Wada et al.
4
SO .
5
-[(2-(3-P yr idylm eth oxy)ph en yl)-10,15,20-tr iph en ylpor -
saturated aqueous NaCl (20 mL × 2) and dried over Na
Evaporation of the solvent and purification by preparative
thin-layer chromatography (SiO , CHCl /MeOH ) 50/1) af-
forded Ni‚3 as a pink solid (27 mg, 95%): H NMR (CDCl ) δ
2
p h yr in a to]zin c(II) (Zn ‚2). This compound was prepared from
F B‚2 (78 mg, 108 µmol) in a manner similar to that for Zn ‚1
2
3
1
1
(
)
71 mg, 84%): H NMR (DMSO-d
6
) δ 5.12 (s, 2H), 6.68 (dd, J
3
5.0 Hz, 7.5 Hz, 1H), 6.91 (d, J ) 5.0 Hz, 1H), 7.41 (t, J ) 7.5
7.37 (dd, J ) 4.0 Hz, 7.5 Hz, 1H), 7.64 (m, 9H), 7.84 (t, J ) 7.5
Hz, 1H), 7.97 (m, 4H), 8.01 (m, 2H), 8.19 (d, J ) 8.0 Hz, 1H),
8.27 (d, J ) 7.0 Hz, 1H), 8.38 (m, 1H), 8.40 (d, J ) 4.5 Hz,
2H), 8.61 (m, 1H), 8.62 (d, J ) 4.5 Hz, 2H), 8.71 (AB quartet,
Hz, 1H), 7.56 (d, J ) 7.5 Hz, 1H), 7.79 (m, 9H), 7.85 (m, 1H),
7
(
.99 (m, 3H), 8.17 (m, 6H), 8.74 (m, 8H); UV-vis (CH
2
Cl
2
) λmax
+
log ꢀ) 426 (5.67), 562 (4.11), 603 (3.82); HRMS (FAB) (M )
calcd for C50
-Qu in olin ebor on ic Acid (12). To a solution of anhydrous
copper(II) halide (42.88 g, 192 mmol) and tert-butyl nitrite
35.5 mL, 320 mmol) in anhydrous CH CN (640 mL) was added
-aminoquinoline (10) (23 g, 160 mmol) at room temperature
H
33
N
5
OZn 783.1977, found 783.1995.
J ) 4.5 Hz, 4H); UV-vis (CH
2
Cl
4.26); HRMS (FAB) (M ) calcd for C47
21.1772.
5-(4-Meth oxyca r bon yl-2,6-bis(m eth oxyca r bon ylm eth -
2
) λmax (log ꢀ) 415 (5.40), 528
+
(
29 5
H N
Ni 721.1776, found
8
7
(
8
3
oxy)p h en yl)d ip yr r om eth a n e (15). To a solution of aldehyde
6 (1.5 g, 4.41 mmol) in pyrrole (50 mL, 723 mmol) was added
trifluoroacetic acid (100 µL, 1.31 mmol) at room temperature
2
under N . The reaction mixture was heated to 65 °C and then
stirred for 12 h. The mixture was concentrated, and ether (600
mL) was added. The organic layer was washed with water (200
2
under N . After the mixture stirred for 30 min, triethylamine
mL × 5) and dried over MgSO
4
. Evaporation of the solvent
and distillation under reduced pressure at 160-180 °C (0.4
(417 µL, 3 mmol) was added, and the mixture was concentrated
under reduced pressure. Purification by flash column chro-
mmHg) afforded 8-bromoquinoline (11) as a yellow oil (23.4 g,
matography (SiO
g, 92%): H NMR (CDCl
(bs, 4H), 5.96 (m, 2H), 6.05 (m, 2H), 6.37 (s, 1H), 6.67 (m, 2H),
7.20 (s, 2H), 9.45 (bs, 2H); HRMS (FAB) (M ) calcd for
2
, CHCl
3
) afforded 15 as a white solid (1.86
) δ 3.81 (s, 6H), 3.87 (s, 3H), 4.67
1
7
0%). A solution of 11 (2.68 g, 12.8 mmol) in THF (10 mL)
3
was cooled to -78 °C under N , and n-butyllithium (1.55 M in
2
+
hexane, 10 mL, 15.5 mmol) was added dropwise during 30 min.
After 1 h, trimethyl borate (3 mL) was added dropwise, and
then the ice bath was removed. The mixture was stirred for 1
h at room temperature, and then 3 M HCl (30 mL) was added.
C
C
23
H
H
24
N
N
2
O
O
8
456.1533, found 456.1542. Anal. Calcd for
: C, 60.52; H, 5.30. Found: C, 60.93; H, 5.25.
