Ruthenium-Catalyzed Oxidation of the Porphyrin b,b’-Pyrrolic Ring
5,10,15,20-Tetra(3,5-difluorophenyl)porpholactone
(9):
4.5 Hz, 1H), 7.65 (t, J=8.8 Hz, 4H), 6.94 (dd, J=8.7,
4.7 Hz, 8H), 3.59 (s, 6H), 3.55 (s, 6H), 3.51 (d, J=3.7 Hz,
12H), À1.49 (s, 1H), À1.86 (s, 1H). UV-vis (CH2Cl2): lmax
(log e)=419 (5.19), 518 (3.84), 554 (3.76), 588 (3.59), 642 nm
(3.44); fluorescence (CH2Cl2): lmax =644, 710 nm, f=0.15;
IR: n=724, 794, 961, 982, 1033, 1072, 1111, 1249, 1286, 1431,
1472, 1588, 1732 (C=O), 1767 (C=O), 2854, 2926, 2956,
3337 cmÀ1; ESI-MS: m/z=873.31153, calcd. for C51H45N4O10
[M+H]+: 873.31302.
Following the general procedure with heating at 908C for
6 h, addition of 0.12 mmol Oxoneꢄ and 0.12 mmol NaOH.
1H NMR (400 MHz, CDCl3): d=8.86 (d, J=6.7 Hz, 2H),
8.78 (d, J=4.5 Hz, 1H), 8.65 (dd, J=11.5, 4.3 Hz, 2H), 8.57
(d, J=4.0 Hz, 1H), 7.69 (s, 4H), 7.63 (d, J=6.2 Hz, 2H),
7.49 (d, J=5.9 Hz, 2H), 7.35–7.16 (m, 4H), À1.84 (s, 1H),
À2.19 (s, 1H); 19F NMR (282 MHz, CDCl3): d=À114.80 (t,
J=7.9 Hz, 2F), À115.10–À115.22 (m, 4F), À115.32 (t, J=
7.9 Hz, 2F); UV-vis (CH2Cl2): lmax (log e)=415 (5.47), 516
(4.21), 552 nm (4.16); fluorescence (CH2Cl2): lmax =643,
710 nm, f=0.06; IR: n=715, 790, 843, 868, 931, 988, 1120,
1321, 1362, 1430, 1591, 1620, 1762 (C=O), 1781 (C=O),
5,10,15,20-Tetra(4-glucosylphenyl)porpholactone
(14):
Following the general procedure with heating at 908C for
6 h, addition of 0.12 mmol Oxoneꢄ and 0.12 mmol NaOH.
1H NMR (400 MHz, CDCl3): d=8.80 (d, J=4.8 Hz, 1H),
8.77 (d, J=4.9 Hz, 1H), 8.71 (d, J=4.8 Hz, 1H), 8.63–8.56
(m, 2H), 8.53 (d, J=4.3 Hz, 1H), 8.05–8.01 (m, 6H), 7.92–
7.86 (m, 2H), 7.37 (d, J=7.8 Hz, 8H), 5.51–5.38 (m, 12H),
5.30 (dd, J=13.1, 8.9 Hz, 4H), 4.45–4.37 (m, 4H), 4.36–4.23
(m, 4H), 4.11–3.94 (m, 4H), 2.20 (s, 12H), 2.15–2.07 (m,
36H), À1.73 (s, 1H), À2.09 (s, 1H); UV-vis (CH2Cl2): lmax
(log e)=420 (5.78), 516 (4.35), 552 (4.10), 592 (3.85), 647 nm
(3.79); fluorescence (CH2Cl2): lmax =644, 714 nm, f=0.05;
IR: n=801, 963, 982, 1038, 1068, 1179, 1229, 1373, 1456,
1508, 1607, 1750, 2855, 2924, 2955, 3342 cmÀ1; ESI-MS: m/
3329 cmÀ1
C43H21F8N4O2 [M+H]+: 777.15313.
5,10,15,20-tetra(2,6-difluorophenyl)porpholactone
;
ESI-MS:
m/z=777.15262,
calcd.
for
(10):
Following the general procedure with heating at 808C for
6 h, addition of 0.12 mmol Oxoneꢄ and 0.12 mmol NaOH.
