CHEM01200604012 Dibakar Goswami - Homi Bhabha National ...

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Figure Title Page No. I.1.1 Structure of (R)-2,3-cyclohexylidene glyceraldehyde (1) 2 I.2.1 Chiral compounds having different biological activities 4 I.3.1 Energy profiles for different types of reactions 17 II.1.1 Chiral ligands used in ADH 25 II.1.2 Tetrahedral configuration of Et 2 Zn 28 II.1.3 Chiral ligands used in asymmetric addition of R 2 Zn to carbonyls 29 II.3.1 Cations used in RTILs 37 II.3.2 II.3.3 1 H NMR spectrum of compound 60b 42 13 C NMR spectrum of compound 60b 42 II.3.4 II.3.5 II.3.6 1 H NMR spectrum of the reaction mixture of In and allyl bromide in D 2 O 1 H NMR spectrum of the reaction mixture of In and allyl bromide in RTIL GLC analysis of the time dependent concentration variation of allyl bromide 46 47 51 II.3.7 II.3.8 II.3.9 II.3.10 1 H NMR spectrum of compound 60g 59 13 C NMR spectrum of compound 60g 60 1 H NMR spectrum of compound III 61 13 C NMR spectrum of compound III 62 II.3.11 DSC results of compound IV 65 II.3.12 1 H NMR spectrum of compound IV 65 xxiii
II.3.13 III.1.1 III.1.2 III.1.3 III.1.4 III.1.5 III.1.6 III.1.7 III.1.8 13 C NMR spectrum of compound IV 66 1 H NMR spectrum of compound 68a 80 13 C NMR spectrum of compound 68a 81 1 H NMR spectrum of compound 68b 81 13 C NMR spectrum of compound 68b 82 1 H NMR spectrum of compound 69b 85 13 C NMR spectrum of compound 69b 85 1 H NMR spectrum of compound 69c 86 13 C NMR spectrum of compound 69c 86 III.1.9 Felkin-Anh model for crotylation of aldehyde 1 87 III.1.10 III.2.11 III.1.12 III.1.13 III.1.14 III.1.15 III.1.16 III.1.17 III.1.18 III.1.19 III.1.20 III.1.21 1 H NMR Spectrum of compound 72 90 13 C NMR Spectrum of compound 72 90 1 H NMR spectrum of compound 79b 95 13 C NMR spectrum of compound 79b 95 1 H NMR spectrum of compound 79c 96 1 H NMR Spectrum of compound 79c 96 1 H NMR spectrum of compound 85 101 13 C NMR spectrum of compound 85 102 1 H NMR spectrum of compound 86 102 13 C NMR spectrum of compound 86 103 1 H NMR spectrum of compound 90e 107 13 C NMR Spectrum of compound 90e 107 III.1.22 13 C NMR spectrum of diastereomeric mixture of 91a + 91b 109 xxiv
Page 1: ASYMMETRIC STRATEGIES FOR THE SYNTH
Page 6 and 7: ACKNOWLEDGEMENTS First of all, I wa
Page 8 and 9: CONTENTS SYNOPSIS LIST OF FIGURES L
Page 10: SYNOPSIS
Page 13 and 14: models (e. g. Cram’s model, Felki
Page 15 and 16: 4 1d 4-(CH 3 ) 2 CH-C 6 H 4 1 : 1.5
Page 17 and 18: 14. 1n C 6 H 5 CO C 6 H 5 2n 8 77 1
Page 19 and 20: imetallic systems. In all the cases
Page 21 and 22: For the benzylation reaction, the c
Page 23 and 24: O O 3 CHO i O O + OH 13a O O OH O O
Page 25 and 26: 10 3.5 Ga (2.5) THF KI+LiCl 10 55 5
Page 27 and 28: multidrug-resistant (MDR) cancer ce
Page 29 and 30: directly afforded the furanose, whi
Page 31 and 32: References 1. Stephenson, G. R. Adv
Page 33: LIST OF FIGURES
Page 37 and 38: IV.5.2 IV.5.3 IV.5.4 IV.5.5 1 H NMR
Page 39 and 40: Table Title Page No. II.3.1 II.3.2
Page 41 and 42: II. .11 PPREAMBLE Demand for specia
Page 43 and 44: II. .22 IINTRODUCTIION TO CHIIRALII
Page 45 and 46: The most dramatic example in this a
Page 47 and 48: H H 2 N OH COOH i PhH 2 CO O H N H
Page 49 and 50: Methods of Asymmetric Synthesis: 15
Page 51 and 52: O O O O i, ii iii iv HO HO N N OH O
Page 53 and 54: Models for Asymmetric Synthesis. 21
Page 55 and 56: If a strongly electronegative group
Page 57 and 58: enantiomeric products are formed at
