Nie and Wang
Compound 7C: 11%, colorless crystal, mp 91-93 °C; 1H NMR
(300 MHz, CDCl3) δ 7.46-7.43 (m, 2H), 7.36-7.34 (m, 3H), 5.50
(s, 1H), 5.34 (t, 1H, J ) 9.8 Hz), 4.81 (d, 1H, J ) 3.8 Hz), 4.31
(dd, 1H, J ) 9.9, 4.7 Hz), 3.88-3.82 (m, 1H), 3.76 (t, 1H, J ) 9.9
Hz), 3.71-3.64 (m, 1H), 3.59 (t, 1H, J ) 9.6 Hz), 3.48 (s, 3H),
2.37 (t, 2H, J ) 7.4 Hz), 2.27-2.19 (m, 4H), 1.68-1.57 (m, 2H),
1.54-1.42 (m, 4H), 1.40-1.11 (m, 22H), 0.87 (t, 3H, J ) 6.6 Hz);
13C NMR (62.5 MHz, CDCl3) δ 173.8, 137.0, 129.2, 128.2, 126.1,
101.4, 100.1, 78.7, 77.6, 72.0, 71.8, 68.9, 65.3, 65.2, 62.7, 55.5,
34.4, 31.9, 29.5, 29.4, 29.3, 29.0, 28.8, 28.7, 28.3, 28.2, 25.0, 22.6,
19.1, 14.1; HRMS calcd for C37H54O7 + H 611.3948, found
611.3966.
Hz), 3.74 (t, 1H, J ) 9.8 Hz), 3.53 (t, 1H, J ) 9.8 Hz), 3.38 (s, 3
H), 2.52 (dd, 2H, J ) 7.8, 6.8 Hz), 2.33 (t, 2H, J ) 6.8 Hz), 2.21
(t, 2H, J ) 6.8 Hz), 1.88-1.81 (m, 2H), 1.52-1.45 (m, 2H), 1.39-
1.25 (m, 10H), 0.86 (dd, 3H, J ) 6.8, 5.9 Hz); 13C NMR (100
MHz, CDCl3) δ 172.6, 137.0, 129.3, 128.3, 126.3, 102.0, 97.5, 81.4,
78.1, 75.7, 73.5, 68.8, 68.6, 66.3, 65.0, 62.0, 55.4, 32.8, 31.8, 29.6,
29.0, 28.8, 28.2, 23.4, 22.6, 19.1, 18.4, 14.0; HRMS calcd for
C30H40O7 + H 513.2852, found 513.2853.
Compound 9C: 7%, colorless crystal, mp 93-95 °C; 1H NMR
(400 MHz, CDCl3) δ 7.44-7.41 (m, 2H), 7.37-7.32 (m, 3H), 5.47
(s, 1H), 5.31 (t, 1H, J ) 9.8 Hz), 4.78 (d, 1H, J ) 3.9 Hz), 4.29
(dd, 1H, J ) 10.7, 4.9 Hz), 3.87-3.81 (m, 1H), 3.76-3.70 (m,
1H), 3.64 (dd, 1H, J ) 3.91 Hz), 3.56 (t, 1H, J ) 9.8 Hz), 3.45 (s,
3H), 2.48 (dd, 2H, J ) 7.8, 6.8 Hz), 2.27 (t, 2H, J ) 6.8 Hz), 2.21
(t, 2H, J ) 6.8 Hz), 1.86-1.79 (m, 2 H), 1.52-1.45 (m, 2 H),
1.38-1.23 (m, 10H), 0.89 (dd, 3H, J ) 6.8, 5.9 Hz); 13C NMR
(100 MHz, CDCl3) δ 173.0, 137.0, 129.1, 128.2, 126.1, 101.5,
100.2, 78.7, 78.0, 72.3, 71.8, 68.9, 66.1, 62.7, 55.6, 33.2, 31.8, 29.2,
29.1, 28.8, 28.3, 23.8, 22.7, 19.2, 18.5, 14.1; HRMS calcd for
C30H40O7 + H 513.2852, found 513.2848.
Reaction of (+)-(4,6-O-Benzylidiene)methyl-R-D-glucopyra-
noside with 8,10-Heneicosadiynoic Chloride, Total Yield 90%.
