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

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Chapter 1 15 25c O H O O N Ph 14/5 2 25 70 79 2.3:1 98 [b] / 96 [c] 16 48b O H O O N Ph 15/5 2 25 6 85 1:1 93 [b] / 94 [c] 17 25c O H Br O O N Ph 14/5 2 25 84 81 11:2 99 [b] / 96 [c] 18 48a O H O O N Ph 15/10 2 25 4 96 2:1 99 [b] / 96 [c] 19 48a O H O O N p-Cl 15/10 2 25 4 98 2:1 99 [b] / 99 [c] 33
Chapter 1 20 48a O H O O N Ph 15/10 2 25 1 99 2:1 99 [b] / 97 [c] [a] Equivalent ratio aldehyde used. [b] ee of major diastereomer. [c] ee of minor diastereomer Wang and coworkers 25c presented a primary amine thiourea catalyst (Figure 1.3, 14) for direct asymmetric Michael addition of aldehydes (unsubstituted and α-substituted) to maleimides. Their catalyst showed brilliant activity with unsubstituted aldehydes and the only α-substituted aldehyde was isobutyraldehyde (Table 1.4, entry 1). For aldehydes like cyclopentanecarboxyaldehyde and cyclohexanecarboxyaldehdye they increased their catalyst loading from 1 mol% to 15 mol% and up to 10 equivalents of aldehyde but still they did not achieve a high isolated yield (Table 1.4, entries 7 and 10). They also tried α,α'-substituted aldehyes to get contiguous quaternary-tertiary stereogenic carbons (Table 1.4, entries 15 and 17). The observed enantioselectivities were comparable to their previous examples but the reaction times were 70h and 84h with poor drs of 2.3:1 and 11:2 respectively. Similarly, the reports 48 show that symmetrical α-substituted aldehydes can give a similar product profile (Table 1.4, entries 2-6, 8, 9, 11, and 12) when using the same type of catalyst (Figure 1.3, 15 and 16). Liang and Ye 48a performed additions of asymmetrical α-substituted aldehydes to maleimides (Table 1.4, entries 13, 14, 18 and 20). They were unable to report the absolute stereochemistry for their products. Their catalyst loading used to synthesize these products was always high (10-20 mol%) and the diastereoselectivity was again a remaining challenge. 34
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 and 8: Abstract The asymmetric Michael add
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: Chapter 1 Table 1.4: Summary for th
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
Page 93 and 94: 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
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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)
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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
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Chapter 6 HPLC of 1-(2,5-dioxo-1-ph
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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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