Synthesis of A2B6-type [36]octaphyrins: Copper(II)-metalation-induced fragmentation reactions to porphyrins and N-fusion reactions of meso-(3-thienyl) substituents

Article abstract of DOI:10.1002/asia.201100919

5,10,15-Tris(pentafluorophenyl)tetrapyrromethane was efficiently prepared through a route involving stepwise diaroylation of 5- pentafluorophenyldipyrromethane. A₂B₆-type [36]octaphyrins were prepared by the cross condensation of the

Full text of DOI:10.1002/asia.201100919

DOI: 10.1002/asia.201100919
Synthesis of A2B6-Type [36]Octaphyrins: Copper(II)-Metalation-Induced
Fragmentation Reactions to Porphyrins and N-Fusion Reactions of meso-(3-
Thienyl) Substituents
Hirotaka Mori,[a] Naoki Aratani,[a, b] and Atsuhiro Osuka*[a]
Abstract: 5,10,15-Tris(pentafluorophe-
nyl)tetrapyrromethane was efficiently
prepared through a route involving
stepwise diaroylation of 5-pentafluoro-
bearing 2,4,6-trifluorophenyl, 2,6-di-
chlorophenyl, and phenyl substituents
underwent
AB3-type CuII porphyrins. A2B6-type
[36]octaphyrin bearing 3-thienyl sub-
stituents underwent thermal N-thienyl
fusion reactions to provide a modestly
aromatic [38]octaphyrin, which, upon
treatment with MnO2, underwent fur-
ther N-thienyl fusion and subsequent
oxidation to give a nonaromatic doubly
N-thienyl fused [36]octaphyrin.
CuII-metalation-induced
fragmentation to give two molecules of
phenyldipyrromethane.
A2B6-type
[36]octaphyrins were prepared by the
cross condensation of the tetrapyrro-
methane with aryl aldehydes in moder-
ate yields. A2B6-type [36]octaphyrins
Keywords: aromaticity · fragmenta-
tion reactions · fusion reactions ·
octaphyrin · porphyrinoids
Introduction
has been shown to become a Mçbius aromatic molecule
upon diprotonation.[11b] Despite these findings, the chemistry
of [36]octaphyrins has remained at its infant stage, since
[36]octaphyrin bearing only meso-pentafluorophenyl sub-
stituents has been studied so far.[10,11] As a part of our pro-
gram to explore the chemistry of expanded porphyrins, we
decided to investigate the chemistry of A2B6 [36]octaphyrins
bearing other aryl substituents.
Since the first report on the synthesis of the expanded
porphyrins,[2] size-selective syntheses of expanded porphyr-
ins have been developed by using 5-(2,3,4,5,6-pentafluoro-
phenyl)dipyrromethane (2) or 5,10-bis(2,3,4,5,6-pentafluoro-
In the last two decades, considerable efforts have been de-
voted to the exploration of expanded porphyrins in light of
their potential applications in near-IR absorbing dyes, non-
linear optical materials with large two-photon absorption
cross sections, anion sensors, explosives sensors, molecular
recognition hosts, and so on.[1] We entered this chemistry
since our serendipitous finding that a series of meso-(penta-
fluorophenyl)-substituted expanded porphyrins were effi-
ciently formed in the acid-catalyzed condensation of penta-
fluorobenzaldehyde (1) and pyrrole at rather high concen-
tration (ca. 67 mm each).[2] With these expanded porphyrins,
we have revealed their intriguing chemistry such as pro-
nounced nonlinear optical properties,[3] rich coordination
chemistry,[4] unprecedented skeletal rearrangements,[5,6] and
formation of electronically novel species, including stable
Hꢀckel antiaromatic molecules, Mçbius aromatic and antiar-
omatic molecules,[7,8] and stable radicals.[9] Among these ex-
panded porphyrins, [36]octaphyrins possess a unique posi-
tion, since they show unprecedented reactions such as frag-
mentation to two molecules of porphyrins in a metathesis-
like reaction mode[10] and hydrolytic cleavage of a constitu-
ent pyrrole.[11a] Furthermore, nonaromatic [36]octaphyrin
phenyl)tripyrromethane (3).[12] In these syntheses, penta-
fluorophenyl substituent has been commonly employed, be-
cause they play an important role in providing steric hin-
drance at the meso-position to direct the condensation
reactions towards larger macrocycles and to protect linear
and cyclic oligopyrromethane intermediates from oxidative
degradation. Dipyrromethane 2 was previously prepared by
trifluoroacetic acid (TFA) catalyzed condensation of 1 with
pyrrole as a solvent (Lindsey method),[13] and its large-scale
preparation was achieved by the condensation in water
(Dehaen method).[14] Tripyrromethane 3 was prepared from
TFA-catalyzed condensation of 2 with pyrrole[12a,15] or from
TFA-catalyzed condensation of dipyrromethane monocarbi-
nol[16] with pyrrole.[12c] Compound 3 is an important precur-
sor in the synthesis of [32]heptaphyrin[17] and meso-unsubsti-
[a] H. Mori, Dr. N. Aratani, Prof. Dr. A. Osuka
Department of Chemistry
Graduate School of Science, Kyoto University
Sakyo-ku, Kyoto 606-8502 (Japan)
Fax : (+81)75-753-3970
E-mail: osuka@kuchem.kyoto-u.ac.jp
[b] Dr. N. Aratani
PRESTO Japan Science and Technology Agency (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201100919.