23
24
2
8
5
-(8-Qu in olyl)dipyr r om eth an e (17). A mixture of 8-formyl-
The aqueous layer was washed with Et
solid NaHCO . The resulting light brown precipitate was
collected, which was recrystallized from acetone/hexane to give
2
O and neutralized with
quinoline 16 (2.5 g, 15.9 mmol) and pyrrole (78 mL, 1127
mmol) was stirred for 12 h at 120 °C. The mixture was
concentrated under reduced pressure. Purification by flash
3
1
1
7
7
8
3
2 as a pale yellow solid (1.38 g, 60%): H NMR (CD OD) δ
column chromatography (SiO
recrystallization from CH Cl /hexane afforded 17 as an ivory-
white solid (2.44 g, 56%): H NMR (CDCl
.09 (q, J ) 7.5 Hz, 2H), 6.58 (bs, 1H), 6.66 (m, 2H), 7.39 (dd,
2 3
, CHCl /AcOEt ) 10/1) and
.56 (t, J ) 7.5 Hz, 1H), 7.69 (dd, J ) 5.0 Hz, 7.5 Hz, 1H),
.80 (d, J ) 7.5 Hz, 1H), 8.10 (dd, J ) 1.5 Hz, 7.5 Hz, 1H),
2
2
1
3
) δ 5.92 (m, 2H),
.52 (d, J ) 7.5 Hz, 1H), 8.57 (dd, J ) 1.5 Hz, 5.0 Hz, 1H);
6
+
HRMS (EI) (M ) calcd for C
9
H
8
BNO
2
173.0648, found 173.0649.
J ) 7.5 Hz, 5.0 Hz, 1H), 7.48 (dd, J ) 8.0 Hz, 7.5 Hz, 1H),
Anal. Calcd for C
C, 62.41; H, 4.55; N; 8.07.
,10,15-Tr ip h en yl-20-(8-qu in olyl)p or p h yr in (F B‚3). A
mixture of 5,15-dibromo-10,20-diphenylporphyrin 13 (240 mg,
87 µmol), 8-quinolylboronic acid 12 (67 mg, 387 µmol),
phenylboronic acid 14 (47 mg, 387 µmol), and tetrakis-
triphenylphosphine)palladium (27 mg, 23 µmol) in a mixed
solvent of toluene (40 mL), ethanol (4 mL), and a deoxygenated
9 8 2
H BNO : C, 62.49; H, 4.66; N; 8.10. Found:
7
1
.64 (dd, J ) 7.5 Hz, 1.0 Hz, 1H), 7.71 (dd, J ) 8.0 Hz, 1.0 Hz,
H), 8.16 (dd, J ) 8.0 Hz, 2.0 Hz, 1H), 8.78 (bs, 2H), 8.91(dd,
+
5
J ) 5.0 Hz, 2.0 Hz, 1H); HRMS (FAB) (M ) calcd for C18
273.1266, found 273.1264. Anal. Calcd for C18
H
15
N
3
15 3
H N : C, 79.10;
3
H, 5.53; N; 15.37. Found: C, 79.02; H, 5.55; N; 14.99.
cis-5,15-Bis(4-m eth oxyca r bon yl-2,6-bis(m eth oxyca r bo-
n ylm eth oxy)p h en yl)-10,20-bis(8-qu in olyl)p or p h yr in (F B‚
(
4
). Aldehyde 16 (504 mg, 3.2 mmol) and dipyrromethane 15
2
1
M Na
3 h under N
2
CO
3
aqueous solution (8 mL) was stirred at 80 °C for
. After AcOEt (30 mL) was added, the organic
(1.46 g, 3.2 mmol) were dissolved in CH
2
Cl
2
(320 mL) under
2
N
, and then trifluoroacetic acid (440 µL, 5.70 mmol) was
2
layer was washed successively with 3 M HCl (40 mL), satur-
ated aqueous Na CO (50 mL), and saturated aqueous NaCl
100 mL × 3) and dried over Na SO . Evaporation of the sol-
vent and purification by flash column chromatography (SiO
CHCl
added. After the reaction mixture was stirred at room tem-
perature for 30 min, 2,3-dichloro-5,6-dicyanobenzoquinone (930
mg, 4.1 mmol) was added, and the mixture was stirred for 1
h. The solution was then neutralized by addition of triethyl-
amine (793 µL, 5.70 mmol) and concentrated. Purification by
2
3
(
2
4
2
,
3
/AcOEt ) 100/1 to 10/1) afforded F B‚3 as a purple solid
1
(
4
1
3
67 mg, 26%): H NMR (CDCl ) δ -2.59 (s, 2H), 7.37 (dd, J )
column chromatography (SiO
