A Route to Carbasugar Analogues - Jonathan Clayden - The ...
A Route to Carbasugar Analogues - Jonathan Clayden - The ... A Route to Carbasugar Analogues - Jonathan Clayden - The ...
Experimental for chapter 2 5.55 (dd, 1H, J 6.0, 10.0, H3), 4.87 (d, 1H, J 7.5, CHPh), 3.95 (quin, 1H, J 6.5, NCH), 2.39-2.33 (m, 1H, H2), 1.85-1.72 (m, 1H, CHMe 2 ), 1.36 (s, 3H, H7), 1.31 (d, 3H, J 6.5, CHMe), 0.85 (d, 3H, J 7.0, CHMe A Me b ), 0.82 (d, 3H, J 7.0, CHMe a Me B ); 13 C- NMR (CDCl 3 , 75 MHz) δ 169.8 (C=N), 140.8 (ipso-Ph), 132.4, 128.7, 128.1, 125.4, 124.2, 123.8, 121.4, (C3, C4, C5, C6 & Ph), 87.6 (COPh), 70.5 (CN), 47.5 (C2), 31.2 (CMe 2 ), 25.2 (C7), 21.6 (CNMe), 21.2 (CMe A Me b ), 16.7 (CHMe a Me B ). 113 R f : 0.42 (4:1 petrol:EtOAc); [α] 23 D : +122 (c = 0.2, EtOH); MS m/z (CI+): 252 (100%, MH + ), 253 (17%, (M+1)H + ); HRMS (ESI+) m/z found 252.1382 (MH calcd. 252.1383); IR ν max (film)/cm -1 : 2964 (C–H), 1643 (C=N), 1453 (m), 1317 (m), 1039; 1 H-NMR (CDCl 3 , 300 MHz) δ 7.79-7.76 (m, 1H, H6), 7.31-7.20 (m, 6H, Ar), 7.17- 7.11 (m, 2H, Ar), 4.96 (d, 1H, J 7.5, CHPh), 4.13 (quin, 1H, J 6.5, CHMe), 2.53 (s, 3H, ortho-Me), 1.39 (d, 3H, J 6.5, Me); 13 C-NMR (CDCl 3 , 75 MHz) δ 163.2 (C=N), 140.7 (C), 138.8 (C), 131.2, 130.6, 129.9, 128.8, 128.2, 125.6 (Ar) 87.4 (PhCO), 71.2 (MeCN), 21.8 (NCMe), 21.7 (ortho-Me). 114 R f : 0.38 (4:1 petrol:EtOAc); [α] 23 D : +97 (c = 0.2, EtOH); MS m/z (CI+): 266 (100%, MH + ), 253 (18%, (M+1)H + ); HRMS (ESI+) m/z found 266.1538 (MH calcd. 266.1539); IR ν max (film)/cm -1 : 2975 (C-H), 1643 (C=N), 1448, 1319, 1266, 1037; 1 H- NMR (CDCl 3 , 300 MHz) δ 7.89-7.86 (m, 1H, H6), 7.44-7.23 (m, 9H, Ar), 4.34 (q, 1H, J 7.0, CHMe), 2.63 (s, 3H, ortho-Me), 1.65 (s, 3H, CMePh), 1.47 (d, 3H, J 7.0, CHMe); 13 C-NMR (CDCl 3 , 75 MHz) δ 162.4 (C=N), 149.3 (C), 146.6 (C), 138.6, 131.2, 130.5 129.9, 128.8, 128.5, 127.2, 125.6, 124.0 (Ar), 88.5 (OCPh), 71.7 (NCMe); 22.4 (OCMe) 21.7 (NCMe), 16.8 (ortho-Me). 209
Experimental for chapter 2 Synthesis of (4R*,5R*)-2-(2-ethyl-4-methoxyphenyl)-4,5-diphenyloxazoline (120) Ph Ph Ph Ph O N i) i-PrLi (3 eq.), DMPU (6 eq) −78 °C O 1 N ii) MeI 6 2 OMe 5 4 OMe 3 General procedure 4 was used employing oxazoline 103b (250 mg, 0.73 mmol) i-PrLi (2.19 mmol in pentane), DMPU (0.52 cm 3 , 6 eq) in THF to give a wine red solution, and a methyl iodide (0.27 cm 3 ) quench after 5 min. Flash chromatography (19:1 to 9:1 petrol:EtOAc) yielded oxazoline 120 (170 mg, 65%) as a colourless oil. R f : 0.39 (4:1, petrol:EtOAc); MS m/z (ES+) 358 (100%, MH + ), 359 (30%, (M+1)H + ); HRMS: found 