Volume 2018, Issue 26 p. 3391-3402
Full Paper

A Phenyl-Ethynyl-Macrocycle: A Model Compound for “Geländer” Oligomers Comprising Reactive Conjugated Banisters

Linda Maria Bannwart

Linda Maria Bannwart

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

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Lukas Jundt

Lukas Jundt

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

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Thomas Müntener

Thomas Müntener

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

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Markus Neuburger

Markus Neuburger

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

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Daniel Häussinger

Daniel Häussinger

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

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Marcel Mayor

Corresponding Author

Marcel Mayor

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

Institute for Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), P. O. Box 3640, 76021 Karlsruhe, Germany

Lehn Institute of Functional Materials (LIFM), School of Chemistry, Sun Yat-Sen University, 510275 Guangzhou, China

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

E-mail: [email protected]

http://www.chemie.unibas.ch/~mayor/index.html

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Dedicated to the memory of Fritz Vögtle (8. March, 1939 – 3. January, 2017)
First published: 01 June 2018
Citations: 5

Graphical Abstract

The conjugation in the helical banister of “Geländer” oligomers is reflected in the compounds electronic and optical properties. The synthesized diyne macrocycle 1 serves as model compound for the development of the chemistry, and to investigate the reactivity of the strained dialkyne subunit, enabling e.g. its engagement in [2+3] cycloadditions.

Abstract

Macrocycle 1 is assembled as smallest member of a series of “Geländer” oligomers with a conjugated banister comprising exclusively sp2- and sp-hybridized carbon atoms. The synthesis of 1 is based on an acetylene scaffolding approach, comprising Sonogashira cross-coupling reactions in combination with protection group strategies and a final cyclization based on an oxidative acetylene coupling using Eglinton-Breslow reaction conditions. Macrocycle 1 serves as model compound for the investigation of the structural integrity of the strained 1,3-diyne subunit. An enhanced reactivity of the strained 1,3-diyne subunit is documented by its engagement in Huisgen's (2+3) cycloaddition when exposed to an azide at elevated temperature. Both structures, macrocycle 1 and cycloaddition-product 2, are fully characterized including their solid-state structure obtained by X-ray diffraction analysis.