4
M. CHEN ET AL.
þ
J ¼ 7.9 Hz, 1H), 7.62 (d, J ¼ 9.9 Hz, 1H), 7.47 (t, J ¼ 8.0 Hz, [M þ H] calculated for C H BrN O S: m/z 629.0550,
23
25
4 10
1
H), 6.63 (s, 1H), 4.28 (dd, J ¼ 12.5, 4.4 Hz, 1H), 4.12 (dd, found 629.0552.
J ¼ 12.5, 2.1 Hz, 1H), 3.85–3.82 (m, 1H), 2.04 (s, 6H), 2.02
(2R,3R,4S,5R)-2-(acetoxymethyl)-6-[(3-(2-fluorobenza-
1
3
(
s, 3H), 2.00 (s, 3H); C NMR (125 MHz, CDCl ) d: 170.69, mido)-1H-1,2,4-triazol-5-yl)thio]tetrahydro-2H-pyran-3,4,5-
70.19, 169.43, 169.39, 166.06, 159.30, 158.52, 134.11, triyl triacetate (4k). White solid, yield 70%, 183–185 C; H
33.57, 132.90, 131.20, 129.54, 129.48, 82.48, 76.19, 73.87, NMR (600 MHz, CDCl
3
ꢀ
1
1
1
6
) d: 8.25 (s, 1H), 8.10 (d, J ¼ 7.9 Hz,
3
1
1
2
2
1
H), 7.62 (d, J ¼ 9.9 Hz, 1H), 7.47 (t, J ¼ 8.0 Hz, 1H), 6.63 (s,
H), 4.28 (dd, J ¼ 12.5, 4.4 Hz, 1H), 4.12 (dd, J ¼ 12.5,
.1 Hz, 1H), 3.86–3.82 (m, 1H), 2.04 (s, 6H), 2.02 (s, 3H),
.00 (s, 3H); C NMR (150 MHz, DMSO-d ) d: 170.71,
70.20, 169.37, 169.32, 165.20, 159.06, 157.61, 134.28,
9.35, 67.90, 61.81, 20.73, 20.66, 20.65, 20.63; HRMS
þ
[
M þ H] calculated for C H ClN O S: m/z 585.1048,
23
25
4 10
found 585.1055.
13
(
2R,3R,4S,5R)-2-(acetoxymethyl)-6-[(3-(4-chlorobenza-
6
mido)-1H-1,2,4-triazol-5-yl)thio]tetrahydro-2H-pyran-3,4,5-
ꢀ
130.81, 123.85, 116.27, 116.13, 82.56, 76.10, 73.91, 69.32,
triyl triacetate (4g). White solid, yield 71%, m.p. 193–195 C;
þ
1
6
7.92, 61.64, 20.73, 20.61; HRMS [M þ H] calculated for
H NMR (600 MHz, CDCl ) d: 8.25 (s, 1H), 8.10 (d,
3
C H FN O S: m/z 569.1352, found 569.1349.
2
3
25
4 10
J ¼ 7.9 Hz, 1H), 7.62 (d, J ¼ 9.9 Hz, 1H), 7.47 (t, J ¼ 8.0 Hz,
(
2R,3R,4S,5R)-2-(acetoxymethyl)-6-[(3-(3-fluorobenza-
mido)-1H-1,2,4-triazol-5-yl)thio]tetrahydro-2H-pyran-3,4,5-
triyl triacetate (4l). White solid, yield 68%, m.p. 184–185 C;
H NMR (600 MHz, CDCl ) d: 8.25 (s, 1H), 8.10 (d,
1
H), 6.63 (s, 1H), 4.28 (dd, J ¼ 12.5, 4.4 Hz, 1H), 4.12 (dd,
J ¼ 12.5, 2.1 Hz, 1H), 3.86–3.83 (m, 1H), 2.04 (s, 6H), 2.02
ꢀ
1
3
(
s, 3H), 2.00 (s, 3H); C NMR (150 MHz, CDCl ) d: 170.62,
3
1
3
1
1
6
70.18, 169.38, 169.36, 166.43, 159.00, 158.40, 140.27,
32.83, 129.59, 128.54, 82.52, 76.18, 73.85, 69.40, 68.08,
J ¼ 7.9 Hz, 1H), 7.62 (d, J ¼ 9.9 Hz, 1H), 7.47 (t, J ¼ 8.0 Hz,
þ
1H), 6.63 (s, 1H), 4.28 (dd, J ¼ 12.5, 4.4 Hz, 1H), 4.12 (dd,
13
1.97, 20.71, 20.64, 20.62; HRMS [M þ H] calculated for
J ¼ 12.5, 2.1 Hz, 1H), 3.83–3.79 (m, 1H), 2.04 (s, 6H), 2.02
C H ClN O S: m/z 585.1048, found 585.1053.
