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

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s sep t tBu tert temp TFA THF TLC TMS Ts TsOH Ti(OiPr) 4 Singlet ( 1 H NMR) Septet ( 1 H NMR) Triplet ( 1 H NMR) Tertiary butyl Tertiary Temperature Trifluoroacetic acid Tetrahydrofuran Thin layer chromatography Trimethylsilane Tosyl p-Toluenesulfonic acid Titanium(IV) isopropoxide V
Abstract The asymmetric Michael addition of nucleophilic carbonyls (via enamine) to a diverse number of Michael acceptors produces an important carbon-carbon bond, producing a truly large number of products. Over the past decade an enormous number of organocatalysts have been developed for the asymmetric Michael addition. Challenging nucleophilic carbonyl additions, e.g. α-substituted carbonyls and some cyclic carbonyls, e.g. cyclopentanone, remain and require attention in terms of stereoselectivity, catalyst loading reaction time and yield. Here we have focused on designing new organocatalysts with primary amines to overcome the above outlined challenges. We have developed two types of organocatalysts: 1) primary-tertiary diamine organocatalysts and 2) non-covalent bifunctional organocatalysts. Diamines were found to be better organocatalysts for the asymmetric Michael addition of cyclopentanone to various nitroolefins. While the assembled catalysts were found to be superior for the asymmetric Michael addition of α-substituted aldehydes addition to maleimides. VI
Page 1 and 2: Bifunctional Organocatalysts Contai
Page 3 and 4: Acknowledgements I would like to co
Page 5: EtOAc GC h HPLC HRMS Hz IR J m M Me
Page 9 and 10: 1.5 Research goals: bifunctional ba
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
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Chapter 2 Table 2.4: Asymmetric Mic
Page 63 and 64:
Chapter 2 Ph NH N H H N Ph NH 97 98
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Chapter 2 A final convincing argume
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Chapter 2 References 1. S. H. McCoo
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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
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Chapter 3 Table 3.2: Solvent screen
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Chapter 3 4 71 99 10 O t Bu-L-threo
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Chapter 3 Table 3.4: Asymmetric Mic
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Chapter 3 20 B H O O N Ph O 134 16
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Chapter 3 16 [b], [d] 1,2-dimethoxy
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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
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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
Page 103 and 104:
Page 105 and 106:
Chapter 3 Please refer to α-ethyl
Page 107 and 108:
Chapter 3 13 C NMR (100 MHz, CDCl 3
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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
Page 151 and 152:
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
Page 167 and 168:
Page 169 and 170:
Page 171 and 172:
Chapter 6 HPLC of 3-(benzo[d][1,3]d
Page 173 and 174:
Chapter 6 HPLC of 2-methyl-2-(2,5-d
Page 175 and 176:
Chapter 6 164
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Chapter 6 166
Page 179 and 180:
Chapter 6 168
Page 181 and 182:
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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