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Synthesis and Characterization of Sequence-Defined Stiff Oligomers Using the Sonogashira Reaction

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Synthesis and Characterization of Sequence-Defined Stiff Oligomers Using the Sonogashira Reaction Zur Erlangung des akademischen Grades einer DOKTORIN DER NATURWISSENSCHAFTEN (Dr. rer. nat.) der KIT-Fakultät für Chemie und Biowissenschaften des Karlsruher Instituts für Technologie (KIT) genehmigte DISSERTATION von M.Sc. Rebekka Valerie Schneider 1. Referent: Prof. Dr. Michael A. R. Meier 2. Referent: Prof. Dr. Uli Lemmer Tag der mündlichen Prüfung: 19.07.2018 Meinen Eltern und Nico "To achieve great things, two things are needed: a plan, and not quite enough time." after Leonard Bernstein Die vorliegende Arbeit wurde von Januar 2015 bis Juli 2018 unter Anleitung von Prof. Dr. Michael A. R. Meier am Institut für Organische Chemie (IOC) des Karlsruher Instituts für Technologie (KIT) durchgeführt. Hiermit versichere ich, dass ich die Arbeit selbstständig angefertigt, nur die angegebenen Quellen und Hilfsmittel benutzt und mich keiner unzulässigen Hilfe Dritter bedient habe. Insbesondere habe ich wörtlich oder sinngemäß aus anderen Werken übernommene Inhalte als solche kenntlich gemacht. Die Satzung des Karlsruher Instituts für Technologie (KIT) zur Sicherung wissenschaftlicher Praxis habe ich beachtet. Des Weiteren erkläre ich, dass ich mich derzeit in keinem laufenden Promotionsverfahren befinde, und auch keine vorausgegangenen Promotionsversuche unternommen habe. Die elektronische Version der Arbeit stimmt mit der schriftlichen Version überein und die Primärdaten sind gemäß der Satzung zur Sicherung guter wissenschaftlicher Praxis des KIT beim Institut abgegeben und archiviert. Karlsruhe, 19.07.2018 Danksagung Zu Beginn möchte ich mich ganz herzlich bei Prof. Dr. Michael Meier danken. Zum einen für die Möglichkeit dieses Thema in seiner Arbeitsgruppe zu bearbeiten, vor allem aber auch für die exzellente Betreuung. Auch dem restlichen Arbeitskreis (inklusive der Alumni und Pinar Sancar) möchte ich für die angenehme Arbeitsatmosphäre danken. Der Deutschen Forschungsgemeinschaft (DFG) danke ich für die Einrichtung des Sonderforschungsbereich 1176 und der daraus resultierenden Förderung, inklusive der Möglichkeit an mehreren Konferenzen teilzunehmen. Fabian Hundemer aus der Arbeitsgruppe von Prof. Dr. Bräse ist für die Bereitstellung von Molekülen mit TADF-Funktion zu danken. Dr. Andreas Arndt aus der Gruppe von Prof. Dr. Lemmer, sowie Dr. Ian Howard haben durch Absorptions- und Emissionsmessungen zu dieser Arbeit beigetragen. Allen, die an der Synthese von jeglichen Molekülen, die in dieser Arbeit beschrieben sind möchte ich danken: Lea Bayer, Pascal Rauthe, Rieke Schulte und Thomas Sattelberger. Der größte Dank gebührt aber Rebecca Seim, die maßgeblich zum Gelingen dieser Arbeit beigetragen hat. Der Analytikabteilung des IOC danke ich für Messungen von IR, FAB und verschiedenen NMR Experimenten. Auf diesem Wege möchte ich auch Andreas Boukis, Benjamin Bitterer und Eduard Spuling für Messungen am 500 MHz Spektrometer und Maximiliane Frölich für ESI-MS-Messungen erwähnen. Kevin Waibel, Gregor Klein, Philipp Bohn, Maximiliane Frölich und Michael Schneider haben diese Arbeit Korrektur gelesen und damit einen wichtigen Beitrag zum Entstehen geleistet. Abstract Conjugated rod-like oligomers are interesting compounds for electronic applications. Several iterative procedures for the synthesis of monodisperse oligo(phenylene ethynylene)s (OPEs) were described, but only one example to sequence-defined OPEs is known to date. Sequence-defined conjugated oligomers offer the unique opportunity to investigate quantitative structure- property relationships. In this work, a solution-based, linear procedure to sequence-defined OPEs is introduced. Therefore, several aromatic building blocks exhibiting