Transition metal-catalyzed olefin isomerization for remote functionalization strategies

Abstract

Remote functionalization represents the opportunity to achieve a given transformation at a remote position with respect to an existing functional group. In this thesis, we disclosed the Pd-catalyzed deconjugative long-range isomerization of a,b−unsaturated carbonyl compounds bearing a remote hydroxyl-group for the preparation of a,w−dicarbonyl compounds. Next, two multicatalytic sequential systems were developed for the isomerization of alkenyl methyl ethers to methyl vinyl ethers and subsequent Ni-catalyzed cross-coupling with Grignard reagents. An Ir/Ni system was used with allyl methyl ethers and the enantioselective variant of the reaction was achieved, too. A Pd/Ni system allowed the remote functionalization of alkenyl methyl ethers. The long-range isomerization/borylation of a,b−unsaturated carbonyl compounds bearing a terminal aromatic group was attained using a multicatalytic sequential approach. A Pd-based system was able to discriminate between the two similar olefins of the starting material and the vinyl arene intermediate, which was engaged in a one-pot Cu-catalyzed b−borylation.