Synthesis of β-arylporphyrins and oligophenylenediporphyrins by the suzuki-miyaura reaction

Article abstract of DOI:10.1055/s-0029-1217114

Several β-aryl-substituted porphyrins were prepared in good yields by Suzuki-Miyaura cross-coupling of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5,10,15,20-tetraphenylporphinatozinc(II) with various aryl bromides. Additionally, syntheses of β,β-dip

Full text of DOI:10.1055/s-0029-1217114

510
PAPER
Synthesis of b-Arylporphyrins and Oligophenylenediporphyrins by the
Suzuki–Miyaura Reaction
b-Arylporphyrins
and
O
ligophe
n
nylenedipor
a
Augusto C. Tomé,a Artur M. S. Silva,a José A. S. Cavaleiro*a
a
Department of Chemistry, University of Aveiro, 3810–193 Aveiro, Portugal
Departamento de Química Orgânica, Instituto de Qímica, Universidade Federal Fluminense, Outeiro de São João Baptista,
b
24020–141 Niterói, RJ, Brazil
Fax +351(234)370084; E-mail: jcavaleiro@ua.pt
Received 9 September 2009; revised 16 September 2009
Dedicated to Professor Peter Stanetty, Vienna University of Technology, on the occasion of his 65th birthday
versatility of the Suzuki–Miyaura coupling reaction in the
preparation of meso-tetraarylporphyrins bearing aryl
groups at the b-positions of the pyrrole rings. We found
that this method can be successfully used to synthesize a
Abstract: Several b-aryl-substituted porphyrins were prepared in
good yields by Suzuki–Miyaura cross-coupling of 2-(4,4,5,5-tetra-
methyl-1,3,2-dioxaborolan-2-yl)-5,10,15,20-tetraphenylporphinato-
zinc(II) with various aryl bromides. Additionally, syntheses of b,b¢-
diporphyrins linked by biphenylene or quaterphenylene units were range of b-aryl-substituted porphyrins, including com-
examined.
pounds that contain two porphyrin units linked through an
oligophenylene group.
Key words: Suzuki–Miyaura reaction, cross-coupling, oligophe-
nylenes, porphyrins, coupling
The starting porphyrin boronate 3 was prepared by a
method similar to that reported by Suslick.11 The palladi-
um-catalyzed Suzuki coupling reaction of 2-bromo-
The search for new tetrapyrrole macrocycles with partic-
ular features for specific applications (e.g., photodynamic
therapy (PDT) of cancer, catalysis, electronics, solar-cell
production, etc.) has become a target for several research
groups.1 Many approaches have been explored to develop
or improve methods that permit the synthesis of novel
porphyrin derivatives by such reactions as macrocycle
modification,2 Diels–Alder,3 1,3-dipolar cycloaddition,4
electrocyclization,5 or cyclopropanation6 reactions.
5,10,15,20-tetraphenylporphinatozinc(II)
(1)
with
4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2; pinacolbo-
rane) was carried out in a sealed Schlenk tube in degassed
anhydrous 1,2-dichloroethane at 65 °C overnight
(Scheme 1).
The porphyrin boronate 3 was then treated with a series of
aryl bromides (4a–d) to give high yields of the corre-
sponding b-aryl-substituted porphyrins 5a–d (Scheme 2).
The reactions were carried out in a mixture of toluene
and N,N-dimethylformamide containing tetrakis(triphe-
nyl)palladium as a catalyst and cesium carbonate as the
base.
b-Functionalization of porphyrins merits considerable at-
tention because of the diversity of structural features that
can be introduced into the macrocycle. Of particular im-
portance are methods that lead to reduced porphyrins
(chlorins or bacteriochlorins) or to p-extended porphyrin
derivatives that show strong absorption of light at wave-
lengths near or above 600 nm, a requirement for photosen-
sitizers used in PDT.1,7
The method was also used to functionalize the bromopor-
phyrin derivative 5b. In this way, the Suzuki coupling re-
action of 5b with porphyrin 3 gave the b,b-diporphyrin 6
in 18% yield (Scheme 3). Most of the unreacted porphyrin
5b was recovered from the reaction mixture. All attempts
to react the bromoporphyrin 5a with porphyrin 3 to afford
the corresponding phenylenediporphyrin were unsuccess-
ful, probably as a result of steric hindrance.