Chem. Asian J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1
&
&
&
These are not the final page numbers! ÞÞ

FULL PAPERS
tuted hexaphyrin.[9] 5,10,15-Tris(pentafluorophenyl)tetrapyr-
romethane (4) was prepared from a diacylated dipyrrome-
thane by Lindsey method[16b] and was used for the synthesis
of a [32]heptaphyrin.[17]
Herein, we disclose an improved synthesis of 4 and its use
for the synthesis of A2B6 [36]octaphyrins(1.1.1.1.1.1.1.1) 8 by
the cross condensation with aryl aldehydes. This protocol al-
lowed the incorporation of two different meso-aryl substitu-
ents at the 5- and 25-positions of [36]octaphyrins.
Scheme 2. Synthesis of octaphyrin 8a–e. DDQ=2,3-dichloro-5,6-dicyano-
p-benzoquinone.
Results and Discussion
Tetrapyrromethane 4 was prepared by the reaction route
shown in Scheme 1, in which the diaroylation of 2 is a key
25% yield by the reaction in CH2Cl2 at 08C. The absence of
heptaphyrin and nonaphyrin byproducts facilitated the isola-
tion of 8a. Under similar conditions, octaphyrins 8b (Ar=
2,4,6-trifluorophenyl), 8c (Ar=2,6-dichlorophenyl), and 8d
(Ar=phenyl) were prepared in 15, 10, and 15% yields, re-
spectively. The UV/Vis absorption spectra of 8b–d in
CH2Cl2 are similar to that of 8a with regard to broad bands
1
around 410 and 640 nm (Figure 1). The H NMR spectra of
Scheme 1. Synthesis of tetrapyrromethane 4.
step. Diaroylated product 5 was originally prepared in 25%
yield on the basis of a sequential EtMgBr/C6F5COCl proce-
dure developed by Lindsey et al.,[16] and its yield was recent-
ly improved to 69% by using mesityl Grignard reagent for
activation of dipyrromethane.[18] After extensive experimen-
tation, we found that sequential additions of 1) phenyl
Grignard reagent (3.0 equiv) and C6F5COCl (2.0 equiv) and
2) phenyl Grignard reagent (1.5 equiv) and C6F5COCl
(1.0 equiv) in toluene reproducibly provided 5 in more than
83% yield. This reaction protocol allowed large-scale prepa-
ration of 5 (18.6 g) from 2 (10.0 g). Diaroylated dipyrrome-
thane 5 was reduced with NaBH4 to dipyrromethane dicar-
binol 6, which reacted with pyrrole with the aid of TFA to
give 4, which was isolated in 73% yield for two steps.
Then, the synthesis of octaphyrins 8 was examined by the
cross condensation of 4 with aryl aldehydes (Scheme 2). Ini-
tially, the synthesis of 8a by the reaction of 1 with 4 was ex-
amined as a benchmark case. The use of BF3·OEt2 as an
acid led to extensive scrambling even at 08C, as indicated by
the formation of heptaphyrin and nonaphyrin detected by
TLC analysis and electrospray ionization time-of-flight
(ESI-TOF) mass spectrometry. Scrambling was considerably
suppressed by the use of methanesulfonic acid; however,
scrambled byproducts that hampered the isolation of 8a
were still observed. We found that p-toluenesulfonic acid (p-
TsOH) did not cause scrambling and gave octaphyrin 8a in
Figure 1. UV/Vis absorption spectra of 8a, 8b, 8c, and 8d in CH2Cl2.
8b–d are also roughly similar to that of 8a. Crystals of 8b
suitable for X-ray diffraction analysis were obtained from
slow diffusion of heptane into its chloroform solution. The
solid-state structure of 8b shows a figure-eight conformation
similar to that of 8a.[2b] Interestingly, less hindered 2,4,6-tri-
fluorophenyl substituents occupy the sterically congested
hinge positions of the figure-eight conformation (Figure 2).
Bond-length alternation is evident for the structure of 8b,
hence suggesting its nonaromatic character. It is thus con-
ceivable that octaphyrins 8b–d take figure-eight conforma-
tions mainly in nonpolar solvents, while they have consider-
able conformational flexibility.
