Selective Synthesis of Tripyrranes, Tetrapyrranes, and Corroles

Article abstract of DOI:10.1002/ejoc.201501062

A new, catalytic, and general methodology was developed for the direct synthesis of unsymmetrical AB-type tripyrranes by reaction of dipyrromethanesulfonamides with pyrrole. Key structure dipyrromethanesulfonamides were synthesized by the addition of meso

Full text of DOI:10.1002/ejoc.201501062

FULL PAPER
DOI: 10.1002/ejoc.201501062
Selective Synthesis of Tripyrranes, Tetrapyrranes, and Corroles
Gokcen Aydin,[a] Baris Temelli,[a] and Canan Unaleroglu*[a]
Keywords: Synthetic methods / Nitrogen heterocycles / Corroles / Tosylimines / Porphyrinoids
A new, catalytic, and general methodology was developed
for the direct synthesis of unsymmetrical AB-type tripyrranes
by reaction of dipyrromethanesulfonamides with pyrrole.
Key structure dipyrromethanesulfonamides were synthe-
sized by the addition of meso-substituted dipyrromethanes to
Cu(OTf)2-activated tosylimines. The introduced method en-
ables selective preparation of tetrapyrranes in high yields by
tuning the conditions of the addition reaction. The oxidation
of tetrapyrranes by 2,3-dichloro-5,6-dicyano-1,4-benzoquin-
one afforded only corresponding A3- and trans-A2B-corroles.
Thereupon, the first studies in the literature mainly focused
on the chemistry of meso-substituted dipyrromethanes. In
Introduction
Porphyrins and their expanded and contracted analogs the following years, growing interest in the synthesis of ex-
have found widespread applications in catalysis, medicinal panded and contracted porphyrins has increased the syn-
chemistry, materials science, and supramolecular chemis- thetic importance of tripyrranes and tetrapyrranes, because
try.[1] Acyclic oligopyrromethanes, such as dipyrrometh- they are crucial building blocks for these macrocyclic het-
anes, tripyrranes, and tetrapyrranes are important precur- eroaromatics (Scheme 1).[3]
sors for the construction of these heteroaromatics. Among
Acid-catalyzed condensation of aldehyde and pyrrole is
these, meso-substituted dipyrromethanes have been an in- the most straightforward method for the synthesis of oligo-
dispensable structure in synthetic porphyrin chemistry.[2] pyrroles should identical meso-substituents be desired. This
Scheme 1. Building blocks for hexaphyrins and corroles.
[a] Hacettepe University, Chemistry Department,
method requires excessive amounts of pyrrole to suppress
Beytepe, 06800 Ankara, Turkey
the polymerization reaction and usually forms dipyrro-
methanes as a main product and other oligocondensates
(tripyrranes, tetrapyrranes, and so on) as side products.[4]
The necessity for long chromatographic separation of all
E-mail: canan@hacettepe.edu.tr
http://www.chem.hacettepe.edu.tr/en/personnel/
canan-unaleroglu/
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201501062.
Eur. J. Org. Chem. 2015, 7583–7593
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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G. Aydin, B. Temelli, C. Unaleroglu
FULL PAPER
Scheme 2. Preparation of tripyrranes 4 and tetrapyrranes 5.
oligopyrroles and low yields of tripyrranes and tetrapyrr- veloped to form A3 and A2B corroles by oxidative ring clo-
anes are drawbacks of this method. The major synthetic sure of bilanes.[10a,10b] Then, Gryko made an important
limitation of this method is that it is not possible to place contribution to the large-scale preparation of meso-substi-
different substituents selectively at the methylene bridge in tuted triarylcorroles.[10c] These improvements allowed their
tripyrranes or tetrapyrranes. Although reported methods use in various fields ranging from materials chemistry to
are mainly focused on the synthesis of symmetrical oligo- photophysics.[11] Although significant synthetic progress
pyrroles, a very limited number of methods for unsymmetri- has been made for meso-substituted corroles, there is still a
cal derivatives have been developed to date, which include need for alternative synthetic approaches.
the treatment of pyrroles or dipyrromethanes with 2-(acet-
oxymethyl)pyrroles,[5] reactions of dipyrromethane carbi- cols for the synthesis of meso-substituted dipyrromethanes,
nols with dipyrromethanes[6] or pyrroles.[7]
porphyrins, and [26]hexaphyrin by using tosylimines as ef-
Previously, we have successfully developed facile proto-
Due to the importance of oligopyrromethanes in por- fective reagents in the presence of metal triflate catalysts.[12]
phyrin chemistry, developing a new method for the synthe- As part of our ongoing research on oligopyrromethanes
sis of tripyrranes and tetrapyrranes with non-identical sub- and macrocyclic aromatic compounds, herein we present an
stituents at the methylene bridges is in great demand. A efficient synthetic methodology for symmetrical or unsym-
new stepwise method for the synthesis of these compounds metrical tripyrranes 4 and tetrapyrranes 5 by starting from
would also establish a convenient synthetic procedure to dipyrromethanesulfonamides 3. In addition, the use of tet-
build up more complex members of the porphyrinoid fam- rapyrranes for the synthesis of A3 as well as trans-A2B cor-
ily. Among them, corroles, analogs of porphyrins that have roles 6 is described (Scheme 2).
one less carbon atom, are the most well-known contracted
porphyrinoids because of their interesting properties, such
Results and Discussion
as stabilization of higher oxidation states of metal ions,
higher fluorescence quantum yields, and larger Stokes
shifts.[8] Despite these features, synthetic developments for
corroles remained stagnant until 1999, at which time Gross
Synthesis of Dipyrromethanesulfonamides
Our study was initiated by optimizing the synthesis of
and Paolesse published three papers on the direct syntheses dipyrromethanesulfonamides by using the reaction of 5-
of A3-type meso-substituted corroles by reaction of pyrrole phenyldipyrromethane (1a) with N-benzylidene-4-methyl-
with aldehydes.[9] Thereafter, some other methods were de- benzenesulfonamide (2a; Scheme 3).
Scheme 3. Preparation of dipyrromethanesulfonamide 3a and bilane 5a.
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Selective Synthesis of Tripyrranes, Tetrapyrranes and Corroles
In accordance with our previously reported procedure Table 1. Optimization of conditions for dipyrromethanesulfon-
amide synthesis.[a]
for the synthesis of pyrrolesulfonamides,[12f] initial condi-
tions for the reaction were chosen as 10% Cu(OTf)2, di-
pyrromethane 1a/tosylimine 2a (3:1), tetrahydrofuran
(THF), 0 °C (Table 1, Entry 1). Under these conditions, di-
pyrromethanesulfonamide 3a and bilane 5a were obtained
in 60 and 10% yields, respectively. Next, the influence of
the 1a/2a ratio was investigated (Table 1, Entries 1–3).
When the ratio of 1a/2a was taken as 1:1 (Table 1, Entry 3),
the yield of dipyrromethanesulfonamide slightly increased
to 65%, and the yield of bilane decreased to 2%. The ratio
1:1 for 1a/2a was chosen as the optimum ratio for further
reactions. Subsequently, the effect of temperature on the di-
pyrromethanesulfonamide formation was studied. The reac-
tion at room temperature furnished 3a in decreased yield
with a sharp increase in the yield of 5a (Table 1, Entry 4).
By lowering the temperature to –20 °C a decrease in the
yield of 3a (40%) occurred (Table 1, Entry 5). The best re-
sult was obtained at 0 °C. Then the effects of different sol-
vents on the reaction were investigated. Among the
screened solvents (Table 1, Entries 3, 6–11), THF was found
to be the best. Next, we explored the effect of different cata-
lysts, including Lewis acids and clays on the model reaction
(Table 1, Entries 12–21). ZnCl2, Mont. K-10, CuBr and
InCl3 gave 3a in low yields (15–30% yields; Table 1, En-
tries 16, 18, 20, and 21). Comparable yields were obtained
if Cu(OTf)2, Yb(OTf)3, Gd(OTf)3, or FeCl3 were used
Entry Temp. [°C] Solvent 1a/2a
Catalyst
Yield [%][b]
3a
5a
1
2
0
0
THF
THF
THF
THF
THF
DMF
CH3CN
toluene
CH2Cl2
CH3OH
CHCl3
THF
THF
THF
THF
THF
THF
THF
THF
THF
3:1
2:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Gd(OTf)3
Yb(OTf)3
FeCl3
60
63
65
48
40
Ͻ 1
Ͻ 1
55
43
30
48
60
58
55
–
10
5
2
27
–
–
3
0
4
5
6
r.t.