1
Compound 8A: 20%, colorless crystal, mp 36-37 °C; H NMR
(400 MHz, CDCl3) δ 7.42-7.39 (m, 2H), 7.35-7.30 (m, 3 H),
5.58 (t, 1H, J ) 9.8 Hz), 5.48 (s, 1H), 4.92 (d, 1H, J ) 3.9 Hz),
4.89-4.86 (m, 1H), 4.28 (dd, 1H, J ) 9.8, 4.9 Hz), 3.90 (dt, 1H,
J ) 9.8, 4.9 Hz), 3.75 (t, 1H, J ) 9.8 Hz), 3.62 (t, 1H, J ) 9.8
Hz), 3.38 (s, 3H), 2.37-2.20 (m, 10H), 2.13 (t, 2H, J ) 6.8 Hz),
1.62-1.23 (m, 48H), 0.85 (t, 6H, J ) 6.8 Hz); 13C NMR (100
MHz, CDCl3) δ 173.0, 172.3, 136.9, 129.0, 128.2, 126.1, 101.5,
97.6, 79.2, 77.6, 77.1, 77.0, 71.4, 68.8, 68.6, 65.4, 65.2, 65.1, 62.3,
55.3, 34.2, 34.0, 31.8, 29.5, 29.4, 29.2, 29.0, 28.8, 28.4, 28.3(2),
28.27, 28.0, 27.9, 24.8, 24.6, 22.6, 19.1(2), 19.0, 14.1; HRMS calcd
for C56H82O8 + H 883.6088, found 883.6080.
Reaction of (+)-(4,6-O-Benzylidiene)methyl-R-D-glucopyra-
noside with Heptan-4,6-diynoic Acid Chloride, Total Yield 96%.
Compound 10A: 20%, colorless crystal, mp 72-73 °C; 1H NMR
(400 MHz, CDCl3) δ 7.42-7.40 (m, 2H), 7.35-7.31 (m, 3H), 5.58
(t, 1H, J ) 9.7 Hz), 5.49 (s, 1H), 4.94 (d, 1H, J ) 3.7 Hz), 4.90
(dd, 1H, J ) 9.7, 3.7 Hz), 4.28 (dd, 1H, J ) 10.2, 4.8 Hz), 3.93-
3.87 (m, 1H), 3.75 (t, 1H, J ) 10.3 Hz), 3.64 (t, 1H, J ) 9.6 Hz),
3.39 (s, 3H), 2.57-2.50 (m, 8H), 2.22-2.15 (m, 4H), 1.56-1.45
(m, 4H), 0.97-0.92 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 170.9,
170.4, 136.9, 129.0, 128.2, 126.1, 101.5, 97.6, 79.1, 78.4, 78.2,
74.9, 74.6, 71.8, 69.3, 68.3, 66.3, 66.0, 65.2, 62.3, 55.5, 33.0, 21.8,
21.1, 15.2, 13.5; HRMS calcd for C34H38O8 + H 575.2645, found
575.2633.
Compound 8B: 63%, colorless crystal, mp 56-57 °C; 1H NMR
(400 MHz, CDCl3) δ 7.48-7.46 (m, 2H), 7.39-7.33 (m, 3 H),
5.52 (s, 1H), 4.93 (d, 1H, J ) 3.9 Hz), 4.77 (dd, 1H, J ) 9.8, 3.9
Hz), 4.27 (dd, 1H, J ) 9.8, 3.9 Hz), 4.15 (t, 1H, J ) 9.8 Hz), 3.82
(dt, 1H, J ) 9.8, 4.9 Hz), 3.73 (t, 1H, J ) 9.8 Hz), 3.53 (t, 1H, J
) 9.8 Hz), 3.37 (s, 3H), 2.37 (t, 2H, J ) 7.8 Hz), 2.22-2.18 (m,
4H), 1.69-1.56 (m, 2H), 1.41-1.23 (m, 22H), 0.84 (t, 3H, J )
6.8 Hz); 13C NMR (100 MHz, CDCl3) δ 173.3, 137.0, 129.2, 128.3,
126.3, 101.9, 97.5, 81.4, 77.1, 76.7, 73.4, 68.8, 68.6, 65.4, 65.1,
62.0, 55.3, 33.9, 31.8, 29.5, 29.4, 29.2, 29.0, 28.8, 28.4, 28.3, 28.28,
28.0, 24.7, 22.6, 19.1, 19.0, 14.1; HRMS calcd for C35H50O7 + H
583.3635, found 583.3642.
