The Journal of Organic Chemistry
ARTICLE
(s, 4H, HC12,13,17,18 pyrrole), 8.76 (d, 2H, HC2,8 pyrrole), 8.57 (m, 2H,
m-carboxyphenyl), 8.37 (m, 8H, o-carboxyphenyl and o-phenyl), 7.80
(m, 9H, m- and p-phenyl), 7.12 (t, 3H, OH), 6.84 (t, 3H, OH), 6.62 (t,
3H, OH), 6.46 (t, 3H, OH), 4.8 (d, 3H, J = 7.4 Hz, HC1), 4.64 (m, 2H,
CH2 glycine), 4.46 (m, 12H, HC2,4,6), 4.18 (m, 6H, CH2a-O-galactosyl
and HC3), 4.07 (m, 3H, HC5), 3.99 (m, 3H, CH2b-O-galactosyl), 3.72
(m, 6H, CH2-NH), 2.62 [broad s, 6H, (CH2)3-C], 2.52 (broad s, 6H,
CH2-CO), -2.43 (s, 2H, NH). 13C NMR (pyridine-d5): δ (ppm) 173.9
(CO-den), 169.7 (CO glycine), 168.6 (CO carboxyphenyl), 145.3 (C1
carboxyphenyl), 142.3 (C1 phenyl), 134.8 (o-phenyl and o-carboxyphenyl),
134.2 (p-carboxyphenyl), 131.7 (C pyrrole), 128.2 (p-phenyl), 127.7 (m-
phenyl), 126.8 (m-carboxyphenyl), 120.9 (meso-C15), 120.8 (meso-C10,20),
119.7 (meso-C5), 105.3 (C1), 77 (C5), 75.2 (C3), 72.6 (C2), 70.3 (C4), 69.5
(CH2-O-galactosyl), 62.4 (C6), 58.8 (C-NH), 44.7 (CH2 glycine), 40.4
(CH2-NH), 31.5 [(CH2)3-C], 31 (CH2CO).
Rt = 13.51 min. MALDI-TOF MS calcd for C87H106N9O26 (MHþ)
1692.72, found 1692.73. UV-vis spectrum in MeOH/pyridine (24/1,
v/v): λmax, nm (ε, L mmol-1 cm-1) 414 (294.7), 512.5 (11.6), 548
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(5.9), 590.5 (3.7), 643.5 (2.2). H NMR (pyridine-d5): δ (ppm) 9.92
(broad s, 1H, NH glycine), 9.07 (d, 2H, J = 4.7 Hz, HC3,7 pyrrole), 9.03
(s, 4H, HC12,13,17,18 pyrrole), 9.02 (d, 2H, J = 4.7 Hz, HC2,8 pyrrole),
8.76 (d, 2H, m-carboxyphenyl), 8.59 (broad t, 3H, NH-CH2), 8.39 (m,
2H, o-carboxyphenyl), 8.37 (m, 6H, o-phenyl), 7.80 (m, 9H, m- and p-
phenyl), 7.20 (t, 3H, OH), 6.77 (t, 3H, OH), 6.54 (t, 3H, OH), 6.43 (t,
3H, OH), 4.82 (d, 3H, J = 7.6 Hz, HC1), 4.64 (m, 2H, CH2 glycine), 4.55
(m, 3H, HC4), 4.45 (m, 9H, HC2 and HC6), 4.18 (m, 6H, HC3 and
CH2a-O-galactosyl), 4.04 (m, 3H, HC5), 3.90 (m, 3H, CH2b-O-
galactosyl), 3,64 (m, 18H, 2CH2O and CH2NH), 2.67 (m, 6H,
CH2CO), 2.57 [m, 6H, (CH2)3-C], -2.42 (s, 2H, NH). 13C NMR
(pyridine-d5): δ (ppm) 173.8 (CO-den), 169.6 (CO glycine), 168.3
(CO phenyl), 145.2 (C1 carboxyphenyl), 142.2 (C1 phenyl), 134.8 (o-
phenyl and o-carboxyphenyl), 134.3 (p-carboxyphenyl), 131.6 (C pyrrole),
128.2 (p-phenyl), 127.2 (m-phenyl), 126.7 (m-carboxyphenyl), 120.9
(meso-C15), 120.8 (meso-C10,20), 119.6 (meso-C5), 105.1 (C1), 77 (C5),
75.1 (C3), 72.3 (C2), 70.3 (CH2O), 70.1 (C4), 70 (CH2O), 68.7 (CH2-O-
galactosyl), 62.2 (C6), 58.7 (C-NH), 44.7 (CH2 glycine), 39.6 (CH2-NH),
31.3 [(CH2)3-C], 30.8 (COCH2).
