S-But-3-ynyl and gem-dimethyl S-but-3-ynyl Thioglycoside Donors
355
1.7 Hz, 1 H), 3.77–3.82 (m, 1 H), 3.73–3.77 (m, 2 H), 3.65 (dt, J = 9.9, 3.0 Hz,
1 H), 3.55 (dd, J = 10.8, 8.1 Hz, 1 H), 2.99 ppm (s, 3 H). 13C NMR (150 MHz,
CDCl3): δ = 166.0, 166.0, 165.6, 138.4, 138.3, 138.3, 134.0, 133.7, 133.6, 133.3,
132.2, 130.2, 130.1, 130.0, 129.5, 129.4, 129.1, 128.8, 128.7, 128.7, 128.5, 128.4,
128.3, 128.2, 128.2, 128.1, 127.9, 127.7, 123.4, 99.5, 96.6, 79.8, 79.6, 77.6, 77.1,
75.4, 75.3, 75.2, 73.7, 72.3, 70.7, 69.8, 69.6, 68.7, 68.6, 56.2, 55.1. ESIHRMS
[M+Na]+ calculated C63H57NO15Na 1090.36, found 1090.40.
Methyl 3,4,6-tri-O-benzyl-2-deoxy-2-phthalamido-β-D-glucopyrano
syl-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranoside (30) was obtained in
23
62% yield from 15a and 79% yield from 15b under optimal condition. [α]D
= 43.2◦ (c = 1.0, CHCl3). H NMR (600 MHz, CDCl3): δ = 7.81 (br. s., 1 H),
1
7.61–7.74 (m, 2 H), 7.59 (br. s., 1 H), 7.41–7.18 (m, 25 H), 6.97–7.01 (m, 2 H),
6.85–6.95 (m, 3 H), 5.45 (d, J = 8.3 Hz, 1 H), 5.06 (d, J = 11.6 Hz, 1 H), 4.90
(d, J = 11.6 Hz, 1 H), 4.79–4.86 (t, J = 12 Hz, 2 H), 4.72 (d, J = 12.1 Hz, 1
H), 4.65–4.68 (m, 1 H), 4.54–4.59 (m, 2 H), 4.48–4.53 (m, 2 H), 4.44 (d, J =
12.1 Hz, 1 H), 4.27–4.37 (m, 3 H), 4.21 (dd, J = 10.8, 8.4 Hz, 1 H), 3.94–3.99
(t, J = 9.2 Hz, 1 H), 3.89 (t, J = 9.2 Hz, 1 H), 3.78–3.84 (t, J = 9.2 Hz, 1
H), 3.54–3.61 (m, 2 H), 3.48–3.54 (m, 1 H), 3.36–3.46 (m, 4 H), 3.27 (s, 3 H).
13C NMR (150 MHz, CDCl3): δ = 139.9, 138.8, 138.6, 138.3, 138.2, 138.2, 134.0,
128.8, 128.8, 128.7, 128.6, 128.6, 128.6, 128.5, 128.4, 128.4, 128.4, 128.3, 128.3,
128.2, 128.2, 128.1, 128.0, 128.0, 128.0, 127.9, 127.7, 127.7, 127.6, 127.5, 127.4,
127.2, 98.4, 97.8, 80.5, 80.0, 79.6, 79.4, 75.5, 75.5, 75.2, 75.1, 73.8, 73.7, 73.0,
69.7, 68.6, 68.4, 57.1, 55.5, 30.0. ESILRMS [M+Na]+ calculated C63H63NO12Na
1048.42, found 1048.50.
Methyl 3,4,6-tri-O-benzyl-2-deoxy-2-azido-(β)α-D-glucopyranosyl-
(1→6)-2,3,4-tri-O-benzoyl-α-D-glucopyranoside (31) was obtained in 67%
yield (α/β = 1/1) from 17a and 77% yield (α/β = 1/1) from 17b under optimal
condition. Specifically, 31α was characterized as: [α]D = 11.0◦ (c = 1.0,
23
1
CHCl3). H NMR (600 MHz, CDCl3): δ = 7.97–8.00 (m, 2 H), 7.94–7.97 (m, 2
H), 7.84–7.88 (m, 2 H), 7.49–7.54 (m, 2 H), 7.40–7.44 (m, 1 H), 7.22–7.40 (m,
19 H), 7.13–7.17 (m, 2 H), 6.18 (ddd, J = 11.3, 9.5, 1.6 Hz, 1 H), 5.54 (dd, J
= 10.1, 9.5 Hz, 1 H), 5.23–5.27 (m, 2 H), 4.90 (d, J = 10.8 Hz, 1 H), 4.79 (d,
J = 10.8 Hz, 2 H), 4.51–4.57 (m, 2 H), 4.45 (d, J = 12.1 Hz, 1 H), 4.34–4.37
(m, 1 H), 4.29–4.34 (m, 1 H), 4.10 (dd, J = 11.3, 2.1 Hz, 1 H), 3.76 (dd, J =
11.4, 6.6 Hz, 1 H), 3.66 (d, J = 3.1 Hz, 2 H), 3.58–3.64 (m, 1 H), 3.50 (s, 3 H),
3.41–3.45 (m, 2 H), 3.39 (dt, J = 9.9, 3.2 Hz, 1 H). 13C NMR (150 MHz, CDCl3):
δ = 166.2, 166.1, 165.8, 138.3, 138.3, 138.2, 133.8, 133.7, 133.4, 130.3, 130.2,
130.0, 129.6, 129.4, 129.2, 128.8, 128.8, 128.7, 128.7, 128.6, 128.4, 128.2, 128.2,
128.1, 128.0, 102.8, 97.2, 83.4, 77.9, 75.9, 75.4, 75.4, 73.8, 72.4, 70.7, 70.0,
69.2, 68.9, 68.7, 66.9, 55.9. ESILRMS [M+Na]+ calculated C55H53N3O13Na
986.35, found 986.40.
Methyl 3,4,6-tri-O-benzyl-2-deoxy-2-azido-(β)α-D-glucopyranosyl-
(1→4)-2,3,4-tri-O-benzyl-α-D-glucopyranoside (32) was obtained in 44%