1
Compound 10B: 65%, colorless crystal, mp 110-111 °C; H
NMR (400 MHz, CDCl3) δ 7.49-7.46 (m, 2H), 7.38-7.34 (m,
3H), 5.52 (s, 1H), 4.93 (d, 1H, J ) 3.7 Hz), 4.79 (dd, 1H, J ) 9.6,
3.7 Hz), 4.27 (dd, 1H, J ) 9.9, 4.5 Hz), 4.15 (dd, 1H, J ) 9.6, 9.4
Hz), 3.85-3.79 (m, 1H), 3.72 (dd, 1H, J ) 10.2, 9.9 Hz), 3.53
(dd, 1H, J ) 9.4, 9.2 Hz), 3.38 (s, 3H), 2.64-2.53 (m, 4H), 2.19
(t, 2H, J ) 7.0 Hz), 1.56-1.47 (m, 2H), 0.95 (t, 3H, J ) 7.4 Hz);
13C NMR (100 MHz, CDCl3) δ 171.3, 137.0, 129.3, 128.4, 126.3,
102.0, 97.5, 81.3, 78.4, 74.7, 73.9, 68.9, 68.6, 66.3, 65.1, 62.0, 55.5,
33.0, 21.8, 21.2, 15.2, 13.5; HRMS calcd for C24H28O7 + H
429.1913, found 429.1917.
Compound 8C: 7%, colorless crystal, mp 76-78 °C; 1H NMR
(400 MHz, CDCl3) δ 7.46-7.39 (m, 2H), 7.36-7.30 (m, 3H), 5.47
(s, 1H), 5.32 (t, 1H, J ) 9.8 Hz), 4.78 (d, 1H, J ) 3.9 Hz), 4.28
(dd, 1H, J ) 9.8, 4.9 Hz), 3.88-3.82 (m, 1H), 3.73 (t, 1H, J ) 9.8
Hz), 3.64 (dd, 1H, J ) 9.8, 3.9 Hz), 3.56 (t, 1H, J ) 9.8 Hz), 3.45
(s, 3H), 2.34 (t, 2H, J ) 6.8 Hz), 2.22 (t, 2H, J ) 6.8 Hz), 2.14 (t,
2H, J ) 6.8 Hz), 1.64-1.56 (m, 2H), 1.52-1.45 (m, 2H), 1.42-
1.14 (m, 20H), 0.87 (t, 3H, J ) 6.8 Hz); 13C NMR (100 MHz,
CDCl3) δ 173.7, 137.0, 129.0, 128.2, 126.1, 101.5, 100.1, 78.7,
77.6, 72.0, 71.8, 68.9, 65.3, 65.2, 62.7, 55.5, 34.3, 31.8, 29.7, 29.5,
29.4, 29.3, 29.1, 28.8, 28.4(2), 24.9, 22.7, 19.2, 19.1, 14.1; HRMS
calcd for C35H50O7 + H 583.3635, found 583.3641.
1
Compound 10C: 11%, colorless crystal, mp 155-157 °C; H
NMR (400 MHz, CDCl3) δ 7.43-7.41 (m, 2H), 7.36-7.32 (m,
3H), 5.48 (s, 1H), 5.31 (t, 1H, J ) 9.7 Hz), 4.78 (d, 1H, J ) 3.7
Hz), 4.28 (dd, 1H, J ) 10.1, 4.6 Hz), 3.87-3.81 (m, 1H), 3.73 (t,
1H, J ) 10.2 Hz), 3.68-3.62 (m, 1H), 3.57 (t, 1H, J ) 9.6 Hz),
3.44 (s, 3H), 2.63-2.53 (m, 4H), 2.21-2.16 (m, 2H), 1.55-1.46
(m, 4 H), 0.95 (t, 1H, J ) 7.3 Hz); 13C NMR (100 MHz, CDCl3)
δ 171.6, 137.0, 129.0, 128.3, 126.2, 101.5, 100.1, 78.6, 78.1, 74.9,
72.7, 71.7, 68.9, 66.1, 65.2, 62.7, 55.6, 33.1, 21.7, 21.1, 15.2, 13.5;
HRMS calcd for C24H28O7 + H 429.1913, found 429.1914.
