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 102j R f : 0.32 (9:1, petrol:EtOAc); [α] 22 D : –105 (c = 1, CHCl 3 ); MS m/z (ES+) 414 (100%, MH + ), 415 (32%, (M+1)H + ); HRMS: found 414.2421, MH requires 414.2428; IR ν max (film)/cm⎯¹ 2918 (m), 1658 (C=N), 1588, 1453 (m), 1268 (m), 1189 (m), 1083; ¹H-NMR (CDCl 3 , 500 MHz) δ 7.43-7.34 (m, 5H, Ph), 7.33-7.28 (m, 3H, Ph), 7.25- 7.21 (m, 2H, Ph), 6.06-5.96 (m, 2H, H6, H8), 5.82 (dd, 1H, J 9.5, 6.0, H5), 5.38 (dq, 1H, J 17.5, 1.5, H9-trans), 5.25 (dq, 1H, J 10.5, 1.5, H9-cis), 5.21 (d, 1H, J 8.5, CHOPh), 5.09 (d, 1H, J 6.0, H4), 5.07 (d, 1H, J 8.5, CHNPh), 4.35 (ddt, 1H, J 13.0, 5.5, 1.5, H7 a ), 4.29 (ddt, 1H, J 13.0, 5.0, 1.5, H7 b ), 2.41 (d, 1H, J 3.0, H2), 2.07 (pd, 1H, J 7.0, 3.0, CHMe 2 ), 1.55 (s, 3H, Me), 1.09 (d, 3H, J 7.0, i-Pr), 1.03 (d, 3H, J 7.0, i- Pr); ¹³C-NMR (CDCl 3 , 125 MHz) δ 171.4 (C=N), 156.0 (C3), 142.0 (ipso-Ph), 140.5 (ipso-Ph), 133.2 (C8), 128.9, 128.8, 128.3, 127.6, 126.7, 125.7 (Ph), 125.2 (C6), 122.0 (C5), 116.9 (C9), 94.1 (C4), 88.8 (CHOPh), 78.8 (CHNPh), 67.7 (C7), 51.4 (C2), 43.7 (C1), 30.9 (CHMe 2 ), 25.2 (Me), 23.8 (i-Pr), 17.9 (i-Pr). 102j* R f : 0.32 (9:1, petrol:EtOAc); [α] 23 D : –56 (c = 0.5, CHCl 3 ); MS m/z (ES+) 414 (100%, MH + ), 415 (34%, (M+1)H + ); HRMS: found 414.2423, MH requires 414.2428; IR ν max (film)/cm⎯¹ 2918 (m), 2362, 1995, 1661 (C=N), 1456 (m); ¹H-NMR (CDCl 3 , 500 MHz) δ 7.44-7.34 (m, 6H, Ph), 7.34-7.28 (m, 2H, Ph), 7.24-7.20 (m, 2H, Ph), 6.29 (dd, 1H, J 6.0, 1.5, H7), 6.08 (d, 1H, J 9.5, H6), 5.81 (dd, 1H, J 9.5, 6.0, H5), 5.27 (d, 1H, J 6.0, H4), 5.23 (d, 1H, J 8.5, CHOPh), 5.08 (d, 1H, J 8.5, CHNPh), 4.85 (quin, 1H, J 6.5, H8), 2.48 (d, 1H, J 3.0, H2), 2.09 (pd, 1H, J 7.0, 3.0, CHMe 2 ), 1.66 (dd, 3H, J 7.0, 1.5, H9), 1.57 (s, 3H, Me), 1.11 (d, 3H, J 7.0, CHMe A Me b ), 1.07 (d, 3H, J 7.0, CHMe a Me B ); ¹³C-NMR (CDCl 3 , 125 MHz) δ 171.1 (C=N), 154.5 (C3), 141.9 (ipso- Ph), 140.4 (ipso-Ph), 139.3 (C7), 128.9, 128.8, 128.4, 127.6, 126.7, 126.5, 125.7 (Ph), 121.5 (C5), 107.5 (C8), 97.5 (C4), 88.9 (CHOPh), 78.8 (CHNPh), 50.8 (C2), 43.8 (C1), 31.0 (CHMe 2 ), 25.2 (Me), 23.5 (CHMe a Me B ), 17.9 (CHMe A Me b ), 9.6 (C9). 142 (major diastereoisomer) R f : 0.16 (9:1, petrol:EtOAc); [α] 22 D : +52 (c = 1, CHCl 3 ); MS m/z (ES+) 370 (100%, MH + ), 371 (74%, (M+1)H + ), 392 (30%, MNa + ), 761 (56%, 2MNa + ); HRMS: found 370.1800, MH requires 370.1802; IR ν max (film)/cm⎯¹ 2918 (w), 1649 (C=N), 1451 (m), 1243, 1078; ¹H-NMR (CDCl 3 , 500 MHz) δ 7.41-7.34 (m, 6H, Ph), 7.33-7.29 (m, 2H, Ph), 7.23-7.18 (m, 2H, Ph), 6.38 (dd, 1H, J 6.0, 2.5, H7), 6.00 (dq, 1H, J 10.0, 2.0, H5), 5.79 (dt, 1H, J 10.0, 3.0, H6), 5.50 (dt, 1H, J 16.0, 1.5, 205
