Berthold et al.
JOCNote
Experimental Section
chromatography on silica gel (THF/PE, 60:40 f THF). The
combined fractions containing 9 were evaporated and the residue
(93 mg) was dissolved in a minimum of THF (3 mL) and
precipitated in MeOH/water to yield 9 after centrifugation and
evaporation with PhMe (86 mg, 21 μmol, 72%). Mp 155-167 °C
(240 °C dec.); Rf 0.90 (25:75, PE/acetone), 0.83 (30:70, PE/
Synthesis of {2,3,9,10,16,17,23,24-Octakis[O-(N-1-(2,3,4,6-
tetra-O-acetyl-β-D-glucopyranosyl)carbamoyloxy)methyl]phthalocy-
aninato} Zinc(II) (3). ZnPc-op-CH2OH (1; 51 mg, 60 μmol)
was dissolved in dry pyridine (5.0 mL, 62 mmol) in a screw
cap vial by means of sonification and 2,3,4,6-tetra-O-acetyl-
β-D-glucopyranosyl isocyanate (2; 0.38 g, 1.0 mmol) was
quickly added. The mixture was stirred in a preheated aluminum
block at 50 °C for 64 h. The solvent was evaporated and the
remaining residue (0.46 g) was purified by column chromato-
graphy on silica gel (gradient from EA f 10% MeCN). Evapora-
tion of the solvent yielded the peracetylated glucosyl carbamate
acetone); [R]20 °C
589nm transmission too low; UV-vis (DMSO) λmax
(log ε) = 680 (5.44), 613 (4.67), 354 (4.95); 1H NMR (400 MHz,
DMSO-d6, 25 °C) δ 9.50 (br s, 8H, H-3), 8.59 (br s, 8H, H-8), 6.34
3
3
(d, JH-1 ,H-2 = 9.3 Hz, 8H, H-10), 5.68 (dd, JH-1 ,H-2 = 9.5 Hz,
0
0
0
0
3
3
JH-2 ,H-3 = 9.8 Hz, 8H, H-2 ), 5.50 (dd, JH-2 ,H-3 = 10.0 Hz,
0
0
0
0
0
0
3
0
0
JH-3 ,H-4 = 2.8 Hz, 8H, H-3 ), 5.44 (br s, 8H, H-4 ), 5.20 (br s, 16H,
0
H-5), 4.95 (br s, 16H, H-6), 4.62 (br dd, 3JH-5 ,H-6 a = 3JH-5 ,H-6 b
=
=
=
0
0
0
0
ZnPc 3 as blue, shiny plates (190 mg, 50 μmol, 82%). Mp 276 °C;
2
5.8-6.0 Hz, 8H, H-5 ), 4.13 (dd, JH-6 a,H-6 b = 11.0 Hz, 3JH-5 ,H-6 a
0
0
0
0
0
0
20 °C
Rf 0.22 (EA); [R]
transmission too low; UV-vis (DMSO)
2
5.0-6.8 Hz, 8H, H-6 a), 4.03 (dd, JH-6 a,H-6 b = 11.6 Hz, 3JH-5 ,H-6 b
589nm
max (logε) = 680 (5.39), 613 (4.61), 351 (4.86); 1H NMR (400 MHz,
3
0
0
0
0
λ
0
7.3 Hz, 8H, H-6 b), 2.16, 1.96, 1.93, 1.89 (s, 4 ꢁ 24H, 4 ꢁ -OC(O)CH3);
13C NMR (100 MHz, DMSO-d6,25°C) δ169.9, 169.8, 169.4, 168.6 (4 ꢁ
-OC(O)CH3), 153.2 (C-1), 144.6 (C-7), 138.7 (C-4), 0137.4 (C-2), 123.6
0
DMSO-d6, 25 °C) δ 9.55 (br s, 8H, H-3), 8.64 (br d, JH-1 ,NH
=
8.9 Hz, 8H, NH), 5.83 (d, 2JH-5a,H-5b = 12.7 Hz, 8H, H-5a), 5.77
(d, 2JH-5a,H-5b = 14.5 Hz, 8H, H-5b), 5.39 (dd, 3JH-2 ,H-3 = 9.4 Hz,
0
0
0
0
(C-8), 122.6 (C-3), 84.4 (C-1 ), 72.9 (C-5 ), 70.4 (C-3 ), 69.6 (C-5), 67.9
JH-3 ,H-4 = 9.7 Hz, 8H, H-3 ), 5.32 (dd, JH-1 ,NH = 3JH-1 ,H-2
=
3
3
0
3
0
0
0
0
0
(C-2 ), 67.3 (C-40), 63.1 (C-6), 61.5 (C-60), 20.4, 20.3, 20.2, 20.0 (4 ꢁ
0
9.4 Hz, 8H, H-10), 4.97 (dd, JH-1 ,H-2 = 9.2 Hz, 3JH-2 ,H-3 = 9.4