The Suzuki–Miyaura coupling reaction of organoboron
compounds with aryl halides in the presence of a palladi-
um-catalyst is one of the most versatile methods for con-
structing carbon–carbon bonds, particularly those in
unsymmetrical bisaryl systems.8 Suzuki–Miyaura cou-
pling reactions have also been extensively used in the
functionalization of porphyrins, mainly at the meso posi-
tions.9,10
The use of bromoaryl porphyrins 5a and 5b as aryl bro-
mides in Suzuki coupling reactions with other pinacol bo-
ranes was also studied. We found that these porphyrins
react with the commercially available 4-hydroxy-3,5-
dimethylphenylboronic acid pinacol ester 7 under con-
ventional Suzuki coupling conditions (Scheme 4) to give
the expected cross-coupling products 8a and 8b in 37%
and 26% yields, respectively. In these reactions, the
dimeric products 6 and 9 were also formed in 19% and
41% yields, respectively, through self-coupling of the aryl
bromide. The self-coupling of aryl bromides under the
Suzuki–Miyaura coupling conditions has been previously
reported.16
However, there are few reports of studies involving this
type of reaction in the structural modification of meso-
tetraarylporphyrins at the b-position of the pyrrole moi-
eties.11–15 With this in mind, we decided to explore the
SYNTHESIS 2010, No. 3, pp 0510–0514
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x
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x
x
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0
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Advanced online publication: 20.11.2009
DOI: 10.1055/s-0029-1217114; Art ID: Z19309SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
b-Arylporphyrins and Oligophenylenediporphyrins
511
O
O
O
O
Ph
Zn
Br
Ph
Zn
B
H
B
2
N
N
N
N
N
N
N
N
Pd(PPh3)2Cl2
Ph
Ph
Ph
Ph
1,2-DCE
65 °C, 18 h
68%
Ph
Ph
3
1
Scheme 1 Synthesis of the starting porphyrin boronate 3 by a Suzuki–Miyaura Reaction
Ph
Ar
Ph
Ph
Ph
2
20
Br
N
Zn
N
O
O
Ar-Br 4a–d
Pd(PPh3)4, Cs2CO3
B
OH
N
N
N
+
N
N
Ph
3
Zn
Ph
5
toluene–DMF (2:1)
80 °C, 5 h
15
N
7
Ph
10
Pd(PPh3)4, Cs2CO3
toluene–DMF (2:1)
Ph
5a, n = 1
5b, n = 2
4a, Ar =
Br
5a, 88%
5b, 83%
5c, 75%
5d, 51%
4b, Ar =
4c, Ar =
Br
Ph
OH
Ph
Ph
N
N
Zn
N
N
8a, n = 1, 37%
8b, n = 2, 26%
4d, Ar =
Ph
+
Ph
N
Ph
Scheme 2 The Suzuki–Miyaura reaction of porphyrin boronate 3
and with aryl bromides 4
N
Ph
N
N
Ph
Zn
n
Zn
Br
N
Ph
Ph
Ph
Ph
N
N
N
N
6, n = 1, 19%
9, n = 2, 41%
Ph
N
Zn
N
3
+
N
Ph
Scheme 4 Suzuki–Miyaura reaction between b-bromoarylporphy-
rins 5 and 4-hydroxy-3,5-dimethylphenylboronic acid pinacol ester
(7)
Ph
Ph
Pd(PPh3)4, Cs2CO3
The structures of the new compounds were assigned on
the basis of their 1H and 13C NMR spectra, and their mo-
lecular formulas were confirmed by high-resolution mass
spectroscopy. 2-D NMR correlation spectroscopy (CO-
SY), heteronuclear multiple bond correlation (HMBC)
spectroscopy, and heteronuclear single quantum coher-
ence (HSQC) spectroscopy were also obtained to identify
the resonances of some protons unequivocally. Because
compounds 5c and 5d have already been prepared by an-
other method,17 their spectral data are not reported (their
NMR spectra were identical to those already reported).
