References (139) Yoon, Y.-J.; Joo, J.-E.; Lee, K.-Y.; Kim, Y.-H.; Oh, C.-Y.; Ham, W.-H. Tetrahedron Lett. 2005, 46, 739. (140) Chen, Y.-J.; Lei, F.; Liu, L.; Wang, D. Tetrahedron 2003, 59, 7609. (141) Li, Y.; Manickam, G.; Ghoshal, A.; Subramaniam, P. Synth. Commun. 2006, 36, 925 - 928. (142) <strong>Clayden</strong>, J.; Dufour, J.; Grainger, D. M.; Helliwell, M. J. Am. Chem. Soc. 2007, 129, 7488-7489. (143) Kiessling, A. J.; McClure, C. K. Synth. Commun. 1997, 27, 923-937. (144) Johansen, M.; Bundgaard, H. J. Pharm. Sci. 1983, 72, 1294-1298. (145) Buur, A.; Bundgaard, H. Int. J. Pharm. 1984, 18, 325. (146) estimated as 6 x half-life of oxazolidine derived from pivalaldehyde and ephedrine, adjusted for ambient temperature (20 ºC drop in temperature gives c. four-fold decrease in reaction rate (147) Fife, T. H.; Hutchins, J. E. C. J. Org. Chem. 1980, 45, 2099-2104. (148) Walker, R. B.; Huang, M.-J.; Leszczynski, J. J. Mol. Struct. <strong>The</strong>ochem 2001, 549, 137. (149) Sigma-Aldrich, As of Apr 2008: (1S,2R)-(+)-2-Amino-1,2-diphenylethanol (CAS 23364-44-5) Sigma-Aldrich 331880, £21.50 / 1g; (1R,2S)-(−)-2-Amino- 1,2-diphenylethanol (CAS 23190-16-1) Sigma-Aldrich 331899 £36 for 1g. (150) McCasland, G. E.; Furuta, S.; Durham, L. J. J. Org. Chem. 1966, 31, 1516- 1521. (151) McCasland, G. E.; Furuta, S.; Durham, L. J. J. Org. Chem. 1968, 33, 2841- 2844. (152) Miwa, I.; Hara, H.; Okuda, J.; Suami, T.; Ogawa, S. Biochem. Int. 1985, 11, 809-16. (153) Miller, T. W.; Arison, B. H.; Albers-Schonberg, G. Biotechnol. Bioeng. 1973, 15, 1075-1080. (154) Marco-Contelles, J. Eur. J. Org. Chem. 2001, 2001, 1607-1618. (155) Chen, X.; Fan, Y.; Zheng, Y.; Shen, Y. Chem. Rev. 2003, 103, 1955-1978. (156) Arjona, O.; Gomez, A. M.; Lopez, J. C.; Plumet, J. Chem. Rev. 2007, 107, 1919-2036. (157) Johansson, L.; Lindskog, A.; Silfversparre, G.; Cimander, C.; Nielsen, K. F.; Lidén, G. Biotech. Bioeng. 2005, 92, 541-552. (158) Bradley, D. Nat. Rev. Drug Discov. 2005, 4, 945. (159) Acros Organics quote £31 for 100 mg, vs. £14 for 100 g for myo-inosi<strong>to</strong>l (Feb 2008) (160) Ogawa, S.; Ara, M.; Kondoh, T.; Sai<strong>to</strong>h, M.; Masuda, R.; Toyokami, T.; Suami, T. Bull. Chem. Soc. Jpn. 1980, 53, 1121. (161) Angelaud, R.; Landais, Y. Tetrahedron Lett. 1997, 38, 8841. (162) Ley, S. V.; Sternfeld, F.; Taylor, S. Tetrahedron Lett. 1987, 28, 225. (163) Carless, H. A. J.; Malik, S. S. J. Chem. Soc., Chem. Commun. 1995, 2447- 2448. (164) Haller, J.; Strassner, T.; Houk, K. N. J. Am. Chem. Soc. 1997, 119, 8031-8034. (165) Hodgson, R.; Majid, T.; Nelson, A. J. Chem. Soc., Perkin Trans. 1 2002, 1444 - 1454. (166) Alibes, R.; Bayon, P.; deMarch, P.; Figueredo, M.; Font, J.; Marjanet, G. Org. Lett. 2006, 8, 1617-1620. (167) Rubot<strong>to</strong>m, G. M.; Gruber, J. M.; Juve, H. D.; Charleson, D. Org. Synth. 1990, Coll. Vol 7, 282. (168) Adam, W.; Wirth, T. Acc. Chem. Res. 1999, 32, 703-710. 189
References (169) McCormick, J. P.; Tomasik, W.; Johnson, M. W. Tetrahedron Lett. 1981, 22, 607. (170) Deubel, D. V.; Frenking, G. Acc. Chem. Res. 2003, 36, 645-651. (171) VanRheenen, V.; Cha, D. Y.; Hartley, W. M. Org. Synth. 1978, 58, 43. (172) Poli, G. Tetrahedron Lett. 1989, 30, 7385. (173) Lockwood, S. F.; O'Malley, S.; Watumull, D. G.; Hix, L. M.; Jackson, H.; Nadolski, G.; (USA): 2005, p 130 pp, Cont -in-part of U S Ser No 629,538. (174) Bordwell, F. G.; Fried, H. E.; Hughes, D. L.; Lynch, T. Y.; Satish, A. V.; Whang, Y. E. J. Org. Chem. 1990, 55, 3330-3336. (175) Olmstead, W. N.; Margolin, Z.; Bordwell, F. G. J. Org. Chem. 1980, 45, 3295- 3299. (176) Eames, J.; Mitchell, H. J.; Nelson, A.; O'Brien, P.; Warren, S.; Wyatt, P. J. Chem. Soc., Perkin Trans. 1 1999, 1095-1103. (177) Luche, J. L. J. Am. Chem. Soc. 1978, 100, 2226-2227. (178) Gemal, A. L.; Luche, J. L. J. Am. Chem. Soc. 1981, 103, 5454-5459. (179) Krishnamurthy, S.; Brown, H. C. J. Org. Chem. 1977, 42, 1197-201. (180) Kumamo<strong>to</strong>, T.; Tabe, N.; Yamaguchi, K.; Yagishita, H.; Iwasa, H.; Ishikawa, T. Tetrahedron 2001, 57, 2717. (181) D. J. Dixon, personal communication (182) Wigfield, D. C. Tetrahedron 1979, 35, 449. (183) Leo A. Paquette, D. C., Philip L. Fuchs and Gary Molander e-EROS Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, Ltd., 2006. (184) Czernecki, S.; Georgoulis, C.; Provelenghiou, C. Tetrahedron Lett. 1976, 17, 3535. (185) Owensby, D. A.; Parker, A. J.; Diggle, J. W. J. Am. Chem. Soc. 1974, 96, 2682- 2688. (186) Wessel, H. P.; Iversen, T.; Bundle, D. R. J. Chem. Soc., Perkin Trans. 