–20
0
7
0
–
8
0
13
10
5
15
5
6
10
–
9
0
10
11
12
13
14
15
16
17
18
19
20
21
0
0
0
0
0
0
0
0
0
0
0
0
NiCl2
ZnCl2
LiCl
15
–
–
–
Mont. K-10[c]
Mont. KSF[c]
CuBr
30
–
–
–
25
20
–
–
THF
InCl3
[a] All reactions were performed with 1a (0.10 mmol), 2a
(0.10 mmol), and catalyst (0.01 mmol) in solvent (1.5 mL). [b] Iso-
lated yields after column chromatography. [c] Clay catalyst
(100 mg) was used.
(Table 1, Entries 3, 12–14). Among these catalysts, Cu- sponding products with different diastereomeric ratios in
(OTf)2 formed the desired product 3a in the highest yield the range 50–71:29–50 (Table 2, Entries 1, 2, 5–7). Results
(65%), and it was chosen as the optimal catalyst for the of substituent effects on the reaction are depicted in
synthesis of dipyrromethanesulfonamides.
Table 2. Reaction of 1a with tosylimines that bear halogens
With the optimized conditions in hand, a range of di- or methoxy groups gave the desired products 3b–3e in mod-
pyrromethanesulfonamides 3a–3g were synthesized by erate yields (Table 2, Entries 2–5). Tosylimines that bear
using tosylimines 2a–2g with different substituents on the strongly electron-withdrawing cyano and nitro groups
phenyl ring. Compounds 2a, 2b, and 2e–2g gave the corre- formed the corresponding addition products 3f and 3g in
Table 2. Synthesis of dipyrromethanesulfonamides.[a]
Entry
2
R
Yield [%][b]
3a–3g (dr)
5a–5g
1
2
3
4
5
6
7
2a
2b
2c
2d
2e
2f
H
F
Cl
65 (50:50)
65 (71:29)
52 (–)
2
8
3
2
3
5
2
Br
63 (–)
CH3O
CN
NO2
45 (52:48)
68 (69:31)
70 (63:37)
2g
[a] All reactions were performed with 1a (1.0 mmol), 2 (1.0 mmol), and Cu(OTf)2 (0.1 mmol) in THF (15 mL). [b] Isolated yields after
column chromatography.
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G. Aydin, B. Temelli, C. Unaleroglu
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slightly higher yields (Table 2, Entries 6 and 7). In all reac- cess the desired tripyrranes 4, pyrrole was used both as sol-
tions, side products 5a–5g were formed in very low yields vent and reactant.
(2–8%; Table 2, Entries 1–7).
Synthesis of Tripyrranes
After completion of the synthesis of dipyrromethane-
sulfonamides, our next goal was to use them to construct
oligopyrrolic structures. Although there are various meth-
ods that involve acid-catalyzed condensation of pyrrole
with aldehydes for the syntheses of symmetrical tripyrr-
anes,[13] the only synthetic protocol for unsymmetrical AB-
type tripyrranes was reported by Osuka et al.[7] The method
consists of three steps: (i) benzoylation of dipyrromethanes;
(ii) reduction of the benzoyl group; and (iii) reaction of di-
pyrromethane carbinols with pyrrole. In addition, the
method requires Grignard reagents and inert reaction con-
ditions. Consequently, we directed our attention toward the
Scheme 4. Synthesis of tripyrranes 4.
synthesis of unsymmetrical tripyrranes 4 by nucleophilic
We have examined the reaction conditions for dipyrro-
substitution reaction of pyrrole with dipyrromethanesulfon- methanesulfonamide 3a and pyrrole in detail with various
amides 3 (Scheme 4a) under mild reaction conditions. We catalysts. The best yield (35%) was obtained with 40 equiv.
have recently shown that dipyrromethanesulfonamides af- of pyrrole in the presence of Cu(OTf)2 catalyst (see Sup-
forded meso-substituted porphyrins if the reaction was porting Information, Table S1, Entry 3). In an attempt to
carried out in dichloromethane at room temperature increase the yield of tripyrrane product, the reaction was
(Scheme 4b).[12d] To avoid this cyclisation reaction and ac- run at different temperatures (Scheme 5). The yield of 4a
Scheme 5. Effect of temperature on the preparation of 4a.
Scheme 6. Fragmentation of tripyrrane at high temperature.
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Selective Synthesis of Tripyrranes, Tetrapyrranes and Corroles
improved by increasing the temperature from room temp. substituents (Table 3, Entries 1 and 5). Dipyrromethane-
to 50 °C and reached 52% yield. Further increases in tem- sulfonamides that bear electron-withdrawing cyano and
perature decreased the yield of 4a and caused the formation nitro groups produced the corresponding products 4f and
of 5-phenyldipyrromethane (1a). At 100 °C, 1a was isolated 4g at 80 °C (Table 3, Entries 6 and 7). This new synthetic
as the only product in 40% yield (Scheme 5).
To understand the course of the reaction at high tem-
peratures and test the sensitivity of the reaction to tempera-
Table 3. Synthesis of tripyrranes.[a]
ture, the same reaction was repeated by using dipyrro-
methanesulfonamide 3g that bears two different substitu-
ents (phenyl and p-nitrophenyl) at 100 °C. After chromato-
graphic separation, 5-phenyldipyrromethane (1a), 5-(p-
nitrophenyl)dipyrromethane (7), and 5-phenyl-10-(p-nitro-
phenyl)tripyrrane (4g) were isolated in 25, 20 and 1% yields,
respectively (Scheme 6).
The formation of 1a and 7 above 50 °C could be ex-
plained by temperature-dependent fragmentation of tripyrr-
ane 4g formed under the applied reaction conditions. As a
result, the temperature was found to be the most important
parameter for the formation of tripyrrane structures. In the
next step, all reactions were performed at different tempera-
tures for each substituent. The optimal temperatures for
each one are depicted in Table 3. The optimal temperature
was found to be 60 °C for halogen-bearing tripyrranes 4b–
Entry
Temperature [°C]
R
Product
Yield [%][b]
1
2
3
4
5
6
7
50
60
60
60
50
80
80
H
F
Cl
4a
4b
4c
4d
4e
4f
52
55
80
70
67
60
80
Br
CH3O
CN
NO2
4g
[a] All reactions were performed with 3 (0.25 mmol), pyrrole
(10 mmol), and Cu(OTf)2 (0.025 mmol). [b] Isolated yields after
4d (Table 3, Entries 2–4) and 50 °C for phenyl and methoxy column chromatography.
Scheme 7. Synthesis of bilanes through dipyrromethanesulfonamide intermediates.
Table 4. Synthesis of bilanes.[a]
Entry
R1
R2
Product
Yield [%][b]
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
H
F
Cl
NO2
H
F
Cl
5a
5b
5c
5d
5e
5f
55
65
58
70
60
75
85
50
65
34
Br
CH3O
CN
NO2
F
Cl
NO2
5g
5h
5i
10
5j
[a] All reactions were performed with 1 (3.0 mmol), 2 (1.0 mmol), and Cu(OTf)2 (0.1 mmol). [b] Isolated yields after column chromatog-
raphy.
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G. Aydin, B. Temelli, C. Unaleroglu
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strategy has rendered possible the synthesis of tripyrranes graphic separation procedures because of the formation of
bearing different substituents at the 5- and 10-positions in some other aromatic macrocycles. By the introduced meth-
moderate to high yields.
odology, the selective synthesis of tetrapyrranes in high
yields could be a significant advantage in the formation of
corroles without side products. Therefore, we directed our
efforts toward the synthesis of meso-substituted corroles by
oxidation of tetrapyrranes. Optimization of the reaction
conditions is the most important step in corrole synthesis.
For this purpose, various reaction parameters (solvent,
bilane concentration, and temperature) were investigated.
Initially, the role of solvent on the oxidation of 5a was ex-
plored. All solvents except CH3OH afforded 33–82% yield
of the desired corrole 6a (Table 5, Entries 1–7). The highest
yield was obtained in toluene (82%), and thus it was chosen
as the solvent for further studies. Next, the effect of the
Synthesis of Bilanes
Encouraged by the results of the tripyrrane synthesis, the
scope of the strategy was expanded for the synthesis of
bilanes through dipyrromethanesulfonamide intermediates
(Scheme 7). The advantage of this methodology is that it
enables the selective synthesis of A3- or A2B-bilanes with-
out any side product.
