CHEM01200604012 Dibakar Goswami - Homi Bhabha National ...

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(t, 2 J F = 13.5 Hz), 119.4, 132.4, 137.5 (m), 140.5 (m), 144.7 (m). Anal. Calcd. for C 10 H 7 F 5 O: C, 50.43; H, 2.96%. Found: C, 50.24; H, 3.14%. (E)-1-Phenylhexa-1,5-dien-3-ol 59g. Colourless liquid; IR: 3425, 916 cm -1 ; 1 H NMR: δ 1.84 (broad s, 1H), 2.33-2.42 (m, 2H), 4.31-4.41 (m, 1H), 5.13-5.22 (m, 2 H), 5.75-5.93 (m, 1H), 6.18-6.29 (dd, J = 6.2 Hz and 16.0 Hz, 1H), 6.61 (d, J = 16.0 Hz, 1H), 7.23-7.40 (m, 5H); 13 C NMR: δ 41.8, 71.6, 118.3, 126.3, 127.5, 128.4, 130.2, 131.4, 133.9, 136.5. Anal. Calcd. for C 12 H 14 O: C, 82.72; H, 8.10%. Found: C 82.56; H 7.94%. 2-Methylhex-5-en-3-ol 59h. Colourless liquid; IR: 3419, 908 cm -1 ; 1 H NMR: δ 0.90 (d, J = 5.4 Hz, 5H), 1.61-1.67 (m, 1H), 2.01-2.16 (m, 2H), 2.22 (broad s, 1H), 3.31-3.38 (m, 1H), 5.06-5.14 (m, 2H), 5.71-5.92 (m, 1H); 13 C NMR: δ 17.5, 18.7, 33.0, 38.8, 75.3, 117.7, 135.4. Anal. Calcd. for C 7 H 14 O: C, 73.63; H, 12.36%. Found: C, 73.42; H, 12.15%. 1-Decen-4-ol 59i. Colourless liquid; IR: 3408, 912 cm -1 ; 1 H NMR: δ 0.85 (t, J = 6.4 Hz, 3H), 1.22-1.60 (m, 10H), 1.92 (broad s, 1H), 2.02-2.29 (m, 2H), 3.52-3.65 (m, 1H), 4.98- 5.17 (m, 2H), 5.65-5.93 (m, 1H); 13 C NMR: δ 14.0, 22.6, 25.6, 29.3, 31.8, 36.8, 41.9, 70.6, 117.8, 134.9. Anal. Calcd. for C 10 H 20 O: C, 76.86; H, 12.90%. Found: C 76.61; H 13.05%. 1-Tridecen-4-ol 59j. Colourless liquid; IR: 3462, 908 cm -1 ; 1 H NMR: δ 0.91 (t, J = 6.4 Hz, 3H), 1.29-1.47 (m, 16H), 1.75 (broad s, 1H), 2.08-2.37 (m, 2H), 3.59-3.68 (m, 1H), 5.12-5.18 (m, 2H), 5.76-5.93 (m, 1H); 13 C NMR: δ 14.0, 22.6, 25.6, 29.3, 29.6, 31.8, 36.7, 41.8, 70.6, 117.7, 134.9. Anal. Calcd. for C 13 H 26 O: C, 78.72; H, 13.21%. Found: C, 78.57; H, 13.15%. 1-(3-Indolyl) -but-3-en-1-ol 59k. Colourless liquid, IR: 3458, 910 cm -1 ; 1 H NMR: δ 2.04 (broad s, 1H), 2.42-2.53 (m, 1H), 2.82-2.90 (m, 1H), 4.07-4.18 (m, 1H), 4.97-5.13 (m, 2H), 5.84-5.96 (m, 1H), 6.95-7.01 (m, 1H), 7.07-7.26 (m, 1H), 7.34-7.37 (m, 1H), 7.59-7.69 (m, 71
1H), 7.90-7.93 (m, 1H); 13 C NMR: δ 41.3, 60.3, 110.9, 114.5, 116.2, 118.8, 119.0, 121.0, 121.8, 138.7. Anal. Calcd. for C 12 H 13 NO: C, 76.98; H, 7.00; N 7.48%. Found: C, 76.81; H, 6.92; N, 7.34%. 2-Phenylpent-4-en-2-ol 59l. Colourless liquid, IR: 3499, 925 cm -1 ; 1 H NMR: δ 1.54 (s, 3H), 1.98 (broad s, 1H), 2.44-2.74 (m, 2H), 5.08-5.18 (m, 2H), 5.56-5.64 (m, 1H), 7.23- 7.46 (m, 5H); 13 C NMR: δ 29.8, 48.4, 73.6, 119.4, 124.7, 126.5, 128.1, 128.5, 133.6, 147.6. Anal. Calcd. for C 11 H 14 O: C, 81.44; H, 8.70%. Found: C, 81.51; H, 8.45%. 1,1-Diphenylbut-3-en-1-ol 59m. Colourless liquid, IR: 3434, 929 cm -1 ; 1 H NMR: δ 2.04 (broad s, 1H), 3.08 (d, J = 8 Hz, 2H), 5.15-5.28 (m, 2H), 5.56-5.73 (m, 1H), 7.21-7.35 (m, 7H), 7.43-7.47 (m, 3H); 13 C NMR: δ 46.5, 77.2, 120.3, 125.8, 126.7, 128.0, 133.2, 146.3. Anal. Calcd. for C 16 H 16 O: C, 85.68; H, 7.19%. Found: C, 85.82; H, 7.05%. 