Experimental for chapter 4.2 Synthesis of (1S*,2R*,3S*,4S*,5S*)-4-(hydroxymethyl)-5-isopropyl-4- methylcyclohexane-1,2,3-triol (315) BnO HO HO H 2 , Pd/C HO 6 1 2 HO OBn (±) HO 5 4 OH 3 (±) A solution of oxazoline 314 (12 mg, 0.03 mmol) in methanol (1.5 cm 3 ) was passed thorough the H-cube (1 cm 3 /min, 10 bar, Pd/C) and the eluent collected for 15 min. <strong>The</strong> solvent was removed by rotary evaporation <strong>to</strong> give amide 315 (6 mg, 93%) as a colourless oil. R f : 0.11 (EtOAc); MS m/z (ES+) 241 (100%, MNa + ), 459 (30%, 2MNa + ); HRMS: found 241.1400, MNa requites 241.1410; IR ν max (film)/cm⎯¹ 3375 (br, O-H), 2958 (CH), 1030; ¹H-NMR (CD 3 OD, 500 MHz) δ 3.87 (d, 1H, J 3.0, H6), 3.70 (d, 1H, J 11.0, H7), 3.74-3.69 (m, 1H, H4), 3.58-3.53 (m, 1H, H5), 3.49 (d, 1H, J 11.0, H7'), 1.93 (p, 1H, J 7.0, CHMe 2 ), 1.70-1.63 (m, 2H, H3), 1.36-1.28 (m, 1H, H2), 1.09 (s, 3H, Me), 0.95 (d, 3H, J 7.0, i-Pr), 0.80 (d, 3H, J 7.0, i-Pr); ¹³C-NMR (CD 3 OD, 75.5 MHz) δ 76.5, 75.0, 72.0, 65.6, 45.6, 44.0, 30.2, 26.3, 25.4, 21.7, 19.6. Synthesis of (1R,2R,5S,6S)-6-isopropyl-5-methyl-5-(N-methyl-(4R,5R)-4,5- diphenyloxazolidin-2-yl)cyclohex-3-ene-1,2-diol (310) Ph Ph Ph Ph Ph Ph O N O NMe O NMe MeOTf, then NaBH 4 1 6 2 6 1 2 OH 5 4 3 OH 5 4 3 OH O OH OH 310 316 General procedure 3 was employed using oxazoline 276 (300 mg, 0.77 mmol) and methyl triflate (150 µl, 1.54 mmol) for 7 hr. <strong>The</strong> resulting yellow oil was purified by flash chroma<strong>to</strong>graphy (4:1 <strong>to</strong> 2:1 petrol:EtOAc) <strong>to</strong> give oxazolidine 310 (245 mg, 78%) and oxazolidine 316 (4 mg, 1%) as colourless oils. 265
Experimental for chapter 4.2 310 R f : 0.30 (40%, EtOAc in petrol); [α] 24 D : +135 (c = 1.0, CHCl 3 ); MS m/z (ES + ) 430 (100%, MNa + ), 408 (27%, MH + ), 838 (39%, [2M]Na + ); HRMS: found 430.2349, MNa requires 430.2353; IR ν max (film)/cm⎯¹ 3364 (br, O-H), 2947 (m), 2360 (w, C=C), 1453 (m); ¹H-NMR (CDCl 3 , 500 MHz) δ 7.31-7.25 (m, 3H, Ar), 7.23-7.16 (m, 5H, Ar), 7.05-7.00 (m, 2H, Ar), 6.06 (dd, 1H, J 10.0, 2.0, H5), 5.65 (dd, 1H, J 10.0, 2.0, H6), 4.74 (d, 1H, J 9.0, CHOPh), 4.54 (s, 1H, CHON), 4.24 (dd, 1H, J 11.5, 7.0, H3), 3.95 (br d, 1H, J 7.0, H4), 3.30 (d, 1H, J 9.0, CHNPh), 2.37 (s, 3H, NMe), 2.31-2.10 (m, 3H, CHMe 2 , OH), 1.48 (d, 1H, J 11.5, H2), 1.29 (d, 3H, J 7.0, CHMe A Me b ), 1.21-1.17 (m, 6H, Me & CHMe a Me B ); ¹³C-NMR (CDCl 3 , 75.5 MHz) δ 138.6 (ipso-Ph), 137.6 (ipso-Ph), 134.7 (C5), 128.3 (C6), 128.1, 128.0, 127.8, 127.7, 126.4 (Ph), 99.9 (CHON), 85.6 (CHOPh), 79.6 (CHNPh), 76.1 (C4), 74.1 (C3), 55.1 (C2), 48.6 (C1), 41.9 (NMe), 27.3 (CHMe a Me B ), 25.9 (CHMe 2 ), 24.7 (Me), 17.9 (CHMe A Me b ). 316 R f : 0.32 (2:1, petrol:EtOAc); [α] 24 D : +217 (c = 1.0, CHCl 3 ); MS m/z (ES + ) 430 (100%, MNa + ); HRMS: found 430.2348, MNa requires 430.2353; IR ν max (film)/cm⎯¹ 3368 (br, O-H), 2957 (m, C-H), 1604 (m, C=C), 1453 (C-Me); ¹H-NMR (CDCl 3 , 500 MHz) δ 7.33-7.28 (m, 3H, Ph), 7.26-7.22 (m, 3H, Ph), 7.22-6.98 (m, 2H, Ph), 7.05- 7.01 (m, 2H, Ph), 6.29 (d, 1H, J 10.0, H6), 6.00 (dd, 1H, J 10.0, 5.0, H5), 4.67 (d, 1H, J 9.5, CHOPh), 4.61 (s, 1H, CHON), 4.52 (dd, 1H, J 12.0, 5.0, H3), 3.99 (t, 1H, J 5.0, H4), 3.31 (d, 1H, J 9.5, CHNPh), 2.39 (s, 3H, NMe), 2.21 (p, 1H, J 7.0, CHMe 2 ), 2.08 (br s, 1H, OH), 1.86 (br s, 1H, OH), 1.52 (d, 1H, J 12.0, H2), 1.35 (d, 3H, J 7.0, i-Pr), 1.23-1.20 (m, 6H, Me & i-Pr); ¹³C-NMR (CDCl 3 , 125 MHz) δ 138.7 (ipso-Ph), 138.5 (ipso-Ph), 137.6 (C5), 128.3 (C6), 128.1, 128.0, 127.8, 127.7, 126.5, 126.2 (Ph), 100.0 (CHON), 85.7 (CHOPh), 79.5 (CHNPh), 69.1, 66.7 (C3, C4), 50.4 (C2), 48.8 (C1), 41.8 (NMe), 27.6 (i-Pr), 25.8 (i-Pr), 24.7 (Me), 17.7 (i-Pr). 266
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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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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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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