It was found that under the optimized conditions for di-
pyrromethanesulfonamides, the reaction of tosylimines with
3 equiv. of dipyrromethanes at room temperature afforded
the corresponding A3- and A3B-bilanes 5a–5j. The experi-
mental results are summarized in Table 4. For tosylimines
bearing halogen and methoxy substituents, the reaction re-
sulted in the desired products 5b–5e in moderate to good
yields (Table 4, Entries 2–5). When the reaction was run
with tosylimines substituted with electron-withdrawing
cyano and nitro groups, the yields of bilanes increased to
75 and 85%, respectively (Table 4, Entries 6 and 7).
Table 5. Optimization of the conditions for the corrole synthesis.[a]
Entry
Solvent
Concentration of 5a [mm]
Yield [%][b]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
CH2Cl2
THF
CH3CN
DMF
CH3OH
CHCl3
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
5
5
5
5
5
5
5
1
2.5
10
20
40
80
5
57
64
33
44
–
36
82
49
70
66
60
58
48
34[c]
Synthesis of Corroles
After the synthesis of bilanes as precursors of corroles,
we focused on the oxidation of these important building
blocks to obtain meso-substituted A3- and A2B-corroles. A
number of synthetic protocols are available for the prepara-
tion of meso-substituted triarylcorroles by condensation re-
actions of aldehydes with pyrrole or dipyrromethanes.
[a] All reactions were performed with 5a (0.10 mmol) and 2,3-
dichloro-5,6-dicyano-1,4-benzoquinone (DDQ; 0.15 mmol).
[b] Isolated yields after column chromatography. [c] At reflux tem-
These methods mainly need time-consuming chromato- peratures in toluene.
Table 6. Synthesis of corroles by oxidation of tetrapyrranes.[a]
Entry
R1
R2
Product
Yield [%][b]
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
H
F
Cl
NO2
H
F
Cl
6a
6b
6c
6d
6e
6f
82
53
42
41
32
22
34
59
35
25
Br
CH3O
CN
NO2
F
Cl
NO2
6g
6h
6i
10
6j
[a] All reactions were performed with 5 (0.2 mmol) and DDQ (0.3 mmol). [b] Isolated yields after column chromatography.
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Selective Synthesis of Tripyrranes, Tetrapyrranes and Corroles
lows: s = singlet, d = doublet, dd = doublet of doublets, m = mul-
tiplet, br. s = broad singlet. High-resolution mass spectra (HRMS)
were recorded with an Agilent 1200/6210 high-resolution-mass
time-of-flight (TOF) LC/MS spectrometer. Samples were dissolved
and measured in MeOH or CH3CN. Infrared spectra were recorded
with an ATR (Nicolet iS10) instrument. Tosylimines 1 were synthe-
sized in high yields by the reaction of p-toluenesulfonamide and
aldehydes in the presence of p-toluenesulfonic acid. Dipyrro-
methanes 2[12e] were synthesized in accordance to reported pro-
cedures. Peaks that represent both the major and minor dia-
concentration of bilane 5a on the yield of corrole 6a was
studied (Table 5, Entries 8–13). The optimum concentration
of bilane was determined as 5 mm. When the reaction mix-
ture was heated at reflux in toluene for 12 h, a sharp de-
crease in the reaction yield was observed (34%; Table 5, En-
try 14).
Then, the direct synthesis of A3- and trans-A2B-corroles
from the corresponding tetrapyrranes under the optimized
conditions was performed. The highest yield of A3-corrole
was obtained for phenyl-substituted tetrapyrrane 5a with a stereomers are donated by an asterisk (*). Square brackets indicate
peaks that arise from the minor diastereomer as applicable.
yield of 82% (Table 6, Entry 1). Halogen-bearing tetrapyr-
ranes 5h and 5i gave the corresponding A3-type corroles in
59 and 35% yields, respectively (Table 6, Entries 8 and 9).
The electron-withdrawing nitro group on the tetrapyrrane
decreased the reaction yield, and 5,10,15-tris(4-nitrophenyl)
corrole (6j) was obtained in 27% yield (Table 6, Entry 10).
Unsymmetrical tetrapyrranes that with halogens, electron-
withdrawing (CN and NO2), and electron-donating (CH3O)
groups, were employed to synthesize trans-A2B-corroles
(Table 6, Entries 2–7). Tetrapyrranes with halogen substitu-
ents 5b–5d gave of corroles 6b–6d in moderate 41–53%
yields (Table 6, Entries 2–4). Electron-donating methoxy-
substituted tetrapyrrane 5e provided 6e in 36% yield
(Table 6, Entry 5). The lowest yield of trans-A2B-corrole
was 22% obtained with tetrapyrranes that had the electron-
withdrawing cyano substituent, (Table 6, Entry 6). Com-
pounds 6a–6f and 6h–6j were fully characterized by 1H
NMR and UV/Vis spectroscopy and HRMS analysis. Be-
General Procedure for the Synthesis of Dipyrromethanesulfonamides
3a–3g:
A mixture of tosylimine 2 (1 mmol) and Cu(OTf)2
(0.1 mmol) was stirred in THF (10 mL) at 0 °C for 30 min. A solu-
tion of dipyrromethane 1 (1 mmol) in THF (5 mL) was added
dropwise. The reaction was monitored by TLC. After completion
of the reaction, the mixture was passed through a short column
packed with silica gel and eluted with ethyl acetate to remove Cu-
(OTf)2. The eluent was evaporated under reduced pressure. The
crude product was purified by flash column chromatography with
silica gel 60 (230–400 mesh; ethyl acetate/hexane, 1:6).
4-Methyl-N-(phenyl{5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl)benzenesulfonamide (3a):[12d] Brown viscous oil (65 %
yield). dr = 50:50. R = 0.45 (EtOAc/hexane, 1:3). IR (ATR): ν
˜
f
max
= 3349, 3066, 2919, 2848, 1700, 1597, 1493, 1453, 1320, 1260, 1153,
1089, 1027, 801, 724, 698, 664, 557 cm–1 1H NMR (400 MHz,
.
CDCl3): δ = 2.37 (s, 6 H)*, 5.17–5.24 (m, 2 H)*, 5.32 (d, J = 5.6 Hz,
2 H)*, 5.43–5.47 (m, 4 H)*, 5.61–5.65 (m, 2 H)*, 5.83 (br. s, 2 H)*,
6.08 (br. s, 2 H)*, 6.60 (br. s, 2 H)*, 7.08–7.28 (m, 24 H)*, 7.52 (d,
cause compound 6g was not very soluble, a good-quality J = 8.2 Hz, 4 H)*, 7.90 (br. s, 2 H)*, 8.27 (br. s, 1 H), [8.29 (br. s,
1 H)] ppm. 13C NMR (100 MHz, CDCl3): δ = 21.6*, 44.1*, 55.9*,
NMR spectrum was not recorded. This compound was
107.4*, 107.4, [107.4], [108.6], 108.6, 108.6*, 117.2, [117.2], 127.0*,
characterized by UV/Vis spectroscopy and HRMS analysis.
127.3*, 127.3*, 127.8*, [128.5], 128.5, 128.6, [128.6], 129.4*, 130.1*,
130.2*, 132.2*, [133.8], 133.8, [137.5], 137.5, 138.9*, 142.1*,
143.1* ppm. HRMS (ESI): calcd. for C29H26N3O2S [M – H]–
Conclusions
480.1751; found 480.1754.
Dipyrromethanesulfonamide derivatives have been syn-
thesized by Cu(OTf)2-catalysed addition of meso-substi-
N-[(4-Fluorophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-4-methylbenzenesulfonamide (3b): Brown viscous oil
tuted dipyrromethanes to tosylimines. A new and general
method has been developed to access unsymmetrical AB-
type tripyrranes by using dipyrromethanesulfonamides,
which have important applications in the syntheses of vari-
ous aromatic macrocycles. The same synthetic strategy has
been applied to the synthesis of A3- and A2B-tetrapyrranes
just by tuning the reaction conditions. Tetrapyrranes have
been obtained in high yields at room temperature under
mild reaction conditions. A3- and trans-A2B-corroles have
been directly synthesized by oxidizing the corresponding
tetrapyrranes with DDQ.
