Experimental for chapter 4.1 Ph), 7.22-7.18 (m, 2H, Ph), 6.78 (d, 1H, J 10.0, H6), 6.18 (d, 1H, J 10.0, H5), 5.22 (d, 1H, J 10.5, CHO), 5.09 (d, 1H, J 10.5, CHN), 4.68 (dd, 1H, J 13.0, 2.0, H3), 3.62* (d, 1H, J 2.0, OH), 2.40 (p, 1H, J 7.5, CHMe 2 ), 1.99 (d, 1H, J 13.0, H2), 1.63 (s, 3H, Me), 1.70 (d, 3H, J 7.5, CHMe a Me b ), 1.15 (d, 3H, J 7.5, CHMe a Me b ); 13 C-NMR (CDCl 3 , 100 MHz) δ 201.7 (C=O), 167.4 (C=N), 153.9 (C6), 140.5 (ipso-Ph), 138.5 (ipso-Ph), 129.0, 128.9, 128.8, 127.9, 126.7, 126.2, 124.7 (Ph), 90.1 (CHO), 77.9 (CNH), 55.2 (COH), 44.1 (C1), 27.1 (CHMe 2 ), 25.9 (CHMe a Me b ), 25.5 (CHMe a Me b ), 17.3 (Me). 283 R f : 0.18 (4:1 petrol:EtOAc); [α] 21 D : +197.5 (c = 2.1, CHCl 3 ); MS m/z (CI+): 388 (100%, MH + ), 389 (27%, (M+1)H + ), 194 (70%, [M-Ph 2 CHO]H + ); HRMS (ESI+) m/z found 388.1911 (MH calcd. 388.1907); IR ν max (film)/cm -1 : 3391 (m, O-H), 2931 (w, C-H), 1643 (C=O); 1 H-NMR (CDCl 3 , 300 MHz) δ 7.43-7.26 (m, 8H, Ph), 7.24-7.18 (m, 2H, Ph), 7.04 (d, 1H, J 10.0, H6), 6.64 (s, 1H, OH), 6.49 (d, 1H, J 10.0, H5), 5.23 (d, 1H, J 8.5, CHO), 5.18 (d, 1H, J 8.5, CHN), 2.61 (p, 1H, J 2.5, CHMe 2 ), 1.75 (s, 3H, Me), 1.34 (d, 3H, J 7.0, CHMe a Me b ), 1.28 (d, 3H, J 7.0, CHMe a Me b ); 13 C-NMR (CDCl 3 , 75 MHz) δ 181.1 (C4), 167.1 (C=N), 152.8, 145.1 (C3, C6), 141.2 (ipso-Ph), 138.8 (ipso-Ph), 136.0 (C5), 128.9 (meta-Ph), 128.9 (meta-Ph), 127.9 (para-Ph), 126.6 (ortho-Ph), 126.5 (ortho-Ph), 125.6 (C2), 90.3 (CHO), 77.6 (CHN), 46.9 (CMe), 30.4 (CHMe 2 ), 22.9 (Me), 19.9 (CHMe a Me b ), 19.4 (CHMe a Me b ). Synthesis of (1R,2R,5S,6S)-5-((4R,5R)-4,5-diphenyloxazolin-2-yl)-6-isopropyl-5- methylcyclohex-3-ene-1,2-diol (213) Ph Ph Ph Ph O N O N NaBH 4 EtOH, 0 °C OH O 6 5 1 2 3 4 OH OH Sodium borohydride (24 mg, 0.63 mmol) was added in a single portion <strong>to</strong> a stirred solution of enone 276 (220 mg, 0.57 mmol) in ethanol (6 cm 3 ) at 0 °C. When judged complete by TLC (PMA stain c. 6 hr) acetic acid was added <strong>to</strong> the cooled reaction mixture until effervescence ceased and warmed <strong>to</strong> room temperature. <strong>The</strong> solvent was removed from the reaction mixture, which was partitioned between water (10 cm 3 ) and CH 2 Cl 2 (20 cm 3 ) and the aqueous layer further washed (2 x 20 cm 3 CH 2 Cl 2 ) and the 249
Experimental for chapter 4.1 combined organic layers washed with brine before being dried over sodium sulphate. Removal of solvent gave a white crystalline solid which was purified by recrystallisation from diethyl ether <strong>to</strong> give colourless cubes of allyl alcohol 213 (216 mg, 98%) R f : 0.31 (1:1, petrol:EtOAc); Mpt: 155-156 ºC (Et 2 O); [α] 25 D : +174 (c = 1.0, CHCl 3 ); MS m/z (CI+) 392 (100%, MH + ), 393 (24%, (M+1)H + ), 303 (15%, [M-PhCH] + ), 285 (22%, [M-PhCHO] + ); HRMS: found 392.2228, MH requires 392.2220; Microanalysis found (%): C 75.03, H 7.56, N 3.48, C 25 H 29 NO 3 requires (%): C 76.70, H 7.47, N 3.58; IR ν max (film)/cm⎯¹ 3359 (br, OH), 2970 (m, C-H), 1638 (C=N), 1050 (C-OH); ¹H- NMR (CDCl 3 , 500 MHz) δ 7.33-7.25 (m, 5H, Ph), 7.24-7.20 (m, 1H, Ph), 7.20-7.16 (m, 2H, Ph), 7.15-7.11 (m, 2H, Ph), 5.53 (d, 1H, J 10.0, H6), 5.44 (d, 1H, J 10.0, H5), 5.07 (d, 1H, J 10.5, CHOPh), 4.94 (d, 1H, J 10.5, CHNPh), 3.93-3.87 (m, 2H, H4, H3), 3.32 (br s, 1H, OH), 2.44 (br s, 1H, OH), 2.23 (p, 1H, J 7.0, CHMe 2 ), 1.51 (d, 1H, J 10.5, H2), 1.37 (s, 3H, Me), 1.09 (d, 3H, J 7.0, CHMe a Me b ), 1.00 (d, 3H, J 7.0, CHMe a Me b ); ¹H-NMR (C 6 D 6 , 300 MHz) δ 7.28-7.22 (m, 2H, Ph), 7.20-7.03 (m, 8H, Ph), 5.64 (d, 1H, J 10.0, H6), 5.45 (dd, 1H, J 10.0, 2.0, H5), 5.12 (s, 2H, CHPh), 4.21 (ddd, 1H, J 11.5, 7.5, 2.0, H3), 4.04 (br d, 1H, J 7.5, H4), 2.89 (br s, 2H, OH), 2.41 (p, 1H, J 7.0, CHMe 2 ), 1.64 (d, 1H, J 11.5, H2), 1.40 (s, 3H, Me), 1.36 (d, 3H, J 7.0, CHMe a Me b ), 1.33 (d, 3H, J 7.0, CHMe a Me b ); ¹³C-NMR (CD 3 OD, 75.5 MHz) δ 171.8 (C=N), 140.8 (ipso-Ph), 138.4 (ipso-Ph), 132.5 (C5), 129.2 (C6), 128.7, 127.9, 127.0, 126.3 (Ph), 90.6 (CHOPh), 77.5 (CHNPh), 74.7 (CHOH), 72.7 (CHOH), 53.1 (C2), 44.3 (C1), 26.9 (CHMe 2 ), 25.7 (CHMe a Me b ), 25.5 (Me), 17.0 (CHMe a Me b ). 250
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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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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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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