Asymmetric transannular [1,5] carbon shift of transiently generated C3 ammonium enolates

• Applicant: Professor Dr. Jan Paradies
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 545934529

The project focusses on the development of the so far unkown asymmetric [1,5]-carbon shift for the synthesis of tetrahydroquinoline-4-ones, which is triggered by the transient formation of ammonium enolates. According to our recent results, this reaction is initiated by the intramolecular addition of a tertiary anilin fragment to a Michael-acceptor that generates the reactive ammonium enolate as starting point for the [1,5]-carbon shift. In order to realize the asymmetric reaction, a series of chiral boron and metal compounds will be synthesized, which will serve as chiral Lewis acid catalysts for the novel reaction. This will open up for the asymmetric synthesis of diverging tetrahydroquinoloine-4-ones bearing quaternary stereocenters, annelated rings or bicyclic alkaloid structures. Furthermore, the reaction mechanism will be studied in detail by kinetic and computational experiments.

• DFG Programme: Research Grants