2-Hydroxy-1,2-diphenylpent-4-en-1-one 59n. Colourless liquid, IR: 3478, 917 cm -1 ; 1 H NMR: δ 2.16 (broad s, 1H), 2.91-3.19 (m, 2H), 4.96-5.13 (m, 2H), 5.63-5.80 (m, 1H), 7.24-7.52 (m, 8H), 7.71-7.75 (m, 2H); 13 C NMR: δ 43.7, 81.2, 111.9, 120.2, 125.4, 127.9, 128.7, 129.9, 132.1, 132.6, 134.3, 141.5, 200.6. Anal. Calcd. for C 17 H 16 O 2 : C, 80.93; H, 6.39%. Found: C, 81.21; H, 6.15%. (E)-1,3-Diphenylhexa-1,5-dien-3-ol 59o. Colourless liquid; IR: 3431, 911 cm -1 ; 1 H NMR: δ 2.17 (broad s, 1H), 2.82 (d, J = 6.8 Hz, 2H), 5.18-5.27 (m, 2H), 5.64-5.85 (m, 1H), 6.50-6.72 (m, 2H),7.23-7.42 (m, 8H),7.52-7.56(m, 2H); 13 C NMR: δ 47.1, 75.7, 120.1, 125.0, 125.5, 126.4, 127.0, 127.4, 127.8, 128.2, 128.3, 132.5, 135.2, 137.4, 145.3. Anal. Calcd. for C 18 H 18 O: C, 86.36; H, 7.25%. Found: C, 86.60; H, 7.01%. 72
Page 1:
ASYMMETRIC STRATEGIES FOR THE SYNTH
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ACKNOWLEDGEMENTS First of all, I wa
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CONTENTS SYNOPSIS LIST OF FIGURES L
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SYNOPSIS
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models (e. g. Cram’s model, Felki
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4 1d 4-(CH 3 ) 2 CH-C 6 H 4 1 : 1.5
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14. 1n C 6 H 5 CO C 6 H 5 2n 8 77 1
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imetallic systems. In all the cases
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For the benzylation reaction, the c
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O O 3 CHO i O O + OH 13a O O OH O O
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10 3.5 Ga (2.5) THF KI+LiCl 10 55 5
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multidrug-resistant (MDR) cancer ce
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directly afforded the furanose, whi
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References 1. Stephenson, G. R. Adv
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LIST OF FIGURES
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II.3.13 III.1.1 III.1.2 III.1.3 III
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IV.5.2 IV.5.3 IV.5.4 IV.5.5 1 H NMR
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Table Title Page No. II.3.1 II.3.2
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II. .11 PPREAMBLE Demand for specia
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II. .22 IINTRODUCTIION TO CHIIRALII
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The most dramatic example in this a
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H H 2 N OH COOH i PhH 2 CO O H N H
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Methods of Asymmetric Synthesis: 15
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O O O O i, ii iii iv HO HO N N OH O
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Models for Asymmetric Synthesis. 21
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If a strongly electronegative group
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enantiomeric products are formed at
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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
Page 97 and 98: 5 3.0 5.0 THF LiCl+KI c 14 d 71 6 1
Page 99 and 100: 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: 1-(4-Bromophenyl)-but-3-en-1-ol 59b
Page 115 and 116: 662, 980, 1079, 1332, 1374 cm -1 .
