Ph.D. Thesis_AS_Publishing version for IRC_12 ... - Jacobs University

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Table of Contents Chapter 1. Introduction ........................................................................................................... 1 1.1 Organocatalysis ........................................................................................................... 2 1.2 Enamine catalysis ........................................................................................................ 4 1.3 First asymmetric examples of various enamine based reactions ................................. 6 1.3.1 Enamine promoted asymmetric Aldol reaction ........................................................... 6 1.3.2 Enamine promoted asymmetric Michael reaction ....................................................... 7 1.3.3 Enamine promoted asymmetric Mannich reaction ...................................................... 8 1.3.4 Enamine promoted asymmetric α-amination .............................................................. 9 1.3.5 Enamine promoted asymmetric α-alkylation .............................................................. 9 1.4 Asymmetric Michael addition ................................................................................... 10 1.4.1 Generic mechanism of bifunctional catalysts ............................................................ 11 1.4.2 Classification of organocatalysts ............................................................................... 13 1.4.2.1 Steric based catalysts .......................................................................................... 15 1.4.2.2 Thiourea based bifunctional catalysts ................................................................ 17 1.4.2.3 Amino-sulfonamides, Amino-thiophosphoramides and Amino-amides ............ 19 1.4.2.4 Proline based diamine catalysts .......................................................................... 21 1.4.2.5 Cinchona based bifunctional catalysts ............................................................... 23 1.4.2.6 Miscellaneous bifunctional catalysts .................................................................. 23 1.4.2.7 Proline based electrostatic catalysts ................................................................... 24 1.4.3 Asymmetric Michael addition to nitroolefins ............................................................ 25 1.4.4 Asymmetric Michael addition to maleimides ............................................................ 30 VII
1.5 Research goals: bifunctional based asymmetric Michael additions .......................... 35 1.5.1 Primary-tertiary diamine for addition of cyclopentanone to nitroolefins .................. 35 1.5.2 Non-covanlent catalysts for addition of α-substituted aldehydes to maleimides ...... 35 References ................................................................................................................................ 36 Chapter 2. Results and discussion: Diamine catalysts ........................................................ 40 2.1 Introduction ............................................................................................................... 41 2.2 Synthesis of chiral primary-tertiary diamines ........................................................... 42 2.3 Model reaction: cyclopentanone addition to trans-β-nitrostyrene ............................. 44 2.3.1 Diamine catalyst screening ........................................................................................ 44 2.3.2 Solvent screening ....................................................................................................... 45 2.3.3 Acid and additive screening ...................................................................................... 46 2.4 Asymmetric Michael addition of cyclopentanone to various nitroolefins................. 48 2.5 Asymmetric Michael addition of isobutyraldehyde to various nitroolefins .............. 49 2.6 Mechanism ................................................................................................................. 51 2.7 Absolute and relative stereochemistry ....................................................................... 54 2.8 Conclusion ................................................................................................................. 55 References ................................................................................................................................ 56 Chapter 3. Results and discussion: Assembled bifunctional catalysts .............................. 57 3.1 Introduction ............................................................................................................... 58 3.2 Non-covalent bifunctional catalyst for asymmetric Michael additions ..................... 59 3.3 Model reaction: isobutyraldehyde addition to N-phenylmaleimide .......................... 62 3.3.1 Solvent screening ....................................................................................................... 63 VIII
Page 1 and 2: Bifunctional Organocatalysts Contai
Page 3 and 4: Acknowledgements I would like to co
Page 5 and 6: EtOAc GC h HPLC HRMS Hz IR J m M Me
Page 7: Abstract The asymmetric Michael add
Page 11 and 12: Chapter 6. Spectra (HPLCs and NMRs)
Page 13 and 14: Chapter 1 1.1 Organocatalysis In pa
Page 15 and 16: Chapter 1 • Easy and promising pr
Page 17 and 18: Chapter 1 Scheme 1.5 shows a possib
Page 19 and 20: Chapter 1 O O O N R (S)-proline DMS
Page 21 and 22: Chapter 1 1.4 Asymmetric Michael ad
Page 23 and 24: Chapter 1 O R Michael product R' Ar
Page 25 and 26: Chapter 1 bifunctional catalysts st
Page 27 and 28: Chapter 1 proposed that the seconda
Page 29 and 30: Chapter 1 Ph NH 2 Ph N H S N H NH N
Page 31 and 32: Chapter 1 Amino-sulfoneamides N H 2
Page 33 and 34: Chapter 1 acetone with only 16% ee.