2
3
25
4
10
(
s, 3H), 2.00 (s, 3H); C NMR (150 MHz, DMSO-d ) d:
6
(
2R,3R,4S,5R)-2-(acetoxymethyl)-6-[(3-(2-bromobenza-
1
1
7
70.69, 170.20, 169.43, 169.39, 159.12, 158.55, 129.92,
29.87, 127.16, 127.14, 120.77, 120.63, 118.54, 118.37, 82.50,
mido)-1H-1,2,4-triazol-5-yl)thio]tetrahydro-2H-pyran-3,4,5-
triyl triacetate (4h). White solid, yield 66%, m.p.
2
ꢀ
06–208 C; H NMR (600 MHz, CDCl ) d: 7.68 (d,
3
1
6.20, 73.86, 69.36, 67.96, 61.83, 20.69, 20.62, 20.60; HRMS
þ
[
M þ H] calculated for C H FN O S: m/z 569.1352,
2
3
25
4
10
J ¼ 7.4 Hz, 1H), 7.58–7.31 (m, 3H), 6.63 (s, 2H), 5.31–4.91
found 569.1349.
(
m, 4H), 4.20 (dd, J ¼ 12.5, 4.0 Hz, 1H), 3.95 (dd, J ¼ 12.6,
(
2R,3R,4S,5R)-2-(acetoxymethyl)-6-[(3-(4-fluorobenza-
2
2
1
1
6
.0 Hz, 1H), 3.54–3.50 (m, 1H), 2.05 (s, 3H), 2.02 (s, 6H),
mido)-1H-1,2,4-triazol-5-yl)thio]tetrahydro-2H-pyran-3,4,5-
triyl triacetate (4m). White solid, yield 60%, m.p.
1
3
.01 (s, 3H); C NMR (150 MHz, DMSO-d ) d: 170.69,
6
70.21, 169.37, 169.28, 167.31, 159.36, 157.49, 134.72,
33.00, 132.33, 129.57, 126.96, 120.04, 82.60, 76.01, 73.91,
9.27, 67.83, 61.55, 20.76, 20.63, 20.62, 20.59; HRMS
ꢀ
80–182 C; H NMR (600 MHz, CDCl ) d: 8.32 (d,
3
1
1
J ¼ 9.0 Hz, 2H), 7.20 (d, J ¼ 17.3 Hz, 2H), 6.57 (s, 1H), 5.46
d, J ¼ 10.3 Hz, 2H), 5.38 (t, J ¼ 10.0 Hz, 1H), 5.13 (dd,
J ¼ 9.7, 3.4 Hz, 1H), 4.23–3.97 (m, 3H), 2.15 (s, 3H), 2.05 (s,
(
þ
[
M þ H] calculated for C H BrN O S: m/z 629.0550,
23
25
4 10
found 629.0552.
13
3
H), 2.00 (s, 3H), 2.00 (s, 3H); C NMR (150 MHz, DMSO-
(
2R,3R,4S,5R)-2-(acetoxymethyl)-6-[(3-(3-bromobenza-
d6) d: 170.33, 170.23, 170.04, 170.02, 169.60, 166.25, 159.10,
58.54, 156.49, 134.37, 134.31, 115.54, 115.40, 83.15, 74.74,
mido)-1H-1,2,4-triazol-5-yl)thio]tetrahydro-2H-pyran-3,4,5-
1
7
ꢀ
triyl triacetate (4i). White solid, yield 58%, m.p. 207–209 C;
1.84, 67.13, 66.84, 61.35, 20.74, 20.68, 20.66, 20.59; HRMS
1
H NMR (600 MHz, CDCl ) d: 8.25 (s, 1H), 8.10 (d,
þ
3
[M þ H] calculated for C H FN O S: m/z 569.1352,
23
25
4
10
J ¼ 7.9 Hz, 1H), 7.62 (d, J ¼ 9.9 Hz, 1H), 7.47 (t, J ¼ 8.0 Hz,
found 569.1349.