1 1985, 2247-2250. (187) Henbest, H. B.; Wilson, R. A. L. J. Chem. Soc. 1957, 1958 - 1965. (188) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974-5976. (189) McKittrick, B. A.; Ganem, B. Tetrahedron Lett. 1985, 26, 4895. (190) Sharpless, K. B.; Michaelson, R. C. J. Am. Chem. Soc. 1973, 95, 6136-6137. (191) Cha, J. K.; Christ, W. J.; Kishi, Y. Tetrahedron 1984, 40, 2247. (192) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 95, 1761-1795. (193) Evans, D. A.; Kaldor, S. W. J. Org. Chem. 1990, 55, 1698-1700. (194) In Haller & Houk, 1997, the final sentence of the results and discussion reads "<strong>The</strong> Kishi model is also valid in cyclic alkenes where the stereogenic centre is fixed in a position resembling that dictated by the 1,3-allylic strain." (195) Donohoe, T. J.; Garg, R.; Moore, P. R. Tetrahedron Lett. 1996, 37, 3407. (196) Arjona, O.; de Dios, A.; Plumet, J.; Saez, B. J. Org. Chem. 1995, 60, 4932- 4935. (197) Pearlman, W. M. Tetrahedron Lett. 1967, 8, 1663. (198) Jacobsen, E. N.; Marko, I.; France, M. B.; Svendsen, J. S.; Sharpless, K. B. J. Am. Chem. Soc. 1989, 111, 737-739. (199) Donohoe, T. J.; Blades, K.; Moore, P. R.; Waring, M. J.; Winter, J. J. G.; Helliwell, M.; Newcombe, N. J.; Stemp, G. J. Org. Chem. 2002, 67, 7946- 7956. (200) Fürst, A.; Plattner, P. A. Helv. Chim. Acta 1949, 32, 275-283. (201) Gonzalez, C.; Carballido, M.; Castedo, L. J. Org. Chem. 2003, 68, 2248-2255. 190
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Dearomatising Addition of Organolit
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2.3 Synthetic Scope 64 2.3.1 Organo
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Abstract Dearomatising Addition of
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The Author The Author graduated fro
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Abbreviations & Conventions Ac acet
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RDS rate determining step R f RC rt
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Chapter 1: Introduction Chapter 1 -
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Chapter 1: Introduction controlled
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Chapter 1: Introduction diastereome
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Chapter 1: Introduction combine mor
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Chapter 1: Introduction O Ar Cl TMP
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Chapter 1: Introduction conditions,
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Chapter 1: Introduction chiral oxaz
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Chapter 1: Introduction Again a lar
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Chapter 1: Introduction 34 Scheme 1
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Chapter 1: Introduction The amino a
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Chapter 1: Introduction It was envi
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Chapter 1: Introduction COR' i) ATP
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Chapter 1: Introduction O i) ATPH,
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Chapter 1: Introduction 1.4 Nucleop
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Chapter 1: Introduction Unlike the
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Chapter 1: Introduction Diene (-)-8
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Chapter 1: Introduction A scheme su
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Chapter 1: Introduction Cl R + 93 S
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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Chapter 2 - Dearomatising additions
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3.1 - Oxazoline synthesis 3.1.1.a H
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3.1 - Oxazoline synthesis O Ar OH i
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3.1 - Oxazoline synthesis 3.1.2 Gen
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3.1 - Oxazoline synthesis mCPBA O N
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3.1 - Oxazoline synthesis 3.1.4.b M
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3.1 - Oxazoline synthesis Ph Ph Ph
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3.2 - Oxazoline removal O N O OH 3N
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3.2 - Oxazoline removal O Me O N OM
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3.2 - Oxazoline removal However, th
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3.2 - Oxazoline removal 3.2.3 Reduc
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3.2 - Oxazoline removal Ph O N Ph P
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3.2 - Oxazoline removal 3.2.3.c Ami
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3.2 - Oxazoline removal Ph Ph Ph Ph
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3.2 - Oxazoline removal 3.2.5.b N-A