(65% yield). dr = 71:29. Rf = 0.49 (EtOAc/hexane, 1:3). IR (ATR):
= 3367, 2961, 2918, 1704, 1600, 1507, 1451, 1259, 1224, 1154,
ν
˜
max
1091, 1027, 845, 793, 725, 664, 578 cm–1 1H NMR (400 MHz,
.
CDCl3): δ = 2.34 (s, 6 H)*, 5.26 (s, 1 H), [5.29 (s, 1 H)], 5.40–5.47
(m, 4 H)*, 5.59 (br. s, 2 H)*, 5.77 (br. s, 2 H)*, 6.02 (br. s, 4 H)*,
[6.50 (br. s, 1 H)], 6.52 (br. s, 1 H), 6.74–6.80 (m, 4 H)*, 6.99–7.24
(m, 18 H)*, 7.44 (d, J = 8.0 Hz, 4 H)*, 8.07 (br. s, 2 H)*, 8.54 (br.
s, 1 H), [8.59 (br. s, 1 H)] ppm. 13C NMR (100 MHz, CDCl3): δ =
21.5, [21.6], 44.0*, 55.3*, 107.2*, 107.3*, 108.4*, 108.6*, 115.1 (d,
2JC,F = 21.5 Hz)*, 117.2, [117.3], 126.5*, 126.8*, 128.4*, 128.4*,
3
129.1 (d, JC,F = 8.0 Hz)*, 129.6*, 129.8, [129.9], 132.5*, [134.1],
134.1, 134.7*, 134.7*, [137.3], 137.3, [142.2], 142.2, 143.1*, 162.1
1
( d , J C , F = 24 5. 3 H z) * p pm . H RM S ( ES I) : c al cd . for
C29H27FN3O2S [M + H]+ 500.1803; found 500.1740.
Experimental Section
N-[(4-Chlorophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
General Information: All reagents were purchased from commercial yl}methyl]-4-methylbenzenesulfonamide (3c): Brown viscous oil
suppliers and used without purification. Thin layer chromatog-
raphy was performed on pre-coated silica gel 60 F254 plates (0.060–
0.200 mm). Silica gel (230–400 mesh) was used for column
(52 % yield). R = 0.40 (EtOAc/hexane, 1:3). IR (ATR): ν
=
˜
f
max
3385, 3279, 2928, 1723, 1581, 1495, 1322, 1152, 1085, 1038, 912,
810, 722 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.37 (s, 3 H), 5.32
(br. s, 1 H), 5.38 (d, J = 8.2 Hz, 1 H), 5.46 (s, 1 H), 5.49 (br. s, 1
H), 5.67 (br. s, 1 H), 5.85 (br. s, 1 H), 6.12 (br. s, 1 H), 6.64 (br. s,
1 H), 7.01 (d, J = 8.4 Hz, 2 H), 7.08–7.17 (m, 5 H), 7.20–7.31 (m,
4 H), 7.49 (d, J = 8.0 Hz, 2 H), 7.96 (br. s, 1 H), 8.23 (br. s, 1 H)
1
chromatography. H NMR (400 MHz) and 13C NMR (100 MHz)
spectra were recorded with a Bruker Ultrashield FT NMR spec-
trometer. Chemical shifts (δ) are reported downfield from
tetramethylsilane. Data for 1H NMR spectra are reported as fol-
Eur. J. Org. Chem. 2015, 7583–7593
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7589

G. Aydin, B. Temelli, C. Unaleroglu
FULL PAPER
ppm. 13C NMR (100 MHz, CDCl3): δ = 21.5, 44.0, 55.2, 107.3,
107.3, 108.4, 108.6, 117.3, 127.0, 127.1, 128.3, 128.5, 128.6, 128.7,
129.5, 129.5, 132.3, 133.7, 134.2, 136.9, 137.1, 141.8, 143.6 ppm.
[8.60 (br. s, 1 H)] ppm. 13C NMR (100 MHz, CDCl3): δ = 21.5*,
43.9*, 55.2*, 107.3*, 107.5*, 108.4*, 108.9*, 117.3*, 123.3*, 126.9*,
127.0*, 128.2*, 128.3*, 128.5*, 129.5*, 132.3*, 134.8*, 136.9*,
HRMS (ESI): calcd. for C29H25ClN3O2S [M – H]– 514.1361; found 141.9*, 143.7*, 145.9*, 147.2* ppm. HRMS (ESI): calcd. for
514.1364.
C29H25N4O4S [M – H]– 525.1602; found 525.1636.
General Procedure for the Synthesis of Tripyrranes 4a–4g: Dipyrro-
methanesulfonamide 3 (0.25 mmol) was dissolved in excess pyrrole
(10 mmol). Cu(OTf)2 (0.025 mmol) was added to the reaction mix-
ture at the temperature indicated in Table 4. The reaction was mon-
itored by TLC. After completion of the reaction, the mixture was
passed through a short column packed with silica gel and eluted
with ethyl acetate to remove Cu(OTf)2. The eluent was evaporated
under reduced pressure. The crude product was purified by flash
column chromatography with silica gel 60 (230–400 mesh; ethyl
acetate/hexane, 1:6).
N-[(4-Bromophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-4-methylbenzenesulfonamide (3d): Brown viscous oil
(63 % yield). R = 0.43 (EtOAc/hexane, 1:3). IR (ATR): ν
=
˜
f
max
3370, 3255, 2925, 1664, 1597, 1487, 1322, 1156, 1097, 1069, 1030,
1010, 908, 810, 770 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.39
(s, 3 H), 5.12 (d, J = 7.2 Hz, 1 H), 5.34 (s, 1 H), 5.44 (d, J = 7.2 Hz,
1 H), 5.49 (br. s, 1 H), 5.66–5.69 (m, 1 H), 5.86 (br. s, 1 H), 6.14
(br. s, 1 H), 6.67 (br. s, 1 H), 6.97 (d, J = 8.3 Hz, 2 H), 7.11–7.18
(m, 5 H), 7.23–7.33 (m, 4 H), 7.51 (d, J = 8.0 Hz, 2 H), 7.90 (br.
s, 1 H), 8.14 (br. s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
21.5, 44.0, 55.3, 107.3, 107.4, 108.4, 108.6, 117.3, 121.9, 127.1,
128.3, 128.7, 129.0, 129.4, 129.6, 131.5, 132.1, 134.1, 136.9, 137.5,
141.7, 143.7 ppm. HRMS (ESI): calcd. for C29H25BrN3O2S [M –
H]– 558.0856; found 558.0811.
2-(Phenyl{5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-yl}methyl)-
1H-pyrrole (4a):[4g] Black viscous oil (52 % yield). Rf = 0.63
(EtOAc/hexane, 1:3). IR (ATR): ν
= 3362, 3059, 3023, 2925,
˜
max
1698, 1450, 1247, 1028, 963, 884, 767, 717, 698 cm–1. 1H NMR
(400 MHz, CDCl3): δ = 5.17 (br. s, 2 H), 5.60–5.63 (m, 2 H), 5.72
(br. s, 2 H), 5.97 (br. s, 2 H), 6.46 (br. s, 2 H), 7.02–7.06 (m, 4 H),
7.08–7.20 (m, 6 H), 7.54 (br. s, 1 H), 7.64 (br. s, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 44.0, 107.3, 107.6, 108.6, 117.1,
126.9, 128.4, 128.6, 132.3, 132.4, 142.2 ppm. HRMS (ESI): calcd.
for C26H22N3 [M – H]– 376.1819; found 376.1850.
