n-Pentenyl Glycosides as Precursors to Spacer Functionalities
J . Org. Chem., Vol. 65, No. 4, 2000 961
in the general procedure. Flash chromatography (CHCl3-
MeOH 5:1) yielded 7 (0.266 g, 0.82 mmol) in 88%: [R]D -22.8°
138.0, 138.3, 138.4, 155.5; HRMS calcd for C46H59O8NS [M +
H]+ 786.4040, found 786.4014.
1
(c 1.2, MeOH); H NMR (CD3OD, selected data) δ 1.45-1.66
5-(Th iobu tyl)p en tyl â-D-Glu cop yr a n osid e (13). This
compound was prepared according to the general procedure
starting from 1 (239 mg, 0.96 mmol), AIBN (63 mg, 0.37 mmol),
and butanethiol (1.55 mL, 14.46 mmol). Flash chromatography
CHCl3-MeOH 8:1) of the crude product yielded 13 (247 mg,
0.73 mmol) in 76%: [R]D -12.7° (c 0.9, MeOH); 1H NMR (CD3-
OD, selected data) δ 0.92 (t, 3H), 1.37-1.66 (m, 10H), 2.51 (t
+ t, 2H each), 4.25 (d, 1H, J ) 7.97 Hz); 13C NMR (CD3OD) δ
14.0, 22.9, 26.3, 30.3, 30.5, 32.5, 32.7, 32.9, 62.6, 70.5, 71.5,
74.9, 77.7, 77.9, 104.1. Anal. Calcd for C15H30O16S: C, 53.23;
H, 8.93; S, 9.47. Found: C, 53.11; H, 8.90; S, 9.57.
5-(Th iobu tyl)p en tyl 2,3,4,6-Tetr a -O-a cetyl-â-D-glu cop y-
r a n osid e (14). This compound was prepared according to the
general procedure starting from 2 (111 mg, 0.27 mmol), AIBN
(9 mg, 0.05 mmol), and butanethiol (427 µL, 3.99 mmol).
Purification by flash chromatography gave 14 (126 mg, 0.25
mmol, 94%): [R]D -15.7° (c 1.3, CHCl3); 1H NMR (CDCl3,
selected data): δ 0.91 (t, 3H), 1.36-1.61 (m, 10H), 2.50 (t, 4H),
3.48 (m, 1H), 4.85 (m, 1H), 4.49 (d, 1H, J ) 7.69 Hz); 13C NMR
(CDCl3) δ 13.6, 20.5, 20.6, 20.7, 22.0, 25.1, 29.0, 29.3, 31.7,
31.8, 32.0, 61.9, 68.4, 69.8, 71.3, 72.8, 100.8, 169.2, 169.3, 170.2,
170.6. Anal. Calcd for C23H38O10S: C, 54.53; H, 7.56; S, 6.33.
Found: C, 54.65; H, 7.69; S, 6.37.
5-(Th iobu tyl)pen tyl 2,3,4,6-Tetr a-O-ben zyl-â-D-glu copy-
r a n osid e (15). Pent-4-enyl glucoside 3 (254 mg, 0.42 mmol)
was reacted with AIBN (27 mg, 0.17 mmol) and butanethiol
according to the general procedure. The crude product was
subjected to flash chromatography to give 15 (240 mg, 0.34
mmol, 82%): [R]D +4.8° (c 1.0, CHCl3); 1H NMR (CDCl3,
selected data) δ 0.87 (t, 3H), 1.34-1.1.68 (m, 10H), 2.45 (m,
4H); 13C NMR (CDCl3) δ 13.7, 22.0, 25.5, 29.4, 29.5, 31.8, 31.9,
32.0, 68.9, 69.7, 73.3, 74.6, 74.7, 74.8, 75.5, 77.8, 82.1, 84.6,
103.4, 127.3, 127.4, 127.5, 127.6, 127.7, 127.8, 127.9, 128.1,
137.8, 137.9, 138.3, 138.4; HRMS calcd for C43H55O6S [M +
H]+ 699.3719, found 699.3693.
P en tyl â-D-Glu cop yr a n osid e (16). Pd/C (10%, 35 mg) was
added to a solution of 1 (124 mg, 0.50 mmol) in MeOH (5 mL).
The mixture was hydrogenated (120 psi) for 2 h, filtered
through Celite, and evaporated. Purification of the residue on
a Sephadex LH-20 gel column eluated with MeOH gave 16
(114 mg, 0.46 mmol, 96%): [R]D -16.4° (c 1.7, MeOH); 1H NMR
(CD3OD, selected data) δ 0.92 (t, 3H), 1.33-1.34 (m, 4H), 1.60-
1.65 (m, 2H), 3.49-3.57 (m, 1H), 3.83-3.93 (m, 2H), 4.24 (d,
1H, J ) 7.69 Hz); 13C NMR (CD3OD) δ 14.4, 23.6, 29.3, 30.5,
62.7, 70.8, 71.6, 75.0, 77.8, 78.0, 104.2.
