Synthesis of Conjugated Linear and Cyclic Polyynes by Selective Alkyne Metathesis
Abstract
ABSTRACT The formation of polyynes with an odd number of conjugated triple bonds is synthetically demanding, particularly for complex architectures, since most established methods rely on irreversible C–C bond‐forming reactions and operate under kinetic control. To address this problem, we have developed the synthesis of triynes via molybdenum‐catalyzed alkyne metathesis of diynes, which allows thermodynamic control through reversible cleavage and formation of carbon–carbon triple bonds. We demonstrate the potential of this method through the synthesis of challenging, more complex products, including triyne precursors to [7]cumulenes, a pentayne, a heptayne, and dehydrobenzannulene macrocycles containing triynes. The key to the success of the proposed methodology is achieving a balance between the selectivity and reactivity of the molybdenum catalyst with the diyne precursors.
Article Details
Authors (13)
Julien Escudero
Univ Rennes, École Nationale Supérieure de Chimie de Rennes Rennes France
Jonathan Long
The Crop Science Centre, Department of Plant Sciences, University of Cambridge
Dylan Bouëtard
Univ Rennes, École Nationale Supérieure de Chimie de Rennes Rennes France
Jennifer Morvan
Univ Rennes, École Nationale Supérieure de Chimie de Rennes, CNRS, ISCR UMR 6226
Mehdi Koohgard
Institut Für Anorganische und Analytische Chemie Technische Universität Braunschweig Braunschweig Germany
Angelika Neitzel
Institut Für Anorganische und Analytische Chemie Technische Universität Braunschweig Braunschweig Germany
Dirk Bockfeld
Institut Für Anorganische und Analytische Chemie Technische Universität Braunschweig Braunschweig Germany
Shedrack Nwachukwu
Department of Chemistry University of Alberta Edmonton Alberta Canada
Thierry Roisnel
Universite de Rennes
Rik R. Tykwinski
Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, Edmonton, Alberta T6G 2G2, Canada
Matthias Tamm
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany
Marc Mauduit
Universite de Rennes
Yann Trolez
Univ Rennes, École Nationale Supérieure de Chimie de Rennes Rennes France