title: Divergent Gold(I)-Catalyzed Skeletal Rearrangements of 1,7-Enynes.
abstract: The gold(I) complex catalyzed cycloisomerization and skeletal rearrangement of 1,n-enynes (n=5-7) is a powerful methodology for the efficient synthesis of complex molecular architectures. In contrast to 1,6-enynes, readily accessible homologous 1,7-enynes are largely unexplored in such transformations. Here, the divergent skeletal rearrangement of all-carbon 1,7-enynes by catalysis with a cationic gold(I) complex is reported. Depending on electronic and steric factors, differently substituted 1,7-enynes react via different carbocations formed from a common gold carbene intermediate to yield on the one hand novel exocyclic allenes and on the other hand tricyclic hexahydro-anthracenes through a novel dehydrogenative Diels-Alder reaction.
authors.affiliation: Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Straße 11, 44227 Dortmund (Germany).|Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Otto-Hahn-Straße 6, 44221 Dortmund (Germany).
authors.forename: Rebecca
authors.initials: R
authors.lastname: Meiß
authors.affiliation: Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Straße 11, 44227 Dortmund (Germany). kamal.kumar@mpi-dortmund.mpg.de.|Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Otto-Hahn-Straße 6, 44221 Dortmund (Germany). kamal.kumar@mpi-dortmund.mpg.de.
authors.forename: Kamal
authors.initials: K
authors.lastname: Kumar
authors.affiliation: Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Straße 11, 44227 Dortmund (Germany). herbert.waldmann@mpi-dortmund.mpg.de.|Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Otto-Hahn-Straße 6, 44221 Dortmund (Germany). herbert.waldmann@mpi-dortmund.mpg.de.
authors.forename: Herbert
authors.initials: H
authors.lastname: Waldmann
keywords: catalysis; enynes; gold; synthesis design; synthetic methods