1624
J.-C. Lee et al. / Tetrahedron Letters 47 (2006) 1621–1624
11. Witczak, Z. J.; Czernecki, S. Adv. Carbohydr. Chem.
Biochem. 1998, 53, 143.
12. Hashimoto, S.; Honda, T.; Ikegami, S. J. Chem. Soc.,
Chem. Commun. 1989, 685.
(CH), 119.4 (CH), 117.3 (CH2), 114.4 (CH), 97.8 (CH),
79.9 (CH), 75.0 (CH2), 74.7 (CH · 2), 73.2 (CH2), 72.7
(CH), 72.6 (CH2), 72.2 (CH2), 69.6 (CH2), 69.1 (CH2);
HRMS (FAB, MNa+) calcd for C43H44O7Na 695.2994,
28
13. Zhang, Z. Y.; Wong, C.-H. In Carbohydrates in Chemistry
found 695.2985. Compound 28: ½aꢁD +77.1 (c 0.8, CHCl3);
and Biology; Ernst, B., Hart, G. W., Sinay, P., Eds.; Wiley-
IR (CHCl3) m 3031, 2913, 2867, 1719, 1651, 1637, 1451,
¨
VCH: Weinheim, 2000; Vol. 1, pp 117–134.
14. Kim, K. S.; Kim, J. H.; Lee, Y. J.; Lee, Y. J.; Park, J. J.
Am. Chem. Soc. 2001, 123, 8477.
15. Garcia, B. A.; Gin, D. Y. J. Am. Chem. Soc. 2000, 122,
4269.
16. Kitaori, K.; Furukawa, Y.; Yoshimoto, H.; Otera, J. Adv.
Synth. Catal. 2001, 343, 95.
17. Tai, C.-A.; Kulkarni, S. S.; Hung, S.-C. J. Org. Chem.
2003, 68, 8719.
18. Wang, C.-C.; Luo, S.-Y.; Shie, C.-R.; Hung, S.-C. Org.
Lett. 2002, 4, 847.
19. Maeta, H.; Matsumoto, T.; Suzuki, K. Carbohydr. Res.
1993, 249, 49.
20. Lee, J.-C.; Lu, X.-A.; Kulkarni, S. S.; Wen, Y.-S.; Hung,
S.-C. J. Am. Chem. Soc. 2004, 126, 476.
21. General procedure for coupling of the glycosyl donor 11
with various alcohols. Trifluoromethanesulfonic acid
(0.3 equiv) was added to a solution of compound 11
(1.2 equiv), an alcohol (1.0 equiv, 14–21), and N-iodosuc-
cinimide (2.0 equiv) in dichloromethane (20 mL per gram
of 11) at room temperature under nitrogen. The reaction
was monitored by TLC till the total consumption of
starting material (ꢀ4 h). Triethylamine (5.0 equiv) was
added to the solution, the mixture was filtered through
paper, and the filtrate was sequentially washed by 5%
1360, 1270, 1102 cmꢂ1 1H NMR (400 MHz, CDCl3) d
;
8.01 (dd, J = 7.4, 0.7 Hz, 2H, Bz-H), 7.59 (t, J = 7.4 Hz,
1H, ArH), 7.45 (t, J = 7.4 Hz, 2H, ArH), 7.36–7.25 (m,
18H, ArH), 7.21–7.45 (m, 5H, ArH), 7.45–7.10 (m, 2H,
ArH), 5.50 (d, J = 1.8 Hz, 1H, H-10), 5.13 (d, J = 1.9 Hz,
1H, H-1), 5.03 (dd, J = 8.2, 1.8 Hz, 1H, H-20), 4.86 (d,
J = 10.8 Hz, 1H, PhCH2), 4.83 (t, J = 4.3 Hz, 1H, H-3),
4.67–4.54 (m, 8H, PhCH2), 4.50 (d, J = 10.8 Hz, 1H,
PhCH2), 4.04 (d, J = 8.0 Hz, 1H, H-5), 3.94 (dd, J = 8.0,
4.3 Hz, 1H, H-4), 3.91–3.84 (m, 2H, H-30, H-6a0), 3.81 (dd,
J = 9.0, 3.0 Hz, 1H, H-6b0), 3.74–3.64 (m, 5H, H-6a, H-
6b, H-2, H-40, H-50); 13C NMR (100 MHz, CDCl3) d 165.8
(C), 139.2 (C), 138.9 (C), 138.3 (C), 138.11 (C), 138.10 (C),
133.4 (CH), 130.0 (CH), 129.1 (C), 128.5 (CH), 128.3
(CH), 128.0 (CH), 127.9 (CH), 127.8 (CH), 127.7 (CH),
100.8 (CH), 99.3 (CH), 80.7 (CH), 79.6 (CH), 78.8 (CH),
76.7 (CH), 75.37 (CH2), 75.33 (CH), 75.1 (CH), 74.8
(CH2), 74.4 (CH), 73.6 (CH2), 72.9 (CH), 72.8 (CH2), 72.4
(CH2), 69.5 (CH2), 65.9 (CH2); HRMS (FAB, M+) calcd