(m, 6H), 2.56 (t, 2H), 2.63 (t, 2H), 4.25 (d, 1H, J ) 7.69 Hz);
13C NMR (CD3OD) δ 26.2, 30.3, 30.6, 32.9, 35.1, 62.4, 62.6,
70.5, 71.5, 74.9, 77.7, 77.9, 104.1. Anal. Calcd for C13H26O7S:
C, 47.84; H, 8.03; S, 9.82. Found: C, 47.71; H, 7.88; S, 9.78.
5-(2-Hyd r oxyth ioeth yl)p en tyl 2,3,4,6-Tetr a -O-a cetyl-â-
D-glu cop yr a n osid e (8). Pent-4-enyl glucoside 2 (104 mg,
0.249 mmol) was reacted with AIBN (8 mg, 0.05 mmol) and
mercaptoethanol (262 µL, 3.73 mmol) according to the general
procedure. Purification of the crude product by flash chroma-
tography (CH2Cl2-acetone 9:1) gave 8 (120 mg, 0.24 mmol,
97%): [R]D -17.7° (c 0.7, CHCl3); 1H NMR (CDCl3, selected
data) δ 1.19-1.62 (m, 6H), 2.00, 2.03, 2.05, 2.09 (s, 3H each),
2.52 (t, 2H), 2.72 (t, 2H), 3.48 (m, 1H), 3.82-3.89 (m, 1H), 4.49
(d, 1H, J ) 7.69 Hz); 13C NMR (CDCl3) δ 20.6 (2 signals), 20.7,
20.8, 25.1, 29.0, 29.3, 31.6, 35.3, 60.4, 62.0, 68.5, 69.9, 71.4,
71.8, 72.9, 100.3, 169.4, 170.3, 170.7. Anal. Calcd for
C
21H34O11S: C, 51.00; H, 6.93; S, 6.48. Found: C, 50.96; H,
6.96; S, 6.37.
5-(Hyd r oxyth ioeth yl)p en tyl 2,3,4,6-Tetr a -O-ben zyl-â-
D-glu cop yr a n osid e (9). This compound was prepared ac-
cording to the general procedure starting from benzylated
pent-4-enyl glucoside 3 (269 mg, 0.44 mmol), AIBN (29 mg,
0.18 mmol), and mercaptoethanol (465 µL, 6.63 mmol). Flash
chromatography (toluene-EtOAc 6:1) of the crude product
gave 9 (260 mg, 0.42 mmol, 86%) as a white solid: [R]D +3.7°
(c 1.1, CHCl3); 1H NMR (CDCl3, selected data) δ 1.33-1.54
(m, 6H), 2.32 (t, 2H), 5.52 (t, 2H), 3.80 (m, 1H), 4.24 (d, 1H, J
) 7.97); 13C NMR (CDCl3) δ 25.4, 29.4, 29.5, 31.5, 32.2, 60.2,
68.9, 73.4, 74.7, 74.9, 75.6, 77.8, 82.2, 84.6, 103.5, 127.4, 127.5,
127.6, 127.6, 127.7, 127.8 (2C), 128.2, 137.9, 138.0, 138.3,
138.4; HRMS calcd for C41H51O7S [M + H]+ 687.3356, found
687.3336.
5-[2-[(ter t-Bu t oxyca r b on yl)a m in o]-1-t h ioe t h yl]p e n -
tyl â-D-Glu cop yr a n osid e (10). According to the general
procedure, 1 (234 mg, 0.94 mmol) was treated with AIBN (77
mg, 0.47 mmol) and 2-[(tert-butoxycarbonyl)amino]-1-ethaneth-
iol (2,52 g, 14.16 mmol) to give, after flash chromatography
(CHCl3-MeOH 8:1), 10 (297 mg, 0.70 mmol, 74%): [R]D -18.5°
1
(c 1.1, MeOH); H NMR (CD3OD, selected data) δ 1.43-1.67
(s, 9H, m, 6H), 2.53-2.60 (2t, 2H each), 4.25 (d, 1H, J ) 7.69
Hz); 13C NMR (CD3OD): δ 26.2, 28.7, 30.3, 30.5, 32.5, 32.6,
41.3, 62.6, 70.5, 71.5, 74.9, 77.7, 77.9, 104.1, 156.4. Anal. Calcd
for C18H35O8NS: C, 50.81; H, 8.29; S, 7.54. Found: C, 50.67;
H, 8.17; S, 7.52.
Anal. Calcd for C11H22O6: C, 52.79; H, 8.86. Found: C, 52.70;
H, 8.72.
