I. Sylvain et al. / Bioorg. Med. Chem. 10 (2002) 57–69
65
0
(1C, C-1 ose); 112.7 (2C, C-3, 5 aryl); 119.6 (1C, C
0
0
removed in vacuo. Purification by TLC on silica gel
(
or 4 ose); 71.9 (1C, C-3 ose); 74.6 (1C, C-5 ose); 84.5
0
CH Cl /EtOH) gave the desired compound.
2
2
meso); 120.1 (3C, C meso); 127.3 (6C, C-3, 5 tolyl); 131.0
(8C, C b pyrrole); 134.5 (6C, C-2, 6 tolyl); 134.6 (1C, C-
1 aryl); 135.6 (2C, C-2, 6 aryl); 137.3 (3C, C-4 tolyl);
139.3 (3C, C-1 tolyl); 145.0–150.0 (8C, C a pyrrole);
5
-[2-(1-S-(2,3,4,6-tetra-O-acetyl-1-thio-ꢀ-D-galactopyra-
nosyl)-3-thio-propanoxy)-phenyl]-10,15,20-tritolylporphy-
rin (6a). Compound 5a and O-acetylated-1-S-acetyl-1-
thio-b-d-galacto-pyranose (1) gave, after 15 h of reac-
tion, 36 mg of 6a (66%). R 0.40 (CH Cl /EtOH, 99:1).
158.6 (1C, C-4 aryl); 169.8, 170.0, 170.2, 170.4 (4C,
+
CH CO). MS (MALDI) m/z 1078 ([M+H] mono-
3
f
3
2
2
ꢁ
UV–vis (CH Cl ) l (eꢃ10 ) 420 (430.9) 516 (15.7) 550
isotopic). Anal. calcd for C H N O S: C, 71.36; H,
10
2
2
64 60
4
1
(
8.5) 592 (4.9) 646 (6.0). H NMR (CDCl , 400 MHz) d
5.61; N, 5.20. Found: C, 71.25; H, 5.72; N, 5.08.
3
ꢁ
2.70 (2H, br s, NH); 1.23 (2H, m, H-b); 1.36 (2H, m,
H-g); 1.57 (3H, s, OAc); 1.68 (1H, m, H-5 ose); 1.77,
0
.86, 1.87 (9H, s, OAc); 2.71 (9H, s, CH tolyl); 2.81
5-[2-(1-S-(2,3,4,6-Tetra-O-acetyl-1-thio-ꢀ-D-glucopyran-
osyl)-3-thio-propanoxy)-phenyl]-10,15,20-tritolylporphy-
rin (7a). Compound 5a and O-acetylated-1-S-acetyl-1-
thio-b-d-gluco-pyranose (2) gave, after 15 h of reaction,
46 mg of 7a (84%). R 0.54 (CH Cl /EtOH, 96:4). UV–
1
3
0
J=10.2 Hz, H-1 ose); 2.93 (1H, dd, J=11.1–7.3 Hz, H-
(
1H, dd, J=11.1–6.6 Hz, H-6a ose); 2.90 (1H, d,
0
6b ose); 3.85 (1H, dd, J=10.2-3.3 Hz, H-3 ose); 3.97
0
0
f
ꢁ3
2
2
0
1H, t, J=10.2 Hz, H-2 ose); 7.30 (1H, br d, J=8.2 Hz,
(
(
2H, m, H-a); 4.37 (1H, d, J=3.3 Hz, H-4 ose); 4.59
vis (CH Cl ) l (eꢃ10 ) 420 (413.0) 516 (13.9) 550 (7.1)
2
2
0
1
590 (4.0) 648 (5.3). H NMR (CDCl , 400 MHz) d
3
H-3 aryl); 7.38 (1H, ddd, J=8.2–7.4–0.5 Hz, H-5 aryl);
.57 (4H, d, J=7.8 Hz, H-3, 5 tolyl); 7.59 (2H, d, J=7.8
ꢁ2.74 (2H, br s, NH); 0.87 (1H, m, H-g); 0.98 (2H, m,
0
(1H, dd, J=12.5–4.8 Hz, H-6a ose); 1.47, 1.51 (6H, s,
7
H-b); 1.17 (1H, ddd, J=9.2–4.8–2.5 Hz, H-5 ose); 1.32
0
OAc); 1.66 (1H, d, J=9.7 Hz, H-1 ose); 1.72, 1.77 (6H,
Hz, H-3, 5 tolyl); 7.76 (1H, br td, J=8.0–1.7 Hz, H-4
aryl); 8.08 (1H, dd, J=7.4–1.7 Hz, H-6 aryl); 8.16 (6H,
m, H-2, 6 tolyl); 8.80, 8.83, 8.90 (4H, s, H-2, 3, 7, 8 b
pyrrole); 8.88, 8.92 (4H, s, H-12, 13, 17, 18 b pyrrole).
