Experimental for chapter 4.2 Data for (1R,2S,3S,4R,5S,6S)-5-(hydroxymethyl)-6-isopropyl-5- methylcyclohexane-1,2,3,4-tetraol (322) HO 7 HO 6 1 2 HO 5 3 4 OH OH R f : 0.47 (EtOAc); [α] 22 D : –104 (c = 0.1, CHCl 3 ); MS m/z (ES+) 275 (100%, [M+H 2 O]Na + ); IR ν max (film)/cm⎯¹ 3357 (br, O-H), 2909, 1993, 1458; ¹H-NMR (CDCl 3 , 500 MHz) δ 4.34 (t, 1H, J 10.5, H5), 3.92 (dd, 1H, J 11.5, 9.0, H3), 3.72 (d, 2H, J 3.5, H7), 3.50-3.43 (m, 2H, H4, H6), 2.81 (d, 1H, J 3.0, OH), 2.64 (br s, 1H, OH), 2.43 (br s, 1H, OH), 2.29 (t, 1H, J 3.5, C7-OH), 2.02 (p, 1H, J 7.0, CHMe 2 ), 1.19 (s, 3H, Me), 1.15 (d, 3H, J 7.0, i-Pr), 1.11 (d, 3H, J 7.0, i-Pr). 273
Experimental for chapter 4.2 5.7 References for Experimental Section (1) Gomez, J. C. C.; Lopez, F. J. S.; 4.8.6 ed.; MestRe-C, Ed. 2005. (2) Gomes, M.; 1.0 ed.; Paulo, U. d. S., Ed.; Universidade de Sao Paulo: 2004. (3) Crosignani, S.; Young, A. C.; Linclau, B. Tetrahedron Lett. 2004, 45, 9611- 9615. (4) Meyers, A. I.; Roth, G. P.; Hoyer, D.; Barner, B. A.; Laucher, D. J. Am. Chem. Soc. 1988, 110, 4611-24. (5) VanRheenen, V.; Cha, D. Y.; Hartley, W. M. Org. Synth. 1978, 58, 43. (6) Hodgson, R.; Majid, T.; Nelson, A. J. Chem. Soc., Perkin Trans. 1 2002, 1444 - 1454. (7) Barner, B. A.; Meyers, A. I. J. Am. Chem. Soc. 1984, 106, 1865-6. (8) Kolb, H.; VanNieuwenhze, M.; Sharpless, K. B. Chem. Rev. 1994, 2483. (9) Wang, Z. M.; Sharpless, K. B. J. Org. Chem. 1994, 8302. (10) Chang, H.-T.; Sharpless, K. B. Tetrahedron Lett. 1996, 37, 3219. (11) Cabedo, N. C.; University of Manchester: 2004-5. (12) Ittah, Y.; Sasson, Y.; Shahak, I.; Tsaroom, S.; Blum, J. J. Org. Chem. 1978, 43, 4271-4273. (13) Heine, H. W.; King, D. C.; Portland, L. A. J. Org. Chem. 1966, 31, 4271-4272. (14) Reyes, A.; Juaristi, E. Chirality 1998, 10, 95-99. (15) Lygo, B., Suggestion <strong>to</strong> use diethyl ether-petrol solvent at low temperature <strong>to</strong> encourage precipitation of Et 3 .HCl salt, reducing free chloride ions which would otherwise attack the aziridine ring. (16) Groundwater, P. W.; Garnett, I.; Mor<strong>to</strong>n, A. J.; Sharif, T.; Coles, S. J.; Hursthouse, M. B.; Nyerges, M.; Anderson, R. J.; Bendell, D.; McKillop, A.; Zhang, W. J. Chem. Soc., Perkin Trans. 1 2001, 2781-2787. (17) Hayashida, M.; Ishizaki, M.; Hara, H. Chem. Pharm. Bull. 2006, 54, 1299. (18) Haak, E.; Siebeneicher, H.; Doye, S. Org. Lett. 2000, 2, 1935-1937. (19) Czernecki, S.; Georgoulis, C.; Provelenghiou, C. Tetrahedron Lett. 1976, 17, 3535. (20) Eames, J.; Mitchell, H. J.; Nelson, A.; O'Brien, P.; Warren, S.; Wyatt, P. J. Chem. Soc., Perkin Trans. 1 1999, 1095-1103. (21) Curtin, D. Y.; Kellom, D. B. J. Am. Chem. Soc. 1953, 75, 6011-6018 274
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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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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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4.2 - Carbasugar synthesis 4.2 Synt
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4.2 - Carbasugar synthesis stereoce
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4.2 - Carbasugar synthesis of the o
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4.2 - Carbasugar synthesis support
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4.2 - Carbasugar synthesis Ox* Ox*
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4.2 - Carbasugar synthesis Ox* Ox*
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4.2 - Carbasugar synthesis Ox* Ox*
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4.2 - Carbasugar synthesis OsO 4 (c
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4.2 - Carbasugar synthesis taken on
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4.2 - Carbasugar synthesis As well
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4.4 - Revised altrose synthesis 4.4
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4.4 - Revised altrose synthesis suf
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4.4 - Revised altrose synthesis ind
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4.5 - Mannose synthesis 4.5 Synthes
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4.5 - Mannose synthesis It is clear
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4.5 - Mannose synthesis considering
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4.5 - Mannose synthesis which would
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4.5 - Mannose synthesis One clear a
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4.5 - Mannose synthesis 4.5.2.b Epo
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4.5 - Mannose synthesis hydrolysis
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4.5 - Mannose synthesis The second
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4.6 - Summary 4.6 Summary & Future
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4.6 - Summary OH CDI, NH 2 OH.HCl,
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184
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References (37) Rawson, D. J.; Meye
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References (105) Gajewski, J. J.; B
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References (169) McCormick, J. P.;
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References 192
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Experimental section 254nm, dodecam
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Experimental section General Proced
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Experimental for chapter 2 Synthesi
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Experimental for chapter 2 (CDCl 3
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Experimental for chapter 2 3H, OMe
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Experimental for chapter 2 Ph), 139
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Experimental for chapter 2 H4), 5.2
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Experimental for chapter 2 108 R f
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Experimental for chapter 2 Synthesi
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Experimental for chapter 3.1 satura
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Experimental for chapter 3.1 Na 2 S
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Experimental for chapter 3.1 Synthe
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Experimental for chapter 3.1 Synthe
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Experimental for chapter 3.1 128.9,
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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