8928
A. Alix et al. / Tetrahedron 64 (2008) 8922–8929
64.4 (C5), 61.0 (–CH2CH3), 50.2 (C6), 48.1 (–OCH3), 17.6 (–CH3), 17.5
(–CH3), 14.3 (–CH2CH3). HRMS (ESI, positive mode) m/z: calcd for
C
20.5 (–CH3 of –OAc), 20.5 (–CH3 of –OAc). HRMS (ESI, positive mode)
m/z: calcd for C24H30N4O9Na 541.1905, found 541.1913 [MþNa]þ.
23H31N3O8SNa 532.1877, found 532.1860 [MþNa]þ.
4.4.8. Compound 3i
4.4.5. Compound 3f
Obtained using general procedure after 18 h stirring at 20 ꢀC.
20
Obtained using general procedure after 17 h stirring at 80 ꢀC.
Isolated as white solid. Yield 81%. Mp 140 ꢀC. [
a
]
ꢂ53.3 (c 1.0,
589
Isolatedaswhite solid, mixtureof
a
/
b
isomers ina 1:3ratio. Yield97%.
CHCl3). IR (KBr): 3142, 2957, 1743, 1499, 1455, 1436, 1369, 1325,
1220, 1158, 1128, 1092, 1039. 1H NMR (CDCl3, 300 MHz): 7.46 (s, 1H,
H–triazole ring), 7.33–7.19 (m, 5H, Ar Ph–), 5.46 (s, 2H, –CH2Ph),
5.18–5.10 (m, 2H, H3þH4), 4.92 (dd, J2–3¼8.4 Hz and J2–1¼7.7 Hz, 1H,
H2), 4.84 (d, J¼12.7 Hz, 1H, –OCH2–triazole), 4.75 (d, J¼12.7 Hz, 1H,
–OCH2–triazole), 4.66 (d, J1–2¼7.7 Hz, 1H, H1), 4.02 (d, J5–4¼9.1 Hz,
1H, H5), 3.66 (s, 3H, –OCH3), 1.96 (s, 3H, –OAc), 1.93 (s, 3H, –OAc),
1.79 (s, 3H, –OAc). 13C NMR (CDCl3, 75 MHz): 169.8 (C]O acetate),
169.2 (C]O acetate), 169.0 (C]O acetate), 167.0 (C]O methyl es-
ter), 144.2 (CIV triazole), 134.4 (CIV Ar Ph–), 128.9 (CIII Ar Ph–), 128.6
(CIII Ar Ph–), 127.9 (CIII Ar Ph–), 122.8 (CIII triazole), 99.5 (C1), 72.2
(C2), 71.7 (C3), 70.9 (C5), 69.1 (C4), 62.8 (–OCH2–triazole), 53.9
(–OCH3), 52.6 (–CH2Ph), 20.4 (–CH3 of –OAc), 20.3 (–CH3 of –OAc).
HRMS (ESI, positive mode) m/z: calcd for C23H27N3O10Na 528.1589,
found 528.1834 [MþNa]þ.
Mp (dec) 196–198 ꢀC. IR (KBr): 3129, 2934, 2863, 2353, 2334, 1717,
1709,1559,1553,1472,1464,1458, 1447,1398,1387, 1377,1363,1332,
1316, 1265, 1252, 1220, 1142, 1081, 1044.
b
Isomer (major): 1H NMR
(CDCl3, 300 MHz): 7.64 (s, 1H, H–triazole ring), 7.22–7.07 (m, 5H, Ar
PhS–), 5.82 (d, J1–2¼9.9 Hz, 1H, H1), 4.36 (q, J¼7.1 Hz, 2H, –CH2CH3),
4.04 (dd, J4–5¼9.7 Hz and J4–3¼9.5 Hz, 1H, H4), 3.93 (d, J6a–5¼2.9 Hz,
1H, H6a), 3.91 (d, J6b–5¼2.2 Hz, 1H, H6b), 3.85 (dd, J3–2¼11.3 Hz and
J3–4¼9.5 Hz, 1H, H3), 3.66 (ddd, J5–4¼9.9 Hz, J5–6a¼2.8 Hz and
J5–6b¼2.5 Hz,1H, H5), 3.53 (dd, J2–3¼11.3 Hz and J2–1¼9.9 Hz,1H, H2),
3.40 (s, 3H, –OCH3), 3.33 (s, 3H, –O CH3), 1.42 (s, 3H, –CH3), 1.38 (t,
J¼7.1 Hz, 3H, –CH2CH3),1.35 (s, 3H, –CH3),1.03–0.89 (m, 21H, –SiiPr3).