and flash column chromatography (SiO
1
2
, CHCl
3
/AcOEt ) 100/1 to 10/1)
, CHCl /AcOEt ) 10/
) afforded F B‚4 as a purple solid (66 mg, yield 4%): H NMR
CDCl ) δ -2.39 (s, 2H), 3.42 (s, 6H), 3.47 (s, 6H), 4.02 (s, 6H),
.0 Hz, 7.5 Hz, 1H), 7.73 (m, 9H), 7.92 (dd, J ) 1.5 Hz, 6.0 Hz,
H), 8.25 (m, 6H), 8.41 (dd, J ) 2.0 Hz, 7.5 Hz, 1H), 8.49 (d,
2
3
1
J ) 1.5 Hz, 1H), 8.50 (m, 1H), 8.51 (d, J ) 4.5 Hz, 2H), 8.57
(
3
(
dd, J ) 1.5 Hz, 7.5 Hz, 1H), 8.73 (d, J ) 4.5 Hz, 2H), 8.82 (m,
4
7
7
4
4
.33 (s, 4H), 4.34 (s, 4H), 7.41 (dd, J ) 7.5 Hz, 4.0 Hz, 2H),
.51 (s, 2H), 7.52 (s, 2H), 7.69 (dd, J ) 5.0 Hz, 3.0 Hz, 2H),
.88 (t, J ) 3.0 Hz, 2H), 8.24 (d, J ) 7.5 Hz, 2H), 8.44 (d, J )
.5 Hz, 4H), 8.45 (dd, J ) 5.0 Hz, 1.5 Hz, 2H), 8.62 (dd, J )
+
4
6
5
8
H); HRMS (FAB) (M ) calcd for C47
65.2577; UV-vis (CH Cl ) λmax (log ꢀ) 419 (5.63), 514 (4.21),
50 (3.72), 590 (3.63), 647 (3.28). Anal. Calcd for C47 : C,
4.79; H, 4.69; N; 10.52. Found: C, 84.94; H, 4.60; N; 10.59.
5,10,15-Tr ip h en yl-20-(8-qu in olyl)p or p h yr in a t o]zin c-
II) (Zn ‚3). This compound was prepared from F B‚3 (54 mg,
1 µmol) in a manner similar to that for Zn ‚1 (58 mg, 98%):
31 5
H N 665.2579, found
2
2
31 5
H N
.0 Hz, 1.5 Hz, 2H), 8.70 (d, J ) 4.5 Hz, 4H); UV-vis (CH
2
-
[
Cl
HRMS (FAB) (M ) calcd for C66
1184.3442. Anal. Calcd for C66
2
) λmax (log ꢀ) 420 (5.88), 514 (4.65), 548 (4.15), 588 (4.18);
+
(
H
N
52
N
6
O
16 1184.3440, found
8
H
52
6
O16: C, 66.89; H, 4.42; N;
1
H NMR (CDCl
3
) δ 7.37 (dd, J ) 4.0 Hz, 7.5 Hz, 1H), 7.70 (m,
7.09. Found: C, 66.97; H, 4.47; N; 7.34.
9
(
(
H), 7.93 (t, J ) 7.5 Hz, 1H), 8.16 (m, 6H), 8.27 (m, 1H), 8.35
[
cis-5,15-Bis(4-m et h oxyca r b on yl-2,6-b is(m et h oxyca r -
m, 1H), 8.44 (dd, J ) 1.5 Hz, 7.5 Hz, 1H), 8.50 (m, 1H), 8.52
bon ylm eth oxy)p h en yl)-10,20-bis(8-qu in olyl)p or p h yr in a -
to]zin c(II) (Zn ‚4). A solution of F B‚4 (20 mg, 17 µmol) and
2 3
Zn(OAc) -saturated methanol (1 mL) in CHCl (5 mL) was
d, J ) 4.5 Hz, 2H), 8.77 (d, J ) 4.5 Hz, 2H), 8.90 (AB quartet,
+
J ) 4.5 Hz, 4H); HRMS (FAB) (M ) calcd for C47
H
29
N
5
Zn
7
(
27.1714, found 727.1716; UV-vis (CH
5.76), 509 (3.30), 548 (4.33), 588 (3.33).
5,10,15-Tr ip h en yl-20-(8-qu in olyl)p or p h yr in a to]n ick -
el(II) (Ni‚3). A solution of F B‚3 (26 mg, 39 µmol) and
Ni(OAc) -saturated methanol (4 mL) in CHCl (20 mL) was
refluxed for 12 h. After cooling, the solution was washed suc-
cessively with saturated aqueous NaHCO
(20 mL × 2) and
2 2
Cl ) λmax (log ꢀ) 420
stirred for 3 h at room temperature. The solution was washed
successively with saturated aqueous NaHCO
(10 mL × 2) and
saturated aqueous NaCl (10 mL × 2) and dried over Na SO
Evaporation of the solvent and purification by preparative
thin-layer chromatography (SiO , AcOEt) afforded Zn ‚4 as a
pink solid (20 mg, 93%): 1H NMR (CDCl
) δ 3.25 (s, 6H), 3.47
(s, 6H), 4.02 (s, 6H), 4.27 (s, 4H), 4.38 (s, 4H), 7.42 (m, 2H),
3
[
2
4
.
2
3
2
3
3
5
130 J . Org. Chem., Vol. 68, No. 13, 2003