toluene–DMF (2:1)
80 °C, 18 h
Ph
Ph
N
N
N
N
Ph
Ph
Zn
Zn
Ph
Ph
N
N
N
N
Ph
Ph
6, 18%
Scheme 3 Synthesis of phenylenediporphyrin 6
Synthesis 2010, No. 3, 510–514 © Thieme Stuttgart · New York

512
A. C. Cunha et al.
PAPER
to the resonances of the biphenyl protons. The signal that
appears as a doublet at 7.64 ppm (J = 8.2 Hz) is due to the
resonance of Hd and the doublet at 7.49 ppm (J = 8.2 Hz)
is due to the resonance of Hc. The signals related to the
resonances of the protons Hb and Ha appear as two multi-
plets at 7.40–7.42 and 7.55–7.57 ppm, respectively. The
resonances of these protons were identified by the COSY,
HMBC, and HSQC spectroscopy.
Ph
Ph
Br
N
Zn
N
N
N
Hb
Ha
Ph
Ph
Ph
Ph
5a
1
The H NMR spectra of porphyrins 8a and 8b are quite
Br
similar. Their distinctive signals are those corresponding
to the OH proton (singlets at 4.51 ppm for 8a and 4.47
ppm for 8b) and the methyl groups (singlets at 2.35 and at
2.31 ppm, respectively, for 8a and 8b). The resonance of
the OH proton disappeared when deuterium oxide was
added to the NMR tube. The 1H NMR spectra of dimers 6
and 9 are very similar to those of the corresponding bro-
mo-substituted porphyrins 5a and 5b. These spectra show
that the two molecules have a high symmetry (Figure 2).
N
Zn
N
Hd
Hc
N
N
Hb
Ha
Ph
Ph
5b
Figure 1 Structures of b-bromophenyl- and b-bromobiphenyl-
porphyrins
Interest in the synthesis of multiporphyrin materials
(dimers and oligomers) is growing because of their poten-
tial applications18 as models in light harvesting,19 as mo-
lecular photonic and electronic wires,20 as catalysts,21 and
as photosensitizers for PDT.22 We have shown that new b-
aryl meso-tetraphenylporphyrins can be obtained in high
yields by Suzuki–Miyaura coupling. We have also shown
that this approach is a powerful tool for preparing novel
compounds containing two porphyrin moieties linked by
an oligophenylene unit. The new compounds are poten-
tially useful for the applications discussed above.