358.1802, MH requires 358.1802; ¹H-NMR (CDCl 3 , 500 MHz) δ 7.89 (d, 1H, J 8.5, H6), 7.31-7.16 (m, 10H, Ph), 6.75 (d, 1H, J 2.5, H3), 6.67 (dd, 1H, J 8.5, 2.5, H5), 5.19 (d, 1H, J 7.5, CHOPh), 5.14 (d, 1H, J 7.5, CHNPh), 3.70 (s, 3H, OMe), 3.11-3.05 (m, 2H, CH 3 ), 1.18 (t, 3H, J 7.5, CH 2 Me); ¹³C-NMR (CDCl 3 , 125 MHz) δ 164.0 (C=N), 161.5 (C4), 147.6 (C2), 142.4 (ipso-Ph), 140.7 (ipso-Ph), 132.3 (C6), 128.8 (meta-Ph), 128.7 (meta-Ph), 128.2 (para-Ph), 127.5 (para-Ph), 126.5 (ortho-Ph), 125.6 (ortho-Ph), 115.3 (C3), 110.6 (C5), 87.8 (CHO), 79.2 (CHN), 55.1 (OMe), 27.8 (CH 2 ), 15.6 (Me). 210
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Experimental for chapter 2<br />
5.55 (dd, 1H, J 6.0, 10.0, H3), 4.87 (d, 1H, J 7.5, CHPh), 3.95 (quin, 1H, J 6.5, NCH),<br />
2.39-2.33 (m, 1H, H2), 1.85-1.72 (m, 1H, CHMe 2 ), 1.36 (s, 3H, H7), 1.31 (d, 3H, J<br />
6.5, CHMe), 0.85 (d, 3H, J 7.0, CHMe A Me b ), 0.82 (d, 3H, J 7.0, CHMe a Me B ); 13 C-<br />
NMR (CDCl 3 , 75 MHz) δ 169.8 (C=N), 140.8 (ipso-Ph), 132.4, 128.7, 128.1, 125.4,<br />
124.2, 123.8, 121.4, (C3, C4, C5, C6 & Ph), 87.6 (COPh), 70.5 (CN), 47.5 (C2), 31.2<br />
(CMe 2 ), 25.2 (C7), 21.6 (CNMe), 21.2 (CMe A Me b ), 16.7 (CHMe a Me B ).<br />
113 R f : 0.42 (4:1 petrol:EtOAc); [α] 23 D : +122 (c = 0.2, EtOH); MS m/z (CI+): 252<br />
(100%, MH + ), 253 (17%, (M+1)H + ); HRMS (ESI+) m/z found 252.1382 (MH calcd.<br />
252.1383); IR ν max (film)/cm -1 : 2964 (C–H), 1643 (C=N), 1453 (m), 1317 (m), 1039;<br />
1 H-NMR (CDCl 3 , 300 MHz) δ 7.79-7.76 (m, 1H, H6), 7.31-7.20 (m, 6H, Ar), 7.17-<br />
7.11 (m, 2H, Ar), 4.96 (d, 1H, J 7.5, CHPh), 4.13 (quin, 1H, J 6.5, CHMe), 2.53 (s,<br />
3H, ortho-Me), 1.39 (d, 3H, J 6.5, Me); 13 C-NMR (CDCl 3 , 75 MHz) δ 163.2 (C=N),<br />
140.7 (C), 138.8 (C), 131.2, 130.6, 129.9, 128.8, 128.2, 125.6 (Ar) 87.4 (PhCO), 71.2<br />
(MeCN), 21.8 (NCMe), 21.7 (ortho-Me).<br />
114 R f : 0.38 (4:1 petrol:EtOAc); [α] 23 D : +97 (c = 0.2, EtOH); MS m/z (CI+): 266<br />
(100%, MH + ), 253 (18%, (M+1)H + ); HRMS (ESI+) m/z found 266.1538 (MH calcd.<br />
266.1539); IR ν max (film)/cm -1 : 2975 (C-H), 1643 (C=N), 1448, 1319, 1266, 1037; 1 H-<br />
NMR (CDCl 3 , 300 MHz) δ 7.89-7.86 (m, 1H, H6), 7.44-7.23 (m, 9H, Ar), 4.34 (q, 1H,<br />
J 7.0, CHMe), 2.63 (s, 3H, ortho-Me), 1.65 (s, 3H, CMePh), 1.47 (d, 3H, J 7.0,<br />
CHMe); 13 C-NMR (CDCl 3 , 75 MHz) δ 162.4 (C=N), 149.3 (C), 146.6 (C), 138.6,<br />
131.2, 130.5 129.9, 128.8, 128.5, 127.2, 125.6, 124.0 (Ar), 88.5 (OCPh), 71.7<br />
(NCMe); 22.4 (OCMe) 21.7 (NCMe), 16.8 (ortho-Me).<br />
209