G. Garcia et al. / Tetrahedron 67 (2011) 4924e4932
4929
(4.8). Anal. Calcd for (C53H36N4O3) 4H2O: C, 74.98; H, 5.22; N, 6.60.
Found: C, 74.39; H, 4.98; N, 6.06.
(C1 phenyl), 150.3 (C phenoxy), 136.2 (C phenyl), 131.7 (C pyrr.),
122.9 (C triazole), 112.4 (C phenoxy), 96.9 (C1 sugar), 69.3 (C2
sugar), 68.9 (C3 sugar), 68.6 (C5 sugar), 65.9 (C4 sugar), 64.0
(CeOesugar), 62.3 (C6 sugar), 60.4 (CH2), 47.1 (CH2), 29.9 (CH2),
29.6 (C acetyl), 20.9 (C acetyl), 20.8 (C acetyl), 20.6 (C acetyl), 20.6 (C
4.2. General procedure followed for metalation of porphyrins
8 and 9
acetyl). UVevis spectrum in CH2Cl2: lmax nm (3 )
, L mmolꢀ1 cmꢀ1
To a well-stirred solution of porphyrin (223
m
mol, 1 equiv) in
423 (439.0), 551 (17.4), 594 (6.9). MALDI-TOF MS calcd for
C104H109N13O33Zn, 2132.66 (m/z 100%), found 2133.61 [MþH]þ and
2156.59 [MþNa]þ. Anal. Calcd for (C104H109N13O33Zn) 1H2O: C,
58.03; H, 5.20; N, 8.46. Found: C, 58.02; H, 5.26; N, 8.02.
CHCl3 (50 mL) was added zinc acetate (1.11 mmol, 5 equiv) in so-
lution of methanol (25 mL) and the mixture was refluxed for 1 h.
CH2Cl2 was added to the crude. The organic layer was washed with
water (3ꢄ), dried over MgSO4, filtered, and concentrated under
reduced pressure, giving Zn-8 and Zn-9 as a purple powder in
quantitative yield. Zn-8 and Zn-9 were used without further
purification. Zn-8: UVevis spectrum in CH2Cl2: lmax nm (normal-
ized absorbance) 423 (1), 553 (0.07), 590 (0.05). Zn-9: UVevis
spectrum in CH2Cl2: lmax nm (normalized absorbance) 422 (1), 551
(0.09), 594 (0.02).
4.2.3. 5,10,15-Tris{4-[N-(20,30,40,60-tetra-O-acetyl-
b-D-glucopyr-
anosyloxyethoxy)ethoxy]-(400-methylenoxytriazole)-phenyl}-20-phe-
nylporphyrin zinc complex (Zn-12). In a reactor were introduced
solutions of Zn-9 (24
ethoxy]-20,30,40,60-tetra-O-acetyl-
7 equiv) in THF (1 mL), copper(II) sulfate (12
0.5 equiv), and sodium -ascorbate in t-BuOH (0.5 mL) and water
m
mol, 20 mg, 1 equiv) and [(2-azido-ethoxy)
-glucose (140 mol, 65 mg,
mol, 1.9 mg,
b
-D
m
m
L
4.2.1. 5,10,15-Tris{4-(20,30,40,60-tetra-O-acetyl-
b
-
D
-glucopyranosylox-
(0.25 mL). The mixture was heated by microwave irradiation (80 W,
85 ꢁC, 3 min) then allowed to cool to room temperature. The
mixture was concentrated under vacuum and then purified by thin-
layer chromatography (CH2Cl2/EtOH, 96/4, v/v) to give the product
Zn-12 (30 mg, 57%) as a purple powder. 1H NMR (300 MHz, CDCl3):
ymethylenetriazolyl)-[N-(400-propyloxy-phenyl)]}-20-phenyl-
porphyrin zinc complex (Zn-10). In a reactor were introduced
solutions of Zn-8 (15
acetyl- -glucopyranosyloxypropynyl (90
toluene (1 mL) and copper(I) chloride (4.5
m
mol, 15 mg, 1 equiv) and 2,3,4,6-tetra-O-
mol, 35 mg, 7 equiv) in
mol, 0.45 mg,
b-
D
m
m
d 8.91 (s, 4H, H pyrr.), 8.88 (s, 4H, H pyrr.), 8.20 (br s, 2H, o-phenyl),
0.3 equiv). The mixture was heated by microwave irradiation
(100 W, 140 ꢁC, 20 min) then allowed to cool to room temperature.