The 1H NMR spectrum of compound 5a shows two dou-
blets at 8.80 and 8.87 ppm, one singlet at 8.86 ppm, and
one multiplet at 8.92–8.97 ppm corresponding to the sev-
en b-pyrrolic protons. The ortho protons of the 5-, 10-,
and 15-phenyl groups give a multiplet between 8.20 and
8.23 ppm, whereas the ortho protons of the 20-phenyl
group appear as a multiplet at 7.84–7.86 ppm. The meta
and para protons of the 5-, 10-, and 15-phenyl groups ap-
pear as multiplets at 7.71–7.77 ppm, whereas the meta and
para protons of the 20-phenyl group appear as multiplets
at 7.25–7.28 and 7.38–7.40 ppm, respectively. The reso-
nance of the Ha protons of the 2-aryl group (Figure 1) ap-
pear as a doublet at 7.25 ppm (J = 8.4 Hz), whereas the
doublet at 7.20 ppm (J = 8.4 Hz) is due to the resonance
2-Bromo-5,10,15,20-tetraphenylporphyrinatozinc(II) was prepared
according to the literature.23 1H and13C NMR spectra were recorded
on a Bruker Avance 300 spectrometer at 300.13 and 75.47 MHz, re-
spectively or on a Bruker Avance 500 spectrometer at 500.13 and
1
of protons Hb. The H NMR spectrum of compound 5b
shows a similar profile to that of 5a, both for the signals
1
125.77 MHz for H and 13C, respectively. CDCl3 was used as the
solvent and TMS as the internal reference, and the chemical shifts
corresponding to the b-pyrrolic protons and the meso-phe- are expressed in d (ppm). Unequivocal 1H assignments were made
by 2D COSY and NOESY experiments (mixing time 800 ms),
nyl protons. The main differences are the signals related
Ph
Ph
Hb
Ha
N
N
N
N
Ph
Ph
Zn
Zn
Ph
Ph
N
N
N
N
6
Ph
Ph
Ph
Ph
Hb
Ha
Ph
Hc
Hd
N
N
N
N
Ph
Ph
Zn
Zn
Ph
N
N
N
N
9
Ph
Ph
Figure 2 Structures of phenylenediporphyrins 6 and 9
Synthesis 2010, No. 3, 510–514 © Thieme Stuttgart · New York

PAPER
b-Arylporphyrins and Oligophenylenediporphyrins
513
whereas 13C assignments were made on the basis of 2D HSQC and
HMBC experiments (the delay for long-range J C/H couplings were
optimized for 7 Hz). HRMS were recorded on a VG AutoSpec M
mass spectrometer using CHCl3 as the solvent and 3-nitrobenzyl al-
cohol (NBA) as the matrix. The UV/Vis spectra were recorded on
an UV-2501 PC Shimatzu spectrophotometer with CHCl3 as the
solvent. Flash chromatography was carried out on silica gel (230–
400 mesh). Preparative TLC was carried out on 20 × 20 cm glass
plates coated with silica gel (1 mm thick). Analytical TLC was car-
ried out on plastic sheets precoated with silica gel (Merck 60, 0.2
mm thick).
2 H, Hd), 7.71–7.77 (m, 9 H, 5,10,15-Ph-Hm,p), 7.88 (d, 2 H, J = 7.5
Hz, 20-Ph-Ho), 8.21–8.24 (m, 6 H, 5,10,15-Ph-Ho), 8.81 (d, J = 4.6
Hz, 1 H, H-12 or H-13), 8.87 (d, J = 4.6 Hz, 1 H, H-13 or H-12),
8.94–8.97 (m, 5 H, H-3,7,8,17,18).
13C NMR (75.47 MHz, CDCl3): d = 121.9, 125.3, 125.7, 125.9,
126.6, 127.5, 128.2, 128.5, 128.6, 129.0, 130.5, 130.7, 131.9, 132.0,
132.2, 134.4, 135.5, 135.8, 136.4, 137.9, 141.4, 147.0, 150.3.
HRMS (ESI): m/z [M + H]+ calcd for C56H36BrN4Zn 907.1409;
found: 907.1401.
2,2¢-(Biphenyl-4,4¢-diyl)bis[(5,10,15,20-tetraphenylporphyrina-
tozinc(II)] (6)
2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-5,10,15,20-tet-
raphenylporphyrinatozinc(II) (3)
1H NMR (500.13 MHz, CDCl3): d = 7.28–7.29 (m, 2 H, 20-Ph-Hp),
7.36–7.39 (m, 8 H, Hb and 20-Ph-Hm), 7.46 (d, J = 8.0 Hz, 4 H, Ha),
7.70–7.74 (m, 18 H, 5,10,12-Ph-Hm,p), 7.94–7.95 (m, 4 H, 20-Ph-
Ho), 8.82–8.27 (m, 12 H, 5,10,15-Ph-Ho), 8.81 (d, J = 4.6 Hz, 2 H,
H-12 or H-13), 8.83 (d, J = 4.6 Hz, 2 H, H-13 or H-12), 8.87–8.89
(m, 4 H, H-b) 8.90–8.91 (m, 6 H, H-b) ppm.