First, CuII metalation reactions of 8b, 8c, and 8d were ex-
amined to confirm the generality of the fragmentation reac-
tion (Scheme 3). When the metalation reactions were con-
ducted with CuACHTNUTRGNEUNG(OAc)2 and sodium acetate at 1108C, octa-
phyrins 8b, 8c, and 8d gave AB3-type CuII porphyrins
9bCu, 9cCu, and 9dCu in 83, 89, and 89% yields, respec-
tively. These results indicate a certain generality of the ther-
mal fragmentation reaction for bis-CuII complexes of [36]oc-
taphyrins despite slight difference in meso-aryl substituent.
&
&
&2
&
www.chemasianj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!

Synthesis of A2B6-Type [36]Octaphyrins
similar to those of [36]octaphyrins 8a–d (Figure 1). Interest-
1
ingly, the H NMR spectrum of 8e shows two sets of signals
in a ratio of 3:1, where the minor set has C2 symmetry and
the major set showed a spectrum of higher symmetry (see
the Supporting Information). These data indicate that 8e
may adopt two main figure-eight conformations with 3-
thienyl substituents at different positions (Scheme 4).[20]
We observed a slow N-thienyl fusion reaction of 8e in so-
lution to provide monofused product 10 (Scheme 5). This N-
Figure 2. X-ray crystal structure of 8b. a) Top view. b) Side view. The
thermal ellipsoids represent 50% probability. meso-Pentafluorophenyl
groups and solvent molecules are omitted for clarity.
Scheme 5. Formation of singly and doubly N-thienyl fused octaphyrins 10
and 11.
Fusion reactions of expanded porphyrins have shown
promise in creating new conjugated systems, since the result-
ing rigid and planar tricyclic ring system will lead to signifi-
cant changes in the structural and electronic properties of
porphyrins.[2a,6b,19] As an interesting case, we recently found
that a 3-thienyl substituent at the meso-position of [26]hexa-
phyrin triggered a facile fusion reaction with the neighbor-
ing pyrrolic nitrogen atom to form an N-thienyl fused
[28]hexaphyrin with distinct Mçbius aromaticity.[19h] Thus, in
order to apply this synthetic strategy to octaphyrins, A2B6-
type [36]octaphyrin 8e was prepared in 15% yield by the re-
action of 4 with 3-thiophenecarbaldehyde. UV/Vis absorp-
tion spectrum of 8e shows two bands at 412 and 622 nm,
fusion reaction occurred very slowly even in the solid state
at room temperature. As a convenient and reproducible
method, N-thienyl fused octaphyrin 10 was obtained in 70%
yield by heating a toluene solution of 8e at reflux for
10 min. The structure of 10 has been revealed by X-ray dif-
fraction analysis as shown in Figure 3. The coplanar tricyclic
segment is located at the hinge position of a roughly figure-
eight structure across a [38]octaphyrin electronic network.
1
In line with this nonsymmetric structure, the H NMR spec-
trum of 10 exhibited five signals at d=11.14, 10.12, 9.93,
9.21, and 6.86 ppm due to the NH protons, and sixteen sig-
nals in the range of d=6.71–4.77 ppm due to the b-protons.
The observed deshielded chem-
ical shifts of the b-protons thus
can be understood in terms of
modest Hꢀckel aromaticity aris-
ing from the doubly twisted 38-
p-electron network. In line with
this interpretation, the UV/Vis
absorption spectrum of 10
Scheme 3. Fragmentation reaction of octaphyrin 8a–d.
shows a sharp and strong Soret-
like band at 737 nm and low-
energy Q-like bands at 985 and
1120 nm (Figure 5). The nu-
cleus-independent
chemical
shift (NICS) values[21] were cal-
culated to be À11.54, À3.05,
and À3.11 ppm at A, B, and C
(designated in Figure 3), respec-
tively.
Scheme 4. Conformational equilibrium of 8e (Ar=3-thienyl).
Chem. Asian J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
3
&
&
&
These are not the final page numbers! ÞÞ

A. Osuka et al.
FULL PAPERS
Figure 3. X-ray crystal structure of 10. a) Top view. b) Side view. The
thermal ellipsoids represent 30% probability. meso-Pentafluorophenyl
groups and solvent molecules are omitted for clarity. A, B, and C indicate
points at which nucleus-independent chemical shift (NICS) values were
calculated. See text for details.
Figure 4. X-ray crystal structure of 11. a) Top view. b) Side view. The
thermal ellipsoids represent 30% probability. meso-Pentafluorophenyl
groups and solvent molecules are omitted for clarity. A and B indicate
points at which NICS values were calculated. See text for details.
The monofused [38]octaphyrin 10 did not show any fur-
ther N-thienyl fusion reactivity under forcing conditions. It
was thought that the N-thienyl fusion reaction would pro-
ceed only from [36]octaphyrin but not from [38]octaphyrin.
