CHEM01200604012 Dibakar Goswami - Homi Bhabha National ...

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1993, 58, 5500. (g) McCluskey, A. Green Chem. 1999, 167. (h) Fukuma, T.; Lock, S.; Miyoshi, N.; Wada, M. Chem. Lett. 2002, 376. 59. (a) Blomborg, C. In: The Barbier Reactions and Related One Step Processes, Springer, Berlin, 1993. (b) Lindstrom, U. M. Chem. Rev. 2003, 103, 2751 and references cited therein. (c) Li. C.J. Chem. Rev. 1993, 93, 2023. (d) Mulzer, J.; Altembach, H. J.; Braun, M.; Krohn, K.; Reissig, H.U. Organic Synthesis Highlights; VCH: Weinheim, 1991, 71. (e) Welton, T. Chem. Rev. 1999, 99, 2071. 60. (a) Petrier, C.; Luche, J. L. J. Org. Chem. 1985, 50, 910. (b) Einhorn, C.; Luche, J. L. J. Organomet. Chem. 1987, 322, 177. (c) Petrier, C. J.; Luche, J. L. Tetrahedron Lett. 1985, 26, 1449. (d) Luche, J. L.; Cintas, P. Active Metals, Furstner, A. ed.; VCH publishers; New York, 1996, pp-133. 61. (a) Li, C. J.; Meng, Y.; Xiang-Hui Y. J. Org. Chem. 1997, 62, 8632-8633. (b) Nokami, J.; Otera, J.; Sudo, T.; Okawara, R. Organometallics 1983, 2, 191. (c) Nokami, J.; Wakabayashi, S.; Okawara, R. Chem. Lett. 1984, 869. (d) Zhou, J. Y.; Chen, Z. G.; Wu, S. H. Chem. Commun. 1994, 2783. (e) Li, X. R.; T. P. Loh, Tetrahedron:Asymmetry 1996, 7, 1535. (f) Wang, Z. Y.; Zha, Z. G.; Zhou, C. L. Org. Lett. 2002, 4, 1683. (g) Zha, Z. G.; Wang, Y. S.; Yang, G..; Zhang, L.; Wang, Z. Y. Green Chem. 2002, 4, 578. (h) Tan, K. T.; Chng, S. S.; Cheng, H. S.; Loh, T. P. J Am. Chem. Soc. 2003, 125, 2958. 62. (a) Akiyama, T.; Iwai, J. Tetrahedron Lett. 1997, 38, 853. (b) LaRonde, F. J.; Brook, M. A. Can. J. Chem. 2003, 81, 1206. (c) Fargeas, V.; Zammattio, F.; Chrétien, J. M.; Bertrand, M, J.; Paris, M.; Quintard, J. P. Eur. J. Org. Chem. 218
2008, 1681. (d) Fargeas, V.; Zammattio, F.; Chrétien, J. M.; Bertrand, M, J.; Paris, M.; Quintard, J. P. Eur. J. Org. Chem. 2008, 1681. 63. (a) Araki, S.; Ito, H.; Butsugan, Y. J. Organomet. Chem. 1988, 347, 5. (b) Smith, K.; Lock, S.; El-Hiti, G. A.; Wada, M.; Miyoshi, M. Org. Biomol. Chem. 2004, 2, 935. (c) Li, L,-H.; Chan, T. H. Can. J. Chem. 2001, 79, 1536. 64. (a) Nair, V.; Ros, S.; Jayan, C. N.; Pillai, B. S. Tetrahedron 2004, 60, 1959. (b) Augé, J.; Lubin-Germain, N. Uziel, J. Synthesis 2007, 1739. 65. (a) Araki, S.; Ito, H.; Butsugan, Y. J. Org. Chem. 1988, 53, 1831. (b) Chan, Y. H.; Yang, Y. J. Am. Chem. Soc. 1999, 121, 3228. (c) Gordon, C. M.; Ritchie, C. Green Chem. 2002, 124. (d) Hirashita, T.; Kamei, T.; Satake, M.; Horie, T.; Shimizu, H.; Araki, S. Org. Biomol. Chem. 2003, 21, 3799. (e) Paquette, L. A.; Mitzel, T. M. J. Am. Chem. Soc. 1996, 118, 1931-1937. (f) Paquette, L. A.; Mitzel, T. M. J. Org. Chem. 1996, 61, 8799-8804. (g) Loh, T.-P.; Tan, K.-T.; Yang, J.-Y.; Xiang, C.-L. Tetrahedron Lett. 2001, 42, 8701. 66. (a) Araki, S.; Ito, H.; Butsugan, Y. Appl. Organomet. Chem. 1988, 2, 475. (b) Wang, Z.; Yuan, S.; Li, C. –J. Tetrahedron Lett. 2002, 43, 5097. (c) Han, Y.; Chi, Z.; Huang, Y.-Z. Synth. Commun. 1999, 43, 1287. (d) Andrews, P. C.; Peatt, A. C.; Raston, C. L. Tetrahedron Lett. 2004, 45, 243. (e) Tsuji, T.; Usugi, S.-I.; Yorimitsu, H.; Shinokubo, H.; Matsubara, S.; Oshima, K. Chem. Lett. 2002, 2. (f) Han, Y.; Huang, Y.-Z. Tetrahedron Lett. 1994, 35, 9433. (g) Lee, P. H.; Kim, H.; Lee, K. Adv. Synth. Catal. 2005, 347, 1219. (h) Gohain, M.; Prajapati, D. Chem. Lett. 2005, 90. (i) Laskar, D. D.; Gohain, M.; Prajapati, D.; Sandhu, J. S. New J. Chem. 2002, 26, 193. (j) Yamaguchi, M.; Sotokawa, 219
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
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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
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: Fig. IV.4.2. 1 H NMR spectrum of 91
Page 219 and 220: Thus, easily accessible 1 has been
Page 221 and 222: 167 and subsequent reduction gave 1
Page 223 and 224: from the appearance of 13 C NMR pea
Page 225 and 226: Fig. IV.5.2. 1 H NMR spectrum of 17
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: 54. Barbero, A.; Pulido, F. J.; Rin
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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