CHEM01200604012 Dibakar Goswami - Homi Bhabha National ...

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165. Lane, C. F. J. Org. Chem. 1974, 39, 1437. 166. (a) Kohl, N. E.; Emini, E. A.; Schleif, W.A.; Davis, L. J.; Heimbach, J. C.; Dixon, R. A. F.; Scholnick, E. M.; Sigal, I. S. Proc. Natl. Acad. Of Sci. U.S.A. 1988, 85, 4686. (b) Flexner, C. New. Engl. J. Med. 1998, 338, 1281. (c) Huff, J. R. J. Med. Chem., 1991, 34, 2305. (d) Martin, J. A. Antiviral. Res. 1992, 17, 265. (e) Tomasselli, A. G.; Heinrikson, R. L. Biochim. Biophys. Acta. 2000, 189. (f) Wlodwer, A.; Erickson, J. W. Annu. Rev. Biochem. 1993, 543. (g) Meek, T. D. J. Enzymol. Inhib. 1992, 5, 65. 167. Glushakova, S.; Dubrovsky, L.; Grivel, J. –C.; Haffer, O.; Bukrinsky, M. Antiviral Res. 2000, 47, 89, and references cited therein. 168. (a) Pearl, L. H.; Taylor, W. R. Nature, 1987, 329, 351. (b) Parkes, K. E. B.; Bushnall, D. J.; Cracjeff, P. H.; Dunsdon, S. J.; Freeman, A.; Gun, M. P.; Popkin, R. A.; Lambert, R. W.; Thomas, G. J. J. Org. Chem. 1994, 59, 3656. (c) Rieger, D. L. J. Org. Chem. 1997, 62, 8546. (d) Yanada, R.; Koh, Y.; Nishimori, N.; Matsumura, A.; Obika, S.; Mitsua, H.; Fuji, N.; Takemoto, Y. J. Org. Chem. 2004, 69, 3417. (e) Honda, Y.; Katayama, S.; Kojima, M.; Suzuki, M.; Kishibata, N.; Izawa, K. Org. Biomol. Chem. 2004, 69, 3417. 169. (a) Izaw, K.; Onishi, T. Chem. Rev. 2006, 106, 2811. (b) Ghosh, A. K.; Bilcer, G.; Sciltz, G. Synthesis 2001, 2203, and references cited therein. (c) Ghosh, A. K.; McKee, S. P.; Lee, H. Y.; Thompson, W. J. J. Chem. Soc. Chem. Commun. 1992, 273. (d) Ghosh, A. K.; Thompson, W. J.; Holloway, M. K.; McKee, S. P.; Duong, T. T.; Lee, H. Y.; Munson, P. M.; Smith, A. M.; Wei, J. M.; Dark, P. 234
L.; Zugay, J. A. J. Med. Chem. 1993, 36, 2300. (e) Kim, B. M.; Bae, S. J.; So, S. M.; Yoo, H. T.; Chang, S. K.; Lee, J. H.; Kang, J. Org. Lett. 2001, 3, 2349. 170. (a) Bennet, F., Girijavallabhan, V. M., Patel, N. J. Chem. Soc. Chem. Commun. 1993, 737. (b) Park, S.; Lee, S.; Kang, H-J. Bull Korean Chem. Soc. 2008, 29, 1073. 171. (a) Gunther, C.; Mosandi, A. Liebigs Ann. Chem. 1986, 2112, and refernces cited therein. (b) Wilkinson, K.; Esley, G. M.; Prager, R. H.; Tanaka, T.; Sefton, M. A. Tetrahedron 2004, 60, 6091. 172. Masuda, M.; Nishimura, K. Chem. Lett. 1981, 1333. 173. (a) Chartchouk, T.; Ollivier, J.; Salaun, J. Tetrahedron: Asymmetry 1997, 8, 1011. (b) Tsuboi, S.; Sakamoto, J.; Yamashita, H.; Sakai, T.; Utaka. M. J. Org. Chem. 1998, 63, 1102. (c) Schlapbach, A.; Hoffman, R. W.; Eur. J. Org. Chem. 2001, 323. (d) Suzuki, K.; Shoji, M.; Kobayashi, E.; Inomata, K. Tetrahedron: Asymmetry 2001, 12, 2789. (e) Ghosh, M.; Bose, S.; Ghosh, S. Tetrahedron Lett. 2008, 49, 5424, and references cited therein. 235
Page 1:
ASYMMETRIC STRATEGIES FOR THE SYNTH
Page 6 and 7:
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
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IIII. .11 IINTRODUCTIION TO CHIIRAL
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Scheme II.1.2 However, availability
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Prof. R. Noyori received the Nobel
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Apart from the cinchona alkaloids,
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ligand, it assumes a tetrahedral co
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Marshall. 53 More recently, Barbero
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Various protocols have been develop
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In the absence of a sterically-bulk
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IIII. .33. . PPRESSENT WORK It is w
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[pyridinium][Sn 2 Cl 5 ] etc. can b
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RCHO 59a-j i R OH 60a-j (i) Allyl b
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Fig. II.3.2. 1 H NMR spectrum of 60
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in [bmim][BF 4 ] using sub-stoichio
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The reaction in THF was also follow
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The integration of the signal at δ
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The standard reduction potential of
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It has also been reported, 83a,b th
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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
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Fig. II.3.8. 13 C NMR spectrum of 6
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Fig. II.3.10. 13 C NMR spectrum of
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fragmentation peak at m/z 138 (19%)
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Fig. II.3.13. 13 C NMR spectrum of
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active catalyst, as suggested for t
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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
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Reaction with crotyl bromide: In ca
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Fig. III.1.5. 1 H NMR spectrum of 6
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The formation of the 2,3-anti addit
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To establish the C-4 configuration
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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
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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
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was treated with excess amount of b
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Fig. III.1.20. 1 H NMR spectrum of
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stereochemistry of allylation of β
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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
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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-
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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
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: 158. Mitsuya, H.; Weinhold, K. J.;
Page 281 and 282: 1. Goswami, D.; Chattopadhyay, A.;
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