13C NMR (CDCl3, 75 MHz): 160.1 (C]O ester), 139.9 (CIV triazole),
133.6 (CIII Ar PhS–),131.9 (CIV Ar PhS–),128.9 (CIII Ar PhS–),128.0 (CIII
Ar PhS–), 125.7 (CIII triazole), 100.6 (CIV Ley acetal), 99.9 (CIV Ley ac-
etal), 89.8 (C1), 77.8 (C5), 70.4 (C3), 66.3 (C4), 61.1 (–CH2CH3), 60.7 (C6),
54.7 (C2), 48.4 (–OCH3), 48.2 (–OCH3), 17.9 (2CIII, –CH of –SiiPr3), 17.7
(CIII, –CH of –SiiPr3),17.7 (–CH3), 17.6 (–CH3),14.3 (–CH2CH3),11.9 (6CI,
–CH3 of –SiiPr3). HRMS (ESI, positive mode) m/z: calcd for
4.4.9. Compound 3j
Obtained using general procedure after 16 h stirring at 80 ꢀC.
20
Isolated as white solid. Yield 72%. Mp 88–92 ꢀC. [
a
]
589 þ51.8 (c 0.8,
C
32H51N3O8SSiNa 688.3058, found 688.3023 [MþNa]þ.
CHCl3). IR (KBr): 3296, 2927, 2857, 1738, 1662, 1537, 1436, 1367,
1220, 1120, 1029. 1H NMR (CDCl3, 300 MHz): 7.57 (s, 2H, H–triazole
4.4.6. Compound 3g
ring), 6.09 (d, J¼9.3 Hz, 2H, NH), 5.18 (dd, J3–2¼10.2 Hz and J3–4¼
Obtained using general procedure after 17 h stirring at 80 ꢀC.
9.7 Hz, 2H, H3), 5.08 (dd, J4–3¼9.7 Hz and J4–5¼9.5 Hz, 2H, H4), 4.87
(d, J1–2¼3.7 Hz, 2H, H1), 4.79 (d, J¼12.4 Hz, 2H, –OCH2–triazole),
4.61 (d, J¼12.4 Hz, 2H, –OCH2–triazole), 4.45–4.27 (m, 6H, triazole–
CH2CH2–þH2), 4.24–4.15 (dd, J6a–6b¼12.4 Hz and J6a–5¼4.2 Hz, 2H,
Isolated as white solid, mixture of a/b isomers in a 3:1 ratio. Yield
75%. Mp 171–174 ꢀC. IR (KBr): 3155, 2921, 2849, 2358, 2342, 1729,
1457, 1436, 1429, 1398, 1386, 1376, 1346, 1207, 1179, 1123, 1034.
a
Isomer (major): 1H NMR (CDCl3, 300 MHz): 8.09 (s, 1H, H–triazole
H
6a), 4.09–3.92 (m, 4H, H5þH6b), 2.05 (s, 6H, –OAc), 2.01–1.89
ring), 8.08 (s,1H, H–triazole ring), 7.40 (m, 2H, Ar PhS–), 7.28 (m, 3H,
Ar PhS–), 6.07 (d, J¼5.9 Hz, 1H, H1), 4.90 (dd, J6a–6b¼12.2 Hz
and J6a–5¼9.3 Hz,1H, H6a), 4.85 (dd, J6b–6a¼12.3 Hz and J6b–5¼5.1 Hz,
(m, 16H, 2ꢁ–OAcþtriazole–CH2CH2–), 1.87 (s, 6H, –NHAc). 13C NMR
(CDCl3, 75 MHz): 171.1 (C]O acetate), 170.6 (C]O acetate), 170.2
(C]O acetate), 169.2 (C]O acetamide), 143.4 (CIV triazole), 143.2
(CIV triazole), 122.9 (CIII triazole), 96.5 (C1), 70.9 (C3), 68.1 (C5), 67.9
(C4), 61.8 (–OCH2–triazole), 60.8 (C6), 51.6 (C2), 49.3 (triazole–
CH2CH2–), 27.0 (triazole–CH2CH2–), 23.0 (–CH3 of –NHAc), 20.6
(–CH3 of –OAc), 20.6 (–CH3 of –OAc), 20.5 (–CH3 of –OAc). HRMS
(ESI, positive mode) m/z: calcd for C38H54N8O18Li 917.3711, found
917.3592 [MþLi]þ.
1H, H6b), 4.50–4.38 (m, 6H, 2ꢁ–CH2CH3þH3þH5), 3.68 (dd, J2–3
¼
¼
12.1 Hz and J2–1¼5.9 Hz, 1H, H2), 3.53 (dd, J4–5¼9.8 Hz and J4–3
9.7 Hz,1H, H4), 3.36(s,3H, –OCH3), 3.30 (s, 3H, –OCH3),1.44(t, J¼7.1 Hz,
3H, –CH2CH3),1.40 (t, J¼7.1 Hz, 3H, –CH2CH3),1.38 (s, 3H, –CH3),1.34
(s, 3H, –CH3). 13C NMR (CDCl3, 75 MHz): 160.7 (C]O ester), 160.4
(C]O ester), 140.4 (CIV triazole), 139.7 (CIV triazole), 133.5 (CIV Ar
PhS–), 132.6 (CIII Ar PhS–), 129.7 (CIII Ar PhS–), 129.0 (CIII triazole),
128.8 (CIII triazole), 128.1 (CIII Ar PhS–), 100.6 (CIV Ley acetal), 85.7
(C1), 71.9 (C5), 68.2 (C3), 67.4 (C4), 61.5 (–CH2CH3), 61.4 (–CH2CH3),
51.3 (C2), 49.3 (C6), 49.0 (–OCH3), 48.1 (–OCH3), 17.6 (–CH3), 17.5
(–CH3), 14.3 (2ꢁ–CH2CH3). HRMS (ESI, positive mode) m/z: calcd
for C28H36N6O9SNa 655.2157, found 655.2153 [MþNa]þ.
