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Chapter 1 O H O NO 2 (S)-proline (30 mol%) DMSO/Acetone (4:1) rt, 4hrs NO 2 O OH N H O OH (S)-proline Yield = 68% ee = 76% Scheme 1.6. First example of asymmetric intermolecular Aldol reaction via enamine. 1.3.2 Enamine promoted asymmetric Michael reaction Asymmetric Michael additions of various enolizable carbonyls to Michael acceptors provide a convenient access to versatile synthetic intermediates e.g. Michael reaction of enamine with a nitroalkene is a useful synthetic method for preparation of nitroalkanes. List reported the first example of an intermolecular enamine-based catalytic asymmetric Michael addition (Scheme 1.7). 15 O Ph NO 2 (S)-proline (15 mol%) DMSO, 16h O Ph NO 2 N H O OH (S)-proline Yield = 94% dr = >20:1 ee = 23% Scheme 1.7. First example of asymmetric Michael addition to nitroolefins via enamine. Asymmetric Michael additions of enolizable carbonyls to maleimides give chiral succinimides. The first (S)-proline catalyzed Michael addition of acetone to maleimide was reported by Barbas (Scheme 1.8). 16 The main aim of the reported article was fluorescent detection of carbon-carbon bond formation, therefore they did not mention enantioselectivity. 7
Chapter 1 O O O N R (S)-proline DMSO O R = O O N R H N N N H O OH (S)-proline Scheme 1.8. First example of Michael addition to maleimides via enamine. 1.3.3 Enamine promoted asymmetric Mannich reaction The Mannich reaction is a well-known reaction for the construction of nitrogen containing compounds. The reaction is catching attraction because most of the drug molecules or natural products also consist of nitrogenous building blocks. Generally the three reacting parts of a Mannich reaction are: carbonyl with an acidic proton at α-position, an aldehyde and an amine which attacks on aldehyde making the electrophilic imine. The final product is a β-amino carbonyl. List in 2000, 17 has shown the first example of proline-catalyzed asymmetric threecomponent Mannich reaction (Scheme 1.9). CHO NH 2 O O HN (S)-proline (35 mol%) DMSO OMe N H O OH (S)-proline NO 2 OMe NO 2 Yield = 50% ee = 94% Scheme 1.9. First example of organocatalytic asymmetric three-component Mannich reaction via enamine. 8
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: Chapter 1 Scheme 1.5 shows a possib
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
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Chapter 3 3.1 Introduction Asymmetr
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Chapter 3 ineraction, as shown in S
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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
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Chapter 3 Ph Me O 3.20 tBuO Ph N N
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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
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Chapter 3 1 H NMR (400 MHz, CDCl 3
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Chapter 3 methyl group of the minor
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Chapter 3 Figure 3.13. Expansion fr
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Chapter 3 Please refer to α-ethyl
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Chapter 3 13 C NMR (100 MHz, CDCl 3
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Chapter 3 129.19, & 131.93 ppm repr
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Chapter 3 References 1. For the reg
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Chapter 3 19. The potassium complex
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Chapter 4 4.1 General information A
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Chapter 4 4.3 Racemate formation 4.
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Chapter 4 O NO 2 (S)-2-((R)-2-nitro
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Chapter 4 MS (EI), m/z (relative in
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Chapter 4 References 1. The two ena
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Chapter 5 5.1 General information R
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Chapter 5 5.2 Racemate formation To
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Chapter 5 The ee was determined by
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Chapter 5 (S)-1-(2,5-dioxo-1-phenyl
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Chapter 5 (S)-3-(benzo[d][1,3]dioxo
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Chapter 5 (S)-2,6-dimethyl-2-((S)-2
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Chapter 6 SPECTRA (HPLCs AND NMRs)
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Chapter 6 HPLC of 2,2,2-trifluoro-N
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Chapter 6 HPLC of 2-(2-nitro-1-p-to
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Chapter 6 HPLC of 2-(1-(furan-2-yl)
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Chapter 6 HPLC of 2,2-dimethyl-4-ni
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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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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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