We thus attempted an oxidation of 10 to the corresponding
36p-congener. A solution of 10 in CH2Cl2 was treated with
an excess amount of MnO2 at room temperature, which in-
duced an instantaneous vivid color change from dark green
to deep blue to indicate the occurrence of the second N-
thienyl fusion reaction. After the usual workup, doubly N-
thienyl-fused [36]octaphyrin 11 was isolated in 80% yield. It
is considered that the fusion reaction of a putative singly N-
thienyl fused [36]octaphyrin is fast at room temperature to
provide doubly N-thienyl fused [38]octaphyrin that is readily
Figure 5. UV/Vis absorption spectra of 8e, 10, and 11 in CH2Cl2.
Conclusions
1
oxidized to 11 under the reaction conditions. The H NMR
spectrum exhibited broad signal due to NH protons, eight
sets of signals due to the b-protons, and two signals due to
the 3-thienyl groups. Fortunately, we revealed the structure
of 11 by X-ray analysis to be a symmetric figure-eight con-
formation (Figure 4). The UV/Vis absorption spectrum
shows broad bands at 425 and 582 nm, which are similar to
those of 8e (Figure 5). These optical data indicate the non-
aromatic properties of 11 with a 36-p-electron circuit. In
line with this consideration, the NICS values were calculated
at points A and B (designated in Figure 4) to be +4.55 and
+4.57 ppm, respectively. As such, the incorporation of 3-
thienyl substituents at meso-positions of [36]octaphyrin trig-
gered the facile N-thienyl fusion reaction, similar to [26]hex-
aphyrins.[19h]
The tetrapyrromethane 4, a key precursor for the synthesis
of octaphyrin, was prepared in good yield and on a large
scale. A2B6-type [36]octaphyrins 8b–e were prepared by the
reaction of 4 with aryl aldehydes in moderate yields and
have been shown to take figure-eight structures in solution.
[36]Octaphyrins 8b–d underwent thermal CuII-metalation-
induced fragmentation reaction to two CuII porphyrins.
[36]Octaphyrin bearing 3-thienyl groups at the meso-posi-
tions underwent facile N-thienyl fusion reaction to provide
N-thienyl fused [38]octaphyrin 10 that is moderately aromat-
ic. Applicability of this synthetic strategy to other expanded
porphyrins is being actively studied in our laboratory.
Experimental Section
General: 1H and 19F NMR spectra were recorded on a JEOL ECA-600
spectrometer (600 MHz for 1H and 565 MHz for 19F). Chemical shifts
were reported as delta scale in ppm relative to the residual solvent as the
1
internal reference for H (d=7.260 ppm); hexafluorobenzene was used as
&
&
&4
&
www.chemasianj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!

Synthesis of A2B6-Type [36]Octaphyrins
external reference for 19F (d=À162.9 ppm). NMR signals were assigned
o-F), À150.83 (br s, 2F; p-F), À152.76 (t, J=22.0 Hz, 2F; p-F),
À154.43(br s, 2F; p-F), À157.46 (d, J=91.7 Hz, 2F; m-F), À159.12 (m,
2F; m-F), À160.83 (m, 6F; m-F), and À161.07 ppm (m, 2F, m-F). UV/Vis
(CH2Cl2): lmax [nm] (e [mÀ1 cmÀ1])=336 (47000), 409 (87000), and 639
(118000). HR ESI-TOF-MS (positive mode): m/z 1907.0638 [M+H]+,
calcd for C88H27N8F30Cl4 =1907.0624.
1
from the H–1H COSY spectra and by comparison with the spectra in the
presence of D2O (signals assigned for NH protons disappear in the pres-
ence of D2O). UV/Vis spectra were recorded on a Shimadzu UV-3100PC
spectrometer. High-resolution ESI-TOF mass spectra of samples in ace-
tonitrile were recorded on a BRUKER microTOF instrument in the posi-
tive or negative ion mode. X-ray data were recorded on a Rigaku-Raxis
imaging plate system. Unless otherwise noted, materials obtained from
commercial suppliers were used without further purification. Silica gel
column chromatography was performed on Wakogel C-300 and C-400.
Thin-layer chromatography (TLC) was carried out on aluminum sheets
coated with silica gel 60 F254 (Merck 5554).