1H NMR (400 MHz, CDCl3): d=8.82 (d, J=4.4 Hz, 1H),
8.78 (t, J=4.8 Hz, 2H), 8.72 (d, J=4.4 Hz, 1H), 8.63 (d, J=
4.3 Hz, 1H), 8.55 (d, J=4.1 Hz, 1H), 7.81- 7.70 (m, 4H),
7.35 (dd, J=14.3, 7.0 Hz, 8H), À1.67 (s, 1H), À2.00 (s, 1H);
19F NMR (282 MHz, CDCl3): d=À109.05 (dt, J=23.6,
6.3 Hz, 4F), À109.75 (t, J=6.5 Hz, 2F), À111.04 (t, J=
6.4 Hz, 2F); UV-vis (CH2Cl2): lmax (log e)=412 (5.44), 511
(4.16), 548 (4.04), 587 (3.83), 641 nm (4.06); fluorescence
(CH2Cl2): lmax =643, 711 nm, f=0.09; IR: n=713, 784, 800,
963, 1004, 1236, 1465, 1623, 1772 (C=O), 1788 (C=O),
z=2017.58773,
calcd.
for
C99H101N4O42
[M+H]+:
2017.58849.
5,10,15,20-Tetra{4-[2-(2-methoxyethoxy)ethoxy]phenyl}-
porpholactone (15): Following the general procedure with
heating at 808C for 4 h, addition of 0.08 mmol Oxoneꢄ and
3344 cmÀ1
;
ESI-MS:
m/z=777.15145,
calcd.
for
1
0.08 mmol NaOH. H NMR (400 MHz, CDCl3): d=8.92 (d,
C43H21F8N4O2 [M+H]+: 777.15313.
J=4.5 Hz, 1H), 8.86 (d, J=3.4 Hz, 2H), 8.88–8.84 (m, 2H),
8.68 (d, J=4.1 Hz, 1H), 8.60 (d, J=3.8 Hz, 1H), 4.79–4.66
(m, 8H), 4.08–4.01ACTHNUTRGNE(NUG m, 8H), 3.88–3.81 (m, 8H), 3.71–6.33
5,10,15,20-Tetra(2,6-dichlorophenyl)porpholactone (11);
Following the general procedure with heating at 808C for
6 h, addition of 0.12 mmol Oxoneꢄ and 0.12 mmol NaOH.
1H NMR (400 MHz, CDCl3): d=8.65 (d, J=4.8 Hz, 1H),
8.58 (dd, J=9.2, 4.7 Hz, 2H), 8.51 (d, J=4.6 Hz, 1H), 8.46
(d, J=4.6 Hz, 1H), 8.37 (d, J=4.5 Hz, 1H), 7.77 (t, J=
8.0 Hz, 8H), 7.73–7.63 (m, 4H), À1.51 (s, 1H), À1.85 (s,
1H); UV-vis (CH2Cl2): lmax (log e)=416 (5.34), 516 (4.05),
553 (3.89), 590 (3.70), 641 nm (3.82); fluorescence (CH2Cl2):
lmax =646, 711 nm, f=0.01; IR: n=709, 717, 778, 803, 965,
(m, 8H), 3.52–3.39 (m, 12H), À1.80 (s, 1H), À2.10 (s, 1H);
UV-vis (CH2Cl2): lmax (log e)=408 (5.30), 510 (4.03), 546
(3.90), 587 (3.74), 641 nm (3.98); fluorescence (CH2Cl2):
lmax =644, 710 nm, f=0.11; IR: 708, 755, 805, 853, 928, 982,
1067, 1109, 1140, 1248, 1356, 1374, 1397, 1430, 1492, 1501,
1651, 1771 (C=O), 2855, 2879, 2897, 2923, 3336 cmÀ1; ESI-
MS: m/z=1393.32772, calcd. for C63H53F16N4O14 [M+H]+:
1393.32973.
