Porphyrins as Dipolarophiles in 1,3-Dipolar Cycloaddition Reactions with Nitrile Oxide

Abstract

Novel isoxazole-fused chlorins and isobacteriochlorins were synthesized by the 1,3-dipolar cycloaddition reactions of meso-tetraphenylporphyrins with nitrile oxide.

porphyrins - nitrile oxides - 1,3-dipolar cycloaddition - chlorines - bacteriochlorins

References

1 Ali H. Lier JE. Chem. Rev.  1999,  99:  2379 

2 Sternberg ED. Dolphin D. Tetrahedron  1998,  54:  4151 

3 Huisgen R. In 1,3-Dipolar Cycloaddition Chemistry   Padwa A. Wiley-Interscience; New York: 1984. 

4 Silva AMG. Tome AC. Neves MGPMS. Silva AMS. Cavaleiro JAS. Chem. Commun.  1999,  1767 

5 Silva AMG. Tome AC. Neves MGPMS. Silva AMS. Cavaleiro JAS. Perrone D. Dondoni A. Tetrahedron Lett.  2002,  43:  603 

6 Silva AMG. Tome AC. Neves MGPMS. Cavaleiro JAS. Synlett  2002,  1155 

7 Flemming J. Dolphin D. Tetrahedron Lett.  2002,  43:  7281 

8

Spectroscopic data for 3. 3a: ¹H NMR (300 MHz, CDCl₃):
d = -1.86 (s, 1 H, NH), -1.93 (s, 1 H, NH), 6.85 (d, J = 4.2 Hz, 1 H, H-3), 6.98 (d, J = 4.2 Hz, 1 H, H-2), 7.46-8.18 (m, 23 H, PhH), 8.38-8.68 (m, 6 H, pyrrole-H); ¹³C NMR (100 MHz, CDCl₃): d = 29.68 (C-3), 60.38 (C-2), 112.77, 112.89 (C-17, C-18), 121.74, 122.40 (C-12, C-13), 127.20, 127.78 (C-7, C-8), 128.12, 128.72, 130.74, 134.44, 134.47, 135.47, 135.71 (ArC), 135.95, 138.67, 138.92 (C-5, C-10, C-15, C-20), 140.09, 140.31, 141.03 (C-6, C-9, C-11, C-14, C-16, C-19), 152.92, 156.45 (C-1, C-4), 160.83 (C-a); IR (KBr): 3352, 2956, 2919, 2850, 1723, 1562, 1432, 1281, 1178, 969, 792, 716, 702 cm^-1; MS-ESI: m/z = 802 (M⁺ + H), 615
(M⁺ - 188 + 2 H); HRMS-FAB: m/z calcd for C₅₁H₃₃Cl₂N₅O (M⁺), 801.2062; found, 801.2026; UV/Vis (CHCl₃): λ_max/nm (log ε) = 417 (5.17), 520 (4.09), 548 (4.11), 594 (3.76), 646 (4.24). 3b: ¹H NMR (300 MHz, CDCl₃): δ = -1.95 (s, 1 H, NH), -2.01 (s, 1 H, NH), 6.88 (d, J = 6.0 Hz, 1 H, H-3), 6.97 (d, J = 4.2 Hz, 1 H, H-2), 7.15-8.24 (m, 19 H, PhH), 8.38-8.68 (m, 6 H, pyrrole-H); ¹³C NMR (100 MHz, CDCl₃): d = 30.89 (C-3), 60.55 (C-2), 113.91 (C-17, C-18), 122.81, 123.48 (C-12, C-13), 126.79, 127.12 (C-7, C-8), 127.36, 127.53, 127.79, 128.00, 128.79, 130.41, 131.69, 132.61, 132.97, 133.99 (ArC), 135.66, 135.79, 136.01 (C-5, C-10 C-15, C-20), 140.46, 141.21, 141.55, 141.83 (C-6, C-9, C-11, C-14, C-16, C-19), 153.31, 156.61 (C-1, C-4), 160.86 (C-a); IR (KBr): 3349, 2957, 2920, 2851, 1568, 1476, 1429, 1359, 1298, 1178, 1091, 1016, 970, 795, 721, 705 cm^-1; MS-ESI: m/z = 940 (M⁺ + 3 H), 753 (M⁺ - 88 + 4 H); HRMS-FAB: m/z calcd for C₅₁H₂₉Cl₆N₅O (M⁺), 937.0503; found, 937.0510; UV/Vis (CHCl₃): λ_max/nm (log ε) = 419 (5.39), 520 (4.30), 549 (4.30), 595 (3.97), 646 (4.52).