5,25-BisACTHNUGRTENUNG(phenyl)-10,15,20,30,35,40-hexakis(pentafluorophenyl)-[36]octa-
phyrin (8d): 1H NMR (600 MHz, CDCl3, 298 K, as conformational mix-
ture; conformer A : conformer B=20:1); conformer A (major): d=12.90
(br s, 2H; NH), 11.67 (br s, 2H; NH), 8.77 (br s, 2H; b-H), 7.71 (t, J=
7.4 Hz, 2H; p-H), 7.60 (br s, 2H; b-H), 6.88 (d, J=4.2 Hz, 2H; b-H), 6.47
(br s, 1H; b-H), 6.21 (d, J=4.2 Hz, 2H; b-H), 6.00 (br s, 2H; b-H), 5.98
(br s, 2H; b-H), and 5.87 ppm (d, 2H; b-H) (o-H and m-H of phenyl
groups are too broad to analyze at 258C); 19F NMR (565 MHz, CDCl3):
d=À133.80 (d, J=22.0 Hz, 2F; o-F), À137.64 (d, J=22.0 Hz, 2F; o-F),
À137.80 (d, J=22.0 Hz, 2F; o-F), À137.33 (dd, J1 =7.3 Hz, J2 =22.0 Hz,
2F; o-F), À139.05 (d, J=22.0 Hz, 2F; o-F), À140.91 (d, J=22.0 Hz, 2F;
o-F), À150.26 (t, J=22.0 Hz, 2F; p-F), À152.69 (d, J=22.0 Hz, 4F; p-F),
À159.22 (m, 2F; m-F), À160.11 (m, 2F; m-F), À160.36 (br s, 2F; m-F),
and À160.83 ppm (m, 6F; m-F). Conformer B (minor): d=13.25 (br s,
2H; NH), 12.43 (br s, 2H; NH), 8.67 (d, J=4.2 Hz, 2H; b-H), 7.92 (br s,
2H; b-H), 7.67 (t, J=7.4 Hz, 2H; p-H), 7.45 (br s, 2H; b-H), 6.66 (br s,
2H; b-H), 6.51 (d, J=4.2 Hz, 2H; b-H), 6.36 (br s, 2H; b-H), and
5.98 ppm (br s, 2H; b-H). Other peaks are overlapped by the peaks of
conformer A or too broad to analyze at 258C. 19F NMR (565 MHz,
CDCl3): d=À133.47 (br s, 2F; o-F), À136.67 (d, J=22.0 Hz, 2F; o-F),
À137.10 (d, J=22.0 Hz, 2F; o-F), À138.01 (dd, J1 =7.3 Hz, J2 =22.0 Hz,
2F; o-F), À138.27 (dd, J1 =7.3 Hz, J2 =22.0 Hz, 2F; o-F), À139.80 (d, J=
22.0 Hz, 2F; o-F), À151.11 (t, J=22.0 Hz, 2F; p-F), À155.06 (d, J=
22.0 Hz, 4F; p-F), À162.80 (m, 2F; m-F), and À163.83 ppm (br s, 2F; m-
F). Other peaks are overlapped by the peaks of conformer A. UV/Vis
(CH2Cl2): lmax [nm] (e [mÀ1 cmÀ1])=338 (75000), 411 (115000), 640
(132000), and 692 (94000). HR ESI-TOF-MS (positive mode): m/z
1769.2167 [M+H]+, calcd for C88H31N8F30 =1769.2187.
1,9-Bis(pentafluorobenzoyl)-5-(pentafluorophenyl)dipyrromethane (5): A
solution of 5-(pentafluorophenyl)dipyrromethane (2, 10.0 g, 32 mmol) in
dry toluene (250 mL) was treated with a solution of PhMgBr in THF
(96 mmol; 1.1m) at 08C. After 15 min, pentafluorobenzoyl chloride
(9.6 mL, 64 mmol) was added slowly to the reaction mixture, and the re-
sultant solution was stirred for an additional 15 min. Then, the slow addi-
tion of PhMgBr (48 mmol; 1.1m) and the aroyl chloride (4.8 mL,
32 mmol) was repeated over a period of 30 min. After being stirred for
15 min, the reaction mixture was quenched by addition of a saturated
aqueous NH4Cl (100 mL). The product was extracted with ethyl acetate.
The combined organic extract was washed with water and dried over an-
hydrous Na2SO4. After the solvent was removed, precipitation from
CH2Cl2 afforded the crude product, which was purified by recrystalliza-
tion from CH2Cl2/hexane to give a white powder of 5 (18.6 g; 83%). The
spectral data were the same as those in the previous report.[16]
5,10,15-Tris(pentafluorophenyl)tetrapyrromethane (4) was prepared by
our previous method.[17]
General procedure for synthesis of A2B6-type [36]octaphyrins (8a–e): A
solution of aryl aldehyde (0.62 mmol) and 4 (500 mg, 0.62 mmol) in
CH2Cl2 (12.5 mL) was placed in a 50 mL round-bottomed flask under ni-
trogen atmosphere at 08C. To the solution was added p-toluenesulfuric
acid monohydrate (6.0 mg; 5 mol%), and the resulting solution was
stirred for 2 h. Then, DDQ (1.1 g; 4.8 mmol) was added and the resulting
mixture was stirred for 1 h and was passed through a short alumina
column to remove the tar. Repeated silica-gel column chromatography
(AcOEt/n-hexane, 1:19; then CH2Cl2/n-hexane, 1:9) gave 8 as a green
fraction. Yields were 25% for 8a, 15% for 8b, 10% for 8c, 15% for 8d,
and 15% for 8e.
