8338
J.C.J.M.D.S. Menezes et al. / Tetrahedron 68 (2012) 8330e8339
6.17 (s, 1H, NH of porphyrin at C-50), 6.54 (d, 1H, J 2.1 Hz, H-40),
6.55e6.59 (m, 1H, H-m-Ph), 6.71e6.75 (m, 1H, H-m-Ph), 7.00 (d, 1H,
J 2.1 Hz, H-60), 7.02e7.07 (m, 1H, H-m-Ph), 7.21 (t, 1H, J 7.5 Hz, H-m-
Ph), 7.48 (s, 1H, H-3 of porphyrin at C-70), 7.56e7.71 (m, 24H, 4 20-
H-o-Ph and 20 H-m,p-Ph), 7.91e8.04 (m, 12H, H-o-Ph), 8.09 (s, 1H,
layer chromatography [light petroleum/chloroform (1:2)]. The
starting material Ni(II)e2-NH2eTPP and the 5,7-di-(2-
aminoporphyrinyl)-substituted indolin-2-one 9c were crystallized
from chloroform/methanol.
6
Procedure (iv) Microwave heating: In a closed glass reactor,
H-3 of porphyrin at C-50), 8.41 (d, 1H, J 5.0 Hz, H-
5.0 Hz, H- ), 8.53e8.74 (m, 10H, H- ); dC (125 MHz, CDCl3) 24.7
b
), 8.44 (d, 1H, J
purged with N2, porphyrin 9b (11.8
(17.9 mol, 1.5 equiv) were dissolved in dry, degassed toluene
(5 mL). To this solution were added Pd(OAc)2 (4.2 mol, 0.29 equiv),
XPhos (3.1 mol, 2.1 equiv).
mol, 0.26 equiv) and KOtBu (24.9
mmol) and Ni(II)e2-NH2eTPP 6
b
b
m
(CH3 ꢃ2); 28.4 (NCH3); 44.1 (C-30); 109.2 (C-40); 110.7 (C-3 of por-
phyrin at C-70); 110.8 (C-60); 111.5 (C-3 of porphyrin at C-50); 115.7,
115.8, 115.9, 118.46, 118.48, 120.21, 120.24, 126.5, 126.89, 126.91,
127.67; 126.4, 126.7, 126.87, 127.1, 127.2, 127.64, 127.74, 127.77, 128.4,
128.5, 128.6, 129.1 (C-m,p-Ph); 129.8 (C-70a); 130.46, 130.51, 131.4,
m
m
m
Similar microwave program was utilized as mentioned earlier. After
irradiation, the reaction mixture was cooled to room temperature,
filtered through a short plug column of CeliteÒ-545 (using chloro-
form) and washed with water. The organic layer was dried over
Na2SO4 and the solvent removed under reduced pressure. Further
purification by preparative thin layer chromatography, using
a mixture of light petroleum/chloroform (1:2), afforded the starting
material 6, 9b and 9c. All compounds were crystallized from
chloroform/methanol.
131.5, 131.7, 131.91, 131.96, 132.0, 132.3, 132.5, 132.8, 132.9 (C-b);
133.0,133.3, 133.5, 133.6, 133.7 (C-o-Ph); 138.4; 139.2 (C-30a); 139.5,
139.6, 140.69, 140.72, 140.75, 141.01, 141.03, 141.45, 141.48, 142.1,
142.81, 142.86, 142.88, 142.91, 143.1, 143.2, 143.3, 146.1, 150.6; 181.5
(C-20); UVevis (CHCl3): lmax (log ε) 414 (5.34), 538 (4.26), 588 (4.30)
ꢀ
nm; HRMS (ESI) m/z calcd for C99H67N11Ni2O (Mþ ) 1541.4231,
found 1541.4226.
The results of all these experiments are summarized in Table 3.