N-[(4-Methoxyphenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-
2-yl}methyl]-4-methylbenzenesulfonamide (3e): Brown viscous oil
(45% yield). dr = 52:48. Rf = 0.33 (EtOAc/hexane, 1:3). IR (ATR):
ν
= 3350, 3251, 2917, 1708, 1598, 1511, 1452, 1259, 1160, 1089,
˜
max
1
1034, 817 cm–1. H NMR (400 MHz, CDCl3): δ = 2.34 (s, 6 H)*,
3.71 (s, 6 H)*, 5.27 (br. s, 1 H), [5.30 (s, 1 H)], 5.38 (d, J = 7.2 Hz,
2 H)*, 5.43–5.47 (m, 2 H)*, 5.57–5.61 (m, 4 H)*, 5.78 (br. s, 1 H),
[5.79 (br. s, 1 H)], 6.00–6.05 (m, 2 H)*, [6.52 (br. s, 1 H)], 6.54 (br.
s, 1 H), 6.62 (d, J = 8.4 Hz, 4 H)*, 6.95 (d, J = 8.4 Hz, 4 H)*, 7.05
(d, J = 8.0 Hz, 4 H)*, 7.12 (d, J = 8.0 Hz, 4 H)*, 7.20–7.28 (m, 6
H)*, 7.47 (d, J = 8.0 Hz, 4 H)*, 8.01 (br. s, 2 H)*, 8.40 (br. s, 1 H),
[8.45 (br. s, 1 H)] ppm. 13C NMR (100 MHz, CDCl3): δ = 21.4*,
43.8*, 54.9*, 55.2*, [107.0], 107.1, 107.1*, [108.1], 108.1, 108.2,
[108.2], 113.5*, 116.9, [117.0], 126.4*, 126.6*, 127.0*, [128.2], 128.3,
128.3*, 129.2*, 129.4*, 130.2, [130.2], 130.8, [130.8], 132.2*, [133.5],
133.6, 137.2, [137.3], 142.0*, 158.9* ppm. HRMS (ESI): calcd. for
C30H28N3O3S [M – H]– 510.1857; found 510.1858.
2-[(4-Fluorophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-1H-pyrrole (4b): Black viscous oil (55% yield). Rf = 0.44
(EtOAc/hexane, 1:3). IR (ATR): ν
= 3366, 3106, 3023, 2921,
˜
max
1712, 1507, 1219, 1026, 849, 774, 731, 695 cm–1 1H NMR
.
(400 MHz, CDCl3): δ = 5.17 (s, 1 H), 5.19 (s, 1 H), 5.53 (br. s, 1
H), 5.56 (br. s, 1 H), 5.64 (br. s, 1 H), 5.67 (br. s, 1 H), 5.92 (br. s,
2 H), 6.47 (br. s, 2 H), 6.80 (t, J = 8.1 Hz, 2 H), 6.93–7.02 (m, 4
H), 7.03–7.15 (m, 3 H), 7.49 (br. s, 1 H), 7.66 (br. s, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 43.3, 44.1, 107.3, 107.3, 107.6, 108.6,
2
108.7, 115.3 (d, JC,F = 21.2 Hz), 117.0, 117.1, 127.0, 128.3, 128.6,
3
129.8 (d, JC,F = 7.8 Hz), 132.0, 132.0, 132.1, 132.4, 137.8, 142.0,
2
161.8 (d, JC,F = 244.8 Hz) ppm. HRMS (ESI): calcd. for
N-[(4-Cyanophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-4-methylbenzenesulfonamide (3f): Brown viscous oil
(68% yield). dr = 69:31. Rf = 0.21 (EtOAc/hexane, 1:3). IR (ATR):
C26H21FN3 [M – H]– 394.1725; found 394.1754.
2-[(4-Chlorophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-1H-pyrrole (4c): Black viscous oil (80% yield). Rf = 0.50
ν
= 3366, 3261, 2923, 2228, 1705, 1560, 1494, 1429, 1323, 1155,
˜
max
1091, 1030, 919, 856, 812, 771, 725 cm–1 1H NMR (400 MHz,
.
(EtOAc/hexane, 1:3). IR (ATR): ν
= 3370, 3094, 2929, 1704,
˜
max
1483, 1176, 1081, 967, 884, 762, 719, 697 cm–1 1H NMR
.
CDCl3): δ = 2.36 (s, 6 H)*, 5.25 (s, 1 H), [5.29 (s, 1 H)], 5.37–5.40
(m, 2 H)*, 5.48–5.54 (m, 2 H)*, 5.60 (br. s, 2 H)*, 5.74–5.83 (m, 3
H)*, 5.91 (d, J = 8.2 Hz, 1 H), 5.99–6.03 (m, 2 H)*, [6.45 (br. s, 1
H)], 6.50 (br. s, 1 H), 7.03–7.11 (m, 8 H)*, 7.15–7.24 (m, 10 H)*,
7.36 (d, J = 8.2 Hz, 4 H)*, 7.40–7.45 (m, 4 H)*, 7.95 (br. s, 2 H)*,
8.43 (br. s, 1 H), [8.53 (br. s, 1 H)] ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.5*, 43.9*, 55.4*, [107.3], 107.4, 107.5*, [108.4],
108.4, 108.9*, 111.6*, 117.3, [117.4], 118.1*, [126.9], 127.0, 128.1*,
128.3*, 128.3*, 128.4*, 128.5*, 129.5*, 131.9*, 132.2*, [134.6],
134.6, [137.0], 137.0, [141.8], 141.9, 143.7*, 144.0* ppm. HRMS
(ESI): calcd. for C30H25N4O2S [M – H]– 505.1704; found 505.1785.
(400 MHz, CDCl3): δ = 5.25–5.32 (m, 2 H), 5.63–5.67 (m, 2 H),
5.77 (br. s, 2 H), 6.04–6.07 (m, 2 H), 6.62 (br. s, 2 H), 7.00–7.24
(m, 9 H), 7.70 (br. s, 1 H), 7.86 (br. s, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 43.5, 44.1, 107.2, 107.3, 107.5, 107.6, 108.4,
108.5, 117.2, 117.4, 127.0, 128.3, 128.6, 128.7, 129.7, 131.8, 132.0,
132.4, 132.6, 132.7, 140.6, 141.9 ppm. HRMS (ESI): calcd. for
C26H21ClN3 [M – H]– 410.1429; found 410.1447.
2-[(4-Bromophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-1H-pyrrole (4d):[7] Black viscous oil (70% yield). Rf =
0.49 (EtOAc/hexane, 1:3). IR (ATR): ν
= 3468, 2929, 1715,
˜
max
4-Methyl-N-[(4-nitrophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H- 1499, 1101, 1042, 1014, 904, 727, 648 cm–1. 1H NMR (400 MHz,
pyrrol-2-yl}methyl]benzenesulfonamide (3g): Brown viscous oil (70%
yield). dr = 63:37. R = 0.26 (EtOAc/hexane, 1:3). IR (ATR): ν
CDCl3): δ = 5.26 (br. s, 1 H), 5.30 (br. s, 1 H), 5.63–5.70 (m, 2 H),
5.75–5.81 (m, 2 H), 6.03–6.10 (m, 2 H), 6.61 (br. s, 2 H), 6.98 (d,
J = 8.3 Hz, 2 H), 7.11 (d, J = 7.4 Hz, 2 H), 7.16–7.22 (m, 1 H),
7.23 (d, J = 7.4 Hz, 2 H), 7.34 (d, J = 8.3 Hz, 2 H), 7.68 (br. s, 1
˜
f
max
= 3363, 2961, 2924, 1705, 1519, 1493, 1346, 1259, 1155, 1090, 1030,
862, 793, 725 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.32 (s, 6
H)*, 5.27 (s, 1 H), [5.29 (s, 1 H)], 5.39 (br. s, 2 H)*, 5.56 (br. s, 2 H), 7.84 (br. s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.5,
H)*, 5.60 (br. s, 4 H)*, 5.77 (br. s, 2 H)*, 6.01 (br. s, 2 H)*, [6.49 44.0, 107.2, 107.3, 107.5, 107.6, 108.4, 108.5, 117.3, 117.4, 120.8,
(br. s, 1 H)], 6.52 (br. s, 1 H), 7.03 (d, J = 7.8 Hz, 4 H)*, 7.08 (d, 127.0, 128.3, 128.7, 130.1, 131.6, 131.9, 132.4, 132.7, 141.1,
J = 7.8 Hz, 4 H)*, 7.18–7.26 (m, 10 H)*, 7.44 (d, J = 7.8 Hz, 4 141.9 ppm. HRMS (ESI): calcd. for C26H21BrN3 [M – H]–
H)*, 7.91 (d, J = 7.8 Hz, 4 H)*, 8.03 (br. s, 2 H)*, 8.57 (br. s, 1 H),
454.0924; found 454.0940.
