ISBN 9783843931380

978-3-8439-3138-0, Reihe Organische Chemie

Thorsten M. Beck
Rhodium-catalyzed atom economic addition of enolizable 1,3-dicarbonyl compounds to allenes and alkynes

540 Seiten, Dissertation Albert-Ludwigs-Universität Freiburg im Breisgau (2017), Softcover, A5

Zusammenfassung / Abstract

This dissertation describes the development of new chemo-, regio- and enantioselective rhodium-catalyzed addition reactions for C–C bond formation. Emphasizing the potential of allenes and alkynes as well as various 1,3-dicarbonyl compounds offers an atom economic access to valuable branched α-allylated 1,3-dicarbonyl compounds. The reactions show a broad functional group tolerance and numerous structural variations on both reaction partners highlight the synthetic potential and flexibility of this method.

Underlining the utility of the developed methods, one step transformations to selected heterocycles, systems of medicinal interest and cyclizations were demonstrated. Moreover, deacetylation or basic saponification followed by decarboxylation provided synthetically valuable γ,δ-unsaturated ketones. In addition, first experimental insights of a plausible reaction mechanism were obtained and keto and enol forms of selected compounds were separated and characterized.