- Page 1: ASYMMETRIC STRATEGIES FOR THE SYNTH
- Page 7 and 8: Jayanta da, Dhanadeep da, Balaji, S
- Page 9 and 10: IV.2.1 Introduction 147 IV.2.2 Prev
- Page 12 and 13: Extensive research on natural produ
- Page 14 and 15: The reaction could also be accompli
- Page 16 and 17: O R 1 R 2 1a-q Scheme 2 Allyl bromi
- Page 18 and 19: thermogavimetric and elemental anal
- Page 20 and 21: 5 CH 3 Zn/aq NH 4 Cl 1 : 3.5 : - 5
- Page 22 and 23: Table 4. Reaction course of Mg/CuCl
- Page 24 and 25: 7 4 Bi (2.5) H 2 O -- 8 62 23.2 : 7
- Page 26 and 27: 3 1.2 In (1.0) [bmim][Br] -- 6 78 1
- Page 28 and 29: and NaBH 4 reduction afforded the s
- Page 30 and 31: the aldehyde 31. Finally, desilylat
- Page 32 and 33: 2001, 7, 1259-1276. (c) Eissler, S.
- Page 34 and 35: Figure Title Page No. I.1.1 Structu
- Page 36 and 37: III.2.1 cyclic TS for metal mediate
- Page 38 and 39: LIST OF TABLES
- Page 40 and 41: CHAPTER I INTRODUCTION
- Page 42 and 43: conversions occurring under the cho
- Page 44 and 45: (R,R,S)-isomer of deltametrine (2)
- Page 46 and 47: II. .33. . SSTRATEGIIESS OFF ENANTI
- Page 48 and 49: c) Kinetic resolution with biochemi
- Page 50 and 51: The new stereogenic centre formed a
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elatively recently that such asymme
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Cram rule actually allows the analy
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quantitative assessment of the 1,2-
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control leads to the predominant fo
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CHAPTER II [bmim][Br]: A GREEN AND
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Asymmetric reduction of ketones: Th
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36e acid-derived boronate ester, wi
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eaction of OsO 4 with olefins which
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Ph OH i Cl Ph 42 43 OH Cl 96% ee 80
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aldehydes in the presence of chiral
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IIII. .22 IINTRODUCTIION TO HOMOALL
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In metal in DMF. In another importa
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Given that the Ga-mediated Barbier-
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earlier, the halogenoaluminate(III)
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processes. Although the aspects of
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Allylation of 59a in H 2 O and THF
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Table II.3.2. Reaction profile of a
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Mechanistic studies: For the mechan
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simultaneous reduction of the signa
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The acceleration of the reaction in
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precursor to partially replenish th
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Once produced, the species II react
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presence or absence of additives et
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acetophenone (59l) under a solvent-
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even without any metal activator, a
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and chemical analysis. 1 H NMR spec
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standard reduction potential (0.641
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Fig. II.3.11. DSC results of compou
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the imidazolium salts to Pt(o) has
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II.4 EXPERIMENTAL SECTION Typical p
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(t, 2 J F = 13.5 Hz), 119.4, 132.4,
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1-Allylcyclohexanol 59p. Colourless
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CHAPTER III DIASTEREOSELECTIVE SYNT
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species is a prerequisite for any m
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undergo in situ isomerization to th
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NMR of 68a and 68b are shown in Fig
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Fig. III.1.4. 13 C NMR spectrum of
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4 Zn/ CuCl 2 , 2H 2 O 1 : 3.0 : 2.5
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Fig. III.1.7. 1 H NMR spectrum of 6
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evealed by its 1 H NMR spectral pat
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Fig. III.1.10. 1 H NMR Spectrum of
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For the allylation, compound 1 was
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4 Zn/CoCl 2 .8H 2 O 78a 1 : 3.0 :3.
