcid.org/0000-0002-0992-722X)
- Aurélien Blanc
- Pierre Locquet
- Noam Boussalem
- Eric Hénon
Institutions
- Centre National de la Recherche Scientifique (FR)
- Institut de Chimie de Strasbourg (FR)
- Institut de Chimie (FR)
- Institut de Chimie Moléculaire de Reims (FR)
- Université de Reims Champagne-Ardenne (FR)
Publication Details
- Journal
- Organic Letters
- Published
- 2026-01-29
- DOI
- https://doi.org/10.1021/acs.orglett.5c05239
- Primary Topic
- Synthesis and Reactivity of Heterocycles
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Agence Nationale de la Recherche
- Centre National de la Recherche Scientifique