Porphyrin 4:35 The title compound was deprotected as in com-
pound 1 from peracetylated porphyrin 4-OAc. Product 4 was
obtained as a red powder and used without other purification (yield
92%). HPLC Rt = 13.79 min. MALDI-TOF MS calcd for C81H94N9O23
(MHþ) 1560.64, found 1560.68. UV-vis spectrum in MeOH/pyridine
(24/1, v/v): λmax, nm (ε, L mmol-1 cm-1) 414 (274.4), 514.5 (12.2),
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548 (5.3), 588.5 (3.6), 645.5 (2.4). 1H NMR (pyridine-d5): δ (ppm) 10
(broad s, 1H, NH glycine), 9.05 (m, 8H, HC pyrrole), 8.78 (s, 2H, m-
carboxyphenyl), 8.73 (m, 1H, NH-CH2), 8.42 (s, 2H, o-carboxyphenyl),
8.37 (m, 6H, o-phenyl), 7.81 (m, 9H, m- and p-phenyl), 6.97 (t, 3H,
OH), 6.77 (t, 3H, OH), 6.70 (t, 3H, OH), 6.56 (t, 3H, OH), 5.41 (s, 3H,
HC1), 4.58 (d, 2H, CH2 glycine), 4.58 (m, 12H, HC2,3,4,6a), 4.39 (m,
6H, HC5,6b), 4.12 (m, 3H, HC2a-O-mannosyl), 3.80 (m, 3H, HC2b-O-
mannosyl), 3.74 (m, 6H, CH-NH), 2.71 (m, 6H, CH2-CO), 2.60 [m,
6H, (CH2)3-C], -2.41 (s, 2H, NH). 13C NMR (pyridine-d5): δ (ppm)
174 (CO-den), 169.9 (CO glycine), 168.6 (CO carboxyphenyl), 145.4
(C1 carboxyphenyl), 142.4 (C1 phenyl), 135 (o-phenyl and o-
carboxyphenyl), 134.3 (p-carboxyphenyl), 131.7 (C pyrrole), 128.3 (p-
phenyl), 127.3 (m-phenyl), 126.9 (m-carboxyphenyl), 120.9 (meso-
C10,15,20), 119.8 (meso-C5), 101.8 (C1), 75.5 (C5), 72.8 (C2,3,4), 72
(C2,3,4), 69.1 (C2,3,4), 67.1 (CH2-O-mannosyl), 63.1 (C6), 59 (C-NH),
44.9 (CH2 glycine), 39.9 (C-NH), 31.7 [(CH2)3-C], 31.2 (COCH2).
Porphyrin 5: The title compound was deprotected as in compound
1 from peracetylated porphyrin 5-OAc. Product 5 was obtained as a
red powder and used without other purification (yield 94%). HPLC
Rt = 13.55 min. MALDI-TOF MS calcd for C87H106N9O26 (MHþ)
1692.72, found 1692.72. UV-vis spectrum in MeOH/pyridine (24/1,
v/v): λmax, nm (ε, L mmol-1 cm-1) 414 (298.5), 513 (12.4), 546
Porphyrin 7:35 The title compound was deprotected as in com-
pound 1 from peracetylated porphyrin 7-OAc. Pure title com-
pound was obtained as a red powder and used without other purification
(yield 95%). HPLC Rt = 13.73 min. MALDI-TOF MS calcd for
C87H106N9O26 (MHþ) 1692.71, found 1692.78. UV-vis spectrum in
MeOH/pyridine (24/1, v/v): λmax, nm (ε, L mmol-1 cm-1) 414
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(347), 513 (14.2), 546.5 (6.4), 589 (4.3), 644.5 (3.1). 1H NMR
(pyridine-d5): δ (ppm) 9.88 (t, 1H, J = 5.1 Hz, NH glycine), 9.08 (d,
2H, J = 4.4 Hz, HC3,7), 9.03 (s, 6H, HC12,13,17,18), 9.02 (d, 2H, HC2,8),
8.76 (d, 2H, J = 8 Hz, m-carboxyphenyl), 8.64 (broad s, 1H, NH-CH2),
8.58 (broad s, 3H, NH-CH2), 8.40 (m, 6H, o-carboxyphenyl), 8.36 (m,
2H, o-phenyl), 7.80 (m, 9H, m- and p-phenyl), 5.39 (s, 3H, HC1), 4.61
(m, 3H, CH2), 4.55 (m, 12H, C2,3,4,6), 4.36 (m, 6H, HC5), 4.36 (d, 3H,
J = 8.4 Hz, HaC6), 4.06 (m, 3H, CH2a-O-mannosyl), 3.72 (m, 3H, CH2b-
O-mannosyl), 3.63 (m, 14H, CH2), 2.70 [s, 6H, (CH2)3-C], 2.58 (broad
s, 6H, CH2CO), -2.44 (s, 2H, NH). 13C NMR (pyridine-d5): δ (ppm)
173.9 (CO-den), 169.7 (CO glycine), 168.4 (CO-phenyl), 145.4 (C1
carboxyphenyl), 142.4 (C1 phenyl), 135 (o-carboxyphenyl and o-
phenyl), 134.5 (p-carboxyphenyl), 131.8 (C pyrrole), 128.3 (p-phenyl),
127.4 (m-phenyl), 126.9 (m-carboxyphenyl), 121 (meso-C15), 120.9
(meso-C10,20), 119.8 (meso-C5), 101.6 (C1), 75.3 (C5), 72.9 (C2,3,4), 72
(C2,3,4), 70.4 (CH2-O-mannosyl), 70.2 (CH2), 69.2 (C2,3,4), 66.8 (CH2-
O-mannosyl), 63.3 (C6), 58.8 (C-NH), 44.8 (CH2 glycine), 40 (CH2-
NH), 31.5 [(CH2)3-C], 31 (COCH2).