0
0
(9H, s, CH tolyl); 2.87 (1H, m, H-3 ose); 3.84 (1H, m,
s, OAc); 1.78 (1H, m, H-g); 1.81 (1H, m, H-6 ose); 2.69
b
0
3
1
3
0
C NMR (CDCl , 100 MHz) d 20.1, 20.3, 20.4, 20.5
H-a); 3.82 (1H, t, J=9.3 Hz, H-4 ose); 4.01 (1H, m, H-
2 ose); 4.01 (1H, m, H-a); 7.24 (1H, dd, J=7.6–0.5 Hz,
3
0
(
(
4C, CH CO); 21.4 (3C, CH tolyl); 27.7 (1C, C-g); 29.7
3
3
0
1C, C-b); 60.4 (1C, C-6 ose); 66.3 (1C, C-a); 66.4 (1C,
H-3 aryl); 7.45 (1H, ddd, J=8.1–7.4–0.5 Hz, H-5 aryl);
7.57 (4H, d, J=7.8 Hz, H-3, 5 tolyl); 7.60 (2H, d, J=7.8
Hz, H-3, 5 tolyl); 7.72 (1H, ddd, J=8.2–7.6–1.7 Hz, H-4
aryl); 8.06 (1H, dd, J=7.4–1.7 Hz H-6 aryl); 8.20 (6H,
m, H-2, 6 tolyl); 8.73 (1H, d, J=4.8 Hz, H b pyr-
role);8.82 (2H, d, J=4.8 Hz, H b pyrrole);8.85, 8.87,
0
0
0
1C, C-5 ose); 84.4 (1C, C-1 ose); 111.9 (1C, C-3 aryl);
C-4 ose); 67.2 (1C, C-2 ose); 71.0 (1C, C-3 ose); 72.7
(
0
0
1
1
15.9 (1C, C meso); 119.8 (1C, C-5 aryl); 120.0, 120.1,
20.5 (3C, C meso); 127.5, 127.6 (6C, C-3, 5 tolyl); 130.0
(
1C, C-4 aryl); 131.1 (8C, C b pyrrole); 131.4 (1C, C-1
1
3
aryl); 134.7, 134.8 (6C, C-2, 6 tolyl); 135.6 (1C, C-6
aryl); 137.5 (3C, C-4 tolyl); 139.3, 139.4 (3C, C-1 tolyl);
8.88, 8.92, 8.96 (5H, d, J=4.8 Hz, H b pyrrole).
C
NMR (CDCl , 100 MHz) d 20.3, 20.4, 20.6, 20.7 (4C,
3
1
1
45.0–150.0 (8C, C a pyrrole); 158.7 (1C, C-2 aryl);
CH CO); 21.7 (3C, CH tolyl); 27.7 (1C, C-g); 29.9 (1C,
3
3
0
0
69.4, 169.5, 170.0, 170.1 (4C, CH CO). MS (MALDI)
+
C-b); 59.0 (1C, C-6 ose); 66.1 (1C, C-4 ose); 66.7 (1C,
3
0 0
C-a); 70.0 (1C, C-2 ose); 73.0 (1C, C-3 ose); 77.0 (1C,
C-5 ose); 83.3 (1C, C-1 ose); 112.0 (1C, C-3 aryl); 116.1
m/z 1077 ([M+H] monoisotopic). Anal. calcd for
C H N O S: C, 71.36; H, 5.61; N, 5.20. Found: C,
0
0
6
4
60
4
10
7
1.22; H, 5.72; N, 5.17.
(1C, C meso); 119.9 (1C, C-5 aryl); 120.2, 120.3, 120.8
(3C, C meso); 127.5, 127.6, 127.8 (6C, C-3, 5 tolyl);
5
-[4-(1-S-(2,3,4,6-tetra-O-acetyl-1-thio-ꢀ-D-galactopyra-
130.1 (1C, C-4 aryl); 131.1 (8C, C b pyrrole); 131.5 (1C,
C-1 aryl); 134.7, 134.9, 135.0 (6C, C-2, 6 tolyl); 135.3
(1C, C-6 aryl); 137.5, 137.6 (3C, C-4 tolyl); 139.3, 139.4,
139.5 (3C, C-1 tolyl); 145.0–150.0 (8C, C a pyrrole);
nosyl)-3-thio-propanoxy)-phenyl]-10,15,20-tritolylporphy-
rin (6b). Compound 5b and O-acetylated-1-S-acetyl-1-
thio-b-d-galacto-pyranose (1) gave, after 6 h of reac-
tion, 37 mg of 6b (67%). R 0.68 (CH Cl /EtOH, 98:2).
