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Development and Application of New Solid-Supported Bis (Oxazolines) In Development and Application of New Solid-Supported Bis(oxazolines) in the Area of Asymmetric Catalysis INAUGURALDISSERTATION zur Erlangung des Doktorgrades der Fakultät für Chemie, Pharmazie und Geowissenschaften der Albert-Ludwigs-Universität Freiburg im Breisgau vorgelegt von Claudia Stork aus Freiburg April 2009 Die vorliegende Arbeit wurde am Institut für Organische Chemie und Biochemie der Albert- Ludwigs-Universität Freiburg in der Zeit von Mai 2006 bis April 2009 im Arbeitskreis von Herrn Prof. Dr. W. Bannwarth angefertigt. Vorsitzender des Promotionsausschusses: Prof. Dr. R. Schubert Referent: Prof. Dr. W. Bannwarth Koreferent: Prof. Dr. Ch. Janiak Datum der Promotion: 05.11.2009 Danksagung Herrn Prof. Dr. Bannwarth danke ich für die interessante Aufgabenstellung, die gewährten Freiheiten bei der Ausgestaltung des Themas sowie die großzügige Unterstützung. DSM danke ich für die finanzielle Unterstützung der vorliegenden Arbeit. Herrn Prof. Dr. Bonrath (DSM) möchte ich für die wertvollen Diskussionen und die gute Zusammenarbeit danken. Für die freundliche Übernahme des Koreferats danke ich Herrn Prof. Dr. Janiak. Allen ehemaligen und gegenwärtigen Mitarbeitern unserer Arbeitsgruppe danke ich für die ständige Diskussionsbereitschaft, die angenehme Arbeitsatmosphäre und die Hilfsbereitschaft. Namentlich genannt seinen dabei vor allem: Dominik Altevogt, Luigi Rumi, Rolf Kramer und Hartmut Rapp. Für das sorgfältige Korrekturlesen dieser Arbeit danke ich Jan-Frederik Blank, Luigi Rumi und Dominik Altevogt. Bei Fr. Hirth-Walter bedanke ich mich für die Durchführung der AAS-Messungen. Herrn Dr. Harald Scherer danke ich für die Aufnahme der HR-MAS-NMR Spektren. Selbstverständlich sei auch allen Mitgliedern der Service-Abteilungen gedankt. Besonders hervorheben möchte ich Herrn Fehrenbach für die zahlreichen HPLC-Messungen. Mein größter Dank geht jedoch an meine Familie und Jan-Frederik für ihre Geduld und ihre moralische Unterstützung. Darüber hinaus danke ich meinen Eltern auch für ihre kontinuierliche finanzielle Unterstützung. Für meine Familie und Jan-Frederik Table of Contents 1 Introduction .......................................................................................................................... 1 2 Theoretical Background....................................................................................................... 3 2.1 Asymmetric Catalysis...................................................................................................... 3 2.1.1 History...................................................................................................................... 3 2.1.2 Principles.................................................................................................................. 4 2.1.3 Selected Chiral Ligands ........................................................................................... 5 2.1.4 Chiral Bis(Oxazoline) Ligands in Asymmetric Catalysis........................................ 7 2.1.5 Metal Complexes of Bis(oxazoline) Ligands[37, 59] .................................................. 8 2.2 Heterogeneous Asymmetric Catalysis ........................................................................... 11 2.2.1 Immobilization of Chiral Bis(oxazoline) Ligands[89] ............................................. 13 2.3 Supercritical Fluids (SCFs) ............................................................................................ 28 2.3.1 General Aspects[115]................................................................................................ 28 2.3.2 Properties of Supercritical Fluids[115] ..................................................................... 28 2.3.3 Reactions in scCO2................................................................................................. 30 3 Aim of the Thesis ................................................................................................................. 32 4 Results and Discussion....................................................................................................... 34 4.1 Ligand Synthesis............................................................................................................ 34 4.1.1 Synthesis of the Linker Building Blocks 37 and 38............................................... 38 4.1.2 Synthesis of the Functionalized Ligands................................................................ 39 4.2 Coupling to Solid Support.............................................................................................. 42 4.3 Preparation of the Catalysts............................................................................................ 