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(5.5), 589 (3.7), 644.5 (2.7). H NMR (pyridine-d5): δ (ppm) 9.95
(broad s, 1H, NH glycine), 9.05 (d, 2H, J = 4.7 Hz, HC3,7 pyrrole), 9.03
(m, 6H, HC2,8,12,13,17,18 pyrrole), 8.76 (d, 2H, J = 7.7 Hz, m-
carboxyphenyl), 8.61 (broad t, 3H, NH-CH2), 8.38 (m, 8H, o-phenyl
and o-carboxyphenyl), 7.8 (m, 9H, m- and p-phenyl), 7.37 (t, 3H, OH),
7.16 (m, 6H, 2OH), 6.48 (t, 3H, OH), 4.91 (d, 3H, J = 7.3 Hz, HC1),
4.63 (m, 2H, CH2 glycine), 4.49 (m, 3H, HaC6), 4.32 (m, 3H, HbC6),
4.19 (m, 9H, HC3, HC4 and CH2a-O-glucosyl), 4.02 (m, 3H, HC2), 3.88
(m, 6H, HC5 and CH2b-O-glucosyl), 3.64 (m, 18H, CH2NH and
2CH2O), 2.65 (m, 6H, CH2CO), 2.58 [m, 6H, (CH2)3-C], -2.44 (s,
2H, NH). 13C NMR (pyridine-d5): δ (ppm) 173.8 (CO-den), 168.6
(CO glycine), 168.4 (CO phenyl), 145.2 (C1 carboxyphenyl), 142.2 (C1
phenyl), 134.7 (o-phenyl and o-carboxyphenyl), 134.3 (p-carboxyphenyl),
131.4 (C pyrrole), 128.2 (p-phenyl), 127.2 (m-phenyl), 126.7 (m-
carboxyphenyl), 120.9 (meso-C15), 120.8 (meso-C10,20), 119.6 (meso-C5),
104.5 (C1), 78.3 (C3 and C5), 74.9 (C2), 71.3 (C4), 70.3 (CH2O), 70
(CH2O), 69.8 (CH2-O-glucosyl), 62.4 (C6), 58.6 (C-NH), 44.7 (CH2
glycine), 39.6 (CH2-NH), 31.4 [(CH2)3-C], 30.8 (COCH2).
Porphyrin 8: The title compound was deprotected as in compound
1 from peracetylated porphyrin 8-OAc. Pure title compound was
obtained as a red powder powder and used without other purification
(yield 94%). HPLC Rt = 13.74 min. MALDI-TOF MS calcd for
C93H119N9O29 (MHþ) 1825.80, found 1825.82. UV-vis spectrum in
MeOH/pyridine (24/1, v/v): λmax, nm (ε, L mmol-1 cm-1) 414
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(389.3), 513 (15.9), 546 (7.2), 589 (4.9), 645 (3.5). 1H NMR
(pyridine-d5): δ (ppm) 9.97 (t, 1H, J = 5.2 Hz, NH glycine), 9.07 (d,
2H, J = 4.8 Hz, HC3,7 pyrrole), 9.02 (s, 4H, HC2,8,12,13,17,18 pyrrole),
8.75 (d, 2H, J = 8.1 Hz, m-carboxyphenyl), 8.64 (broad s, 1H, NH), 8.60
(broad t, 1H, NH-CH2), 8.41 (d, 2H, J = 8.1 Hz, o-carboxyphenyl), 8.35
(m, 6H, o-phenyl), 7.79 (m, 6H, m- and p-phenyl), 6.97 (t, 6H, 2OH),
6.67 (t, 3H, OH), 6.27 (t, 3H, OH), 5.40 (d, 3H, J = 1.2 Hz, HC1), 4.62
(m, 3H, HC2,3,4,5), 4.60 (s, 2H, CH2 glycine), 4.55 (m, 3H, HaC6), 4.55
(dd, 3H, J = 3.1 and 10.1 Hz, HC2,3,4,5), 4.55 (d, 3H, J = 10 Hz,
HC2,3,4,5), 4.36 (d, 6H, J = 6 and 13.6 Hz, HbC6), 4.34 (m, 3H,
HC2,3,4,5), 4.05 (m, 3H, CH2a-O-mannosyl), 3.72 (m, 3H, CH2b-O-
mannosyl), 3.64 (m, 18H, CH2-NH and CH2), 3.57 (m, 12H, CH2-O),
Porphyrin 6: The title compound was deprotected as in compound
1 from peracetylated porphyrin 6-OAc. Product 6 was obtained as a
red powder and used without other purification (yield 94%). HPLC
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dx.doi.org/10.1021/jo102185d |J. Org. Chem. 2011, 76, 2010–2028