a halogen and a protected triple bonds were synthesized. Different dialkoxy side chains served as solubilizing groups, displaying electron donating features. Furthermore, building blocks with electron accepting properties were prepared. The rod-like oligomers were established by Sonogashira cross-coupling and subsequent deprotection of the triple bond enabling a further Sonogashira reactions in this iterative sequence. Initially, phenylacetylene as starting unit was converted with a building block yielding a monomer. With the formerly mentioned procedure, a monodisperse as well as a sequence-defined rod-like pentamer was synthesized over ten steps. The overall yield of the monodisperse pentamer amounted to 18% and a scale of 116 milligrams; the sequence-defined pentamer exhibited an overall yield of 3.2% and a scale of 73.6 milligrams. The final products and their respective intermediates were fully characterized by 1H and 13C NMR, mass and IR spectroscopy. Additionally, SEC and DSC were performed and the photophysical properties were investigated by UV/Vis spectroscopy. A direct oligomerization approach with a chain stopper to monodisperse rod-like oligomers resulted in a broad oligomer mixture and clearly justifies the iterative reaction procedure. In a second part of this work, monodisperse rod-like oligomers were connected to dyes with thermally activated delayed fluorescence function by Sonogashira cross-coupling. The oligomer-dye conjugates were fully characterized and might be useful compounds to investigate optoelectronic processes in organic solar cells. VII Kurzzusammenfassung Konjugierte Stäbchenmoleküle sind interessante Verbindungen für elektronische Anwendungen. Mehrere iterative Syntheseverfahren zu monodispersen Phenylalkin-Oligomeren wurden publiziert, aber nur ein Beispiel zu derartigen sequenzdefinierten Oligomeren existiert. Dabei könnten sequenzdefinierte, konjugierte Oligomere einen wichtigen Beitrag zur Erforschung von Struktur- Eigenschafts-Beziehungen liefern. In dieser Arbeit wird ein lineares Syntheseverfahren zu sequenzdefinierten Phenylalkin-Oligomeren in Lösung vorgestellt. Dafür wurden verschiedene Bausteinmoleküle mit einem Halogen und einer geschützten Dreifachbindung synthetisiert. Verschiedene Dialkyloxysubstituenten zur besseren Löslichkeit weisen zusätzlich elektronenschiebende Eigenschaften auf. Des Weiteren wurden Elektronenakzeptor-Bausteine hergestellt. Die Stäbchenmoleküle wurden über Zyklen von Sonogashira Kreuzkupplung und anschließender Entschützung der Dreifachbindung realisiert. Zunächst wurde Phenylacetylen als Starteinheit mit einem Bausteinmolekül umgesetzt und das entsprechende Monomer erhalten. Mit dem vorgestellten Syntheseverfahren konnten ein monodisperses und ein sequenzdefiniertes Pentamer in jeweils zehn Reaktionsschritten erhalten werden. Die Ausbeute für das monodisperse Pentamer belief sich dabei auf 18% und 116 Milligramm. Für das sequenzdefinierte Pentamer wurde eine Ausbeute von 3.2% und 73.6 Milligramm erhalten. Die finalen Produkte sowie die entsprechenden Intermediate wurden vollständig mit 1H und 13C-NMR, IR-Spektroskopie und Massenspektrometrie charakterisiert. Zusätzlich wurde SEC und DSC durchgeführt und die photophysikalischen Eigenschaften mit UV/Vis-Spektroskopie untersucht. Ein direkter Oligomerisierungsversuch zu monodispersen Stäbchenmolekülen mit einem Kettenstopper führte zu einem Gemisch aus vielen Oligomeren und rechtfertigt die iterative Reaktionsführung. In dieser Arbeit wurden außerdem Stäbchenmoleküle mit Farbstoffen, die eine thermisch aktivierte verzögerte Fluoreszenz aufweisen, mittels Sonogashira Reaktion verknüpft und vollständig charakterisiert. Mit diesen Verbindungen könnten optoelektronische Vorgänge in organischen Solarzellen untersucht werden. VIII Contents Abstract ............................................................................................................ VII Kurzzusammenfassung ................................................................................... VIII 1. Nature versus Synthetic Chemistry – an Introduction .................................. 