1768
K. A. Stubbs et al. / Carbohydrate Research 341 (2006) 1764–1769
was added and the resulting mixture was stirred vigor-
ously at room temperature (18 h). After a crystalline
precipitate was observed, the solid was collected by
filtration and successively washed with dichlorometh-
ane, water and diethyl ether. The resultant solid was left
overnight to air dry. Recrystallisation of the solid from
ethanol gave the desired thioglycosides in yields ranging
from 60% to 76%. 4-Nitrophenyl 2-acetamido-2-deoxy-
1-thio-b-D-glucopyranoside 221 and 4-tolulyl 2-acetam-
ido-2-deoxy-1-thio-b-D-glucopyranoside 522 are known
compounds and their physical characteristics were
consistent with those found in the literature. The yield
reported for 4-methylumbelliferyl 2-acetamido-2-deoxy-
1-thio-b-D-glucopyranoside 6 is for two steps.
H-6Ar), 7.32 (1H, m, H-2Ar), 7.20 (1H, ddd, JH5Ar–F =
8.4, 10.8, H-5Ar), 4.72 (1H, d, JH1–H2 = 8.4, H-1), 3.89
(1H, dd, JH5–H6 = 1.2, JH6–H6 = 11.6, H-6), 3.73 (1H,
dd, JH2–H3 = 10.0, H-3), 3.67 (1H, ddd, JH4–H5 = 9.6,
JH5–H6 = 4.4, H-5), 3.44 (1H, dd, H-2), 3.34–3.31 (2H,
m, H-4/H-6), 2.00 (3H, s, Ac). 13C NMR (100 MHz,
CD3OD) d 173.6 (1C, C@O), 151.3 (1C, dd, JC–F = 11,
244 Hz, C-3Ar), 132.0 (1C, d, JC–F = 308 Hz, C-4Ar),
132.0 (1C, d, JC–F = 13 Hz, C-1Ar), 129.8 (1C, C-6Ar),
121.9 (1C, d, JC–F = 18 Hz, C-5Ar), 118.5 (1C, d,
JC–F = 18 Hz, C-2Ar), 88.1 (1C, C-1), 82.2, 77.4, 71.9,
62.9, 56.1 (5C, C-2/C-3/C-4/C-5/C-6), 23.0 (1C, Ac).
Anal. Calcd for C14H17F2NO5S: C, 48.13; H, 4.90; N,
4.01. Found: C, 48.39; H, 5.01; N, 4.15.
1.2.2. Method B. To a mixture of 2-acetamido-3,4,6-
tri-O-acetyl-2-deoxy-a-D-glucopyranosyl chloride 1.18
(1 equiv), benzyltriethylammonium chloride (1 equiv),
triphenylphosphine (1 equiv) and the acceptor thiophe-
nol (0.7 equiv), sufficient dichloromethane (1 volume)
was added and the resulting mixture treated as for
Method A. Recrystallisation of the solid from ethanol
gave the 3-nitrophenyl 2-acetamido-2-deoxy-1-thio-b-
D-glucopyranoside 9 in a yield of 62%.
1.5. 4-Methylumbelliferyl 2-acetamido-2-deoxy-1-thio-b-
D-glucopyranoside (6)
1H NMR (400 MHz, (CD3)2SO) d 7.91 (1H, d, JH2–NH
=
9.2, NH), 7.66 (1H, d, JH5Ar–H6Ar = 8.4, H-5Ar), 7.38
(1H, s, H-8Ar), 7.33 (1H, d, H-6Ar), 6.34 (1H, s, H-3Ar),
5.20 (2H, br s, OH), 4.91 (1H, d, JH1–H2 = 10.4, H-1),
4.70 (1H, br s, OH), 3.74–3.63 (2H, br s), 3.47-3.42
(3H, br s), 3.16 (1H, br s), 2.40 (3H, s, CH3), 1.82 (3H,
s, Ac). 13C NMR (100 MHz, (CD3)2SO) d 169.1, 159.5
(2C, C@O), 153.0, 152.9, 141.4, 125.3, 123.6, 117.2,
114.5, 113.4 (8C, Ar), 84.9 (1C, C-1), 81.2, 75.2, 70.1,
60.8, 54.0 (5C, C-2/C-3/C-4/C-5/C-6), 23.0 (1C, COCH3),
17.9 (1C, CH3). Anal. Calcd for C18H21NO7S: C, 54.67;
H, 5.35; N, 3.54. Found: C, 54.52; H, 5.12; N, 3.34.
