CHEM01200604012 Dibakar Goswami - Homi Bhabha National ...

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S. J. Am. Chem. Soc. 1980, 102, 7122. (d) Wilen, S. H.; Collet, A.; Jaques, J. J. Am. Chem. Soc., 1977, 33, 2725. 13. Asymmetric Synthesis, Atiken, A.; Kilenyi, S. N. eds., Blackie Academic & Professional, Glasgow, 1994, 85. 14. (a) Wong, C. H.; Whitesides, G. M. In: Enzymes in Synthetic Organic Chemistry, Elsevier Sci., 1994. (b) Santiniello, E.; Ferraboschi, P.; Grisenti, P.; Manzocchi, A. Chem. Rev. 1992, 92, 1071. 15. (a) Bartlett, P. A. Tetrahedron 1980, 36, 2. (b) Stephenson, G. R., Advanced Asymmetric Synthesis, Chapman & Hall, 1996. (c) Van Draanen, N. A.; Arseniayadis, Crimmins, M. T.; Heathcock, C. H. J. Org. Chem. 1991, 56, 2499. (d) Mulzer, J.; Altenbach, H. J.; Braun M. Krohn, K.; Reissig, H. U. Organic Synthesis Highlights, VCH: Weinheim, 1991, pp-1. (e) Asymmetric Synthesis, Morrison, J. D., ed., Academic Press: New York, 1983, pp-1. (f) Mukaiyama, T. Org. React. 1982, 28, 203. (g) Marshall, J. A. Chem. Rev. 1996, 96, 31. (h) Hoffman, R. W. Angew. Chem. Int. Ed. Engl. 1987, 26, 489. (i) Heathcock, C. H. Comprehensive Organic Synthesis, Trost, B. M., ed., Pergamon Press: Oxford, 1991, Vol. 2, pp-181. (j) Elliel, E. L.; Otsuka, S. Asymmetric Reactions and Processes in Chemistry, ACS Symposium Series 185, pp-982. (k) Masamune, S.; Choy, W.; Peterson, J. S.; Sita, L. R. Angew. Chem. Int. Ed. Engl. 1985, 24, 1. (l) Garcý´a-Fortanet, J.; Murga, J.; Carda, M.; Marco, J. A. Org. Lett. 2003, 5, 1447, and references cited therein. 16. Fischer, E. Berchite 1894, 27, 3210. 210
17. Hanessian, S.; Maji, D. K.; Govindan, S.; Matera, R.; Tintelnot-Blomley, M. J. Org. Chem. 2010, 75, 2861. 18. Myers, A.G.; Yang, B.H.; Chen, H.; Gleason, J.L. J. Am. Chem. Soc. 1994, 116, 9361. 19. Chan, P. C. M.; Chong, J. M. J. Org. Chem. 1988, 53, 5584. 20. Hills, I. D.; Fu, G. C. Angew. Chem. Int. Ed. Engl. 2003, 42, 3921. 21. Mengel, A.; Reiser, O. Chem. Rev. 1999, 99, 1191. 22. (a) Cram, D. J.; Wilson, D. R. J. Am. Chem. Soc. 1963, 85, 1245. (b) Cram, D. J.; Elhafez, F. A. A. J. Am. Chem. Soc. 1952, 74, 5828. (c) Cram, D. J.; Greene, F. D. J. Am. Chem. Soc. 1953, 75, 6004. 23. First direct observation of Cram-Chelate transition states: (a) Rettz, M. T.; Huellmann, M.; Seitz, T. Angew. Chem. 1987, 99, 478. (b) Rettz, M. T.; Huellmann, M.; Seitz, T. Angew. Chem. Int. Ed. Engl. 1987, 26, 477. (c) Rettz, M. T.; Raguse, B.; Seitz, T. Tetrahedron 1993, 49, 8561. (d) Rettz, M. T. Acc. Chem. Res. 1993, 26, 462. 24. (a) Che´rest, M.; Felkin, H.; Prudent, N. Tetrahedron Lett. 1968, 18, 2199. (b) Anh, N. T. Top. Curr. Chem. 1980, 88, 145. (c) Anh, N. T.; Eisenstein, O. Nouv. J. Chim. 1977, 1, 61. (d) Anh, N. T.; Eisenstein, O. Tetrahedron Lett. 1976, 3, 155. 25. (a) Zimmerman, H. E.; Traxler, M. D. J. Am. Chem. Soc. 1957, 79, 1920. (b) Denmark, S. E.; Henke, B. R. J. Am. Chem.Soc. 1991, 113, 2177. 26. (a) Cahn, R. S.; Ingold, C. K.; Prelog, V. Angew. Chem. Intl. Ed. Engl. 1966, 5, 385. (b) Eliel, E. L. Tetrahedron 1974, 30, 1503. 211
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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Fig. IV.2.2. 1 H NMR spectrum of 13
Page 203 and 204: Fig. IV.2.6. 1 H NMR spectrum of 14
Page 205 and 206: IIV. .33: : SSYNTHESSIISS OFF 33' '
Page 207 and 208: For the actual synthesis, (Scheme I
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 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 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: 1. Wender, P. A. Chem. Rev. 1996, 9
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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