4.3.4. 6-[(2-Amino-5,10,15,20-tetraphenylporphyrinato)nickel(II)]-4-
bromo-1,3,3-trimethylindolin-2-one 9d. dH (300 MHz, CDCl3) 1.50 (s,
6H, CH3 ꢃ2), 3.11 (s, 3H, NCH3), 6.32 (s, 1H, NH), 6.47 (d, 1H, J 1.9 Hz,
H-50), 6.64 (d, 1H, J 1.9 Hz, H-70), 7.63e7.83 (2m, 12H, H-m,p-Ph),
7.96e8.01 (m, 8H, H-o-Ph), 8.26 (s, 1H, H-3), 8.58 (d, 1H, J 5.0 Hz, H-
4.4.1. 4,6-Bis[(2-amino-5,10,15,20-tetraphenylporphyrinato)nick-
el(II)]-1,3,3-trimethylindolin-2-one 9f. dH (300 MHz, CDCl3) 1.11 (s,
6H, CH3 ꢃ2), 3.15 (s, 3H, NCH3), 5.92 (d, 1H, J 1.5 Hz, H-70), 5.97 (s,
1H, NH of porphyrin at C-40), 6.25e6.35 (m, 2H, H-m-Ph), 6.38 (s,
1H, NH of porphyrin at C-60), 6.57 (t, 1H, J 7.3 Hz, H-m-Ph), 6.87 (t,
1H, J 7.3 Hz, H-m-Ph), 7.36e7.42 (m, 4H, 20-H-o-Ph), 7.47 (d, 1H, J
1.5 Hz, H-50), 7.54e7.70 (m, 20H, H-m,p-Ph), 7.92e8.05 (m, 12H, H-
o-Ph), 7.95 (s, 1H, H-3 of porphyrin at C-40), 8.23 (s, 1H, H-3 of
b), 8.66e8.72 (m, 5H, H-
b); dC (75 MHz, CDCl3) 21.8 (CH3 ꢃ2); 26.1
(NCH3); 46.0 (C-30); 95.3 (C-70); 112.9 (C-3); 113.8 (C-50); 115.7,
116.2; 118.7, 118.8 (C-40 and C-60); 120.2; 124.9 (C-30a); 126.90,
126.92, 127.0, 127.7, 127.8, 128.6, 128.9 (C-m,p-Ph); 130.8, 131.6,
porphyrin at C-60), 8.32e8.74 (m, 12H, H-
b); dC (75 MHz, CDCl3)
131.9, 132.0, 132.4 (C-
b
); 132.99, 133.03, 133.4, 133.5, 133.6 (C-o-Ph);
22.9 (CH3 ꢃ2); 26.2 (NCH3); 43.9 (C-30); 92.4 (C-70); 100.6 (C-50);
113.0 (C-3 of porphyrin at C-40); 113.37 (C-3 of porphyrin at C-60);
113.43, 115.7; 115.9 (C-30a); 118.4, 120.2, 124.5, 126.8, 126.93, 127.12,
127.9, 129.0, 131.7, 133.2; 126.2, 126.5, 126.89, 127.15, 127.6, 127.8,
128.5, 128.6 (C-m,p-Ph); 130.7, 131.5, 131.8, 131.9, 132.0, 132.5, 132.6,
139.5, 140.62, 140.65, 141.1, 141.3, 141.7, 142.3, 142.8, 142.9, 143.3,
144.7; 145.2 (C-70a); 181.3 (C-20); UVevis (CHCl3): lmax (log ε) 418
(5.02), 544 (3.97), 580 (4.01) nm; HRMS (ESI) m/z calcd for
ꢀ
C55H39BrN6NiO (Mþ ) 936.1717, found 936.1702.
132.8 (C-b); 133.4, 133.59, 133.65, 133.67 (C-o-Ph); 139.57, 139.60,
4.3.5. 6-[(2-Amino-5,10,15,20-tetraphenylporphyrinato)nickel(II)]-
1,3,3-trimethylindolin-2-one 9e. dH (300 MHz, CDCl3) 1.36 (s, 6H,
CH3 ꢃ2), 3.14 (s, 3H, NCH3), 6.31 (dd, 1H, J 2.0, 7.9 Hz, H-50), 6.44 (s,
1H, NH), 6.77 (d, 1H, J 2.0 Hz, H-70), 7.03 (d, 1H, J 7.9 Hz, H-40),
7.61e7.82 (2m, 12H, H-m,p-Ph), 7.97e8.00 (m, 8H, H-o-Ph), 8.25 (s,
139.7, 140.5, 140.6, 140.7, 141.1, 141.6, 142.1, 142.6, 142.81, 142.85,
142.9, 143.0, 143.2, 143.5, 144.79; 144.84 (C-70a); 148.3; 181.5 (C-20);
UVevis (CHCl3): lmax (log ε) 416 (5.34), 544 (4.66), 585 (4.49) nm;
HRMS (ESI) m/z calcd for C99H68N11Ni2O (MþH)þ 1542.4310, found
1542.4356.