47 4.3.1 Preparation of (R,R)-PhBOX Catalysts.................................................................. 47 4.3.2 Preparation of Supported (S,S)-tBuBOX Catalysts ................................................ 49 4.3.3 Preparation of Alternative (R,R)-PhArylBOX Catalyst 69..................................... 57 4.4 Catalytic Reactions......................................................................................................... 58 4.4.1 Diels-Alder Reactions............................................................................................ 58 4.4.2 Hydroxyalkylation.................................................................................................. 68 5 Conclusions ........................................................................................................................ 71 6 Experimental Section......................................................................................................... 74 6.1 General Methods............................................................................................................ 74 6.2 Experimental Procedures................................................................................................ 78 6.2.1 Ligand Synthesis.................................................................................................... 78 6.2.1.1 2,2'-Methylidenebis[4-(R)-(phenyl)-2-oxazoline] (12)[143-145] ..................... 78 6.2.1.2 2,2'-Methylidenebis[4-(S)-(1,1-dimethylethyl)-2-oxazoline] (13)[143-145] .... 79 6.2.1.3 (R)-2-Phenylglycinol (26)[180] ...................................................................... 80 6.2.1.4 (S)-tert-Leucinol (27)[142, 181] ........................................................................ 81 6.2.1.5 2,2'-Ethylidenebis[4-(R)-(phenyl)- 2-oxazoline] (31)[150] ............................ 82 6.2.1.6 2,2'-Ethylidenebis[4-(S)-(1,1-dimethylethyl)-2-oxazoline] (32).................. 83 6.2.1.7 6-Bromo-hexanoic acid methyl ester (37).................................................... 84 6.2.1.8 Methyl-4-(bromomethyl)phenylacetate (38)[148, 149]..................................... 85 6.2.1.9 N,N’-Bis-(2-hydroxy-1-(R)-phenyl-ethyl)-2-methyl-malonamide (43)....... 85 6.2.1.10 N,N’-Bis-(1-hydroxymethyl-2,2-(S,S)-dimethyl-propyl)-2-methyl- malonamide (44) .......................................................................................... 87 6.2.1.11 7,7-Bis((4R)-4-phenyl-4,5-dihydro-oxazol-2-yl)-octanoic acid methyl ester (45) ............................................................................................................... 88 6.2.1.12 7,7-Bis-((4S)-4-tert-butyl-4,5-dihydro-oxazol-2-yl)-octanoic acid methyl ester (46)....................................................................................................... 89 6.2.1.13 Ammonium 7,7-bis (4-phenyl-4,5-dihydro-oxazol-2-yl)-octanoate (47) .... 90 6.2.1.14 Ammonium 7,7-bis-(4-tert-butyl-4,5-dihydro-oxazol-2-yl)-octanoate (48) 91 6.2.1.15 {4-[2,2-Bis-((4R)-4-phenyl-4,5-dihydro-oxazol-2-yl)-propyl]-phenyl}-acetic acid methyl ester (49)................................................................................... 92 6.2.1.16 {4-[2,2-Bis-((4S)-4-tert-butyl-4,5-dihydro-oxazol-2-yl)-propyl]-phenyl}- acetic acid methyl ester (50)......................................................................... 93 6.2.1.17 Ammonium {4-[2,2-bis-(4-phenyl-4,5-dihydro-oxazol-2-yl)-propyl]- phenyl}-acetate (51)..................................................................................... 94 6.2.1.18 Ammonium {4-[2,2-bis-tert-butyl-4,5-dihydro-oxazol-2-yl)-propyl]- phenyl}-acetate (52)..................................................................................... 95 6.2.1.19 7,7-Bis-(4-tert-butyl-4,5-dihydro-oxazol-2-yl)-octanoic acid phenethyl- amide (74) .................................................................................................... 96 6.2.1.20 2-{4-[2,2-Bis-(4-phenyl-4,5-dihydro-oxazol-2-yl)-propyl]-phenyl-N-[2-(2,5- dioxo-2,5-dihydro-pyrrol-1-yl)-ethyl]-acetamide (54)................................. 97 6.2.1.21 2-{4-[2,2-Bis-(4-tert-butyl-4,5-dihydro-oxazol-2-yl)-propyl]-phenyl}N-[2- (2,5-dioxo-2,5-dihydro-pyrrol-1-yl)-ethyl]-acetamide (75)......................... 98 6.2.2 Preparation of Amine 53 ........................................................................................ 99 6.2.2.1 (2-Hydroxy-ethyl)-carbamic acid tert-butyl ester (82)[163]........................... 99 6.2.2.2 [2-(2,5-Dioxo-2,5-dihydro-pyrrol-1-yl)-ethyl]-carbamic acid tert-butyl ester (83)[162] ....................................................................................................... 100 6.2.2.3 2-(2,5-Dioxo-2,5-dihydro-pyrrol-1-yl)-ethyl-ammonium trifluoro-actetate (53)[163] ......................................................................................................
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