4.4.10. Compound 3k
Obtained using general procedure after 16 h stirring at 80 ꢀC.
20
Isolated as white solid. Yield 52%. Mp 152–155 ꢀC. [
a]
ꢂ37.3 (c
589
1.0, CHCl3). IR (KBr): 2926, 2338, 1756, 1717, 1713, 1472, 1464,
1458, 1436, 1419, 1387, 1375, 1228, 1157, 1045. 1H NMR (CDCl3,
300 MHz): 7.59 (s, 2H, H–triazole ring), 5.31–5.16 (m, 4H, H3þH4),
5.00 (dd, J2–3¼9.1 Hz and J2–1¼7.5 Hz, 2H, H2), 4.93 (d, J¼12.6 Hz,
2H, –OCH2–triazole), 4.83 (d, J¼12.6 Hz, 2H, –OCH2–triazole), 4.73
(d, J1–2¼7.5 Hz, 2H, H1), 4.37 (br s, 4H, triazole–CH2CH2–), 4.08 (d,
J5–4¼9.3 Hz, 2H, H5), 3.73 (s, 6H, –OCH3), 2.02 (s, 6H, –OAc), 2.00
(s, 6H, –OAc), 1.98 (s, 6H, –OAc), 1.96–1.89 (m, 4H, triazole–
CH2CH2–). 13C NMR (CDCl3, 75 MHz): 170.0 (C]O acetate), 169.4
(C]O acetate), 169.3 (C]O acetate), 167.3 (C]O methyl ester),
144.3 (CIV triazole), 123.1 (CIII triazole), 100.0 (C1), 72.4 (C2), 71.9
(C3), 71.2 (C5), 69.3 (C4), 63.3 (–OCH2–triazole), 52.9 (–OCH3), 49.3
(triazole–CH2CH2–), 27.0 (triazole–CH2CH2–), 20.6 (–CH3 of –OAc),
20.6 (–CH3 of –OAc), 20.5 (–CH3 of –OAc). HRMS (ESI, positive
mode) m/z: calcd for C36H48N6O20Na 907.2816, found 907.2922
[MþNa]þ.
4.4.7. Compound 3h
Obtained using general procedure after 18 h stirring at 20 ꢀC.
20
Isolated as white solid. Yield 76%. Mp 55 ꢀC. [
a
]
þ68.1 (c 1.0,
589
CHCl3). IR (KBr): 2928,1738,1664,1455,1422,1366,1219,1119,1033,
1012. 1H NMR (CDCl3, 300 MHz): 8.03 (s, 1H, H–triazole ring), 7.45–
7.27 (m, 5H, Ar Ph–), 5.61 (s, 2H, –CH2Ph), 5.22 (dd, J3–2¼11.0 Hz and
J3–4¼10.2 Hz,1H, H3), 5.01 (dd, J4–3¼10.1 Hz and J4–5¼9.9 Hz,1H, H4),
4.91 (d, J1–2¼3.7 Hz,1H, H2), 4.81 (d, J¼12.4 Hz,1H, –OCH2–triazole),
4.68 (d, J¼12.4 Hz, 1H, –OCH2–triazole), 4.24 (dd, J2–3¼11.0 Hz and
J2–1¼3.7 Hz, 1H, H2), 4.21 (dd, J6a–6b¼12.4 Hz and J¼4.2 Hz, 1H, H6a),
4.05–3.95 (m, 2H, H5þH6b), 2.04 (s, 3H, –OAc),1.99 (s, 3H, –OAc),1.94
(s, 3H, –OAc), 1.85 (s, 3H, –NHAc). 13C NMR (CDCl3, 75 MHz): 173.5
(C]O acetamide), 172.3 (C]O acetate), 172.0 (C]O acetate), 171.2
(C]O acetate), 145.2 (CIV triazole), 136.7 (CIV Ar Ph–), 130.1 (CIII Ar
Ph–), 129.7 (CIII Ar Ph–), 129.2 (CIII Ar Ph–), 125.3 (CIII triazole), 98.1
(C1), 72.2 (C3), 70.1 (C5), 69.1 (C4), 63.1 (–OCH2–triazole), 61.8 (C6),
55.0 (–CH2Ph), 52.8 (C2) 22.4 (–CH3 of –NHAc), 20.6 (–CH3 of –OAc),
4.4.11. Compound 3l
Obtained using general procedure after 16 h stirring at 80 ꢀC.
20
Isolated as white solid. Yield 79%. Mp 174 ꢀC. [
a]
ꢂ0.6 (c 1.0,
589