A Route to Carbasugar Analogues - Jonathan Clayden - The ...

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Experimental for chapter 3.1 over celite and evaporation, yielding aroyl aziridine 100c (244 mg, 87%) as a colourless oil. R f : 0.38 (4:1 petrol:EtOAc); IR ν max (film)/cm -1 : 1668 (C=O), 1601, 1510, 1321; 1 H- NMR (CDCl 3 , 400 MHz) δ 7.51 (d, 1H, J 8.0, Ph, H6), 7.71-7.69 (m, 1H, Ph), 7.17- 7.06 (m, 11H, Ph, H5), 6.92 (ddd, 1H, J 8.5, 4.5, 1, H4), 3.95 (s, 2H, CHPh), 3.66 (s, 3H, OMe); 13 C-NMR (CDCl 3 , 100 MHz) δ 175.4 (C=O), 159.3 (C3), 135.7 (ipso-Ph), 140.3 (C1), 129.2 (para-Ph), 128.7 (meta-Ph), 128.2 (ortho-Ph), 121.4 (C4), 119.2 (C6), 113.1 (C2), 55.3 (OMe), 49.4 (CPh). Synthesis of N-((1R,2S)-2-hydroxy-1,2-diphenylethanol)benzamide (165a) Ph O Cl Ph Ph NH 2 HO O NH Ph OH Et 3 N General procedure 1 was used mixing benzoyl chloride (0.23 cm 3 , 1.95 mmol) with amino alcohol 174 (500 mg, 2.34 mmol) and triethylamine (5 cm 3 ) to give the title amide (615 mg, 99%) as a colourless powder. R f : 0.05 (EtOAc); Mpt: 243-246 °C (EtOAc); [α] 25 D : +89 (c = 0.4, DMSO); MS m/z (CI+): 318 (100%, MH + ), 319 (10%, (M+1)H + ); HRMS (ESI+) m/z found 318.1490 (MH calcd. 318.1489); IR ν max (film)/cm -1 : 3337 (s, OH), 1630 (C=O), 1526; 1 H-NMR (DMSO, 300 MHz) δ 8.83 (d, 1H, J 9.0, NH), 7.74-7.67 (m, 2H, ortho-Ph), 7.50-7.34 (m, 7H, Ph), 7.31-7.14 (m, 6H, Ph), 5.10 (d, 1H, J 5.0, OH), 5.13 (t, 1H, J 8.5, CHNH), 4.98 (dd, 1H, J 8.0, 5.0, CHOH); 13 C-NMR (DMSO, 125 MHz) δ 165.2 (CO), 143.6, 141.3, 134.5 (ipso-Ph), 131.0, 128.5, 128.1, 127.6, 127.5, 127.3, 127.0, 126.9, 126.6 (Ph), 74.4 (COH), 59.3 (CH 2 N). 217
Experimental for chapter 3.1 Synthesis of N-((1R,2S)-2-hydroxy-1,2-diphenylethyl)-4-methoxybenzamide (165b) Ph O Cl Ph HO Ph Ph NH 2 O NH 1 OH 2 Et 3 N 3 OMe 4 OMe General procedure 1 was used mixing para-anisoyl chloride (13.9 g, 81.5 mmol) with (1R,2S)-(−)-2-amino-1,2-diphenylethanol 174 (20.0 g, 93.8 mmol) and triethylamine (22.5 cm 3 , 163 mmol) to give the title amide (25.3 g, 98%) as a colourless powder. R f : 0.42 (2:1 petrol:EtOAc); Mpt: 240-244 °C (EtOAc); [α] 25 D : +41 (c = 0.4, DMSO); MS m/z (CI+): 348 (100%, MH + ), 349 (27%, (M+1)H + ), 330 (57%, [M-H 2 O] + ), 96 (61%); HRMS (ESI+) m/z found 348.1586 (MH calcd. 348.1594); IR ν max (film)/cm -1 : 3334 (s, OH), 1632 (C=O), 1526; 1 H-NMR (MeOD, 300 MHz) δ 7.58 (d, 2H, J 9.0, ortho-Ph), 7.44-7.17 (m, 10H, Ph), 6.92 (d, 2H, J 9.0, meta-Ph), 5.32 (d, 1H, J 8.0, CHOH), 5.05 (d, 1H, J 8.0, CHN), 3.81 (s, 3H, OMe); 13 C-NMR (DMSO, 125 MHz) δ 164.9 (CO), 161.8 (ipso-Ph), 144.1 (ipso-Ph), 142.0, 129.3, 128.7, 128.0, 127.9, 127.3, 127.2, 127.1, 127.0 (Ar), 113.7 (C3), 74.9 (COH), 59.3 (CNH), 55.7 (OMe). Synthesis of N-((1R,2S)-2-hydroxy-1,2-diphenylethyl)-3-methoxybenzamide (165c) Ph O Cl Ph Ph NH 2 OH OMe Et 3 N Ph HO O NH 6 5 4 1 2 3 OMe General procedure 1 was used mixing meta-anisoyl chloride (0.30 cm 3 , 2.12 mmol) with the amino alcohol 174 (500 mg, 2.34 mmol) and triethylamine (0.6 cm 3 , 4.25 mmol) to give amide 165c (710 mg, 96%) as colourless needles. 218
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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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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 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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Page 185 and 186: References (37) Rawson, D. J.; Meye
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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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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
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