Chiral guanidine-catalysts for intramolecular allenoate-cyclizations

• Applicant: Professor Dr. Dieter Enders, since 5/2015 (†)
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2014 to 2018
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 256469433

The submitted research project aims at the development of intramolecular allenoate-cyclizations using nucleophilic guanidine-catalysis. In our previous works, guanidines were already identified as superior catalysts for reactions with otherwise hard-to-activate highly substituted allenoate esters. The current research project aims at the further development of substituents from chemically inert alkyl-groups to reactive electrophiles, which should thus enable previously unknown intramolecular allenoate cyclizations. These works shall not only provide insights into the diverse catalytic action of guanidines but also address fundamental questions regarding the mutual impact of axial on central chirality and vice versa. Also, intramolecular allenoate-cyclizations can be used for the quick and efficient synthesis of biologically active heterocycles.As a second focus, the research project will deal with the total-synthesis of novel, chiral guanidine-bases for enantioselective catalysis. An already established new synthetic methodology allows for quick access to both bicyclic as well as basically unknown, yet highly promising tricyclic guanidine structures. Due to their inherent multifunctional catalytic action as both Bronsted- and Lewis-bases as well as H-bond-donor catalysts, chiral guanidines are likely to be suitable both in a wide variety of single-step, as well as organocatalytic cascade reactions. The project will thus not only address fundamental questions in the area of guanidine- and allenoate-chemistry, but will also open new pathways for the quick and efficient synthesis of complex heterocycles. Finally, guanidines will be further developed into novel tools for organic synthesis with a broad scope of applications.

• DFG Programme: Research Grants
• Ehemaliger Antragsteller: Dr. Philipp Severin Selig, until 3/2015