978, 1192, 1428, 1559, 1776 (C=O), 1787 (C=O), 3339 cmÀ1
;
[5,10,15,20-Tetra(pentafluorophenyl)porpholactone]-
nickel(II) (16): Following the general procedure with heat-
ing at 808C for 4 h, addition of 0.08 mmol Oxoneꢄ and
ESI-MS: m/z=904.91609, calcd. for C43H21Cl8N4O2 [M+
H]+: 904.91672.
5,10,15,20-Tetramesitylporpholactone (12); Following the
general procedure with heating at 808C for 6 h, addition of
0.12 mmol Oxoneꢄ and 0.12 mmol NaOH. 1H NMR
(400 MHz, CDCl3): d=8.57 (d, J=4.7 Hz, 1H), 8.51 (d, J=
4.4 Hz, 1H), 8.46 (d, J=4.8 Hz, 1H), 8.41 (dd, J=9.5,
4.5 Hz, 2H), 8.33 (d, J=4.5 Hz, 1H), 7.24 (s, 8H), 2.60 (s,
6H), 2.57 (d, J=3.7 Hz, 6H), 1.91 (s, 6H), 1.86 (d, J=
4.1 Hz, 12H), 1.83 (s, 6H), À1.48 (s, 1H), À1.86 (s, 1H);
UV-vis (CH2Cl2): lmax, (log e)=417 (5.48), 519 (4.12), 556
(4.12), 588 (3.90), 642 nm (3.66); fluorescence (CH2Cl2):
lmax =642, 708 nm, f=0.06; IR: n=725, 803, 971, 1036,
1076, 1116, 1203, 1221, 1273, 1369, 1451, 1559, 1612, 1653,
1731 (C=O), 1771 (C=O), 2856, 2920, 3338 cmÀ1; ESI-MS:
m/z=801.41578, calcd. for C55H53N4O2 [M+H]+: 801.41630.
5,10,15,20-Tetra(2,6-dimethoxylphenyl)porpholactone
(13): Following the general procedure with heating at 808C
for 5 h, addition of 0.12 mmol Oxoneꢄ and 0.12 mmol
1
0.08 mmol NaOH. H NMR (400 MHz, CDCl3): d=8.59 (d,
J=12.7 Hz, 4H), 8.50 (d, J=12.7 Hz,4H); 19F NMR
(282 MHz, CDCl3): d=À136.92–À137.85 (m, 6F), À138.78
(dd, J=22.6, 6.7 Hz, 2F), À150.94 (dt, J=42.6, 21.2 Hz, 3F),
À151.68 (t, J=20.9 Hz, 1F), À160.80–À161.41 (m, 6F),
À161.84 (td, J=21.7, 6.6 Hz, 2F); UV-vis (CH2Cl2): lmax (log
e)=404 (5.04), 549 (3.81), 592 nm (4.49); IR: n=767, 808,
881, 941, 953, 993, 1022, 1064, 1081, 1258, 1303, 1352, 1433,
1498, 1516, 1729 (C=O), 1761 (C=O), 1773 (C=O),
1782 cmÀ1 (C=O); ESI-MS: m/z=1048.96022, calcd. for
C43H7F20N4NiO2 [M+H]+: 1048.95976.
[5,10,15,20-Tetra(pentafluorophenyl)porpholactone]cop-
per(II) (17): Following the general procedure with heating
at 808C for 4 h, addition of 0.08 mmol Oxoneꢄ and
0.08 mmol NaOH. UV-vis (CH2Cl2): lmax (log e)=383 (4.70),
410 (5.44), 556 (4.06), 599 nm (4.65); IR: n=769, 878, 939,
951, 988, 1018, 1057, 1078, 1293, 1325, 1347, 1364, 1457,
1493, 1519, 1561, 1755 (C=O), 1783 (C=O), 1805 cmÀ1 (C=
1
NaOH. H NMR (400 MHz, CDCl3): d=8.58 (d, J=4.9 Hz,
1H), 8.55–8.48 (m, 3H), 8.45 (d, J=4.5 Hz, 1H), 8.36 (d, J=
Adv. Synth. Catal. 2012, 354, 3509 – 3516
ꢃ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3515