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3.2 - Oxazoline removal Ph Ph O N H
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3.2 - Oxazoline removal Ph Me Ph Me
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3.2 - Oxazoline removal 3.2.6 Deter
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Better, however, would be a method
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4.1 - Introduction HO OH OH HO OH O
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4.1 - Introduction (-)-Shikimic aci
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4.1 - Introduction followed by Flem
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Experimental for chapter 3.2 Synthe
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Experimental for chapter 3.2 Synthe
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Experimental for chapter 3.2 Synthe
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Experimental for chapter 3.2 Synthe
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Experimental for chapter 4.1 281 R
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Experimental for chapter 4.1 combin
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Experimental for chapter 4.1 Synthe
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Experimental for chapter 4.1 Synthe
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Experimental for chapter 4.1 291 R
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Experimental for chapter 4.1 3H, OB
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Experimental for chapter 4.1 Synthe
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Experimental for chapter 4.1 307 R
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Experimental for chapter 4.2 (1S*,2
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Experimental for chapter 4.2 310 R
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Experimental for chapter 4.2 10.0,
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Experimental for chapter 4.2 cm 3 )
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Experimental for chapter 4.2 Synthe
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Experimental for chapter 4.2 5.7 Re
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276
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278
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280
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282
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284
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Absolute structure parameter 1.3(11
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_diffrn_standards_interval_time ? _
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H13 H 0.8405 0.7136 -0.0889 0.026 U
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C4 C5 1.454(2) . ? C5 C6 1.324(2) .
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C24 C23 C22 120.0(2) . . ? C24 C23
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. Compound 102c Ph O N Ph Me 102c O
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_diffrn_standards_interval_time ? _
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H11 H 0.8924 0.9592 0.6829 0.022 Ui
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C2 H2 1.0000 . ? C3 C21 1.506(2) .
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C26 C21 C3 121.41(15) . . ? C23 C22
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c. Compound 213 Ph O N Ph Me OH 213
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_cell_volume 1080.9(4) _cell_formul
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_refine_ls_number_reflns 4736 _refi
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H25 H 0.7979 0.2335 0.3365 0.028 Ui
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C4 0.025(4) 0.019(4) 0.018(4) 0.001
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loop_ _geom_bond_atom_site_label_1
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C9 C4 C1 107.1(5) . . ? C10 C4 C1 1
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C36 C38 H38A 109.5 . . ? C36 C38 H3
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C29 C30 C36 C37 -90.4(7) . . . . ?
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The structure was solved by the dir
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_reflns_number_total 2447 _reflns_n
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C7 C 1.1671(4) 0.7629(7) 1.2254(4)
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C3 0.015(3) 0.016(3) 0.021(3) -0.00
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C21 H21A 0.9800 . ? C21 H21B 0.9800
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H21A C21 H21C 109.5 . . ? H21B C21