The Journal of Organic Chemistry
Page 24 of 42
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.0, CHCl ). H NMR (600 MHz, CDCl ) δ 5.25 (dd, J = 10.7, 9.5 Hz, 1H, H ), 5.21 (t, J = 10.7
3 3 4a
Hz, 1H, H ), 5.06 (dd, J = 11.0, 9.5 Hz, 1H, H ), 4.95 (t, J = 10.7 Hz, 1H, H ), 4.93 (t, J = 9.5
2
b
2a
4b
Hz, 1H, H ), 4.57 (d, J = 10.7 Hz, 1H, H ), 4.23 (dd, J = 12.0, 5.3 Hz, 1H, H ), 4.18 (dd, J =
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a
1b
6a
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0
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2.0, 5.6 Hz, 1H, H ), 4.13 (dd, J = 12.0, 3.3 Hz, 1H, H ), 4.09 (dd, J = 12.0, 3.2 Hz, 1H, H ),
6b 6’a 6’b
.99 (d, J = 11.0 Hz, 1H, H ), 3.34 (m, 1H, H ), 3.16 (m, 1H, H ), 3.01 (t, J = 10.8 Hz, 1H,
1
a
5b
5a
H ), 2.35 (s, 3H, SCOCH ), 2.12 (s, 3H), 2.10 (s, 3H), 2.06 (s, 3H), 2.02 (s, 3H), 1.99 (s, 3H),
3b
3
1
3
1
1
6
.98 (s, 3H), 1.95 (s, 3H). C NMR (151 MHz, CDCl ) δ 191.9 (SCOCH ), 170.5, 170.4, 169.7,
3
3
69.3, 169.2, 169.1, 168.9 (OCOCH ), 75.2 (C ), 74.4 (C ), 72.9 (C ), 71.6 (C ), 70.2 (C ),
3
2b
3a
2a
4a
4b
1.6 (C ), 61.0 (C ), 55.1 (C ), 50.5 (C ), 47.2 (C ), 45.8 (C ), 44.6 (C ), 30.5 (SCOCH ),
6a
6b
3b
1a
5b
1b
5a
3
+
20.8, 20.8, 20.6, 20.6, 20.4, 20.4, 20.2 (OCOCH ). HRMS m/z [M+Na] calcd for
3
C H O NaS 765.0991, found 765.0989.
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38 15
4
2
,3,4,6-Tetra-O-acetyl-5-thio-β-D-glucopyranosyl-(1→3)-2,4,6-tri-O-acetyl-3,5-dideoxy-3,5-
dithio-β-D-glucopyranosyl-(1→3)-1,2-O;5-S,6-O-di-isopropylidene-3,5-dideoxy-3,5-dithio-
α-D-glucofuranose (25). Compounds 24 (615 mg, 0.83 mmol) and 18 (507 mg, 1.24 mmol)
were subjected to coupling according to general procedure A to give 25 (510 mg, 64%) as white
crystals. Mp 163-164 °C. [α]23 = +26.5° (c 0.4, CH Cl ). H NMR (600 MHz, CDCl ) δ 5.87 (d,
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D
2
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3
J1c,2c = 3.6 Hz, 1H, H ), 5.26 (dd, J4a,5a = 10.7 Hz, J4a,3a = 9.6 Hz, 1H, H ), 5.16 (t, J = 10.6 Hz,
1c
4a
1
4
H, H ), 5.08 (dd, J
= 11.0 Hz, J2a,3a = 9.5 Hz, 1H, H ), 5.02 – 4.94 (m, 2H, H & H ),
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b
1a,2a
2a
4b
3a
.71 (d, J1c,2c = 3.6 Hz, 1H, H ), 4.39 (dd, J
= 10.5 Hz, J3c,4c = 4.0 Hz, 1H, H ), 4.32 (dd,
4c
2c
4c,5c
J6c,5c = 10.0 Hz, J6c,6’c = 2.5 Hz, 1H, H ), 4.25 (dd, J
= 12.0 Hz, J6a,5a = 5.1 Hz, 1H, H6a),
6c
6a,6’a
4
.22 (dd, J6b,6’b = 12.0 Hz, J6b,5b = 5.4 Hz, 1H, H ), 4.15 – 4.11 (m, 2H, H & H ), 4.09 (dd,
6b 6’a 6’c
J6b,6’b = 12.0 Hz, J6’b,5b = 3.3 Hz, 1H, H ), 4.00 (d, J
= 11.0 Hz, 1H, H ), 3.83 (d, J
=
6’b
1a,2a
1a
1b,2b
10.6 Hz, 1H, H ), 3.64 (m, 1H, H ), 3.55 (d, J
= 4.0 Hz, 1H, H ), 3.25 – 3.14 (m, 2H, H
3c 5a
1
b
5c
3c, 4c
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