Synthetic Models for Heme Proteins
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3.60 (m, 10H; H2-C(24), H2-C
(24’) and H2-C(28)), 1.80–1.60 (m, 4H; H2-C(26) and H2-C(31)), 1.29–
0.67 (m, 28H; H2-C(32) to H2-C(34), H2-C(25), H2-C(25’), H2-C(26), H2-
(26’), and H3-C(29’)), 0.63 ppm (t, J=7.2 Hz, 6H; H3-C(29)), three sig-
G
H2-C
7.2 Hz, 2H; H2-C
(CDCl3, 150 MHz): d=173.22 (C
159.40 (C(21’)), 155.65 (C(14)), 150.74 (C(5)), 150.12 (C(7) or C(10)),
ACHTUNGTRENNUNG
C
N
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C
N
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nals not visible due to signal overlap; 13C NMR (CDCl3, 75 MHz): d=
173.0, 172.7, 159.4, 157.4, 151.5, 150.1, 149.3, 149.2, 148.1, 147.9, 136.8,
135.8, 131.1, 130.8, 130.3, 130.1, 129.5, 129.2, 128.3, 125.5, 124.0, 122.1,
120.0, 118.6, 116.0, 114.0, 111.2, 109.7, 105.8, 105.4, 104.9, 93.7, 77.3, 67.9,
67.5, 66.8, 60.1, 59.5, 46.8, 30.9, 29.7, 29.5, 29.0, 26.3, 25.5, 23.4, 14.2,
13.6 ppm; IR (neat): n˜ =2924 (m), 2359 (w), 1725 (s), 1592 (m), 1520 (w),
1455 (s), 1373 (m), 1294 (m), 1231 (s), 1177 (s), 1089 (vs), 1056 (vs), 1029
(s), 990 (vs), 940 (m), 838 (m), 828 (m), 793 (s), 716 cmÀ1 (s); UV/Vis
(CHCl3): lmax (e)=595 (3.700), 559 (17.200), 426 (434.100), 404 nm
149.92 (C(2)), 148.58 (C(12)), 148.04 (C(10) or C(7)), 140.59 (C(43)),
138.86 (C(45)), 131.94 (C(44)), 131.80 (C(36)), 131.70 (C(3)), 131.29
(C(4)), 131.25 (C(8) or C(9)), 130.80 (C(9) or C(8)), 130.42 (C(16)),
129.62 (C(23)), 123.44 (C(38)), 123.10 (C(40)), 121.56 (C(20)), 120.58
(C(41)), 119.41 (C(17)), 118.69 (C(42)), 117.57 (C(13)), 117.25 (C(11)),
117.16 (C(15)), 115.23 (C(37)), 111.95 (C(6)), 106.18 (C(39)), 105.59
(C(1)), 105.49 (C(22)), 104.87 (C
67.30 (C(24)), 66.65 (C(24’)), 66.39 (C(30)), 59.78 (C
46.27 (C(35)), 29.69 (C(34)), 29.37 (C(26)), 28.61 (C(26’)), 26.12 (C(31)),
25.66 (C(33)), 24.03 (C(25)), 23.89 (C(32)), 23.11 (C(25’)), 14.10 (C(29’)),
ACHTUNGTRENNUNG
A
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(43.600mÀ1 cmÀ1
,
sh); HR-MALDI-MS (3-HPA): m/z: calcd for
A
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C76H80N8O13Zn+: 1376.5131; found: 1376.5150 [M]+; elemental analysis
calcd (%) for C81H83N7O13Zn (1427.98): C 68.13, H 5.86, N 6.87; found: C
68.13, H 5.97, N 6.58.
13.87 ppm (C(29)); IR (neat): n˜ =3362 (w), 2929 (w), 1724 (vs), 1589 (m),
1558 (w), 1520 (w), 1454 (s), 1380 (m), 1357 (w), 1324 (w), 1294 (m),
1281 (m), 1231 (s), 1177 (vs), 1087 (vs), 1056 (vs), 1029 (s), 989 (vs), 940
(m), 838 (m), 829 (m), 793 (s), 716 cmÀ1 (vs); UV/Vis (CH2Cl2): lmax (e)=
594 (4000), 558 (17000), 426 (447900), 404 (37600, sh), 329 nm
(Tetraethyl
[1,3-15N2]imidazol-1-yl)hexyl]oxy}phenyl)porphyrin-5,15-diyl-kN21,kN22,
kN23,kN24]bis [benzene-2,1,3-triylbis
4,4’,4’’,4’’’-{[10-(2-(1H-imidazol-5-ylethynyl)-5-{[6-(1H-
(42900mÀ1 cmÀ1);
HR-MALDI-MS
(3-HPA):
m/z:
calcd
for
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C80H83N8O13Zn+: 1427.5366; found: 1427.5390 [M+H]+; elemental analy-
sis calcd (%) for C80H82N8O13Zn (1428.96): C 67.24, H 5.78, N 7.84;
found: C 67.41, H 5.95, N 7.70.