159.0 (1C, C-2 aryl); 168.9, 169.2, 169.4, 170.0 (4C,
f
3
2
2
ꢁ
+
UV–vis (CH Cl ) l (eꢃ10 ) 420 (471.0) 516 (14.3) 552
CH CO). MS (MALDI) m/z 1078.8 ([M+H] mono-
3
2
2
1
(
9.4) 592 (4.7) 650 (4.2). H NMR (CDCl , 400 MHz) d
isotopic). Anal. calcd for C H N O S: C, 71.36; H,
64 60
3
4
10
ꢁ
2.77 (2H, br s, NH); 2.00, 2.05, 2.11, 2.19 (12H, s,
OAc); 2.28 (2H, m, H-b); 2.72 (9H, s, CH tolyl); 3.01
5.61; N, 5.20. Found: C, 71.27; H, 5.65; N, 5.15.
3
(
1H, dt, J=13.1–6.2 Hz, H-g); 3.11 (1H, dt, J=13.1–5.9
5-[4-(1-S-(2,3,4,6-tetra-O-acetyl-1-thio-ꢀ-D-glucopyrano-
syl)-3-thio-propanoxy)-phenyl]-10,15,20-tritolylporphyrin
(7b). Compound 5b and O-acetylated-1-S-acetyl-1-thio-
b-d-gluco-pyranose (2) gave, after 6 h of reaction, 43
mg of 7b (79%). R 0.68 (CH Cl /EtOH, 97:3). UV–vis
0
1H, dd, J=11.3–6.5 Hz, H-6a ose); 4.33 (1H, dd,
Hz, H-g); 3.99 (1H, td, J=6.7–1.0 Hz, H-5 ose); 4.16
0
J=11.3–6.8 Hz, H-6b ose); 4.34 (2H, t, J=6.0 Hz, H-
(
0
0
J=10.0–3.4 Hz, H-3 ose); 5.33 (1H, t, J=10.0 Hz, H-2
a); 4.60 (1H, d, J=10.0 Hz, H-1 ose); 5.10 (1H, dd,
f
ꢁ3
2
2
0
0
(CH Cl ) l (eꢃ10 ) 420 (433.0) 516 (13.7) 552 (8.7) 592
2
2
0
1
ose); 5.47 (1H, dd, J=3.4–1.0 Hz, H-4 ose); 7.25 (1H,
d, J=8.7 Hz, H-3 aryl); 7.28 (1H, d, J=8.6 Hz, H-5
aryl); 7.53 (6H, d, J=7.8 Hz, H-3, 5 tolyl); 8.08 (6H, d,
J=7.8 Hz, H-2, 6 tolyl); 8.10 (2H, d, J=8.6 Hz H-2, 6
aryl); 8.84 (8H, s, H b pyrrole). C NMR (CDCl3,
1
(4.4) 648 (4.6). H NMR (CDCl , 400 MHz) d ꢁ2.71
3
(2H, br s, NH); 2.06, 2.14, 2.15 (12H, s, OAc); 2.30 (2H,
m, H-b); 2.72 (9H, s, CH tolyl); 3.05 (2H, m, H-g); 3.77
3
0
J=12.5–2.5 Hz, H-6 ose); 4.32 (1H, dd, J=12.5–4.8
(1H, ddd, J=9.2–4.6–2.4 Hz, H-5 ose); 4.16 (1H, dd,
0
1
3
a
0
(1H, d, J=9.7 Hz, H-1 ose); 5.15 (1H, dd, J=9.7–8.7
00 MHz) d 20.6, 20.7 (4C, CH CO); 21.5 (3C, CH
Hz, H-6b ose); 4.35 (2H, br t, J=6.9 Hz, H-a); 4.62
3
3
0
0
Hz, H-2 ose); 5.21 (1H, t, J=9.1 Hz, H-4 ose); 5.30
tolyl); 27.3 (1C, C-g); 29.5 (1C, C-b); 61.5 (1C, C-6 ose);
6
0
0
0
0
0
6.4 (1C, C-a); 66.7 (1C, C-2 or 4 ose); 67.3 (1C, C-2