Page 59 and 60: vi) The balance between chiral auxi
Page 61 and 62: IIII. .11 IINTRODUCTIION TO CHIIRAL
Page 63 and 64: Scheme II.1.2 However, availability
Page 65 and 66: Prof. R. Noyori received the Nobel
Page 67 and 68: Apart from the cinchona alkaloids,
Page 69 and 70: ligand, it assumes a tetrahedral co
Page 71 and 72: Marshall. 53 More recently, Barbero
Page 73 and 74: Various protocols have been develop
Page 75 and 76: In the absence of a sterically-bulk
Page 77 and 78: IIII. .33. . PPRESSENT WORK It is w
Page 79 and 80: [pyridinium][Sn 2 Cl 5 ] etc. can b
Page 81 and 82: RCHO 59a-j i R OH 60a-j (i) Allyl b
Page 83 and 84: Fig. II.3.2. 1 H NMR spectrum of 60
Page 85 and 86:
in [bmim][BF 4 ] using sub-stoichio
Page 87 and 88:
The reaction in THF was also follow
Page 89 and 90:
The integration of the signal at δ
Page 91 and 92:
The standard reduction potential of
Page 93 and 94:
It has also been reported, 83a,b th
Page 95 and 96:
IIII. .33. .33 Gaal lliuum meeddi i
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5 3.0 5.0 THF LiCl+KI c 14 d 71 6 1
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3 59d 4-(CH 3 ) 2 CH-C 6 H 4 H 60d
Page 101 and 102:
Fig. II.3.8. 13 C NMR spectrum of 6
Page 103 and 104:
Fig. II.3.10. 13 C NMR spectrum of
Page 105 and 106:
fragmentation peak at m/z 138 (19%)
Page 107 and 108:
Fig. II.3.13. 13 C NMR spectrum of
Page 109 and 110:
active catalyst, as suggested for t
Page 111 and 112:
1-(4-Bromophenyl)-but-3-en-1-ol 59b
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1H), 7.90-7.93 (m, 1H); 13 C NMR:
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662, 980, 1079, 1332, 1374 cm -1 .
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IIIIII. .11 DIIASSTEREOSSELECTIIVE
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cyclohexylideneglyceraldehyde (1) 3
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mixture of Zn dust, allyl or γ-sub
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Fig. III.1.2. 13 C NMR spectrum of
Page 125 and 126:
Reaction with crotyl bromide: In ca
Page 127 and 128:
Fig. III.1.5. 1 H NMR spectrum of 6
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The formation of the 2,3-anti addit
Page 131 and 132:
To establish the C-4 configuration
Page 133 and 134:
Allylation with (E) and (Z)-1-bromo
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(i) Zn, aqueous satd. NH 4 Cl, THF,
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Fig. III.1.12. 1 H NMR spectrum of
Page 139 and 140:
Allylation with 1-Bromo-4-(tert)-bu
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fast and gave a significantly bette
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espectively) due to the cyclohexyli
Page 145 and 146:
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was treated with excess amount of b
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Fig. III.1.20. 1 H NMR spectrum of
Page 151 and 152:
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stereochemistry of allylation of β
Page 155 and 156:
of the products were modest (48-62%
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6 1.2 In (2.0) H 2 O LiCl+ KI 14 72
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are consistent with our previous re
Page 161 and 162:
III.3 EXPERIMENTAL SECTION: General
Page 163 and 164:
(2R,3R)-1,2-Cyclohexylidenedioxy-5-
Page 165 and 166:
for an additional 2 h, gradually br
Page 167 and 168:
(m, 2H), 5.82-5.98 (m, 1H), 7.25-7.