The mixture was concentrated under vacuum and then purified by
flash chromatography over silica gel (CH2Cl2/MeOH, 99/1, v/v) to
give 21 mg (65%) of Zn-10 as a purple powder. 1H NMR (300 MHz,
8.07 (br d, 6H, o-phenoxy), 7.80 (s, 3H, H triazole), 7.72 (br s, 3H,
m-phenyl and p-phenyl), 7.16 (br d, 6H, m-phenoxy), 5.05e4.92 (m,
6H, H2 sugar, H3 sugar and H4 sugar), 4.57 (d, 3H, J¼7.6 Hz, H1
sugar,), 4.35 (m, 3H, H6 sugar), 4.11e4.00 (m, 15H, CH2, H60 sugar
and CH2eOtriazole) 3.59e3.29 (m, 24H, CH2), 3.42 (m, 3H, H5
sugar), 2.06 (s, 9H, acetyl), 2.03 (s, 9H, acetyl), 1.99 (s, 9H, acetyl),
CDCl3):
d 8.93 (s, 8H, H pyrr.), 8.26 (br s, 2H, o-phenyl), 8.12 (d, 6H,
J¼7.7 Hz, o-phenoxy), 7.77 (br s, 3H, m-phenyl and p-phenyl), 7.16
(d, 6H, J¼7.7 Hz, m-phenoxy), 7.07 (s, 3H, H triazole), 5.14 (t, 3H,
J¼9.4 Hz, H3 sugar), 5.01 (t, 3H, J¼9.5 Hz, H4 sugar), 4.84 (br t, 3H,
H2 sugar), 4.30e3.50 (m, 6H, CH2eOesugar), 4.26 (br s, 6H, CH2),
4.23 (d, J¼8.5 Hz, H1 sugar), 4.20 (br dd, 3H, J¼3.2 and 11.0 Hz, H60
sugar), 4.00 (br d, 3H, J¼12.0 Hz, H6 sugar), 3.81 (br s, 6H, CH2), 3.54
(m, 3H, H5 sugar), 2.24 (br s, 6H, CH2), 2.02 (s, 9H, acetyl), 2.00 (s,
9H, acetyl), 1.97 (s, 9H, acetyl), 1.92 (s, 9H, acetyl). 13C NMR
1.94 (s, 9H, acetyl). 13C NMR (75.3 MHz, CDCl3):
d 169.9 (C]O
acetyl), 169.5 (C]O acetyl), 169.1 (C]O acetyl), 168.3 (C]O acetyl),
161.4 (C4 phenoxy), 149.3(C1 phenyl), 134.7 (C phenoxy), 133.6
(C phenyl), 130.6 (C pyrr.), 125.3 (C triazole), 119.2 (C phenyl), 111.7
(C phenoxy), 99.7 (C1 sugar), 71.6 (C2 sugar or C3 sugar), 70.7 (C2
sugar or C3 sugar), 70.2 (C5 sugar), 69.1 (OeCetriazole), 67.8 (C6
sugar), 67.2 (C4 sugar), 60.7 (CH2), 49.5 (CH2), 19.6 (C acetyl), 19.5 (C
acetyl). UVevis spectrum in CH2Cl2: lmax nm (3 )
, L mmolꢀ1 cmꢀ1
(75.3 MHz, CDCl3):
d
170.6 (C]O acetyl), 170.2 (C]O acetyl), 169.4
423 (453.1), 553 (18.0), 596 (7.5). MALDI-TOF MS calcd for
C107H115N13O36Zn, 2222.69 (m/z 100%), found 2161.71 [MþHꢀZn]þ.
Anal. Calcd for (C107H115N13O36Zn) 1H2O: C, 57.31; H, 5.26; N, 8.12.
Found: C, 57.31; H, 5.16; N, 8.78.
(C]O acetyl), 169.3 (C]O acetyl), 158.0 (C4 phenoxy), 135.6 (C1
phenyl), 134.7 (C phenoxy), 131.7 (C pyrr.), 126.5 (C phenyl),122.5 (C
triazole), 112.4 (C phenoxy), 100.1 (C1 sugar), 72.6 (C3 sugar), 71.8
(C5 sugar), 71.1 (C2 sugar), 68.1 (C4 sugar), 63.8 (C6 sugar), 62.2
(CeOesugar), 61.6 (CH2), 46.8 (CH2), 29.4 (CH2), 20.7 (C acetyl), 20.6
4.2.4. 5,10,15-Tris[4-(N-(20,30,40,60-tetra-O-acetyl-
a-D-mannopyr-
(C acetyl), 20.6 (C acetyl). UVevis spectrum in CH2Cl2: lmax nm (
3,
anosyloxyethoxy)ethoxy)-(400-methylenoxytriazole)-phenyl]-20-phe-
nylporphyrin zinc complex (Zn-13). Prepared as compound Zn-12.