2-Bromo-5,10,15,20-tetraphenylporphyrinatozinc(II) (37.6 mg,
49.7 mmol), Pd(PPh3)2Cl2 (8.92 mg, 12.7 mmol), anhyd DCE (12
mL), Et3N (0.17 mL), and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(0.3 mL, 2079 mmol) were placed in a 50-mL Schlenk tube. The sol-
vent was degassed by repeated sonication for 0.5–1 min under re-
duced pressure and then the mixture was stirred for 18 h at 65 °C.
The reaction was quenched with aq NaCl (25 mL) and the mixture
was extracted with CH2Cl2 (2 × 25 mL). The organic layer was
washed with H2O (25 mL), dried (Na2SO4), and concentrated. The
residue was purified by flash chromatography (CHCl3); yield: 68%.
The NMR data were identical to those previously reported.11
13C NMR (75.47 MHz, CDCl3): d = 119.9, 120.2, 120.7, 125.58,
125.6, 126.9, 130.4, 126.9, 130.4, 131.4, 131.6, 132.8, 134.3, 134.4,
134.7, 135.5, 135.8, 137.4, 138.7, 142.0, 143.3, 143.5, 145.4, 146.5,
147.6, 148.0, 149.8, 149.9, 150.0, 150.1, 150.9 ppm.
UV/Vis (CHCl3): lmax (log ε) = 425 (5.07), 551 (3.81), 587 (3.16),
632 (2.89) nm.
HRMS (ESI): m/z [M + H]+ calcd for C100H63N8Zn2: 1503.3753;
found: 1503.3730.
Coupling of Boranes 3 or 7 with Aryl Halides 4 or 5; General
Procedure
A 25-mL Schlenk tube was charged with borane 3 or 7 (47.3 mmol),
aryl bromide 4 or 5 (144 mmol), Cs2CO3 (42 mg, 128.9 mmol),
Pd(PPh3)4 (25 mg, 21.6 mmol), DMF (1 mL), and toluene (2 mL).
The solvent was degassed by repeated sonication for 0.5–1 min un-
der reduced pressure, and the mixture was stirred for 5 h (or 18 h)
at 80 °C. The reaction was quenched with aq NaCl (25 mL) and the
mixture was extracted with CH2Cl2 (2 × 25 mL). The organic layer
was washed with H2O (25 mL), dried (Na2SO4), and concentrated.
The residue was purified by preparative TLC [gradient: hexane–
CHCl3 (2:1) to CHCl3].
2-(4¢-Hydroxy-3¢,5¢-dimethylbiphenyl-4-yl)-5,10,15,20-tetra-
phenylporphyrinatozinc(II) (8a)
Yield: 37%.
UV/Vis (CHCl3): lmax (log e) = 425 (5.09), 552 (3.80), 593 (3.13),
652 nm (2.15).
1H NMR (300.13 MHz, CDCl3): d = 2.35 (s, 6 H, CH3), 4.51 (s, 1
H, OH), 7.13–7.38 (m, 9 H, Ha, Hb, Hc, 20-Ph-Hm,p), 7.71–7.77 (m,
9 H, 5,10,15-Ph-Hm,p), 7.87–7.90 (m, 2 H, 20-Ph-Ho), 8.23–8.25 (m,
6 H, 5,10,15-Ph-Ho), 8.81 (d, J = 4.6 Hz, 1 H, H-12 or H-13), 8.87
(d, J = 4.6 Hz, 1 H, H-13 or H-12), 8.92–8.97 (m, 5 H, H-
3,7,8,17,18).