Page 117 and 118: IIIIII. .11 DIIASSTEREOSSELECTIIVE
Page 119 and 120: cyclohexylideneglyceraldehyde (1) 3
Page 121 and 122: mixture of Zn dust, allyl or γ-sub
Page 123 and 124: 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
Page 129 and 130: 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
Page 135 and 136: (i) Zn, aqueous satd. NH 4 Cl, THF,
Page 137 and 138: Fig. III.1.12. 1 H NMR spectrum of
Page 139 and 140: Allylation with 1-Bromo-4-(tert)-bu
Page 141 and 142: fast and gave a significantly bette
Page 143 and 144: espectively) due to the cyclohexyli
Page 147 and 148: was treated with excess amount of b
Page 149 and 150: Fig. III.1.20. 1 H NMR spectrum of
Page 153 and 154: stereochemistry of allylation of β
Page 155 and 156: of the products were modest (48-62%
Page 157 and 158: 6 1.2 In (2.0) H 2 O LiCl+ KI 14 72
Page 159 and 160: are consistent with our previous re
Page 161 and 162: III.3 EXPERIMENTAL SECTION: General
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(2R,3R)-1,2-Cyclohexylidenedioxy-5-
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for an additional 2 h, gradually br
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(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
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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
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Fig. IV.1.4. 1 H NMR spectrum of 10
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the unit-C contribute positively to
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tartrate, Ti(O-i-Pr) 4 , CH 2 Cl 2
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Based on this hypothesis, the alcoh
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OR 3 O R 1 R 2 NaBH 4 H H R 1 R 1 +
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(OH). Oxidative cleavage of its α-
Page 201 and 202:
Page 203 and 204:
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IIV. .33: : SSYNTHESSIISS OFF 33' '
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For the actual synthesis, (Scheme I
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IV.4: SSYNTHESSIISS OFF 22( (SS) )-
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(i) PhCHO, triethyl orthoformate, M
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O N 3 II Ph HO OH b1 N 3 Ph O O Ben
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Thus, easily accessible 1 has been
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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
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As described earlier, compound 108
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19.5, 23.8, 23.9, 25.1, 26.9, 34.6,
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74.2, 74.4, 110.1, 116.7, 127.6, 12
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mmol) in MeOH (10 mL), work up, fol
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7.51 (m, 3H), 7.92-8.08 (m, 2H); 13
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subsequent isolation afforded rotam
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4.18 (t, J = 3.4 Hz, 1H), 4.75-4.84
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-4.21 (c 1.2, CHCl 3 ); IR: 3466, 1
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(3R)- 3,4-O-Cyclohexylidene-2-oxo-1
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Water and EtOAc was added to the mi
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24 179. Yield: 1.49 g (77.5%); colo
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24 furnished pure 183. Yield: 0.37
Page 253 and 254:
1. Wender, P. A. Chem. Rev. 1996, 9
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17. Hanessian, S.; Maji, D. K.; Gov
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32. For some selective references s
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43. (a) Cleare, M. J.; Hydes, P. C.
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54. Barbero, A.; Pulido, F. J.; Rin
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2008, 1681. (d) Fargeas, V.; Zammat
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72. Karodia, N.; Guise, S.; Newland
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Kaminski, J.; Millhauser, G.; Ortiz
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Böhm, V. P. W.; Reisinger, C. J. O
Page 271 and 272:
119. Wender, P. A.; Holt, D. A.; Si
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140. (a) Chemler, S. R.; Roush, W.
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Lett. 1996, 107, 53. (c) Smith, C.
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158. Mitsuya, H.; Weinhold, K. J.;
Page 279 and 280:
L.; Zugay, J. A. J. Med. Chem. 1993
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1. Goswami, D.; Chattopadhyay, A.;
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