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Palladium/Di-1-Adamantyl-N-Butylphosphine-Catalyzed Carbonylation Reactions

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Palladium/Di-1-Adamantyl-N-Butylphosphine-Catalyzed Carbonylation Reactions Leibniz-Institut für Katalyse e.V. an der Universität Rostock Palladium/di-1-adamantyl-n-butylphosphine-catalyzed Carbonylation Reactions Kumulative Dissertation zur Erlangung des akademischen Grades Doctor rerum naturalium (Dr. rer. nat.) vorgelegt der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Rostock von Dipl.-Chem. Anne Brennführer aus Rostock geb. am 16.08.1981 in Rostock Rostock, 28. November 2008 Die vorliegende Arbeit entstand in der Zeit von Oktober 2005 bis November 2008 unter der Leitung von Herrn Prof. Dr. Matthias Beller am Leibniz-Institut für Katalyse e.V. an der Universität Rostock. Gutachter: Gutachter 1: Prof. Dr. Matthias Beller Leibniz-Institut für Katalyse e.V. an der Universität Rostock Gutachter 2: Prof. Dr. Herbert Plenio Eduard-Zintl-Institut für Anorganische und Physikalische Chemie, Technische Universität Darmstadt Die vorliegende Dissertation wurde am 30.03.2009 verteidigt. Für meine Eltern Maria und Norbert Brennführer Danksagung Herzlicher Dank gebührt meinem sehr verehrten Doktorvater Prof. Dr. Matthias Beller für die freundliche Aufnahme in seine Arbeitsgruppe, die ausgezeichneten Arbeitsbedingungen, die unerschöpflichen wertvollen Anregungen und für sein großes Interesse am Gelingen dieser Arbeit. Dank sagen möchte ich auch meinem Themenleiter Dr. Helfried Neumann sowie allen weiteren Mitgliedern der Arbeitsgruppe „Übergangsmetallkatalysierte Synthesen von Feinchemikalien” (Dr. Sandra Hübner, Dr. Stefan Klaus, Dr. Alexey Sergeev, Christian Torborg und Thomas Schulz) für eine gute Zusammenarbeit und ein freundliches Arbeitsklima. Insbesondere möchte ich mich bei Sandra Leiminger für die sowohl berufliche als auch private Freundschaft bedanken. Dr. Dirk Michalik danke ich für die stets gewährte, fachkundige Hilfe bei der Aufklärung von „Strukturfragen” und für die Aufnahme und Auswertung zahlreicher NMR-Spektren. Weiterhin möchte ich mich bei der Analytikabteilung des LIKAT für die Durchführung der Routinemessungen bedanken. Allen anderen Mitarbeitern des LIKAT sei gedankt für die schöne Zeit im Institut. Der Deutschen Forschungsgemeinschaft danke ich für die finanzielle Unterstützung. Außerdem möchte ich mich herzlich bei meinen Freunden bedanken, die alle auf ihre Weise zum Gelingen dieser Arbeit beigetragen haben. Angelika Preetz danke ich für das Korrekturlesen meiner Arbeit und für ihre anhaltende Freundschaft und Unterstützung bei allen Fragen und Problemen. Mein ganz besonderer Dank gilt meinen Eltern und meinem Freund, die mich mit allen Kräften unterstützt haben und ohne die ich sicherlich nicht so weit gekommen wäre. University of Rostock Abstract Palladium/di-1-adamantyl-n-butylphosphine-catalyzed Carbonylation Reactions Anne Brennführer Leibniz-Institut für Katalyse e.V. an der Universität Rostock Within this thesis several homogeneous palladium-catalyzed carbonylation reactions in the presence of carbon monoxide were investigated. In the course of our studies, the superior performance of the catalyst system palladium acetate/di-1-adamantyl-n-butylphosphine (cataCXium® A) in comparison to established palladium catalysts was demonstrated for both reductive carbonylations and alkoxycarbonylations of aryl and vinyl bromides. Hence, a variety of (hetero)aromatic aldehydes and carboxylic acid derivatives (esters, amides, acids) were successfully synthesized, among them novel biologically interesting indolylmaleimides. Furthermore, an efficient method for the synthesis of non-steroidal anti-inflammatory drugs such as ketoprofen and suprofen was developed. In der vorliegenden Dissertation wurden verschiedene, homogen palladiumkatalysierte Carbonylierungsreaktionen in Gegenwart von Kohlenmonoxid untersucht. Dabei konnte gezeigt werden, dass das System Palladiumacetat/Di-1-adamantyl-n-butylphosphin (cataCXium® A) sowohl in der reduktiven Carbonylierung als auch in der Alkoxycarbonylierung von Aryl- und Vinylbromiden die bekannten Palladium-Katalysator- Systeme an Aktivität, Selektivität und Produktivität übertrifft. Eine Vielzahl von (hetero)aromatischen Aldehyden und Carbonsäurederivaten (Ester, Amide, Säuren) konnte erfolgreich hergestellt werden, darunter auch bisher nicht beschriebene biologisch interessante Indolylmaleinimide. Darüber hinaus wurde im Rahmen dieser Arbeit eine effiziente Methode zur Synthese von nicht-steroidalen, entzündungshemmenden Arzneimitteln (z.B. Ketoprofen, Suprofen) entwickelt. Table of Contents 1 Preface 1 2 Palladium-catalyzed carbonylation reactions 2 2.1 Carbonylation of aromatic (pseudo)halides 2 2.1.1 Synthesis of carboxylic acid derivatives from aryl bromides or iodides 4 2.1.2 Synthesis of carboxylic acid derivatives from aryl chlorides 14 2.1.3 