New applications of the Enantioselective Heck Reaction using Arenediazonium Salts

Abstract

The Heck reaction emerges as one of the most preeminent organic chemistry tools for the formation of C-C bonds. Its asymmetric version has raised great interest, unveiling potential in the formation of enantiomerically enriched products for organic synthesis. Bidentade chiral ligands and electrophiles that form non-coordinating species towards palladium have displayed the best results in the asymmetric Heck reaction. Such electrophiles, for instance diazonium salts, favor the cationic pathway of the reaction, ensuing in a more effective asymmetric induction. Amongst challenges related with the asymmetric Heck reaction, one may point to the functionalization of acyclic olefins which leads to a mixture of regioisomers. Similarly the use of cyclopentenes has resulted in the formation of such mixtures. Professor Correia's group has published promising innovative results on the asymmetric Heck reaction between cyclic olefins, or symmetric allylic systems, and arenediazonium salts, involving bisoxazolines as chiral ligands. Accordingly, the present project has the purpose to further develop, and comprehend, the asymmetric Heck-Matsuda intermolecular reaction. Indeed, the aim is to improve it into a valid organic synthetic tool for the preparation of complex biologically active molecules. Namely, we intend to expand the reaction scope to other substrates, cyclic and acyclic olefins, allylic and bis-allylic alcohols, and to investigate different potential chiral ligands, bisoxazolines and related ligands.