In presence of [(2-azido-ethoxy)ethoxy]-20,30,40,60-tetra-O-acetyl-
L mmolꢀ1 cmꢀ1) 423 (471.1), 551 (19.7), 594 (8.2). MALDI-TOF MS
calcd for C104H109N13O33Zn, 2132.66 (m/z 100%), found 2071.70
[MþHꢀZn]þ. Anal. Calcd for (C104H109N13O33Zn): C, 58.52; H, 5.29;
N, 8.20. Found: C; 59.08; H; 5.29; N, 8.20.
a-
D
-mannose. After purification by thin-layer chromatography
(CH2Cl2/EtOH, 96/4, v/v), 24 mg (45%) of porphyrin Zn-13
was obtained as a purple powder. 1H NMR (300 MHz, CDCl3):
8.95
d
4.2.2. 5,10,15-Tris{4-(20,30,40,50-tetra-O-acetyl-
anosyloxymethylenetriazolyl)-[N-(400-propyloxyphenyl)]}-20-phenyl-
porphyrin zinc complex (Zn-11). Prepared as compound Zn-10.
In presence of 2,3,4,6-tetra-O-acetyl-
ypropynyl (7 equiv). Porphyrin Zn-11 (22 mg (68%)) was obtained
as a purple powder. 1H NMR (300 MHz, CDCl3):
8.94 (s, 4H, H
pyrr.), 8.92 (s, 4H, H pyrr.), 8.26 (br s, 2H, o-phenyl), 8.13 (d, 6H,
J¼7.1 Hz, o-phenoxy), 7.76 (br s, 3H, m-phenyl and p-phenyl), 7.35
(m, 3H, H triazole), 7.20 (d, 6H, J¼7.1 Hz, m-phenoxy), 5.14 (br s, 3H,
H3 sugar), 5.01 (br s, 3H, H4 sugar), 4.84 (br s, 3H, H2 sugar), 4.23
(s, 3H, H1 sugar), 4.73 (br s, 6H, CH2eOesugar), 4.21e4.26 (dd, 3H,
J¼4.3 and 12.1 Hz, H60 sugar), 4.15e3.90 (m, 15H, CH2, and H6
sugar), 3.85 (m, 3H, H5 sugar), 2.37 (br s, 6H, CH2), 2.12 (s, 9H,
acetyl), 2.08 (s, 9H, acetyl),1.98 (s, 9H, acetyl),1.92 (s, 9H, acetyl). 13C
a
-
D
-mannopyr-
(s, 4H, H pyrr.), 8.91 (s, 4H, H pyrr.), 8.25 (br s, 2H, o-phenyl), 8.09 (d,
6H, J¼8.0 Hz, o-phenoxy), 7.76 (br s, 3H, m-phenyl and p-phenyl),
7.13 (d, 6H, J¼8.0 Hz, m-phenoxy), 7.39 (s, 3H, H triazole), 5.28
(m, 3H, H2 sugar or H3 sugar or H4 sugar), 5.27 (m, 3H, H2 sugar or
H3 sugar or H4 sugar), 5.21 (m, 3H, H2 sugar or H3 sugar or H4
sugar), 4.82 (s, 3H, H1 sugar), 4.25e4.05 (m, 18H, CH2), 4.17e4.00
(m, 6H, CH2eOetriazole), 3.99 (m, 3H, H60 sugar), 3.68 (m, 3H, H6
sugar), 3.68e3.54 (m, 18H, CH2), 3.42 (m, 3H, H5 sugar), 2.13 (s, 9H,
acetyl), 2.05 (s, 9H, acetyl), 2.03 (s, 9H, acetyl), 1.98 (s, 9H, acetyl).
a-D-mannopyranosylox-
d
13C NMR (75.3 MHz, CDCl3):
d 170.6 (C]O acetyl), 170.1 (C]O
acetyl), 169.9 (C]O acetyl), 169.7 (C]O acetyl), 157.6 (C4 phenoxy),
143.1 (C1 phenyl), 134.7 (C phenoxy), 131.6 (C pyrr.), 126.3 (C phe-
nyl), 123.2 (C triazole), 112.7 (C phenoxy), 100.1 (C1 sugar), 70.0
(CH2), 69.5 (C5 sugar), 69.2 (C6 sugar), 68.9 (C4 sugar), 68.5
(C3 sugar), 67.1 (C2 sugar), 66.1 (OeCetriazole), 62.4 (CH2), 50.1
(CH2), 20.9 (C acetyl), 20.1 (C acetyl). UVevis spectrum in CH2Cl2:
NMR (75.3 MHz, CDCl3):
169.9 (C]O acetyl), 169.7 (C]O acetyl), 158.0 (C4 phenoxy), 150.3
d 170.7 (C]O acetyl), 170.0 (C]O acetyl),