1 2. Theoretical Background ............................................................................... 6 2.1 Monodisperse and Sequence-Defined Conjugated Oligomers ............ 6 2.1.1 Liquid Phase Approaches ................................................................ 7 2.1.2 Solid Phase Approaches ................................................................ 35 2.1.3 Fluorous-Supported Synthesis and Polymer-Tethered Approach .. 44 2.2 Cross-Coupling Reactions ................................................................. 46 2.2.1 The Sonogashira Reaction – A Cross-Coupling Reaction .............. 48 2.2.2 The Glaser Coupling – A Coupling Reaction .................................. 56 2.2.3 Outlook: Direct Heteroarylation ...................................................... 58 2.3 Applications of Conjugated Polymers and Oligomers ........................ 60 2.3.1 Organic and Polymer Light Emitting Diodes ................................... 60 2.3.2 Organic and Plastic Photovoltaic Cells ........................................... 64 3. Motivation .................................................................................................. 67 4. Results and Discussion ............................................................................. 69 4.1 Syntheses of Building Blocks ............................................................. 69 4.1.1 Building Blocks with Electron Donating Properties ......................... 69 4.1.2 Building Blocks with Electron Accepting Properties ....................... 75 4.2 Monodisperse and Sequence-Defined Rod-Like Oligomers .............. 77 4.2.1 Monodisperse Rod-Like Oligomers ...............................................
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  • A Mild Aqueous Sonogashira Reaction As a Fluorescent Labeling Strategy for 5-Bromide-20-Deoxyuridine

    A Mild Aqueous Sonogashira Reaction As a Fluorescent Labeling Strategy for 5-Bromide-20-Deoxyuridine

    molecules Article A Mild Aqueous Sonogashira Reaction as a Fluorescent Labeling Strategy for 5-Bromide-20-Deoxyuridine Shufang Wang 1, Yongxin Gao 2, Shigang Shen 3, Hui Wen 1 and Huaqing Cui 1,* ID 1 State Key Laboratory of Bioactive Substances and Function of Natural Medicine, Institute of Materia Medica, Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100050, China; [email protected] (S.W.); [email protected] (H.W.) 2 Beijing Key Laboratory of Active Substances Discovery and Drugability Evaluation, Institute of Materia Medica, Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100050, China; [email protected] 3 Key Lab of Analytical Science and Technology of Hebei Province, College of Chemistry and Environmental Science, Hebei University, Baoding 071000, China; [email protected] * Correspondence: [email protected]; Tel.: +86-10-6303-7952 Received: 15 December 2017; Accepted: 11 January 2018; Published: 12 January 2018 Abstract: C5-modified uridines are a valuable class of nucleoside analogues, both as potent chemotherapy agents and through their use as the conjunction site in DNA labeling strategies. As an important C5-modified uridine, BrdU has been used in cell proliferation assays since the 1980s. Currently, the detection of BrdU relies on traditional immunostaining; however, this approach has its limitations. Thus, it is desirable, albeit difficult, to develop chemistry methods to fluorescently label BrdU in a cellular context. In the present study, we report our efforts toward developing a robust chemistry methodology for BrdU fluorescent labeling. The Sonogashira reaction was chosen as the key reaction, and various alkynyl groups (aliphatic or aryl) containing fluorescent dyes were synthesized to cross-couple with BrdU.