7590
www.eurjoc.org
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 7583–7593

Selective Synthesis of Tripyrranes, Tetrapyrranes and Corroles
2-[(4-Methoxyphenyl)(1H-pyrrol-2-yl)methyl]-5-[phenyl(1H-pyrrol-
2-yl)methyl]-1H-pyrrole (4e):[7] Black viscous oil (67% yield). Rf =
viscous oil (65% yield). Rf = 0.43 (EtOAc/hexane, 1:3). IR (ATR):
= 3362, 3059, 3023, 2960, 2929, 2874, 1715, 1601, 1503, 1456,
ν
˜
max
0.57 (EtOAc/hexane, 1:3). IR (ATR): ν
= 3362, 3094, 3035,
1423, 1219, 1156, 1089, 1030, 967, 908, 845, 758, 723 cm–1 1H
.
˜
max
1
2925, 1715, 1519, 1243, 1168, 1034, 845, 766, 715 cm–1. H NMR NMR (400 MHz, CDCl3): δ = 5.21 (br. s, 1 H), 5.32 (br. s, 2 H),
(400 MHz, CDCl3): δ = 3.77 (s, 3 H), 5.28 (s, 1 H), 5.33 (s, 1 H), 5.65 (br. s, 2 H), 5.69 (br. s, 2 H), 5.82 (br. s, 2 H), 6.09 (br. s, 2
5.70 (br. s, 2 H), 5.81 (br. s, 2 H), 6.04–6.09 (m, 2 H), 6.60 (br. s, H), 6.61 (br. s, 2 H), 6.91–6.97 (m, 2 H), 7.06–7.11 (m, 6 H), 7.22–
2 H), 6.79 (d, J = 8.6 Hz, 2 H), 7.05 (d, J = 8.6 Hz, 2 H), 7.15 (d, 7.30 (m, 6 H), 7.72 (br. s, 2 H), 7.87 (br. s, 2 H) ppm. 13C NMR
J = 7.4 Hz, 2 H), 7.21–7.30 (m, 3 H), 7.64 (br. s, 1 H), 7.80 (br. s, (100 MHz, CDCl3): δ = 43.2, 43.9, 107.1, 107.3, 107.4, 108.4, 115.1
2
3
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.1, 44.0, 54.9,
107.0, 107.1, 107.2, 107.4, 108.4, 108.4, 113.7, 116.7, 116.8, 126.7,
(d, JC,F = 21.2 Hz), 117.0, 126.9, 128.2, 128.4, 129.7 (d, JC,F =
4
7.8 Hz), 131.9, 132.2, 132.3, 137.7 (d, JC,F = 3.1 Hz), 141.9, 161.6
1
128.2, 128.4, 129.2, 131.9, 132.1, 132.4, 132.5, 134.0, 142.0, (d, JC,F = 244.3 Hz) ppm. HRMS (ESI): calcd. for C37H30FN4
158.4 ppm. HRMS (ESI): calcd. for C27H24N3O [M – H]– 406.1925;
found 406.1925.
[M – H]– 549.2460; found 549.2487.
2-[(4-Chlorophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrole (5c): Black
viscous oil (58% yield). Rf = 0.49 (EtOAc/hexane, 1:3). IR (ATR):
4-[{5-[Phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-yl}(1H-pyrrol-2-
yl)methyl]benzonitrile (4f): Black viscous oil (60% yield). Rf = 0.40
(EtOAc/hexane, 1:3). IR (ATR): ν
= 3360, 3040, 2915, 2227,
˜
max
ν
˜
= 3420, 3098, 3058, 2923, 1728, 1489, 1089, 1028, 913, 764,
max
1715, 1495, 1259, 1090, 1027, 787, 721, 674 cm–1 1H NMR
.
724, 700 cm–1. H NMR (400 MHz, CDCl3): δ = 5.18 (br. s, 1 H),
5.32 (br. s, 2 H), 5.66 (br. s, 2 H), 5.70 (br. s, 2 H), 5.83 (br. s, 2
H), 6.08–6.12 (m, 2 H), 6.61 (br. s, 2 H), 7.06 (d, J = 8.2 Hz, 2 H),
7.11–7.19 (m, 5 H), 7.21–7.31 (m, 5 H), 7.68 (br. s, 2 H), 7.83 (br.
s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.4, 43.9, 107.1,
107.4, 108.4, 117.0, 126.8, 128.2, 128.5, 129.5, 131.6, 132.2, 132.3,
132.6, 140.5, 141.9 ppm. HRMS (ESI): calcd. for C37H30ClN4 [M –
H]– 565.2164; found 565.2175.
1
(400 MHz, CDCl3): δ = 5.33 (s, 1 H), 5.37 (s, 1 H), 5.61–5.65 (m,
1 H), 5.71 (br. s, 1 H), 5.75 (br. s, 1 H), 5.81 (br. s, 1 H), 6.07 (br.
s, 2 H), 6.61 (br. s, 1 H), 6.64 (br. s, 2 H), 7.13 (d, J = 7.0 Hz, 2
H), 7.20–7.30 (m, 4 H), 7.55 (d, J = 8.2 Hz, 2 H), 7.72 (br. s, 1 H),
7.82 (br. s, 1 H), 7.89 (br. s, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 44.1, 44.1, 107.4, 107.8, 108.0, 108.7, 108.9, 111.1,
117.2, 117.6, 118.3, 127.1, 128.3, 128.6, 129.1, 130.6, 130.7, 131.9,
132.2, 133.0, 135.0, 141.8, 147.5 ppm. HRMS (ESI): calcd. for
C27H21N4 [M – H]– 401.1772; found 401.1797.
2-[(4-Bromophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrole (5d): Black
viscous oil (70% yield). Rf = 0.46 (EtOAc/hexane, 1:3). IR (ATR):
2-[(4-Nitrophenyl)(1H-pyrrol-2-yl)methyl]-5-[phenyl(1H-pyrrol-2-
yl)methyl]-1H-pyrrole (4g): Black viscous oil (80% yield). Rf = 0.34
ν
˜
= 3425, 3059, 2925, 1664, 1585, 1487, 1392, 1259, 1073, 1026,
max
(EtOAc/hexane, 1:3). IR (ATR): ν
= 3383, 3080, 2920, 1712,
˜
max
1006, 908, 723, 695 cm–1. 1H NMR (400 MHz, CDCl3): δ = 5.23
(s, 1 H), 5.36 (br. s, 2 H), 5.67 (br. s, 2 H), 5.72 (br. s, 2 H), 5.85
(br. s, 2 H), 6.13 (br. s, 2 H), 6.68 (br. s, 2 H), 7.02 (d, J = 8.4 Hz,
2 H), 7.14–7.20 (m, 5 H), 7.23–7.32 (m, 5 H), 7.39 (d, J = 8.4 Hz,
2 H), 7.72 (br. s, 2 H), 7.90 (br. s, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 43.6, 44.0, 107.1, 107.2, 107.4, 107.5, 108.4, 117.2,
127.0, 128.4, 128.6, 128.6, 130.1, 131.6, 132.4, 132.5, 141.1,
141.9 ppm. HRMS (ESI): calcd. for C37H30BrN4 [M – H]–
609.1659; found 609.1669.
1514, 1344, 1259, 1089, 1027, 787, 721, 700 cm–1 1H NMR
.
(400 MHz, CDCl3): δ = 5.33 (s, 1 H), 5.41 (s, 1 H), 5.64 (br. s, 1
H), 5.71 (br. s, 1 H), 5.75 (br. s, 1 H), 5.80 (br. s, 1 H), 6.06 (br. s,
2 H), 6.59–6.67 (m, 2 H), 7.12 (d, J = 7.0 Hz, 2 H), 7.17–7.34 (m,
5 H), 7.76 (br. s, 1 H), 7.82 (br. s, 1 H), 7.93 (br. s, 1 H), 8.10 (d,
J = 8.3 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.9,
44.1, 107.3, 107.8, 108.0, 108.7, 109.0, 117.2, 117.7, 123.7, 127.1,
128.3, 128.6, 129.1, 130.5, 130.6, 132.0, 133.1, 135.0, 141.8, 147.0,
149.5 ppm. HRMS (ESI): calcd. for C26H21N4O2 [M – H]–
421.1670; found 421.1698.