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31.6, 32.2, 63.4, 128.8, 133.0. Ana
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23 (2R,3S,4R)-1,2-Cyclohexylidenedi
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(2R,3S,4S)-1,2-Cyclohexylidenedioxy
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(m, 1H), 3.50-4.02 (m, 5H), 4.10-4.
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and dried. Removal of solvent in va
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ine, and dried. Solvent removal und
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IIV. .11 SSYNTHESSIISS OFF ENANTIIO
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Scheme IV.1.1 The same group also d
Page 185 and 186:
IV.1.3: Present work Although sever
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O O C 6 H 13 i O C 6 H 13 ii OH C 6
Page 189 and 190:
Fig. IV.1.4. 1 H NMR spectrum of 10
Page 191 and 192:
the unit-C contribute positively to
Page 193 and 194:
tartrate, Ti(O-i-Pr) 4 , CH 2 Cl 2
Page 195 and 196:
Based on this hypothesis, the alcoh
Page 197 and 198:
OR 3 O R 1 R 2 NaBH 4 H H R 1 R 1 +
Page 199 and 200:
(OH). Oxidative cleavage of its α-
Page 201 and 202:
Page 203 and 204:
Page 205 and 206:
IIV. .33: : SSYNTHESSIISS OFF 33' '
Page 207 and 208:
For the actual synthesis, (Scheme I
Page 209 and 210:
Page 211 and 212:
IV.4: SSYNTHESSIISS OFF 22( (SS) )-
Page 213 and 214:
(i) PhCHO, triethyl orthoformate, M
Page 215 and 216:
O N 3 II Ph HO OH b1 N 3 Ph O O Ben
Page 217 and 218:
Page 219 and 220:
Thus, easily accessible 1 has been
Page 221 and 222:
167 and subsequent reduction gave 1
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from the appearance of 13 C NMR pea
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Page 227 and 228:
IV.6 EXPERIMENTAL SECTION (2R,3S,4R
Page 229 and 230:
As described earlier, compound 108
Page 231 and 232:
19.5, 23.8, 23.9, 25.1, 26.9, 34.6,
Page 233 and 234:
74.2, 74.4, 110.1, 116.7, 127.6, 12
Page 235 and 236:
mmol) in MeOH (10 mL), work up, fol
Page 237 and 238:
7.51 (m, 3H), 7.92-8.08 (m, 2H); 13
Page 239 and 240:
subsequent isolation afforded rotam
Page 241 and 242:
4.18 (t, J = 3.4 Hz, 1H), 4.75-4.84
Page 243 and 244:
-4.21 (c 1.2, CHCl 3 ); IR: 3466, 1
Page 245 and 246:
(3R)- 3,4-O-Cyclohexylidene-2-oxo-1
Page 247 and 248:
Water and EtOAc was added to the mi
Page 249 and 250:
24 179. Yield: 1.49 g (77.5%); colo
Page 251 and 252:
24 furnished pure 183. Yield: 0.37
Page 253 and 254:
1. Wender, P. A. Chem. Rev. 1996, 9
Page 255 and 256:
17. Hanessian, S.; Maji, D. K.; Gov
Page 257 and 258:
32. For some selective references s
Page 259 and 260:
43. (a) Cleare, M. J.; Hydes, P. C.
Page 261 and 262:
54. Barbero, A.; Pulido, F. J.; Rin
Page 263 and 264:
2008, 1681. (d) Fargeas, V.; Zammat
Page 265 and 266:
72. Karodia, N.; Guise, S.; Newland
Page 267 and 268:
Kaminski, J.; Millhauser, G.; Ortiz
Page 269 and 270:
Böhm, V. P. W.; Reisinger, C. J. O
Page 271 and 272:
119. Wender, P. A.; Holt, D. A.; Si
Page 273 and 274:
140. (a) Chemler, S. R.; Roush, W.
Page 275 and 276:
Lett. 1996, 107, 53. (c) Smith, C.
Page 277 and 278:
158. Mitsuya, H.; Weinhold, K. J.;
Page 279 and 280:
L.; Zugay, J. A. J. Med. Chem. 1993
Page 281 and 282:
1. Goswami, D.; Chattopadhyay, A.;
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