2-Zn): The title compound was prepared from 15N-18-Zn (80 mg,
0.06 mmol) according to the general procedure using iodinated precursor
19. Yield 40 mg (48%); m.p. 105–1068C; 1H NMR (300 MHz, CDCl3):
d=9.87 (s, 1H; H-C(1)), 9.09 (d, J=4.2 Hz, 2H; H-C(3)), 8.70 (d, J=
4.2 Hz, 2H; H-C(4)), 8.44 (d, J=4.5 Hz, 2H; H-C(8) or H-C(9)), 8.29 (d,
J=4.5 Hz, 2H; H-C(9) or H-C(8)), 7.65 (t, J=8.4 Hz, 2H; H-C(23)),
7.57 (s, 1H; H-C(13)), 7.16 (d, J=8.4 Hz, 1H; H-C(15) or H-C(16)), 7.02
(d, J=8.4 Hz, 1H; H-C(16) or H-C(15)), 6.96 (d, J=8.4 Hz, 2H; H-C-
(Tetraethyl 4,4’,4’’,4’’’-{[10-(2-(1H-indol-7-ylethynyl)-5-{[6-(1H-imidazol-
1-yl)hexyl]oxy}phenyl)porphyrin-5,15-diyl-kN21,kN22,kN23,kN24]bis[benz-
ene-2,1,3-triylbis
N
pound was prepared from 18-Zn (50 mg, 0.04 mmol) according to the
general procedure using iodinated precursor 21. Yield 40 mg (74%); m.p.
102–1048C; 1H NMR (CDCl3, 500 MHz): d=10.06 (s, 1H; H-C(1)), 9.27
(d, J=4.3 Hz, 2H; H-C(3)), 8.93 (d, J=4.3 Hz, 2H; H-C(4)), 8.78 (d, J=
4.5 Hz, 2H; H-C(8) or H-C(9)), 8.73 (d, J=4.5 Hz, 2H; H-C(9) or H-
C(8)), 7.84 (d, J=8.7 Hz, 1H; H-C(16)), 7.64 (t, J=8.5 Hz, 2H; H-
C(23)), 7.31 (d, J=2.6 Hz, 1H; H-C(13)), 7.26 (dd, J=8.7 Hz, J=2.6 Hz,
ACHTUNGTRENNUNG
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A
R
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7.2 Hz, 6H; H3-C(29)), three signals not visible due to signal overlap;
13C NMR (CDCl3, 75 MHz): d=173.0, 172.7, 159.3, 157.4, 150.1, 149.3,
149.2, 148.1, 147.9, 136.9, 131.1, 130.8, 130.7, 130.3, 130.1, 129.5, 129.2,
123.9, 122.1, 120.0, 118.6, 115.9, 114.0, 111.2, 109.7, 105.8, 105.4, 104.9,
93.7, 77.3, 67.9, 67.5, 66.8, 60.1, 59.5, 46.8, 46.7, 31.9, 30.9, 29.7, 29.6, 29.5,
29.3, 29.1, 29.0, 26.3, 25.5, 24.0, 23.4, 22.7, 14.2, 13.6 ppm; IR (neat): n˜ =
3114 (w), 2933 (m), 2871 (w), 1727 (s), 1592 (m), 1520 (w), 1455 (s), 1380
(m), 1295 (m), 1246 (s), 1179 (s), 1092 (vs), 1057 (s), 1030 (m), 991 (vs),
950 (w), 840 (m), 829 cmÀ1 (m); UV/Vis (CHCl3): lmax (e)=596 (2300),
559 (11900), 427 (312500), 407 (27700, sh), 307 nm (25500mÀ1 cmÀ1);
HR-MALDI-MS (3-HPA): m/z: calcd for C76H8015N2N6O13Zn+:
1378.5072; found: 1378.5080 [M]+.