2-[(4-Methoxyphenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-
2-yl}methyl]-5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrole (5e):
Black viscous oil (60% yield). Rf = 0.32 (EtOAc/hexane, 1:3). IR
General Procedure for the Synthesis of Bilanes 5a–5j: A mixture of
tosylimine 2 (1 mmol) and Cu(OTf)2 (0.1 mmol) was stirred in
THF (3 mL) at room temperature for 30 min. A solution of di-
pyrromethane 1 (3 mmol) in THF (5 mL) was added dropwise. The
reaction was monitored by TLC, and the reaction was complete in
18 h. The mixture was passed through a short column packed with
silica gel and eluted with ethyl acetate to remove Cu(OTf)2. The
eluent was evaporated under reduced pressure. The crude product
was purified by flash column chromatography with silica gel 60
(230–400 mesh; ethyl acetate/hexane, 1:5).
(ATR): ν
= 3305, 3059, 2919, 1710, 1601, 1509, 1247, 1174,
˜
max
1030, 883, 761, 724, 699 cm–1. 1H NMR (400 MHz, CDCl3): δ =
3.76 (s, 3 H), 5.19 (s, 1 H), 5.31 (s, 2 H), 5.64–5.68 (m, 4 H), 5.80
(br. s, 2 H), 6.04–6.08 (m, 2 H), 6.59–6.63 (m, 2 H), 6.74–6.78 (m,
2 H), 7.02 (d, J = 8.4 Hz, 2 H), 7.11–7.30 (m, 10 H), 7.66 (br. s, 2
H), 7.84 (br. s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.2,
43.9, 55.0, 107.1, 107.3, 108.4, 113.7, 116.8, 126.7, 128.2, 128.4,
129.1, 131.9, 132.2, 132.4, 134.0, 134.8, 142.0, 158.3 ppm. HRMS
(ESI): calcd. for C38H33N4O [M – H]– 561.2660; found 561.2673.
2-[Phenyl(1H-pyrrol-2-yl)methyl]-5-(phenyl{5-[phenyl(1H-pyrrol-2-
yl)methyl]-1H-pyrrol-2-yl}methyl)-1H-pyrrole (5a):[12d] Black vis-
cous oil (55% yield). Rf = 0.47 (EtOAc/hexane, 1:3). IR (ATR):
4-(Bis{5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-yl}methyl)-
benzonitrile (5f): Black viscous oil (75% yield). Rf = 0.37 (EtOAc/
hexane, 1:3). IR (ATR): νmax = 3348, 3080, 2923, 2224, 1669, 1603,
ν
= 3420, 3102, 3062, 2959, 1698, 1492, 1451, 1260, 1074, 766,
˜
max
˜
718, 698 cm–1. H NMR (400 MHz, CDCl3): δ = 5.19 (br. s, 1 H),
5.29 (br. s, 2 H), 5.66 (br. s, 4 H), 5.80 (br. s, 2 H), 6.07 (br. s, 2
H), 6.58 (br. s, 2 H), 7.00–7.34 (m, 15 H), 7.67 (br. s, 2 H), 7.81
(br. s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 44.0, 44.1,
107.2, 107.4, 107.5, 108.5, 117.1, 126.9, 128.3, 128.4, 128.5, 128.5,
130.2, 132.2, 132.2, 132.4, 133.5, 142.1 ppm. HRMS (ESI): calcd.
for C37H31N4 [M – H]– 531.2554; found 531.2578.
1
1494, 1260, 1091, 1029, 766, 723, 699 cm–1. 1H NMR (400 MHz,
CDCl3): δ = 5.28 (s, 1 H), 5.32 (s, 2 H), 5.59 (br. s, 2 H), 5.68 (br.
s, 2 H), 5.79 (br. s, 2 H), 6.05–6.09 (m, 2 H), 6.61 (br. s, 2 H), 7.12
(d, J = 7.4 Hz, 4 H), 7.18–7.29 (m, 8 H), 7.52 (d, J = 8.1 Hz, 2 H),
7.69 (br. s, 2 H), 7.81 (br. s, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 44.0, 44.1, 107.3, 107.7, 107.9, 108.6, 111.0, 117.1,
127.0, 128.2, 128.5, 129.0, 130.4, 131.9, 132.1, 132.7, 141.7,
147.4 ppm. HRMS (ESI): calcd. for C38H30N5 [M – H]– 556.2507;
2-[(4-Fluorophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
yl}methyl]-5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrole (5b): Black found 556.2532.
Eur. J. Org. Chem. 2015, 7583–7593
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7591

G. Aydin, B. Temelli, C. Unaleroglu
FULL PAPER
2-[(4-Nitrophenyl){5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-
HRMS (ESI): calcd. for C37H27N4 [M + H]+ 527.2230; found
yl}methyl]-5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrole (5g): Black 527.2284.
viscous oil (85% yield). Rf = 0.29 (EtOAc/hexane, 1:3). IR (ATR):
10-(4-Fluorophenyl)-5,15-diphenylcorrole (6b): Green solid (53%
yield). Rf = 0.71 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε)
= 416 (4.32), 567 (3.72), 615 (3.56), 650 (3.56) nm. 1H NMR
(400 MHz, CDCl3): δ = 7.68–7.73 (m, 4 H), 7.81 (br. s, 4 H), 8.11
(br. s, 2 H), 8.35 (br. s, 4 H), 8.50 (br. s, 2 H), 8.57 (br. s, 2 H),
8.88 (br. s, 2 H), 8.92 (br. s, 2 H) ppm. HRMS (ESI): calcd. for
C37H26FN4 [M + H]+ 545.2136; found 545.2207.
ν
= 3417, 3078, 2980, 1712, 1597, 1515, 1448, 1420, 1349, 1156,
˜
max
1093, 1026, 912, 861, 758, 719 cm–1. H NMR (400 MHz, CDCl3):
δ = 5.30 (s, 1 H), 5.31 (s, 2 H), 5.63 (br. s, 2 H), 5.70 (br. s, 2 H),
5.81 (br. s, 2 H), 6.07 (br. s, 2 H), 6.58 (br. s, 2 H), 7.13 (d, J =
7.4 Hz, 4 H), 7.21–7.30 (m, 8 H), 7.79 (br. s, 2 H), 7.82 (br. s, 2 H),
8.06 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
43.9, 44.0, 107.3, 107.8, 107.9, 108.6, 117.3, 123.6, 127.0, 128.3,
128.6, 129.1, 130.5, 132.1, 133.0, 141.9, 146.8, 149.6 ppm. HRMS
(ESI): calcd. for C37H30N5O2 [M – H]– 576.2405; found 576.2429.
1
10-(4-Chlorophenyl)-5,15-diphenylcorrole (6c): Green solid (42%
yield). Rf = 0.72 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε)
= 416 (4.47), 573 (4.86), 614 (3.91), 649 (3.80) nm. 1H NMR
(400 MHz, CDCl3): δ = 7.71 (br. s, 4 H), 7.81 (br. s, 4 H), 8.10 (br.
s, 2 H), 8.35 (br. s, 4 H), 8.52 (br. s, 2 H), 8.60 (br. s, 2 H), 8.89
(br. s, 2 H), 8.96 (br. s, 2 H) ppm. HRMS (ESI): calcd. for
C37H26ClN4 [M + H]+ 561.1841; found 561.1910.
2-[(4-Fluorophenyl)(1H-pyrrol-2-yl)methyl]-5-[(4-fluorophenyl)-
{5-[(4-fluorophenyl)(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-yl}methyl]-
1H-pyrrole (5h): Black viscous oil (50% yield). Rf = 0.44 (EtOAc/
hexane, 1:3). IR (ATR): νmax = 3464, 3374, 1692, 1597, 1507, 1408,
˜
1215, 1152, 1097, 916, 849, 774, 762, 727 cm–1 1H NMR
.
10-(4-Bromophenyl)-5,15-diphenylcorrole (6d): Green solid (41%
yield). Rf = 0.76 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε)
= 416 (4.71), 576 (4.52), 615 (4.41), 650 (4.39) nm. 1H NMR
(400 MHz, CDCl3): δ = –2.32 (br. s, 3 H), 7.68–8.20 (m, 10 H),
8.32 (br. s, 4 H), 8.48 (br. s, 4 H), 8.79 (br. s, 2 H), 8.84 (br. s, 2 H)
ppm. HRMS (ESI): calcd. for C37H26BrN4 [M + H]+ 605.1335;
found 605.1276.
