Carbon–carbon bond formation is at the hearth of chemistry and the development of new methodology for catalytic enantioselective C-C bond formation continues to be a major challenge for synthesis. After more than 80 years since the introduction of organolithium reagents, no general, highly enantioselective and practical catalytic C-C bond formation with organolithium reagents exists. In preliminary studies, Feringa´s group have recently discovered that simple alkyl lithium reagents (MeLi, n-BuLi) yield excellent enantioselectivities in copper catalyzed asymmetric allylic alkylation. The subject of the project is the development of new methodologies for highly asymmetric catalyzed C-C bond formation using organolithium reagents. In this research project will try to accomplish the catalytic asymmetric allylic substitution with aryllithium reagents, catalytic asymmetric vinylation of allylic halides and the development of other highly desirable transformations (like the asymmetric formation of chiral quaternary centers via allylic substitution or allyllic alkylation with secondary alkyl lithium reagents). The methodology will be explored in a number of challenging transformations outlined above and the catalysts optimized through chiral ligand screening and optimization of reaction parameters.
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