1H, H-3), 8.56 (d, 1H, J 5.0 Hz, H-b), 8.65e8.71 (m, 5H, H-b); dC
(75 MHz, CDCl3) 24.5 (CH3 ꢃ2); 26.0 (NCH3); 43.9 (C-30); 96.5 (C-
70); 110.4 (C-50); 111.0 (C-3); 115.4, 116.8, 119.9, 122.4; 122.9 (C-40);
127.9 (C-3a0); 126.9, 127.0, 127.7, 127.8, 128.5, 128.9 (C-m,p-Ph);
4.4.2. Demetallation of compound 9a to 5-[2-Amino-5,10,15,20-
tetraphenylporphyrin]-1,3,3-trimethylindolin-2-one 9g. Porphyrin
9a (7.33 mmol) was treated with a mixture of 10% H2SO4 in chloro-
130.6, 131.5, 131.8, 132.5, 132.9 (C-
b
); 133.4, 133.5, 133.6 (C-o-Ph);
form (10 mL). The reaction mixture was stirred at room tempera-
ture for 2 min and then neutralized with a saturated solution of
NaHCO3. The aqueous phase was extracted with chloroform, and
the organic phase was dried over Na2SO4 and evaporated in vacuum
to dryness. The resulting residue was purified by preparative TLC. dH
(300 MHz, CDCl3) ꢂ2.54 (s, 2H, NH), 1.37 (s, 6H, CH3 ꢃ2), 3.22 (s, 3H,
NCH3), 6.43 (s, 1H, NH), 6.72 (dd, 1H, J 8.3, 1.9 Hz, H-60), 6.77 (d, 1H, J
8.3, 1.9 Hz, H-70), 7.29 (d, 1H, J 1.9 Hz, H-40), 7.68e7.89 (m, 12H, H-
m,p-Ph), 8.11 (s, 1H, H-3), 8.15e8.23 (m, 8H, H-o-Ph), 8.55 (d, 1H, J
133.0, 136.9, 138.9, 140.0, 140.3, 140.7, 141.2, 141.5, 142.2, 143.0;
143.6 (C-7a0); 145.9; 182.0 (C-20); UVevis (CHCl3): lmax (log ε) 416
(5.02), 542 (3.97), 582 (4.01) nm; HRMS (ESI) m/z calcd for
ꢀ
C55H40N6NiO (Mþ ) 858.2611, found 858.2612.
4.4. General procedures for the reaction (2-amino-5,10,15,20-
tetraphenylporphyrinato)nickel(II) 6 with bromo-indolin-2-
ones 9b,d under Buchwald conditions
4.8 Hz, H-b), 8.73e8.82 (m, 5H, H-b); UVevis (CHCl3): lmax (log ε)
Procedure (iii) Classical heating: In an oven dried Schlenck tube,
purged with N2, 7-(2-aminoporphyrinyl)-5-bromo-indolin-2-one
410 (5.33), 523 (4.39), 574 (4.24), 602 (4.22), 657 (3.97) nm; HRMS
(ESI) m/z calcd for C55H43N6O (MþH)þ 803.3498, found 803.3479.
9b (6.1
dissolved in dried, degassed toluene (5 mL). To this solution were
added Pd(OAc)2 (1.8 mol, 0.29 equiv), XPhos (1.7 mol, 0.28 equiv)
and KOtBu (12.7
mol, 2.1 equiv). The mixture was kept under
mmol) and Ni(II)e2-NH2eTPP 6 (9.1 mmol, 1.5 equiv) were
4.5. Theoretical calculations
m
m
m
Theoretical calculations were performed using density-
functional theory, with Gaussian 03.20 Molecular geometries were
optimized using the B3LYP functional with the 6-311G** basis-set,
having all properties been calculated at the same level over the
optimized structures. Conformational analysis of 9c and 9f was
performed at the scc-dftb level using DFTBþ,2 with parameters
taken from the mio-0-121 and trans3d-0-122 sets (for {C, H, N, O} and
a nitrogen atmosphere for 24 h at 100e110 ꢁC. After cooling to room
temperature and addition of chloroform, the reaction mixture was
filtered through a short plug column of CeliteÒ-545 and washed
several times with water. The organic layer was dried over Na2SO4.
After evaporation of the solvents under reduced pressure, the solid
residue was taken up in CHCl3 and then purified by preparative thin