Experimental for chapter 2 H4), 5.23 (dd, 1H, J 7.5, 1.5, CHOPh), 4.99 (dd, 1H, J 7.0, 2.0, CHNPh), 4.89 (td, 1H, J 6.0, 2.0, H8), 3.13-3.06 (m, 1H, H2), 2.28 (dtd, 1H, J 16.0, 6.0, 2.5, H9), 2.01-1.99 (tm, 1H, J 16.0, H9'), 1.58 (d, 1H, J 1.5, Me); ¹³C-NMR (CDCl 3 , 125 MHz) δ (all peaks) 171.3, 171.3, 150.1, 150.0, 142.1, 141.8, 140.7, 129.1, 129.0, 128.8, 128.7, 128.3, 127.6, 126.5, 126.4, 125.4, 105.3, 105.1, 101.1, 101.1, 88.9, 78.4, 78.4, 40.7, 31.1, 31.1, 28.2, 28.2, 26.9, 26.9; ¹³C-NMR (CDCl 3 , 125 MHz) δ (assigned, ignoring apparent doublets) 171.3 (C=N), 150.1 (C3); 142.1, 141.8, 140.7 (ipso-Ph, C7), 129.1, 129.0, 128.8, 128.7, 128.3, 127.6, 126.5, 126.4, 125.4 (Ph, C6, C5), 105.3, 101.1 (C8, C4), 88.9 (CHOPh), 78.4 (CHNPh), 40.7 (C2), 31.1 (C1), 28.2 (C9), 26.9 (Me). Synthesis of (4S,5S)-2-((1R,6R)-6-isopropyl-4-methoxy-1-methylcyclohexa-2,4- dienyl)-4-(methoxymethyl)-5-phenyloxazoline (105) Ph OMe O N i) i-PrLi, DMPU ii) MeI OMe 104b Ph OMe O N OMe OMe 107 108 22% 4% General procedure 4 was used employing oxazoline 104b (180 mg, 0.60 mmol) i-PrLi (0.96 mmol), DMPU (1.0 cm 3 , 13 eq) and methyl iodide (0.1 cm 3 ) quench after 30 min. Flash chromatography (9:1 petrol:EtOAc) yielded diene 105 (50 mg, 24%), oxazoline 107 (46 mg, 22%), oxazoline 106 (14 mg, 7%) diene 108 (8 mg, 4%) and starting material (18 mg, 10%) as colourless oils. 1 6 5 Me 2 3 4 Ph OMe O N OMe OMe 105 106 24% 7% Ph Me OMe Ph Me OMe O N O N Me 1 Me 1 6 2 5 3 5 4 1 6 5 4 6 2 3 2 3 4 Me 206
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Experimental for chapter 2<br />
102j R f : 0.32 (9:1, petrol:EtOAc); [α] 22 D : –105 (c = 1, CHCl 3 ); MS m/z (ES+) 414<br />
(100%, MH + ), 415 (32%, (M+1)H + ); HRMS: found 414.2421, MH requires 414.2428;<br />
IR ν max (film)/cm⎯¹ 2918 (m), 1658 (C=N), 1588, 1453 (m), 1268 (m), 1189 (m), 1083;<br />
¹H-NMR (CDCl 3 , 500 MHz) δ 7.43-7.34 (m, 5H, Ph), 7.33-7.28 (m, 3H, Ph), 7.25-<br />
7.21 (m, 2H, Ph), 6.06-5.96 (m, 2H, H6, H8), 5.82 (dd, 1H, J 9.5, 6.0, H5), 5.38 (dq,<br />