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Fig. III.1.14. 1 H NMR spectrum of
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HO 80 OH i HO 81 OTBDPS ii Br 82 OT
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possible diastereomers 83a-d in sub
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Fig. III.1.17. 13 C NMR spectrum of
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(B) Benzylation of aldehydes Additi
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Table III.1.5 Reaction course of Cu
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In general, aromatic aldehydes reac
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IIIIII. .22 METAL DEPPENDENT MODULA
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suited for the Barbier type reactio
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the reaction in H 2 O (entry 9, Tab
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higher in [bmim][Br]. The results a
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R H H R R' H O M H R O M R' R O M H
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General procedure for Barbier type
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(2R,3S,4S)-1,2-Cyclohexylidinedioxy
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36.1, 39.8, 65.9, 74.9, 76.7, 109.6
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Non-2-yn-1-ol 76. To a stirred solu
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chromatography (silica gel, 5-10% E
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1H), 3.72-4.00 (m, 4H), 5.22-5.53 (
- Page 174 and 175:
1 H NMR: δ 1.03 (s, 9H),1.40-1.62
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were washed with water and brine, a
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1-(phenyl)-2-phenylethanol 90d. 1 H
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CHAPTER IV ASYMMETRIC SYNTHESIS OF
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IV.1.2: Previous syntheses Given it
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In a more recent report, 144j the a
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appeaence of a sharp peak for the -
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Fig. IV.1.2. 1 H NMR spectrum of 10
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IIV. .22: : SSYNTHESSIISS OFF OCTAD
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IV.2.2: Previous syntheses of unit-
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Scheme IV.2.2 IV.2.3: Present work
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To confirm the 3,5-syn stereochemis
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O O O iii iv O 132a + O O i,ii OR 1
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O O OR 1 OH 132 R 1 = TBDPS O i O i
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Fig. IV.2.4. 1 H NMR Spectrum of 13
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In conclusion, an efficient asymmet
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For the synthesis of a nucleoside a
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O O R O R 2 O R i ii iii 2 O R 2 2
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Fig. IV.3.3. 1 H NMR spectrum of 14
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N 3 O Ph Fig. IV.4.1. Structure of
- Page 214 and 215:
More recently, Park et al. 170b syn
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hydroxyl of 166 and base treatment
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Fig. IV.4.4. 1 H NMR spectrum of VI
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IV.5: SSYNTHESSIISS OFF trraannss-
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O O i O ii O CO 2 Et HO CO 2 Et 171
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O O 69c OH i O O 128 OTPS ii O iii
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Fig. IV.5.4. 1 H NMR spectrum of 18
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IR: 3417, 1358, 1175, 1045, 922 cm
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(2R,3S,4S)-3-(tert)-Butyldiphenylsi
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mmol) in one lot. After stirring fo
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1H); 13 C NMR: δ 12.2, 19.6, 23.9,
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1H), 3.85-3.95 (m, 1H), 4.05-4.16 (
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mixture was concentrated in vacuo,
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36.7, 41.9, 64.4, 72.2, 73.6, 77.8,
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Hz, 3H), 1.58 (s, 3H), 1.62 (s, 3H)
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pyridine (12 mL) was stirred overni
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The organic extracts were washed wi
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(m, 12H), 1.61-1.72 (m, 2H), 3.36-3
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organic layer was separated and the
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REFERENCES
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S. J. Am. Chem. Soc. 1980, 102, 712
- Page 256 and 257:
27. (a) Lee, V. J. In: Comprehensiv
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Shimizu, K.; Ito, K. J. Chem. Soc.,
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49. (a) Noyori, R.; Kitamura, M. An
- Page 262 and 263:
1993, 58, 5500. (g) McCluskey, A. G
- Page 264 and 265:
T.; Hirama, M. Chem. Commun. 1997,
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79. (a) Chan, T. H.; Li, C. J.; Lee
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93. Ott, L. S.; Cline, M. L.; Deetl
- Page 270 and 271:
107. (a) Reike, R. D.; Sell, M. S.;
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129. Sato, F.; Kobayashi, Y.; Takah
- Page 274 and 275:
147. For reviews: (a) Moore, R. E.;
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153. (a) Kobayashi, M.; Wang, W.; O
- Page 278 and 279:
165. Lane, C. F. J. Org. Chem. 1974
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` LIST OF PUBLICATIONS
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enantiopure anti-alzheimer (R)-arun