2R,3R,4S,5R)-2-(acetoxymethyl)-6-[(3-(2-nitrobenza-
1
H), 6.63 (s, 1H), 4.28 (dd, J ¼ 12.5, 4.4 Hz, 1H), 4.12 (dd,
(
J ¼ 12.5, 2.1 Hz, 1H), 3.84–3.82 (m, 1H), 2.04 (s, 6H), 2.02 (s,
mido)-1H-1,2,4-triazol-5-yl)thio]tetrahydro-2H-pyran-3,4,5-
triyl triacetate (4n). Yellow solid, yield 63%, m.p.211–213 C;
1
3
ꢀ
3
1
1
6
H), 2.00 (s, 3H); C NMR (150 MHz, DMSO-d ) d: 170.68,
6
1
70.16, 169.52, 169.43, 169.39, 136.62, 136.53, 134.02, 133.13,
H NMR (600 MHz, CDCl ) d: 8.32 (d, J ¼ 9.0 Hz, 2H), 7.20
3
30.07, 129.92, 129.81, 128.68, 82.34, 76.24, 73.85, 69.42, (d, J ¼ 17.3 Hz, 2H), 6.57 (s, 1H), 5.46 (d, J ¼ 10.3 Hz, 2H),
þ
7.87, 61.83, 20.75, 20.71, 20.64, 20.61; HRMS [M þ H] cal- 5.38 (t, J ¼ 10.0 Hz, 1H), 5.13 (dd, J ¼ 9.7, 3.4 Hz, 1H),
culated for C H BrN O S: m/z 629.0550, found 629.0546.
4.23–3.97 (m, 3H), 2.15 (s, 3H), 2.05 (s, 3H), 2.00 (s, 3H),
2
3
25
4 10
13
(
2R,3R,4S,5R)-2-(acetoxymethyl)-6-[(3-(4-bromobenza-
2.00 (s, 3H); C NMR (150 MHz, DMSO-d ) d: 170.74,
6
mido)-1H-1,2,4-triazol-5-yl)thio]tetrahydro-2H-pyran-3,4,5-
170.18, 169.38, 169.32, 165.97, 156.95, 147.02, 134.18,
ꢀ
triyl triacetate (4j). White solid, yield 60%, m.p. 204–205 C; 132.07, 129.62, 129.07, 128.77, 123.87, 82.54, 75.91, 73.87,
1
þ
H NMR (600 MHz, CDCl ) d: 8.25 (s, 1H), 8.10 (d, 69.34, 67.78, 61.47, 20.74, 20.61, 20.59; HRMS [M þ H] cal-
3
J ¼ 7.9 Hz, 1H), 7.62 (d, J ¼ 9.9 Hz, 1H), 7.47 (t, J ¼ 8.0 Hz, culated for C H N O S: m/z 596.1288, found 596.1290.
23
25 5 12
1
H), 6.63 (s, 1H), 4.28 (dd, J ¼ 12.5, 4.4 Hz, 1H), 4.12 (dd,
J ¼ 12.5, 2.1 Hz, 1H), 3.86–3.82 (m, 1H), 2.04 (s, 6H), 2.02
13
Antifungal activity test in vitro
(s, 3H), 2.00 (s, 3H); C NMR (150 MHz, DMSO-d ) d:
6
1
1
7
70.68, 170.16, 169.52, 169.43, 169.39, 136.62, 136.53, Antifungal activities of the target compounds against
34.02, 133.13, 130.07, 129.92, 129.81, 128.68, 82.34, 76.24, Gibberella zeae (G. zeae), Botryosphaeria dothidea (B. dothi-
3.85, 69.42, 67.87, 61.83, 20.75, 20.71, 20.64, 20.61; HRMS dea), Phompsis sp, Phytophthora infestans (P. infestans), and