1H, J 17.5, 1.5, H9-trans), 5.25 (dq, 1H, J 10.5, 1.5, H9-cis), 5.21 (d, 1H, J 8.5,<br />
CHOPh), 5.09 (d, 1H, J 6.0, H4), 5.07 (d, 1H, J 8.5, CHNPh), 4.35 (ddt, 1H, J 13.0,<br />
5.5, 1.5, H7 a ), 4.29 (ddt, 1H, J 13.0, 5.0, 1.5, H7 b ), 2.41 (d, 1H, J 3.0, H2), 2.07 (pd,<br />
1H, J 7.0, 3.0, CHMe 2 ), 1.55 (s, 3H, Me), 1.09 (d, 3H, J 7.0, i-Pr), 1.03 (d, 3H, J 7.0, i-<br />
Pr); ¹³C-NMR (CDCl 3 , 125 MHz) δ 171.4 (C=N), 156.0 (C3), 142.0 (ipso-Ph), 140.5<br />
(ipso-Ph), 133.2 (C8), 128.9, 128.8, 128.3, 127.6, 126.7, 125.7 (Ph), 125.2 (C6), 122.0<br />
(C5), 116.9 (C9), 94.1 (C4), 88.8 (CHOPh), 78.8 (CHNPh), 67.7 (C7), 51.4 (C2), 43.7<br />
(C1), 30.9 (CHMe 2 ), 25.2 (Me), 23.8 (i-Pr), 17.9 (i-Pr).<br />
102j* R f : 0.32 (9:1, petrol:EtOAc); [α] 23 D : –56 (c = 0.5, CHCl 3 ); MS m/z (ES+) 414<br />
(100%, MH + ), 415 (34%, (M+1)H + ); HRMS: found 414.2423, MH requires 414.2428;<br />
IR ν max (film)/cm⎯¹ 2918 (m), 2362, 1995, 1661 (C=N), 1456 (m); ¹H-NMR (CDCl 3 ,<br />
500 MHz) δ 7.44-7.34 (m, 6H, Ph), 7.34-7.28 (m, 2H, Ph), 7.24-7.20 (m, 2H, Ph), 6.29<br />
(dd, 1H, J 6.0, 1.5, H7), 6.08 (d, 1H, J 9.5, H6), 5.81 (dd, 1H, J 9.5, 6.0, H5), 5.27 (d,<br />
1H, J 6.0, H4), 5.23 (d, 1H, J 8.5, CHOPh), 5.08 (d, 1H, J 8.5, CHNPh), 4.85 (quin,<br />
1H, J 6.5, H8), 2.48 (d, 1H, J 3.0, H2), 2.09 (pd, 1H, J 7.0, 3.0, CHMe 2 ), 1.66 (dd, 3H,<br />
J 7.0, 1.5, H9), 1.57 (s, 3H, Me), 1.11 (d, 3H, J 7.0, CHMe A Me b ), 1.07 (d, 3H, J 7.0,<br />
CHMe a Me B ); ¹³C-NMR (CDCl 3 , 125 MHz) δ 171.1 (C=N), 154.5 (C3), 141.9 (ipso-<br />
Ph), 140.4 (ipso-Ph), 139.3 (C7), 128.9, 128.8, 128.4, 127.6, 126.7, 126.5, 125.7 (Ph),<br />
121.5 (C5), 107.5 (C8), 97.5 (C4), 88.9 (CHOPh), 78.8 (CHNPh), 50.8 (C2), 43.8<br />
(C1), 31.0 (CHMe 2 ), 25.2 (Me), 23.5 (CHMe a Me B ), 17.9 (CHMe A Me b ), 9.6 (C9).<br />
142 (major diastereoisomer) R f : 0.16 (9:1, petrol:EtOAc); [α] 22 D : +52 (c = 1, CHCl 3 );<br />
MS m/z (ES+) 370 (100%, MH + ), 371 (74%, (M+1)H + ), 392 (30%, MNa + ), 761 (56%,<br />
2MNa + ); HRMS: found 370.1800, MH requires 370.1802; IR ν max (film)/cm⎯¹ 2918<br />
(w), 1649 (C=N), 1451 (m), 1243, 1078; ¹H-NMR (CDCl 3 , 500 MHz) δ 7.41-7.34 (m,<br />
6H, Ph), 7.33-7.29 (m, 2H, Ph), 7.23-7.18 (m, 2H, Ph), 6.38 (dd, 1H, J 6.0, 2.5, H7),<br />
6.00 (dq, 1H, J 10.0, 2.0, H5), 5.79 (dt, 1H, J 10.0, 3.0, H6), 5.50 (dt, 1H, J 16.0, 1.5,<br />
205
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