Copper-catalyzed asymmetric transformations with dihalogenated allylic compounds

Abstract

This doctoral thesis focuses on the development of copper-catalyzed asymmetric reactions involving alkyne allylboration with various allylic substrates, meso dibromocycloalkenes and geminal dichlorides, and the borylation of geminal dichlorides. These reactions use the catalytic generation of the LCu-Bpin complex. The thesis introduces a new copper-catalyzed methodology for the asymmetric allylboration of meso dibromocycloalkenes, leading to 1,4 dienes with up to three stereocenters and excellent regio, diastereo and enantioselectivity. By optimizing various parameters, including the use of a specific NHC sulfonate ligand and slow addition of the meso-compound, the reaction yields high enantioselectivity and efficient transformations, demonstrating broad applicability in creating optically active cyclic scaffolds. The second section develops a copper catalyzed alkyne allylboration using geminal dichlorides as electrophiles, which introduces a new challenge due to the formation of E Z isomers. The methodology efficiently generates 1,4 skipped dienes with an alkenylboronate, an alkenyl chloride and a bis-allylic stereocenters with excellent stereoselectivity.