5,25-Bis(3-thienyl)-10,15,20,30,35,40-hexakis(pentafluorophenyl)-[36]octa-
phyrin (8e): 1H NMR (600 MHz, CDCl3, 298 K, as conformational mix-
ture; conformer A : conformer B=3:1); conformer A (major): d=12.96
(br s, 2H; NH), 11.33 (br s, 2H; NH), 8.48 (br s, 2H), 8.06 (br s, 2H),
7.83 (br s, 2H), 7.48 (br s, 2H), 7.03 (d, J=4.6 Hz, 2H; b-H), 6.53 (br s,
2H), 6.20 (d, J=4.6 Hz, 2H; b-H), 6.14 (br s, 2H), 6.06 (d, J=4.6 Hz,
2H; b-H), and 5.99 ppm (br s, 2H). One peak was too broad to analyze
at 258C. 19F NMR (565 MHz, CDCl3): d=À133.77 (d, J=22.0 Hz, 2F; o-
F), À137.20 (br s, 2F; o-F), À138.11 (br s, 2F; o-F), À138.20 (dd, J1 =
7.0 Hz, J2 =22.0 Hz, 2F; o-F), À138.76 (d, J=22.0 Hz, 2F; o-F), À141.12
(br s, 2F; o-F), À150.18 (br s, 2F; p-F), À152.63 (t, J=22.0 Hz, 4F; p-F),
À159.19 (m, 2F; m-F), À160.12 (m, 2F; m-F), À160.25 (br s, 2F; m-F),
À160.70 (m, 2F; m-F), and À160.84 ppm (m, 4F; m-F). conformer B
(minor): d=13.59 (br s, 2H; NH), 12.37 (br s, 2H; NH), 8.64 (br s 2H),
8.62 (d, J=4.6 Hz, 2H; b-H), 8.44 (d, J=4.6 Hz, 2H; b-H), 7.74 (br s,
2H), 7.28 (dd, J1 =2.9 Hz, J2 =9.7 Hz, 2H; thienyl-H), 6.58 (br s, 2H),
6.55 (d, J=4.6 Hz, 2H; b-H), 6.43 (d, J=4.6 Hz, 2H; b-H), 6.09 (d, J=
4.6 Hz, 2H; b-H), 6.04 ppm (d, J=4.6 Hz, 2H; b-H). Other peaks are
overlapped by the peaks of conformer A or too broad to analyze at
258C. 19F NMR (565 MHz, CDCl3): d=À134.43 (br s, 2F; o-F), À136.76
(d, J=22.0 Hz, 2F; o-F), À137.09 (d, J=22.0 Hz, 2F; o-F), À137.80 (dd,
J1 =7.3 Hz, J2 =22.0 Hz, 2F; o-F), À139.42 (dd, J1 =7.3 Hz, J2 =22.0 Hz,
2F; o-F), À141.12 (br 2F; o-F), À151.12 (t, J=22.0 Hz, 2F; p-F),
À154.84 (d, J=22.0 Hz, 2F; p-F), À162.29 (m, 2F; m-F), À163.61 ppm
(br s, 2F; m-F). Other peaks are overlapped by the peaks of conformer
A. UV/Vis (CH2Cl2): lmax [nm] (e [mÀ1 cmÀ1])=342 (71000), 412 (97000),
622 (122000), and 700 (79000). HR ESI-TOF-MS (negative mode): m/z
1779.1124 [MÀH]À, calcd for C88H25N8F30S2 =1779.1159.