2-(4-Bromophenyl)-5,10,15,20-tetraphenylporphyrinato-
zinc(II) (5a)
13C NMR (75.47 MHz, CDCl3–Py-d5): d = 16.8 (CH3), 119.7,
120.0, 120.5, 121.6, 124.7, 125.1, 125.6, 125.9, 126.2, 126.7, 126.8,
127.9, 130.1, 130.7, 131.1, 131.3, 131.4, 132.0, 132.36, 134.2,
137.6, 137.7, 141.7, 143.1, 143.1, 143.3, 146.4, 146.5, 147.4, 150.0,
152.9.
HRMS (ESI): m/z [M]+ calcd for C58H40N4OZn: 872.24936; found:
872.24881.
Yield: 88%.
UV/Vis (CDCl3): lmax (log e) = 422 (5.72), 511 (3.52), 549 (4.32),
586 nm (3.49).
1H NMR (300.13 MHz, CDCl3): d = 7.20 (d, J = 8.4 Hz, 2 H, Hb),
7.25–7.28 (m, 2 H, 20-Ph-Hm), 7.25 (d, J = 8.4 Hz, 2 H, Ha), 7.38–
7.40 (m, 1 H, 20-Ph-Hp), 7.71–7.77 (m, 9 H, 5,10,15-Ph-Hm,p),
7.84–7.86 (m, 2 H, 20-Ph-Ho), 8.20–8.23 (m, 6 H, 5,10,15-Ph-Ho),
8.80 (d, J = 4.7 Hz, 1 H, H-12 or H-13), 8.86 (s, 1 H, H-3), 8.87 (d,
J = 4.7 Hz, 1 H, H-13 or H-12), 8.92–8.97 (m, 4 H, H-7,8,17,18).
13C NMR (75.47 MHz, CDCl3): d = 119.8, 121.6, 126.0, 126.5,
126.6, 127.1, 127.5, 130.2, 131.5, 131.8, 132.0, 132.1, 132.2, 132.7,
134.3, 134.4, 135.1 (C-3), 135.6, 138.2, 141.3, 142.6, 142.8, 146.3,
147.7, 150.2, 150.3, 151.2.
2-(4¢¢-Hydroxy-3¢¢,5¢¢-dimethyl-1,1¢:4¢,1¢¢-terphenyl-4-yl)-
5,10,15,20-tetraphenylporphyrinatozinc(II) (8b)
UV/Vis (CHCl3): lmax (log e) = 422 (5.73), 508 (3.52), 550 (4.34),
586 nm (2.60).
1H NMR (500.13 MHz, CDCl3): d = 2.32 (s, 6 H, CH3), 4.47 (s, 1
H, OH), 7.22–7.24 (m, 1 H, 20-Ph-Hp), 7.30–7.32 (m, 2 H, 20-Ph-
Hm), 7.33–7.34 (s, 2 H, He), 7.38–7.43 (m, 8 H, Ha,b,c,d), 7.71–7.77
(m, 9 H, 5,10,15-Ph-Hm,p), 7.89–7.90 (m, 2 H, 20-Ph-Ho), 8.21–8.25
(m, 6 H, 5,10,15-Ph-Ho), 8.82 (d, J = 4.6 Hz, 1 H, H-12 or H-13),
8.87 (d, J = 4.6 Hz, 1 H, H-12 or H-13), 8.95–8.97 (m, 5 H, H-
3,7,8,17,18).
13C NMR (75.47 MHz, CDCl3): d = 16.1 (CH3), 29.7, 34.8, 78.3,
81.4, 120.9, 123.1, 123.6, 125.8, 125.9, 126.5, 126.7, 126.8, 127.1,
127.2, 127.3, 127.5, 128.6, 128.7, 130.6, 131.4, 131.9, 132.7, 134.3,
134.4, 135.7, 142.7, 142.9, 150.1, 153.2.