9

Spectroscopic data for 4. 4a: ¹H NMR (300 MHz, CDCl₃): d = -1.85 (s, 2 H, NH), 6.75-6.81 (m, 4 H, H-2, 3, 12, 13), 6.96-8.07 (m, 26 H, PhH), 8.10 (d, J = 8.4 Hz, 2 H, H-7, 17), 8.63 (d, J = 7.8 Hz, 2 H, H-8, 18); IR (KBr): 3393, 2951, 2925, 2866, 1721, 1573, 1430, 1365, 1300, 1110, 1034, 956, 915, 821, 786, 705, 649 cm^-1; MS-ESI: m/z = 990 (M⁺ + 2 H), 614 (M⁺ - 376 + 2 H); HRMS-FAB: m/z calcd for C₅₈H₃₆Cl₄N₆O₂ (M⁺), 988.1654; found, 988.1624; UV/Vis (CHCl₃): λ_max/nm (log ε) = 387 (5.17), 507 (3.21), 535 (4.57), 655 (3.22), 706 (4.75); 4b: ¹H NMR (300 MHz, CDCl₃): d = -1.94 (s, 2 H, NH), 6.81-6.83 (m, 4 H, H-2, 3, 12, 13), 6.97-8.08 (m, 22 H, PhH), 8.10 (d, J = 8.1Hz, 2 H, H-7, 17), 8.58 (d, J = 8.4 Hz, 2 H, H-8, 18); IR (KBr): 3395, 2955, 2928, 2866, 1721, 1574, 1487, 1429, 1365, 1398, 1092, 1015, 955, 788, 701, 650 cm^-1; MS-ESI: m/z = 1129 (M⁺ + 5 H), 753 (M⁺ - 376 -5 H); HRMS-FAB: m/z calcd for C₅₈H₃₀Cl₈N₆O₂ (M⁺), 1124.0095; found, 1124.0069; UV/Vis (CHCl₃): λ_max/nm (log ε) = 388 (5.24), 503 (3.30), 534 (4.63), 651 (3.29), 706 (4.81).

10

Spectroscopic data for 5. 5a: ¹H NMR (300 MHz, CDCl₃): d = -1.92 (s, 1 H, NH), -1.85 (s, 1 H, NH), 6.90-6.93 (m, 4 H, H-2, 3, 12, 13), 6.95-7.97 (m, 26 H, PhH), 8.18 (d, J = 1.8 Hz, 2 H, H-7, 8), 8.42 (d, J = 7.2 Hz, 2 H, H-17, 18); IR (KBr): 3395, 2953, 2925, 2867, 1731, 1574, 1431, 1366, 1302, 1110, 1034, 955, 916, 821, 787, 706, 652 cm^-1; MS-ESI: m/z = 991 (M⁺ + 3 H), 615 (M - 376 + 3 H)⁺; HRMS-FAB: m/z calcd for C₅₈H₃₆Cl₄N₆O₂ (M⁺), 988.1654; found, 988.1628; UV/Vis (CHCl₃): λ_max/nm (log ε): 388 (5.21), 507 (3.22), 535 (4.59), 655 (3.22), 705 (4.84). 5b: ¹H NMR (300 MHz, CDCl₃): d = -2.03 (s, 1 H, NH), -1.95 (s, 1 H, NH), 6.92-6.93 (m, 4 H, H-2, 3, 12, 13), 6.95-7.97 (m, 22 H, PhH), 8.20 (d, J = 1.8 Hz, 2 H, H-7, 8), 8.32 (d, J = 7.2 Hz, 2 H, H-17, 18); IR (KBr): 3396, 2961, 2926, 2854, 1722, 1577, 1487, 1431, 1367, 1264, 1092, 1017, 957, 917, 789, 707, 653 cm^-1; MS-ESI: m/z = 1126 (M⁺ + 2 H), 753 (M⁺ - 376 + 3 H); HRMS- FAB: m/z calcd for C₅₈H₃₀Cl₈N₆O₂ (M⁺): 1124.0095; found, 1124.0153; UV/Vis (CHCl₃) =
λ_max/nm (log ε) = 388 (5.16), 502 (3.15), 535 (4.53), 651 (3.18), 706 (4.78).