5-[2-[(ter t-Bu t oxyca r b on yl)a m in o]-1-t h ioe t h yl]p e n -
tyl 2,3,4,6-Tetr a -O-a cetyl-â-D-glu cop yr a n osid e (11). Pent-
4-enyl glucoside 2 (200 mg, 0.479 mmol) was reacted with
AIBN (24 mg, 0.14 mmol) and 2-[(tert-butoxycarbonyl)amino]-
1-ethanethiol (1.28 g, 7.18 mmol) as described in the general
procedure. Flash chromatography (toluene-EtOAc 3:1) of the
crude product gave 11 (234 mg, 0.39 mmol, 82%): [R]D -14.4°
(c 1.0, CHCl3); 1H NMR (CDCl3, selected data) δ 1.45-1.61 (s,
9H, m, 6H), 2.52 (t, 2H), 2.63 (t, 2H), 3.30 (m, 2H), 3.48 (m,
1H), 3.87 (m, 1H), 4.50 (d, 1H, J ) 7.97 Hz); 13C NMR (CDCl3)
δ 20.6 (2 signals), 20.7 (2 signals), 25.0, 28.4, 29.0, 29.2, 31.6,
32.2, 39.9, 61.9, 68.3, 69.7, 71.2, 71.6, 72.7, 100.6, 155.5, 169.0,
169.1, 170.0, 170.3; HRMS calcd for C26H44O12NS [M + H]+
594.2540, found 594.2590.
P en tyl 2,3,4,6-Tetr a -O-a cetyl-â-D-glu cop yr a n osid e (17).
2 (124 mg, 0.30 mmol) was dissolved in EtOAc (4 mL), and
Pd/C (10%, 25 mg) was added. The mixture was hydrogenated
(120 psi) for 2 h, filtered through Celite, and evaporated. Flash
chromatography (toluene-EtOAc 3:1) of the residue gave 17
(122 mg, 0.29 mmol, 98%): [R]D -17.5° (c 1.2, CHCl3); 1H NMR
(CDCl3, selected data) δ 0.89 (t, 3H), 1.24-1.34 (m, 4H), 1.55-
1.1.59 (m, 2H), 3.47 (m, 1H), 3.87 (m, 1H), 4.50 (d, 1H, J )
7.97 Hz); 13C NMR (CDCl3) δ 14.0, 20.6, 20.7, 22.3, 28.0, 29.1,
62.0, 68.5, 70.2, 71.4, 71.7, 72.9, 100.9, 169.3, 169.4, 170.3,
170.7.
Anal. Calcd for C19H30O10: C, 54.54; H, 7.23. Found: C,
54.53; H, 7.29.
5-[2-[(ter t-Bu t oxyca r b on yl)a m in o]-1-t h ioe t h yl]p e n -
tyl 2,3,4,6-Tetr a -O-ben zyl-â-D-glu cop yr a n osid e (12). This
compound was prepared according to the general procedure
starting from pent-4-enyl glucoside 3 (210 mg, 0.34 mmol),
AIBN (28 mg, 0.17 mmol), and 2-[(tert-butoxycarbonyl)amino]-
1-ethanethiol (0.921 g, 5.17 mmol). The crude product was
subjected to flash chromatography (toluene-EtOAc 8:1) to give
P en tyl 2,3,4,6-Tetr a-O-ben zyl-â-D-glu copyr an oside (18).
To a solution of 3 (250 mg, 0.41 mmol) in EtOAc (6 mL) was
added tris(triphenylphosphine)rhodium(I) chloride (25 mg),
and the mixture was hydrogenated in a Parr apparatus (120
psi). After 2 h, the mixture was concentrated and purified by
flash chromatography (toluene-EtOAc 4:1) to give 18 (234 mg,
0.38 mmol, 93%): [R]D +5.8° (c 1.0, CHCl3): 1H NMR (CDCl3,
selected data) δ 0.82 (t, 3H), 1.28-1.33 (m, 4H), 1.57-1.96 (m,
2H), 3.90 (m, 1H), 4.32 (d, 1H, J ) 7.97 Hz); 13C NMR (CDCl3)
δ 14.1, 22.6, 28.4, 29.5, 69.0, 70.1, 73.4, 74.8, 74.8, 74.9, 75.6,
77.9, 82.2, 84.7, 103.6, 127.4, 127.5, 127.6, 127.7, 127.8, 128.0,
128.2, 138.0, 138.1, 138.5. HRMS calcd for C39H47O6 [M + H]+-
611.3373, found 611.3276.
1
12 (160 mg, 0.20 mmol, 59%): [R]D +4.6° (c 1.0, CHCl3); H
NMR (CDCl3, selected data): δ 1.43-1.68 (s, 9H, m, 6H), 2.47
(t, 2H), 2.59 (t, 2H), 3.27 (m, 2H), 4.37 (d, 1H, J ) 7.69 Hz);
13C NMR (CDCl3) δ 25.0, 25.4, 28.1, 28.4, 29.3, 29.4, 31.6, 32.2,
39.8, 68.9, 69.6, 73.4, 74.7, 74.9, 75.6, 76.5, 77.8, 82.1, 84.6,
103.5, 127.4, 127.5, 127.7, 127.8, 127.9, 128.1, 129.5, 137.9,