title: Hydroxy-Directed Ruthenium-Catalyzed Alkene/Alkyne Coupling: Increased Scope, Stereochemical Implications, and Mechanistic Rationale.
abstract: The recognition of the dual binding mode of propargyl and allyl alcohols to [Cp*Ru] fragments fostered the development of a highly regioselective intermolecular Alder-ene-type reaction of alkynes with 1,2-disubstituted alkenes. The increased substrate scope opens new perspectives in stereochemical terms. As the loaded catalyst is chiral-at-metal, stereochemical information is efficiently relayed from the propargylic site to the emerging C-C bond. This interpretation is based on the X-ray structure of the first Cp*Ru complex carrying an intact enyne ligand, and provides valuable insights into bonding and activation of the substrates. Computational data draw a clear picture of the principles governing regio- and stereocontrol.
authors.affiliation: Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
authors.forename: Stephan M
authors.initials: SM
authors.lastname: Rummelt
authors.affiliation: Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
authors.forename: Gui-Juan
authors.initials: GJ
authors.lastname: Cheng
authors.affiliation: Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
authors.forename: Puneet
authors.initials: P
authors.lastname: Gupta
authors.affiliation: Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
authors.forename: Walter
authors.initials: W
authors.lastname: Thiel
authors.affiliation: Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
authors.forename: Alois
authors.identifier: 0000-0003-0098-3417
authors.initials: A
authors.lastname: Fürstner
keywords: alkynes; hydrogen bonds; metallacycles; reaction mechanisms; ruthenium