(400 MHz, CDCl3): δ = 5.25 (br. s, 1 H), 5.33 (br. s, 2 H), 5.67 (br.
s, 4 H), 5.81 (br. s, 2 H), 6.12 (br. s, 2 H), 6.67 (br. s, 2 H), 6.93–
6.99 (m, 6 H), 7.07–7.14 (m, 6 H), 7.75 (br. s, 2 H), 7.94 (br. s, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.3, 43.4, 107.3, 107.5,
107.6, 108.6, 115.4 (d, 2JC,F = 21.2 Hz), 117.3, 129.7, 129.9 (d, 3JC,F
1
= 7.3 Hz), 132.1, 132.1, 132.8, 132.8, 137.7, 161.8 (d, JC-F
=
244.6 Hz) ppm. HRMS (ESI): calcd. for C37H28F3N4 [M – H]–
585.2272; found 585.2289.
10-(4-Methoxyphenyl)-5,15-diphenylcorrole (6e):[14] Green solid
(32% yield). Rf = 0.72 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax
(logε) = 421 (3.89), 514 (2.65), 614 (2.79), 649 (2.83) nm. 1H NMR
(400 MHz, CDCl3): δ = 4.10 (s, 3 H), 7.60–7.88 (m, 8 H), 8.17 (br.
s, 2 H), 8.36 (br. s, 4 H), 8.57 (br. s, 4 H), 8.79–9.00 (m, 4 H) ppm.
HRMS (ESI): calcd. for C38H29N4O [M + H]+ 557.2336; found
557.2322.
2-[(4-Chlorophenyl)(1H-pyrrol-2-yl)methyl]-5-[(4-chlorophenyl){5-
[(4-chlorophenyl)(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-yl}methyl]-
1H-pyrrole (5i): Black viscous oil (65% yield). Rf = 0.47 (EtOAc/
hexane, 1:3). IR (ATR): νmax = 3445, 2937, 2862, 1719, 1582, 1491,
˜
1
1385, 1101, 908, 841, 758, 727 cm–1. H NMR (400 MHz, CDCl3):
δ = 5.21 (br. s, 1 H), 5.29 (br. s, 2 H), 5.67 (br. s, 4 H), 5.81 (br. s,
2 H), 6.11 (br. s, 2 H), 6.66 (br. s, 2 H), 7.04–7.09 (m, 6 H), 7.22–
7.38 (m, 6 H), 7.74 (br. s, 2 H), 7.90 (br. s, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 43.5, 43.5, 107.4, 107.6, 107.7, 108.5, 117.6,
128.7, 129.7, 129.7, 131.9, 132.0, 132.1, 132.8, 140.5, 140.5 ppm.
HRMS (ESI): calcd. for C37H28Cl3N4 [M – H]– 633.1385; found
633.1431.
10-(4-Cyanophenyl)-5,15-diphenylcorrole (6f):[3g] Green solid (22%
yield). Rf = 0.72 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε)
= 421 (4.73), 578 (3.90), 614 (3.76), 649 (3.62) nm. 1H NMR
(400 MHz, CDCl3): δ = –2.11 (br. s, 3 H), 7.60–7.90 (m, 6 H), 8.09
(br. s, 2 H), 8.20–8.70 (m, 10 H), 8.85 (br. s, 4 H) ppm. HRMS
(ESI): calcd. for C38H26N5 [M + H]+ 552.2183; found 552.2160.
2-[(4-Nitrophenyl)(1H-pyrrol-2-yl)methyl]-5-[(4-nitrophenyl){5-[(4-
nitrophenyl)(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-yl}methyl]-1H-
pyrrole (5j): Black viscous oil (34% yield). Rf = 0.25 (1:3 EtOAc/
10-(4-Nitrophenyl)-5,15-diphenylcorrole (6g):[3g] Green solid (34%
yield). Rf = 0.73 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε)
= 421 (4.98), 582 (4.26), 608 (4.11), 648 (3.86) nm. HRMS (ESI):
calcd. for C37H26N5O2 [M + H]+ 572.2081; found 572.2131.
hexane). IR (ATR): ν
= 3411, 2966, 2868, 1702, 1602, 1516,
˜
max
1345, 1115, 915, 865, 830, 774, 729 cm–1. 1H NMR (400 MHz,
CDCl3): δ = 5.34 (br. s, 1 H), 5.41 (br. s, 2 H), 5.62 (br. s, 4 H),
5.77 (br. s, 2 H), 6.09 (br. s, 2 H), 6.68 (br. s, 2 H), 7.18–7.28 (m,
6 H), 7.79 (br. s, 2 H), 7.92 (br. s, 2 H), 8.06–8.11 (m, 6 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 43.9, 43.9, 107.8, 107.9, 108.3,
108.8, 118.2, 123.9, 123.9, 129.2, 130.6, 131.2, 131.5, 147.0, 147.0,
148.9, 149.2 ppm. HRMS (ESI): calcd. for C37H28N7O6 [M – H]–
666.2107; found 666.2173.
5,10,15-Tris(4-fluorophenyl)corrole (6h):[10] Green solid (59% yield).
Rf = 0.73 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε) = 418
1
(4.72), 520 (3.78), 614 (3.89), 648 (3.88) nm. H NMR (400 MHz,
CDCl3): δ = 7.52 (br. s, 6 H), 8.11 (br. s, 2 H), 8.31 (br. s, 4 H),
8.53 (br. s, 4 H), 8.84 (br. s, 2 H), 8.99 (br. s, 2 H) ppm. HRMS
(ESI): calcd. for C37H24F3N4 [M + H]+ 581.1948; found 581.1912.
5,10,15-Tris(4-chlorophenyl)corrole (6i): Green solid (35% yield). Rf
= 0.78 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε) = 420
General Procedure for the Synthesis of Corroles 6a–6j: DDQ
(0.3 mmol) was added to the solution of bilane 5 (0.2 mmol) in
toluene (40 mL) at room temperature under argon. The reaction
was complete in 1 h. The mixture was passed through a short col-
umn packed with silica gel and eluted with ethyl acetate. The eluent
was evaporated under reduced pressure. The crude product was
purified by flash column chromatography with silica gel 60 (230–
400 mesh; ethyl acetate/hexane, 1:10).
1
(4.67), 526 (3.89), 618 (4.02), 654 (4.00) nm. H NMR (400 MHz,
CDCl3): δ = 7.77 (br. s, 2 H), 7.82 (br. s, 4 H), 8.11 (br. s, 2 H),
8.30 (br. s, 4 H), 8.57 (br. s, 4 H), 8.88 (br. s, 2 H), 9.01 (br. s, 2 H)
ppm. HRMS (ESI): calcd. for C37H24Cl3N4 [M + H]+ 629.1061;
found 629.1038.
5,10,15-Tris(4-nitrophenyl)corrole (6j):[8f] Green solid (25% yield).
Rf = 0.70 (EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε) = 450
5,10,15-Triphenylcorrole (6a):[8f] Green solid (82% yield). Rf = 0.74
(4.39), 593 (3.84) nm. H NMR (400 MHz, CDCl3): δ = 8.38 (d, J
1
(EtOAc/hexane, 1:3). UV/Vis (toluene): λmax (logε) = 414 (5.14), = 8.5 Hz, 2 H), 8.55 (d, J = 8.7 Hz, 4 H), 8.59 (d, J = 4.6 Hz, 2
575 (4.32), 613 (4.22), 645 (4.15) nm. 1H NMR (400 MHz, CDCl3):
H), 8.64–8.69 (m, 4 H), 8.72 (d, J = 8.4 Hz, 4 H), 8.91 (d, J =
δ = –2.18 (br. s, 3 H), 7.72 (br. s, 5 H), 7.80 (br. s, 4 H), 8.14 (br. 4.6 Hz, 2 H), 9.11 (d, J = 4.3 Hz, 2 H) ppm. HRMS (ESI): calcd.
s, 2 H), 8.33 (br. s, 4 H), 8.52 (br. s, 4 H), 8.85 (br. s, 4 H) ppm.
for C37H24N7O6 [M + H]+ 662.1783; found 662.1710.
7592
www.eurjoc.org
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 7583–7593

Selective Synthesis of Tripyrranes, Tetrapyrranes and Corroles
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Received: August 17, 2015
Published Online: October 29, 2015
Eur. J. Org. Chem. 2015, 7583–7593
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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