HRMS (ESI): m/z [M]+ calcd for C64H44N4OZn: 948.28066; found:
948.27976.
HRMS (ESI): m/z [M + H]+ calcd for C50H32BrN4Zn: 831.1096;
found: 831.1121.
2-(4¢-Bromobiphenyl-4-yl)-5,10,15,20-tetraphenylporphyrina-
tozinc(II) (5b)
Yield: 83%.
UV/Vis (CHCl3): lmax (log e) = 422 (5.61), 511 (3.42), 549 (4.24),
586 (3.36) nm.
1H NMR (500.13 MHz, CDCl3): d = 7.14–7.16 (m, 1 H, 20-Ph-Hp),
7.20–7.22 (m, 2 H, 20-Ph-Hm), 7.40–7.42 (m, 2 H, Hb), 7.49 (d,
J = 8.2 Hz, 2 H, Hc), 7.55–7.57 (m, 2 H, Ha), 7.64 (d, J = 8.24 Hz,
Synthesis 2010, No. 3, 510–514 © Thieme Stuttgart · New York

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A. C. Cunha et al.
PAPER
2,2¢-(1,1¢:4¢,1¢¢:4¢¢,1¢¢¢-Quaterphenyl-4,4¢¢¢-diyl)bis[5,10,15,20-
tetraphenylporphyrinatozinc(II)] (9)
Yield: 14%.
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2005, 9, 659.
(12) Yamaguchi, S.; Katoh, T.; Shinokubo, H.; Osuka, A. J. Am.
Chem. Soc. 2007, 129, 6392.
(13) Hata, H.; Shinokubo, H.; Osuka, A. J. Am. Chem. Soc. 2005,
UV/Vis (CHCl3–MeOH, 1:99): lmax (log e) = 423 (5.33), 508
(3.40), 550 (4.02), 586 nm (3.31).
1H NMR (500.13 MHz, CDCl3): d = 7.21–7.30 (m, 4 H, 20-Ph-Hm),
7.30–7.31 (m, 2 H, 20-Ph-Hp), 7.38–7.43 (m, 4 H, Hb), 7.52–7.53
(m, 4 H, Ha), 7.68–7.69 (m, 8 H, Ha,b), 7.18–7.77 (m, 18 H, 5,10,15-
Ph-Hm,p), 7.89–7.90 (m, 4 H, 20-Ph-Ho), 8.21–8.25 (m, 12 H,
5,10,15-Ph-Ho), 8.82 (d, J = 4.6 Hz, 2 H, H-12 or H-13), 8.89 (d,
J = 4.6 Hz, 2 H, H-12 or H-13), 8.94–8.97 (m, 10 H, H-
3,7,8,17,18).
13C NMR (75.47 MHz, CDCl3): d = 120.1, 120.6, 120.9, 121.5,
122.4, 122.9, 123.2, 123.3, 125.3, 125.8, 125.9, 126.4, 126.5, 126.6,
126.7, 126.8, 127.1, 127.2, 127.3, 127.4, 127.5, 128.2, 128.6, 129.0
130.6, 131.4, 131.9, 132.0, 132.1, 132.2, 132.7, 134.3, 134.4, 135.7,
137.7, 138.6, 139.6, 139.8, 141.0, 141.4, 142.7, 142.7.
HRMS (ESI): m/z [M + 2H]+ calcd for C112H72N8Zn2: 1656.44629;
found: 1656.44582.
Acknowledgment
Thanks are due to Universidade de Aveiro, Fundação para a Ciência
e a Tecnologia (FCT), FEDER and the GRICES-CAPES collabora-
tive programme for funding this work. A.T.P.C.G.and A.C.C. thank
FCT (SFRH/BD/38528/2007) and CAPES, respectively, for their
research grants.
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Synthesis 2010, No. 3, 510–514 © Thieme Stuttgart · New York