Page 35 and 36: Chapter 1 X X NH 2 COOK NH N Cl 46
Page 37 and 38: Chapter 1 O O O O O O S O 50 51 52
Page 39 and 40: Chapter 1 Summary for the asymmetri
Page 41 and 42: Chapter 1 4 25b 13 / 5 7 120 rt 63
Page 43 and 44: Chapter 1 Table 1.4: Summary for th
Page 45 and 46: Chapter 1 20 48a O H O O N Ph 15/10
Page 47 and 48: Chapter 1 References 1. Selected re
Page 49 and 50: Chapter 1 33. B. Tan, X. Zeng, Y. L
Page 51 and 52: Chapter 2 RESULTS AND DISCUSSION: D
Page 53 and 54: Chapter 2 enamine. Meanwhile, the p
Page 55 and 56: Chapter 2 2.3 Model reaction: cyclo
Page 57 and 58: Chapter 2 2.1, entry 3). THF and a
Page 59 and 60:
Chapter 2 2.4 Asymmetric Michael ad
Page 61 and 62:
Chapter 2 Table 2.4: Asymmetric Mic
Page 63 and 64:
Chapter 2 Ph NH N H H N Ph NH 97 98
Page 65 and 66:
Chapter 2 A final convincing argume
Page 67 and 68:
Chapter 2 References 1. S. H. McCoo
Page 69 and 70:
Chapter 3 3.1 Introduction Asymmetr
Page 71 and 72:
Chapter 3 ineraction, as shown in S
Page 73 and 74:
Chapter 3 CF 3 CF 3 O S O O H 2 N N
Page 75 and 76:
Chapter 3 Table 3.2: Solvent screen
Page 77 and 78:
Chapter 3 4 71 99 10 O t Bu-L-threo
Page 79 and 80:
Chapter 3 Table 3.4: Asymmetric Mic
Page 81 and 82:
Chapter 3 20 B H O O N Ph O 134 16
Page 83 and 84:
Chapter 3 16 [b], [d] 1,2-dimethoxy
Page 85 and 86:
Chapter 3 To better appreciate the
Page 87 and 88:
Chapter 3 Ph Me O 3.20 tBuO Ph N N
Page 89 and 90:
Chapter 3 Figure 3.4. Steric based
Page 91 and 92:
Chapter 3 permit fundamentally diff
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Chapter 3 These combined results de
Page 95 and 96:
Chapter 3 1 H NMR (400 MHz, CDCl 3
Page 97 and 98:
Chapter 3 methyl group of the minor
Page 99 and 100:
Page 101 and 102:
Chapter 3 Figure 3.13. Expansion fr
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Page 105 and 106:
Chapter 3 Please refer to α-ethyl
Page 107 and 108:
Chapter 3 13 C NMR (100 MHz, CDCl 3
Page 109 and 110:
Chapter 3 129.19, & 131.93 ppm repr
Page 111 and 112:
Chapter 3 References 1. For the reg
Page 113 and 114:
Chapter 3 19. The potassium complex
Page 115 and 116:
Chapter 4 4.1 General information A
Page 117 and 118:
Chapter 4 4.3 Racemate formation 4.
Page 119 and 120:
Chapter 4 O NO 2 (S)-2-((R)-2-nitro
Page 121 and 122:
Chapter 4 MS (EI), m/z (relative in
Page 123 and 124:
Chapter 4 References 1. The two ena
Page 125 and 126:
Chapter 5 5.1 General information R
Page 127 and 128:
Chapter 5 5.2 Racemate formation To
Page 129 and 130:
Chapter 5 The ee was determined by
Page 131 and 132:
Chapter 5 (S)-1-(2,5-dioxo-1-phenyl
Page 133 and 134:
Chapter 5 (S)-3-(benzo[d][1,3]dioxo
Page 135 and 136:
Chapter 5 (S)-2,6-dimethyl-2-((S)-2
Page 137 and 138:
Page 139 and 140:
Chapter 6 SPECTRA (HPLCs AND NMRs)
Page 141 and 142:
Chapter 6 HPLC of 2,2,2-trifluoro-N
Page 143 and 144:
Chapter 6 HPLC of 2-(2-nitro-1-p-to
Page 145 and 146:
Chapter 6 HPLC of 2-(1-(furan-2-yl)
Page 147 and 148:
Chapter 6 HPLC of 2,2-dimethyl-4-ni
Page 149 and 150:
Chapter 6 HPLC of 3-(4-methoxypheny
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Chapter 6 140
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Chapter 6 142
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Chapter 6 144
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Chapter 6 146
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Chapter 6 148
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Chapter 6 150
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Chapter 6 HPLC of 2-(1-benzyl-2,5-d
Page 165 and 166:
Chapter 6 HPLC of 1-(2,5-dioxo-1-ph
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Page 169 and 170:
Page 171 and 172:
Chapter 6 HPLC of 3-(benzo[d][1,3]d
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Chapter 6 HPLC of 2-methyl-2-(2,5-d
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Chapter 6 164
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Chapter 6 166
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Chapter 6 168
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Chapter 6 170
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Chapter 6 172
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Chapter 6 174
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Chapter 6 176
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Chapter 6 178
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Chapter 6 180
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Chapter 6 182
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Chapter 6 184
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Publication # 02 Sequential Reducti
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