title: A ligand-directed divergent catalytic approach to establish structural and functional scaffold diversity.
abstract: The selective transformation of different starting materials by different metal catalysts under individually optimized reaction conditions to structurally different intermediates and products is a powerful approach to generate diverse molecular scaffolds. In a more unified albeit synthetically challenging strategy, common starting materials would be exposed to a common metal catalysis, leading to a common intermediate and giving rise to different scaffolds by tuning the reactivity of the metal catalyst through different ligands. Herein we present a ligand-directed synthesis approach for the gold(I)-catalysed cycloisomerization of oxindole-derived 1,6-enynes that affords distinct molecular scaffolds following different catalytic reaction pathways. Varying electronic properties and the steric demand of the gold(I) ligands steers the fate of a common intermediary gold carbene to selectively form spirooxindoles, quinolones or df-oxindoles. Investigation of a synthesized compound collection in cell-based assays delivers structurally novel, selective modulators of the Hedgehog and Wnt signalling pathways, autophagy and of cellular proliferation.
authors.affiliation: Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Straße 11, Dortmund 44227, Germany.|Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Otto-Hahn-Straße 6, Dortmund 44221, Germany.
authors.forename: Yen-Chun
authors.initials: YC
authors.lastname: Lee
authors.affiliation: Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Straße 11, Dortmund 44227, Germany.|Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Otto-Hahn-Straße 6, Dortmund 44221, Germany.
authors.forename: Sumersing
authors.initials: S
authors.lastname: Patil
authors.affiliation: Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Otto-Hahn-Straße 6, Dortmund 44221, Germany.
authors.forename: Christopher
authors.initials: C
authors.lastname: Golz
authors.affiliation: Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Otto-Hahn-Straße 6, Dortmund 44221, Germany.
authors.forename: Carsten
authors.initials: C
authors.lastname: Strohmann
authors.affiliation: Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Straße 11, Dortmund 44227, Germany.
authors.forename: Slava
authors.initials: S
authors.lastname: Ziegler
authors.affiliation: Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Straße 11, Dortmund 44227, Germany.
authors.forename: Kamal
authors.initials: K
authors.lastname: Kumar
authors.affiliation: Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Straße 11, Dortmund 44227, Germany.|Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Otto-Hahn-Straße 6, Dortmund 44221, Germany.
authors.forename: Herbert
authors.initials: H
authors.lastname: Waldmann