5,25-Bis(2,4,6-trifluorophenyl)-10,15,20,30,35,40-hexakis(pentafluoro-
phenyl)-[36]octaphyrin (8b): 1H NMR (600 MHz, CDCl3, 298 K, as con-
formational mixture; almost exclusively conformer A): d=13.48 (br s,
2H; NH), 12.56 (br s, 2H; NH), 9.05 (br s, 2H; b-H), 8.01 (br s, 2H; b-
H), 7.81 (br s, 2H; Ar-H), 6.67 (br s, 2H; b-H), 6.25 (br s, 2H; b-H), 6.15
(d, J=4.6 Hz, 2H; b-H), 6.02 (d, J=4.6 Hz, 2H; b-H), and 5.93 ppm (br
s, 4 H; b-H and Ar-H); 19F NMR (565 MHz, CDCl3): d=À134.28 (d, J=
22.0 Hz, 2F; o-F), À137.66 (d, J=22.0 Hz, 2F; o-F), À138.14 (d, J=
22.0 Hz, 2F; o-F), À138.76 (br s, 2F; o-F), À138.84 (d, J=22.0 Hz, 2F; o-
F), À140.22 (d, J=22.0 Hz, 2F; o-F), À150.62 (br s, 2F; p-F), À152.09 (t,
J=22.0 Hz, 2F; p-F), À152.19 (t, J=22.0 Hz, 2F; p-F), À158.96 (m, 2F;
m-F), À159.85 (m, 2F; m-F), and À160.53 ppm (m, 6F; m-F). UV/Vis
(CH2Cl2): lmax [nm] (e [mÀ1 cmÀ1])=335 (56600), 408 (104000), and 647
(126000). HR ESI-TOF-MS (positive mode): m/z 1877.1605 [M+H]+,
calcd for C88H25F36N8 =1877.1622; crystal data: C88H24F36N8·ACTHNUGRTENUNG(heptane)·
(CHCl3), Mr =2052.0, monoclinic, space group P2/c (No. 13), a=
8.1869(1), b=15.0916(3), c=33.4995(6) ꢂ, b=90.3617(9)8, V=
4138.90(12) ꢂ3, Z=2, 1calcd =1.660 gcmÀ3
, T=93 K, R1 =0.0798 [I>
2s(I)], Rw =0.2341 (all data), GOF=1.054. Crystals were grown from
CHCl3/heptane.
5,25-Bis(2,6-dichlorophenyl)-10,15,20,30,35,40-hexakis(pentafluorophen-
1
yl)-[36]octaphyrin (8c): H NMR (600 MHz, CDCl3, 298 K): d=12.97 (br
General procedure for the fragmentation reaction of A2B6-type [36]octa-
phyrins (8b–d): A solution of [36]octaphyrin (8b–d; 10 mmol) in toluene
was stirred at 1108C in the presence of CuACTHNUTRGENUG(N OAc)2 (10 equiv) and of
NaOAc (10 equiv) for 12 h under dinitrogen atmosphere in the dark. The
reaction was quenched with aqueous NaHCO3 solution and diluted with
CH2Cl2. The organic layer was dried with anhydrous Na2SO4, and the sol-
s, 2H; NH), 12.03 (br s, 2H; NH), 8.61 (br s, 2H; b-H), 7.68 (br s, 2H; b-
H), 7.41 (d, J=8.2 Hz, 2H; m-H), 7.33 (d, J=8.2 Hz, 2H; m-H), 7.29 (d,
J=7.8 Hz, 2H; p-H), 6.44 (br s, 2H; b-H), 6.28 (br s, 2H; b-H), 6.15 (br
s, 2 H; b-H), 6.07 (br s, 4H; b-H), and 6.02 ppm (d, J=4.1 Hz, 2H; b-H);
19F NMR (565 MHz, CDCl3): d=À133.40 (br s, 2F; o-F), À134.12 (br s,
2F; o-F), À136.02 (dd, J1 =22.0 Hz, J2 =95.34, 2F; o-F), À137.17 (m, 6F;
Chem. Asian J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
5
&
&
&
These are not the final page numbers! ÞÞ

A. Osuka et al.
FULL PAPERS
vent was removed under reduced pressure to give the crude mixture. The
separation of the products by silica gel column chromatography gave CuII
porphyrin (9b–d) as a red fraction (9bCu: 83%, 9cCu: 89%, and 9dCu:
89% yield, respectively). These copper(II) porphyrins were demetalated
quantitatively upon treatment with H2SO4 and TFA to provide corre-
sponding free base porphyrins, 9bH2, 9cH2, and 9dH2, respectively.
À160.58 (m, 2F; m-F), and À161.10 ppm (m, 8F; m-F). UV/Vis
(CH2Cl2): lmax [nm] (e [mÀ1 cmÀ1])=458 (69000), 737 (208000), 985
(14000), and 1120 (8000). HR ESI-TOF-MS (positive mode): m/z
1781.1289 [M+H]+, calcd for C84H27N8F30S2 =1781.1316; crystal data :
¯
C84H24F30N8S ·
a=19.4720(4), b=21.0120(4), c=22.7379(4) ꢂ, a=76.5557(4), b=
73.7861(4), g=83.9060(9)8, V=8679.8(3) ꢂ3, Z=4, 1calcd =1.598 gcmÀ3
2 ACHTUNGTRNE(GNU PhCl)2.75, Mr =2087.74, triclinic, space group P1 (No. 2),
,
5,10,15-Tris(pentafluorophenyl)-20-(2,4,6-trifluorophenyl) copper(II) por-
phyrin (9bCu): UV/Vis (CH2Cl2): lmax [nm]=408, 535, and 570. HR ESI-
TOF-MS (positive mode): m/z 999.9978 [M+H]+, calcd for
C44H11N4F18Cu=999.9987.