0
0
0
0
-OC(O)CH3); MALDI-TOF (anthracene-1,8,9-triol) calcd for
3
3
Hz, 8H, H-20), 4.90 (dd, JH-3 ,H-4 = JH-4 ,H-5 = 9.7 Hz, 8H,
0
0
0
0
C
C
176H201N32O80Znþ, 4110.04; C176H200N32NaO80Znþ, 4132.02;
2
H-40), 4.19-4.13 (m, 16H, H-50/H-60a), 3.99 (d, JH-6 a,H-6 b =10.7
Hz, 8H, H-60b), 1.98, 1.96, 1.95, 1.92 (s, 4 ꢁ 24H, 4 ꢁ -OC(O)-
CH3); 13C NMR (100 MHz, DMSO-d6, 25 °C) δ 169.9, 169.5,
169.2, 169.0 (4 ꢁ -OC(O)CH3), 155.6 (C-6), 153.1 (C-1), 137.7 (C-
2), 137.1 (C-4), 123.6 (C-3), 79.8 (C-10), 72.9 (C-30), 71.9 (C-50),
70.5 (C-20), 67.8 (C-40), 64.3 (C-5), 61.7 (C-60), 20.4, 20.3, 20.24,
20.23 (4 ꢁ -OC(O)CH3); MALDI-TOF (anthracene-1,8,9-triol,
m/z (%)) calcd for C160H185N16O88Znþ, 3805.63; found, 3807.00
(100), 3807.98 (96), 3806.09 (95), 3808.96 (84), 3805.15 (69),
3809.87 (61) [M þ H]þ; HRMS (ESI) m/z calcd for C160H186N16-
O88Zn2þ, 1901.493; found, 1901.492 [M þ 2 ꢁ H]2þ; Anal. Calcd
0
0
176H200KN32O80Znþ, 4148.13; found m/z, 4109.1 [M þ H]þ,
4132.2 [M þ Na]þ, 4149.5 [M þ K]þ. HRMS (ESIþ) m/z calcd for
C
Anal. Calcd for C176H200N32O80Zn 6H2O 2PhMe: C, 51.85; H,
176H202N32O80Zn2þ, 2053.600; found, 2053.603 [M þ 2 ꢁ H]2þ
;
3
3
5.22; N, 10.18. Found: C, 51.83; H, 5.20; N, 10.33.
Acknowledgment. We thank Prof. Kopf, Prof. Behrens,
Dr. Hoffmann, and Ms. Nevoigt for performing X-ray
analyses, as well as Dr. Sinnwell and Dr. Hackl for specific
NMR measurements. Special thanks to Ms. Heffter for
fruitful discussions regarding CD measurements. Dedicated
to Rudolf Willinger on the occasion of his 65th birthday.
for C160H184N16O88Zn 4H2O: C, 49.57; H, 4.99; N, 5.78. Found:
3
C, 49.66; H, 5.08; N, 5.67.
Synthesis of {2,3,9,10,16,17,23,24-Octakis[((N-1-(2,3,4,6-tetra-
O-acetyl-β-D-galactopyranosyl)-1H-1,2,3-triazol-4-yl)methoxy)-
methyl]phthalocyaninato} Zinc(II) (9). To a vigorously stirred
solution of peralkynylated ZnPc 5 (33 mg, 29 μmol) in THF
Supporting Information Available: General experimental
methods, additional experimental procedures, compound char-
acterization data, copies of spectra (NMR, MALDI-TOF,
HRMS-ESI, UV-vis, CD), crystallographic information files
(CIFs), thermal ellipsoid plots, and additional tables. This
material is available free of charge via the Internet at http://
pubs.acs.org.
(8 mL) and MeOH (4 mL) was added consecutively CuSO4 5H2O
3
(17 mg, 68 μmol), (þ)sodium L-ascorbate (36 mg, 180 μmol), and
2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl azide (7; 0.457 mg,
1.22 mmol). After 18 h of stirring in the dark at rt, all solvents
were removed and the residue (611 mg) was purified by column
3862 J. Org. Chem. Vol. 75, No. 11, 2010