1H; H-C(15)), 6.98 (d, J=8.6 Hz, 2H; H-CACHTNUTGRNEUNG(22’)), 6.92 (d, J=8.6 Hz, 2H;
H-C(22)), 6.69 (d, J=7.6 Hz, 1H; H-C(42)), 6.62 (d, J=7.6 Hz, 1H; H-
C(40)), 6.40 (t, J=7.6 Hz, 1H; H-C(41)), 4.95 (brs, 1H; H-C(37)), 4.54
(dd, J=3.0 Hz, 2.0 Hz, 1H; H-C(indole at 3-position)), 4.10 (t, J=8.2 Hz,
2H; H2-C(30)), 4.03–3.98 (m, 2H; H2-C(24)), 3.95–3.90 (m, 2H; H2-
C(24)), 3.79 (q, J=7.2 Hz, 4H; H2-C
C(28)), 3.61–3.56 (m, 2H; H2-C(24’)), 3.55 (q, J=7.2 Hz, 2H; H2-C(28)),
3.54–3.49 (m, 2H; H2-C(24’)), 2.63 (brs, 1H; NH), 2.55 (brt, J=6.0 Hz,
ACHTUNGRTEN(NUNG 28’)), 3.71 (q, J=7.2 Hz, 2H; H2-
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2H; H2-C(35)), 2.22 (brs, 1H; H-C(36)), 2.00 (brs, 1H; H-C(38)), 1.75–
1.69 (m, 2H; H2-C(31)), 1.62 (s, 1H; H-C(indole at 2-position)), 1.48
(ddd, J=16.0 Hz, 8.0 Hz, 8.0 Hz, 2H; H2-C(26)), 1.32–1.24 (m, 2H; H2-
C(25)), 1.21 (ddd, J=16.0 Hz, 8.0 Hz, 8.0 Hz, 2H; H2-C(26)), 1.16–1.09
(m, 2H; H2-C(25)), 1.02 (t, J=7.1 Hz, 6H; H3-C
H2-C(32)), 0.93 (t, J=7.1 Hz, 6H; H3-C(29)), 0.87–0.79 (m, 2H; H2-C-
(26’)), 0.80–0.74 (m, 2H; H2-C(34)), 0.72–0.68 (m, 2H; H2-C(25’)), 0.68–
0.64 (m, 2H; H2-C(25’)), 0.63–0.57 (m, 2H; H2-C(26’)), 0.21–0.14 ppm
(m, 2H; H2-C(33)); 13C NMR (CDCl3, 150 MHz): d=173.28 (C
(27’)),
172.61 (C(27)), 159.82 (C(21)), 159.77 (C(21’)), 155.39 (C(14)), 150.62
(C(5)), 150.21 (C(7) or C(10)), 149.66 (C(2)), 148.29 (C(12)), 148.18
(C(10) or C(7)), 134.39 (C(44)), 131.78 (C(36)), 131.38 (C(3)), 131.15
(C(4)), 131.15 (C(8) or C(9)), 130.81 (C(9) or C(8)), 130.53 (C(16)),
129.52 (C(23)), 125.69 (C(43)), 123.47 (C(38)), 122.60 (C(46)), 121.96
(C(20)), 121.86 (C(42)), 119.71 (C(17)), 119.53 (C(40)), 117.95 (C(41)),
117.74 (C(13)), 117.30 (C(11)), 117.17 (C(15)), 115.16 (C(37)), 111.77
ACHTUNGERTN(NUNG 29’)), 1.01–0.96 (m, 2H;
(Tetraethyl
imidazol-1-yl)hexyl]oxy}phenyl)porphyrin-5,15-diyl-kN21,kN22,kN23,kN24]-
bis[benzene-2,1,3-triylbis
(oxy)]}tetrabutanoato(2À))zinc (3-Zn): The title
4,4’,4’’,4’’’-{[10-(2-(1H-benzimidazol-7-ylethynyl)-5-{[6-(1H-
G
ACHTUNGTRENNUNG
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E
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compound was prepared from 18-Zn (64 mg, 0.05 mmol) according to the
general procedure using iodinated precursor 20. Yield 43 mg (60%); m.p.
