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Solvent-Free Multicomponent Reactions and Asymmetric Transformations in Solution and Under Mechanochemical Conditions

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Solvent-Free Multicomponent Reactions and Asymmetric Transformations in Solution and Under Mechanochemical Conditions Solvent-free multicomponent reactions and asymmetric transformations in solution and under mechanochemical conditions Von der Fakultä t fü r Mathematik, Informatik und Naturwissenschaften der RWTH Aachen University zur Erlangung des akademischen Grades einer Doktorin der Naturwissenschaften genehmigte Dissertation vorgelegt von Master of Science Plamena Krasimirova Staleva aus Sliven, Bulgarien Berichter: Universitätprofessor Dr. rer. nat. Carsten Bolm Universitätprofessor Dr. rer. nat. Markus Albrecht Tag der mündlichen Prüfung: 06.02.2020 Diese Dissertation ist auf den Internetseiten der Universitätsbibliothek verfügbar. EIDESSTATTLICHE ERKLÄRUNG Plamena Krasimirova Staleva, erklärt hiermit, dass diese Dissertation und die darin dargelegten Inhalte die eigenen sind und selbstständig, als Ergebnis der eigenen originären Forschung, generiert wurden. Hiermit erkläre ich an Eides statt 1. Diese Arbeit wurde vollständig in der Phase als Doktorandin dieser Fakultät und Universität angefertigt; 2. Sofern irgendein Bestandteil dieser Dissertation zuvor für einen akademischen Abschluss oder eine andere Qualifikation an dieser oder einer anderen Institution verwendet wurde, wurde dies klar angezeigt; 3. Wenn immer andere eigene- oder Veröffentlichungen Dritter herangezogen wurden, wurden diese klar benannt; 4. Wenn aus anderen eigenen- oder Veröffentlichungen Dritter zitiert wurde, wurde stets die Quelle hierfür angegeben. Diese Dissertation ist vollständig meine eigene Arbeit, mit der Ausnahme solcher Zitate; 5. Alle wesentlichen Quellen von Unterstützung wurden benannt; 6. Wenn immer ein Teil dieser Dissertation auf der Zusammenarbeit mit anderen basiert, wurde von mir klar gekennzeichnet, was von anderen und was von mir selbst erarbeitet wurde; 7. Ein Teil dieser Arbeit wurde zuvor veröffentlicht und zwar in: P. Staleva, J. G. Hernández, C. Bolm, Chem. Eur. J. 2019, 25, 9202. Aachen, The work reported herein has been carried out at the Institute of Organic Chemistry of the RWTH Aachen University under the supervision of Prof. Dr. Carsten Bolm between March 2014 and November 2019. I would like to thank Prof. Dr. Carsten Bolm for giving me the opportunity to join his research group and work on exciting topics under excellent working conditions and for his support. Furthermore, I would like to gratefully acknowledge DBU (Die Deutsche Bundesstiftung Umwelt) for the financial support during the first year of my doctoral studies through “MOE- Austauschstipendienprogramm”. For my family “The impediment to action advances action. What stands in the way becomes the way.” Marcus Aurelius TABLE OF CONTENTS 1. INTRODUCTION ............................................................................................................................................. 1 1.1 CHIRALITY AND ASYMMETRIC SYNTHESIS ......................................................................................................... 1 1.2 SOLVENT-FREE REACTIONS – A SUSTAINABLE ROUTE IN CHEMICAL SYNTHESIS ........................................... 2 1.3 MECHANOCHEMISTRY AND ITS APPLICATION IN ASYMMETRIC CATALYSIS .................................................... 3 1.4 SULFOXIMINES – PROPERTIES AND APPLICATIONS ........................................................................................... 7 2. RESULTS AND DISCUSSION ......................................................................................................................... 15 2.1 SOLVENT-FREE SYNTHESIS OF CHIRAL SULFONIMIDOYLALKYL NAPHTHOLS BY BETTI CONDENSATION .. 15 2.1.1 Background of the project ........................................................................................................... 15 2.1.2 Research objective .......................................................................................................................... 20 2.1.3 Optimization of the reaction conditions................................................................................. 21 2.1.3 Substrate scope of the Betti condensation ............................................................................ 23 2.1.4 Determination of the absolute configuration ....................................................................... 25 2.1.5 Postulated reaction mechanism ................................................................................................ 26 2.1.6 Application as ligands in the asymmetric addition of diethylzinc to aldehydes .... 26 2.1.7 Brønsted acid mediated reaction of 62a with indole ........................................................ 28 2.1.8 Biological tests ................................................................................................................................. 31 2.2 STUDIES ON THE RESOLUTION OF RACEMIC MALONIC ACID INDOLE DERIVATIVES IN A REACTION TOWARDS BISINDOLYLMETANES ............................................................................................................................. 32 2.2.1 Background and aim of the project .......................................................................................... 32 2.2.2 Primary experiments on the asymmetric Friedel–Crafts alkylation of indoles catalyzed by a chiral metal-sulfoximine complex .......................................................................... 36 2.2.3 Screening of the reaction conditions for the kinetic resolution of 81a ...................... 37 2.2.4 Substrate scope ................................................................................................................................ 43 2.2.5 Studies towards the elucidation of the reaction mechanism ......................................... 45 2.3 COPPER-CATALYZED ASYMMETRIC MICHAEL-TYPE FRIEDEL–CRAFTS-ALKYLATIONS OF INDOLES WITH ARYLIDENE MALONATES UNDER BALL MILLING CONDITIONS ............................................................................... 48 2.3.1 Background and aim of the project .......................................................................................... 48 2.3.2 Optimization of the chiral ligands ............................................................................................ 49 2.3.3 Screening of Lewis acids............................................................................................................... 51 2.3.4 Optimization of milling conditions and milling auxiliaries ............................................. 53 2.3.5 Optimization of the additives ..................................................................................................... 55 2.3.6 Synthesis of the substrates .......................................................................................................... 58 2.3.7 Substrate scope of the mechanochemical asymmetric Friedel–Crafts alkylation of indoles ............................................................................................................................................................ 58 2.3.8. Liquid assisted grinding experiments .................................................................................... 62 3. SUMMARY AND OUTLOOK .......................................................................................................................... 65 4. EXPERIMENTAL PART ................................................................................................................................ 69 4.1 GENERAL INFORMATION AND TECHNIQUES .................................................................................................... 69 4.2 ANALYTICAL METHODS ..................................................................................................................................... 70 4.3 SYNTHESIS AND CHARACTERIZATION OF THE PRODUCTS .............................................................................. 71 4.3.1. General procedures for the preparation of starting materials, products and ligands ............................................................................................................................................................ 71 4.3.2. Synthesis and analytical data of compounds ....................................................................... 76 5. REFERENCES ............................................................................................................................................. 109 6. ABBREVIATIONS....................................................................................................................................... 117 CURRICULUM VITAE ..................................................................................................................................... 120 ACKNOWLEDGMENTS ................................................................................................................................... 121 INTRODUCTION INTRODUCTION 1. INTRODUCTION 1.1 CHIRALITY AND ASYMMETRIC SYNTHESIS Chirality is one of the most prominent features of natural and bioactive compounds and plays an important role in almost all biochemical pathways and processes taking place in living organisms. The majority of the naturally occurring compounds with important biological activities are existing as a single optical isomer. Moreover, almost all amino acids, carbohydrates, proteins, enzymes, etc. are chiral. Nowadays, chiral molecules are present in various aspects of our daily life including pharmaceuticals, agrochemicals, flavors, fragrances, and modern materials. This explains the growing demand for synthetic methods to provide enantiomerically pure compounds,
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