Kinetic investigations on regioselective and stereoselective metalations of functionalized organic compounds in vitro and by using flow-chemistry (B02)

• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2007 to 2019
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 27112786

A I/Li-exchange will allow us to generate stereoselectively polyfunctional secondary alkyllithiums. We will study their configurational stability (kinetic of epimerization) as well as the stereoselectivity of transmetalation (to Mg-, Zn- or Cu-organometallics). In a second part we will investigate the kinetic of new metalations of unsaturated substrates using simultaneously a Lewis-acid and a sterically hindered base. This methodology will allow the selective metalation of DNA-building blocks and electron-deficient heterocycles and their selective functionalization. In a third part we will perform metalations of complex substrates and generate stereoselectively secondary alkyllithiums using a flow-methodology (in contrast to the usual batch-procedure). Additionally we will perform addition-reactions of organometallics to carbonyl-derivatives activated by an IR-laser irradiation.

• DFG Programme: Collaborative Research Centres
• Subproject of: SFB 749: Dynamics and Intermediates of Molecular Transformations
• Applicant Institution: Ludwig-Maximilians-Universität München
• Project Head: Professor Dr. Paul Knochel