Reaction of (+)-(4,6-O-Benzylidiene)methyl-R-D-glucopyra-
noside with Heptan-4,6-diynoic Acid Chloride, Total Yield 95%.
Compound 11A: 11%, colorless crystal, mp 120-121 °C; 1H
NMR (400 MHz, CDCl3) δ 7.42-7.40 (m, 2H), 7.36-7.32 (m,
3H), 5.59 (t, 1H, J ) 9.7 Hz), 5.49 (s, 1H), 4.95 (d, 1H, J ) 3.7
Hz), 4.91 (dd, 1H, J ) 9.7, 3.7 Hz), 4.29 (dd, 1H, J ) 10.2, 4.8
Hz), 3.91 (dt, 1H, J ) 9.8, 4.7 Hz), 3.75 (t, 1H, J ) 10.3 Hz), 3.65
(t, 1H, J ) 9.6 Hz), 3.39 (s, 3H), 2.60-2.52 (m, 8H), 1.98 (s, 1H),
1.95 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 170.7, 170.2, 136.9,
129.1, 128.3, 126.2, 101.6, 97.5, 79.1, 76.0, 75.8, 71.9, 69.4, 68.8,
68.1, 65.5, 65.4, 62.3, 55.5, 32.6, 15.0; HRMS calcd for C28H26O7
+ H 491.1706, found 491.1701.
Reaction of (+)-(4,6-O-Benzylidiene)methyl-R-D-glucopyra-
noside with 5,7-Hexadecadiynoic Chloride, Total Yield 92%.
Compound 9A: 19%, colorless crystal, mp 43-45 °C; 1H
NMR (400 MHz, CDCl3) δ 7.45-7.39 (m, 2H), 7.38-7.31 (m,
3H), 5.58 (t, 1H, J ) 9.8 Hz), 5.49 (s, 1H), 4.94 (d, 1H, J ) 3.9
Hz), 4.90-4.86 (m, 1H), 4.29 (dd, 1H, J ) 9.8, 4.9 Hz), 3.90 (dt,
1H, J ) 9.8, 4.9 Hz), 3.78-3.72 (m, 1H), 3.62 (t, 1H, J ) 9.8
Hz), 3.39 (s, 3H), 2.54-2.35 (m, 4H), 2.31 (t, 2H, J ) 6.8 Hz),
2.27-2.18 (m, 6H), 1.84-1.74 (m, 4H), 1.53-1.45 (m, 4H), 1.40-
1.17 (m, 20H), 0.86 (t, 6H, J ) 6.8 Hz); 13C NMR (100 MHz,
CDCl3) δ 172.2, 171.7, 136.9, 129.1, 128.2, 126.2, 101.6, 97.6,
79.3, 78.2, 78.0, 75.8, 75.6, 71.6, 68.8, 66.4, 66.2, 65.0, 62.3, 55.4,
32.8, 32.7, 31.8, 29.1, 29.1, 28.9, 28.3, 23.7, 23.4, 22.7, 19.2, 18.5,
18.4, 14.1; HRMS calcd for C46H62O8 + Na 765.4342, found
765.4354.
1
Compound 9B: semisolid, 66%, H NMR (400 MHz, CDCl3)
1
δ 7.49-7.46 (m, 2H), 7.38-7.35 (m, 3H), 5.53 (s, 1H), 4.93 (d,
1H, J ) 3.9 Hz), 4.79 (dd, 1H, J ) 9.8, 3.9 Hz), 4.27 (dd, 1H, J
) 9.8, 4.9 Hz), 4.17-4.13 (m, 1 H), 3.82 (dt, 1H, J ) 9.8, 4.9
Compound 11B: 61%, colorless crystal, mp 172-174 °C; H
NMR (400 MHz, CDCl3) δ 7.48-7.46 (m, 2H), 7.36-7.34 (m,
3H), 5.50 (s, 1H), 4.92 (d, 1H, J ) 3.7 Hz), 4.78 (dd, 1H, J ) 9.6,
4740 J. Org. Chem., Vol. 71, No. 13, 2006