Reductive carbonylations 18 2.2 Carbonylation of unsaturated compounds 23 2.2.1 Hydroxycarbonylation of alkenes 24 2.2.2 Hydroesterification of alkenes 27 2.2.3 Carbonylation of alkynes 30 2.3 Carbonylative cross-coupling reactions 37 2.3.1 Carbonylative Stille coupling reactions 37 2.3.2 Carbonylative Suzuki coupling reactions 39 2.3.3 Carbonylative Sonogashira coupling reactions 42 2.3.4 Indium organometallics in cross-coupling reactions 45 2.4 References 46 3 Objectives of this work 69 4 Publications 71 4.1 Reductive carbonylation of aryl and vinyl halides 71 4.2 Carbonylation of aryl and heteroaryl bromides 79 4.3 Synthesis of novel 3-substituted 4-indolylmaleimides 87 4.4 Synthesis of diarylketones via carbonylative Suzuki coupling reactions 93 4.5 Sequential one-pot-synthesis of suprofen, ketoprofen and other 2-arylpropionic acids 102 4.6 Reductive carbonylation of aryl triflates 109 5 Summary 114 i List of Abbreviations Ac Acetyl BINAP 2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl tol-BINAP 2,2′-Bis(di-p-tolylphosphino)-1,1′-binaphthyl bmim 1-Butyl-3-methylimidazolium Bn Benzyl Boc tert-Butyloxycarbonyl nBu n-Butyl tBu tert-Butyl cataCXium® A Di-1-adamantyl-n-butylphosphine Cy Cyclohexyl DABCO 1,4-Diazabicyclo[2.2.2]octane dba trans,trans-Dibenzylideneacetone DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene dcpp 1,3-Bis(dicyclohexylphosphino)propane deg Degree dippp 1,3-Bis(di-iso-propylphosphino)propane DMAP 4-Dimethylaminopyridine DME 1,2-Dimethoxyethane DMF N,N-Dimethylformamide DMSO Dimethyl sulfoxide DPEphos Bis(2-diphenylphosphinophenyl)ether dppb 1,4-Bis(diphenylphosphino)butane dppe 1,2-Bis(diphenylphosphino)ethane dppf 1,1′-Bis(diphenylphosphino)ferrocene dppm Bis(diphenylphosphino)methane ii List of abbreviations dppp 1,3-Bis(diphenylphosphino)propane dtbpx 1,2-Bis(di-tert-butyl-phosphinomethyl)benzene equiv. Equivalent(s) Et Ethyl Fmoc Fluorenylmethoxycarbonyl HMDS Hexamethyldisilazane IL Ionic liquid MMA Methyl methacrylate Me Methyl MS Molecular sieves MW Microwave NHC N-Heterocyclic carbene NMDPP Neomenthyldiphenylphosphine Norphos 2,3-Bis(diphenylphosphino)-bicyclo[2.2.1]hept-5-ene Nu Nucleophile o Ortho OTf Triflate (trifluoromethanesulfonate) OTs Tosylate (p-toluenesulfonate) p Para Pd/C Palladium on carbon Ph Phenyl Phanephos 4,12-Bis(diphenylphosphino)-[2.2]-paracyclophane PMHS Polymethylhydrosiloxane iPr iso-Propyl Py Pyridine R Organic group rac Racemic List of abbreviations iii RT Room temperature SCE Saturated calomel electrode TBDMSOTf tert-Butyldimethylsilyl triflate Tfp Tri(2-furyl)phosphine THF Tetrahydrofuran TMEDA N,N,N′,N′-Tetramethylethylenediamine TMS Trimethylsilyl TON Turnover number TOF Turnover frequency [h-1] TPPTS Sodium salt of trisulfonated triphenylphosphine X Leaving group, (pseudo)halide Xantphos 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene 1 1 Preface The development of efficient and environmentally benign synthetic processes constitutes one of the most important research targets in modern chemistry. Furthermore, the improvement of existing inefficient synthetic methodologies due to environmental and economic requirements is of major interest. In this regard, homogeneous catalysis offers a great potential for achieving these objectives and, thus, to fulfil today’s demand of sustainable chemistry. Among the many different catalytic transformations, homogeneous transition metal-catalyzed carbon-carbon bond forming reactions (e.g. Heck, Suzuki, and Sonogashira reaction) have found widespread application in organic syntheses in both academic and industrial laboratories. Starting from readily available substrates, a variety of complex and structurally diverse organic compounds can be prepared with high efficiency and selectivity (chemo-, regio-, diastereo-, and enantioselectivity) as well as enhanced atom-economy compared to traditional stoichiometric reactions. In general, palladium complexes are employed as catalysts due to their better performance under mild conditions, versatility and broad tolerance towards functional groups.[1] A reaction, which has been the subject of many patents and publications, is the palladium- catalyzed carbonylation.[2] The functionalization of organic molecules with carbon monoxide as a carbonyl source has become an important and convenient method for the selective preparation of intermediates of naturally or biologically active products, pharmaceuticals and fine chemicals. Thus, a broad range of high-valuable compounds such as aldehydes, ketones, carboxylic acid derivatives, lactones, lactames, etc., are accessible from organic halides or unsaturated substrates in one step. Although much research effort has been done in this field, there still exists considerable interest in the exploration of facile and innovative synthetic strategies. The present dissertation highlights recent achievements in palladium-catalyzed carbonylation
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