109–1118C; 1H NMR (CDCl3, 500 MHz): d=10.09 (s, 1H; H-C(1)), 9.28
(d, J=4.5 Hz, 2H; H-C(3)), 8.94 (d, J=4.5 Hz, 2H; H-C(4)), 8.81 (d, J=
4.5 Hz, 2H; H-C(8) or H-C(9)), 8.73 (d, J=4.5 Hz, 2H; H-C(9) or H-
C(8)), 7.82 (d, J=8.7 Hz, 1H; H-C(16)), 7.65 (t, J=8.3 Hz, 2H; H-
C(23)), 7.40 (d, J=2.7 Hz, 1H; H-C(13)), 7.27 (dd, J=8.7 Hz, 2.7 Hz,
ACHTUNGTRENNUNG
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1H; H-C(15)), 6.97 (d, J=8.3 Hz, 2H; H-CACHTNUTGRNEUNG(22’)), 6.95 (d, J=8.3 Hz, 2H;
H-C(22)), 6.78 (d, J=7.8 Hz, 1H; H-C(42)), 6.73 (d, J=7.8 Hz, 1H; H-
C(40)), 6.54 (t, J=7.8 Hz, 1H; H-C(41)), 4.98 (brs, 1H; H-C(37)), 4.13
(t, J=7.7 Hz, 2H; H2-C(30)), 4.01–3.96 (m, 2H; H2-C(24)), 3.94–3.88 (m,
(C(6)), 105.82 (C(22)), 105.49 (C(39)), 105.09 (C(1)), 105.00 (C
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99.34 (C(45)), 94.22 (C(18)), 89.26 (C(19)), 67.36 (C(24)), 66.95 (CACHTUNGTRENNUNG
66.42 (C(30)), 59.80 (C(28)), 59.63 (C
30.73 (C(26)), 28.60 (C(26’)), 26.20 (C(31)), 24.95 (C(33)), 23.88 (C(25)),
23.83 (C(32)), 23.17 (C(25’)), 14.09 (C(29’)), 14.04 ppm (C(29)); IR
(neat): n˜ =3405 (w), 2931 (m), 2359 (vs), 2340vs, 1728 (vs), 1584 (m),
1521 (m), 1455 (vs), 1374 (m), 1295 (m), 1247 (s), 1180 (vs), 1096 (vs),
1058 (m), 1030 (m), 991 (vs), 792 cmÀ1 (s); UV/Vis (CHCl3): lmax (e)=
594 (4000), 558 (19400), 426 (490200), 405 nm (46800mÀ1 cmÀ1, sh); HR-
MALDI-MS (3-HPA): m/z: calcd for C81H83N7O13Zn+: 1425.5335; found:
1425.5380 [M]+; elemental analysis calcd (%) for C81H83N7O13Zn
(1427.98): C 68.13, H 5.86, N 6.87; found: C 68.13, H 5.97, N 6.58.
ACHTUNGTRENN(UNG 28’)), 46.23 (C(35)), 31.73 (C(34)),
2H; H2-C(24)), 3.84 (q, J=7.2 Hz, 4H; H2-C
ACHTUNGTRENNUNG
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C
A
G
ACHTUNGTRENNUNG
3.51 (q, J=7.2 Hz, 2H; H2-C(28)), 3.27 (brs, 1H; NH), 2.56 (brs, 1H; H-
C(45)), 2.54 (brt, J=6.0 Hz, 2H; H2-C(35)), 2.20 (brs, 1H; H-C(36)),
2.03 (brs, 1H; H-C(38)), 1.79–1.71 (m, 2H; H2-C(31)), 1.48 (ddd, J=
15.3 Hz, 7.6 Hz, 7.6 Hz, 2H; H2-C(26)), 1.31–1.23 (m, 2H; H2-C(25)),
1.18 (ddd, J=15.3 Hz, 7.6 Hz, 7.6 Hz, 2H; H2-C(26)), 1.14–1.08 (m, 2H;
H2-C(25)), 1.07 (t, J=7.0 Hz, 6H; H3-C
C(32)), 0.97 (ddd, J=14.2 Hz, 7.2 Hz, 7.2 Hz, 2H; H2-C
7.0 Hz, 6H; H3-C(29)), 0.86–0.78 (m, 2H; H2-C(25’)), 0.81–0.74 (m, 2H;
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Chem. Eur. J. 2009, 15, 125 – 135
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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