for C54H54O11Na 901.3564, found 901.3578. Compound
23
29: ½aꢁD ꢂ63.0 (c 2.1, CHCl3); IR (CHCl3) m 2908, 2867,
1
2102, 1721, 1453, 1276, 1106, 1052, 1028 cmꢂ1; H NMR
(500 MHz, CDCl3) d 8.05–8.03 (m, 2H, ArH), 7.55–7.52
(m, 1H, ArH), 7.42–7.39 (m, 2H, ArH), 7.33–7.13 (m,
25H, ArH), 5.34 (d, J = 2.6 Hz, 1H, H-10), 4.90 (d,
J = 11.0 Hz, 1H, PhCH2), 4.80 (d, J = 3.4 Hz, 1H, H-1),
4.76 (d, J = 10.8 Hz, 1H, PhCH2), 4.73 (dd, J = 12.0,
2.2 Hz, 1H, H-6a), 4.67 (d, J = 11.8 Hz, 1H, PhCH2), 4.64
(d, J = 10.8 Hz, 1H, PhCH2), 4.59 (d, J = 11.8 Hz, 1H,
PhCH2), 4.53 (d, J = 12.0 Hz, 1H, PhCH2), 4.47 (dd,
J = 12.0, 5.2 Hz, 1H, H-6b), 4.46 (d, J = 10.8 Hz, 1H,
PhCH2), 4.39 (d, J = 12.0 Hz, 1H, PhCH2), 4.31 (d,
J = 12.0 Hz, 1H, PhCH2), 4.23 (d, J = 12.0 Hz, 1H,
PhCH2), 4.04 (t, J = 9.0 Hz, 1H, H-4), 3.94–3.81 (m, 5H,
H-5, H-3, H-50, H-6a0, H-6b0), 3.72 (t, J = 2.6 Hz, 1H, H-
20), 3.70 (dd, J = 11.0, 4.2 Hz, 1H, H-40), 3.60 (dd,
J = 11.0, 2.6 Hz, 1H, H-30), 3.43 (s, 3H, OMe), 3.41 (dd,
J = 10.0, 3.4 Hz, 1H, H-2); 13C NMR (125 MHz, CDCl3)
d 166.1 (C), 138.5 (C), 138.4 (C), 138.36 (C), 138.3 (C),
137.6 (C), 133.0 (CH), 130.0 (C), 129.7 (CH), 128.5 (CH),
128.4 (CH), 128.3 (CH), 128.29 (CH), 128.2 (CH), 128.1
(CH), 128.0 (CH), 127.97 (CH), 127.8 (CH), 127.74 (CH),
127.71 (CH), 127.61 (CH), 127.59 (CH), 127.3 (CH), 127.2
(CH), 127.1 (CH), 101.7 (CH), 98.4 (CH), 80.4 (CH),
79.4(CH), 77.5 (CH), 76.7 (CH), 74.8 (CH2), 74.77 (CH),
74.71 (CH2), 73.5 (CH), 73.3 (CH2), 72.5 (CH2), 72.4
(CH2), 68.9 (CH), 68.8 (CH2), 63.6 (CH2), 63.6 (CH), 55.3
(CH3); HRMS (FAB, MNa+) calcd for C55H57O11N3Na
958.3891, found 958.3895.
Na2S2O3(aq)
, saturated NaHCO3(aq), and brine. The
organic phase was dried over MgSO4, filtered, and
concentrated in vacuo to yield a residue, which was
purified by flash column chromatography to provide the
desired a-mannopyranosylated adducts (Table 2).
22. Spectral data of selected new compounds. Compound 11:
25
½aꢁD +59.3 (c 1.6, CHCl3); IR (CHCl3) m 3064, 2856, 1643,
1592, 1498, 1451, 1358, 1254, 1213, 1112, 1026, 992, 751,
1
697, 668 cmꢂ1; H NMR (400 MHz, CDCl3) d 7.42–7.20
(m, 20H, Ph-H), 7.13 (dd, J = 7.9, 1.4 Hz, 1H, PhH), 7.02–
6.97 (m, 1H, PhH), 6.91–6.85 (m, 2H, PhH), 6.04 (ddt,
J = 17.2, 10.5, 5.2 Hz, 1H, CH@CH2), 5.59 (d, J = 1.7 Hz,
1H, H-1), 5.39 (ddt, J = 17.2, 3.2, 1.6 Hz, 1H, CH@CH2),
5.25 (ddt, J = 10.5, 2.9, 1.4 Hz, 1H, CH@CH2), 4.94 (d,
J = 10.8 Hz, 1H, CH2Ph), 4.79 (s, 2H, CH2Ph), 4.70 (s,
2H, CH2Ph), 4.65 (d, J = 12.0 Hz, 1H, CH2Ph), 4.57 (d,
J = 10.8 Hz, 1H, CH2Ph), 4.51–4.47 (m, 3H,
CH2CH@CH2, CH2Ph), 4.21–4.06 (m, 4H, H-2, H-3, H-
4, H-5), 3.83 (dd, J = 11.0, 4.4 Hz, 1H, H-6a), 3.73 (dd,
J = 11.0, 1.5 Hz, 1H, H-6b); 13C NMR (100 MHz, CDCl3)
d 149.4 (C), 145.8 (C), 138.5 (C), 138.3 (C), 138.2 (C),
133.3 (CH), 128.3 (CH), 128.23 (CH), 128.20 (CH), 128.1
(CH2), 127.8 (CH), 127.7 (CH), 127.62 (CH), 127.60 (CH),
127.49 (CH), 127.46 (CH), 127.3 (CH), 123.5 (CH), 121.3