1.2.3. Method C. The thiol was prepared according to
the procedure of Overman et al.19 and the reagents for
the phase transfer reaction were added as in Method
A. 4-Chlorophenyl 2-acetamido-2-deoxy-1-thio-b-D-
glucopyranoside 7 was prepared in a yield of 49% and
4-methoxyphenyl 2-acetamido-2-deoxy-1-thio-b-D-gluco-
pyranoside 8 in a yield of 53%.
1.6. 4-Chlorophenyl 2-acetamido-2-deoxy-1-thio-b-D-
glucopyranoside (7)
1.3. 2-Nitrophenyl 2-acetamido-2-deoxy-1-thio-b-D-
glucopyranoside (3)
1H NMR (400 MHz, CD3OD) d 7.49, 7.29 (4H, AA0BB0,
Ar), 4.75 (1H, d, JH1–H2 = 10.4, H-1), 3.88 (1H, dd,
1H NMR (400 MHz, (CD3OD/(CD3)2SO)) d 8.11 (1H,
dd, JH3Ar–H5Ar = 1.2, JH3Ar–H4Ar = 7.6, H-3Ar), 7.92
(1H, dd, JH4Ar–H6Ar = 1.2, JH5Ar–H6Ar = 8.0, H-6Ar),
7.66 (1H, ddd, JH4Ar–H5Ar = 8.0, H-5Ar), 7.39 (1H, ddd,
H-4Ar), 4.97 (1H, d, JH1–H2 = 10.4, H-1), 3.92 (1H, dd,
JH5–H6 = 2.0, JH6–H6 = 12.4, H-6), 3.88 (1H, dd, JH2–H3
ꢀ
JH3–H4 = 10.0, H-3), 3.70 (1H, dd, JH5–H6 = 5.6, H-6),
3.46 (1H, dd, H-2), 3.38–3.32 (2H, m, H-4/H-5), 1.99
(3H, s, Ac). 13C NMR (100 MHz, CD3OD) d 173.5 (1C,
C@O), 134.5, 134.4, 133.9, 129.9 (4C, Ar), 88.1 (1C,
C-1), 82.2, 77.4, 71.9, 62.9, 56.2 (5C, C-2/C-3/C-4/C-5/
C-6), 23.0 (1C, Ac). Anal. Calcd for C14H18ClNO5S: C,
48.34; H, 5.22; N, 4.03. Found: C, 48.55; H, 5.24; N, 4.25.
JH5–H6 = 1.2, JH6–H6 = 12.4, H-6), 3.89 (1H, dd, JH2–H3
ꢀ
JH3–H4 = 9.6, H-3), 3.69 (1H, dd, JH5–H6 = 6.0, H-6),
3.54 (1H, dd, H-2), 3.48–3.38 (2H, m, H-4/H-5), 1.96
(3H, s, Ac). 13C NMR (100 MHz, CD3OD/(CD3)2SO)
d 169.1 (1C, C@O), 146.2, 135.0, 134.2, 128.5, 126.0,
125.3 (6C, Ar), 84.0 (1C, C-1), 81.1, 75.3, 70.0, 60.7,
53.9 (5C, C-2/C-3/C-4/C-5/C-6), 22.9 (1C, COCH3).
Anal. Calcd for C14H18N2O7S: C, 46.92; H, 5.06; N,
7.82. Found: C, 46.83; H, 5.03; N, 7.71.
1.7. 4-Methoxyphenyl 2-acetamido-2-deoxy-1-thio-b-D-
glucopyranoside (8)
1H NMR (400 MHz, CD3OD) d 7.47, 6.86 (4H,
AA0BB0, Ar), 4.58 (1H, d, JH1–H2 = 10.4, H-1), 3.85
(1H, dd, JH5–H6 = 2.4, JH6–H6 = 12.4, H-6), 3.78 (3H,
s, OCH3), 3.67 (1H, dd, JH2–H3 ꢀ JH3–H4 = 10.4, H-3),
3.66 (1H, dd, JH5–H6 = 5.6, H-6), 3.43 (1H, dd, H2),
3.32 (1H, m, H-4), 3.23 (1H, ddd, JH4–H5 = 9.6, H-5),
2.01 (3H, s, Ac). 13C NMR (100 MHz, CD3OD) d
173.5 (1C, C@O), 161.4, 136.0, 125.2, 115.4 (4C, Ar),
1.4. 3,4-Difluorophenyl 2-acetamido-2-deoxy-1-thio-b-D-
glucopyranoside (4)
1H NMR (400 MHz, CD3OD) d 7.51 (1H, ddd,
JH2Ar–H6Ar = 2.4,
JH5Ar–H6Ar = 8.4,
JH6Ar–F = 7.6,