T=93 K, R1 =0.1257 [I>2s(I)], Rw =0.3913 (all data), GOF=1.024.
Crystals were grown from PhCl/n-nonane.
Doubly N-thienyl fused [36]octaphyrin 11: Under nitrogen atmosphere,
an excess amount of MnO2 (50 mg) was added to a solution of 10
(10.0 mg, 5.6 mmol) in dichloromethane (10 mL), and the resulting solu-
tion was stirred for 15 min and was then passed through a short Celite
column. Recrystallization from chlorobenzene/n-heptane gave 11
(8.0 mg; 80% yield). 1H NMR (600 MHz, CDCl3, 298 K): d=13.66 (br s,
2H; NH), 8.28 (d, J=4.9 Hz, 2H; b-H), 7.78 (d, J=5.9 Hz, 4H; b-H),
7.60 (d, J=4.8 Hz, 2H; b-H), 7.09 (d, J=5.5 Hz, 4H; b-H), 6.86 (t, J=
4.8 Hz, 2H; b-H), 6.54 (d, J=4.9 Hz, 2H; b-H), 6.22 (m, Hz, 4H; 2b-H
and thienyl-H), and 6.02 ppm (m, 2H; thienyl-H); 19F NMR (565 MHz,
CDCl3): d=À132.27 (d, J=22.0 Hz, 2F; o-F), À135.19 (d, J=22.0 Hz,
2F; o-F), À136.49 (d, J=22.0 Hz, 2F; o-F), À136.66 (d, J=20.7 Hz, 2F;
o-F), À138.12 (d, J=20.7 Hz, 2F; o-F), À138.54 (d, J=22.0 Hz, 2F; o-F),
À150.34 (t, J=22.0 Hz, 2F; p-F), À151.31 (t, J=22.0 Hz, 2F; p-F),
À151.44 (t, J=22.0 Hz, 2F; p-F), À159.41 (m, 2F; m-F), À159.61 (m, 2F;
m-F), À160.07 (m, 2F; m-F), À160.31 (m, 4F; m-F), and À160.69 ppm
(m, 2F; m-F). UV/Vis (CH2Cl2): lmax [nm] (e [mÀ1 cmÀ1])=345 (46900),
425 (56000), and 582 (93400). HR ESI-TOF-MS (positive mode): m/z
1778.1031 [M+H]+, calcd for C84H23N8F30S2 =1778.1035; cryatal data:
5,10,15-Tris(pentafluorophenyl)-20-(2,6-dichlorophenyl) copper(II) por-
phyrin (9cCu): UV/Vis (CH2Cl2): lmax [nm]=410, 537, and 572. HR ESI-
TOF-MS (positive mode): m/z 1015.9453 [M+H]+, calcd for
C44H12N4F15Cl2Cu=1015.9464.
5,10,15-Tris(pentafluorophenyl)-20-phenyl copper(II) porphyrin (9dCu):
UV/Vis (CH2Cl2): lmax [nm]=410, 535, and 570. HR ESI-TOF-MS (posi-
tive mode): m/z 946.9285 [M+H]+, calcd for C44H14N4F15Cu=946.0269.
5,10,15-Tris(pentafluorophenyl)-20-(2,4,6-trifluorophenyl)
porphyrin
(9bH2): 1H NMR (600 MHz, CDCl3, 298 K): d=8.95 (d, J=4.1 Hz, 2H;
b-H), 8.90 (br s, 4H; b-H), 8.88 (d, J=4.1 Hz, 2H; b-H), 7.21 (d, J=
8.3 Hz, 2H; m-H), and À2.90 ppm (br s, 2H; inner NH); 19F NMR
(565 MHz, CDCl3): d=À104.98 (m, 2F; trifluorophenyl-o-F), À105.02
(m, 1F; trifluorophenyl-p-F), À136.43 (m, 6F; o-F), À151.41 (m, 3F; p-
F), and À161.41 ppm (m, 6F; m-F). UV/Vis (CH2Cl2): lmax [nm]=412,
505, and 585. HR ESI-TOF-MS (positive mode): m/z 939.0810 [M+H]+,
calcd for C44H13N4F18 =939.0847.
5,10,15-Tris(pentafluorophenyl)-20-(2.6-dichlorophenyl)
porphyrin
(9cH2): 1H NMR (600 MHz, CDCl3, 298 K): d=8.89 (br s, 4H; b-H),
8.83 (d, J=4.1 Hz, 2H; b-H), 8.81 (d, J=4.1 Hz, 2H; b-H), 7.84 (d, J=
7.8 Hz, 2H; m-H), 7.76 (d, J=7.8 Hz, 1H; p-H), and À2.80 ppm (br s,
2H; inner NH); 19F NMR (565 MHz, CDCl3): d=À136.27 (dd, J1 =
22.0 Hz, J2 =7.3 Hz, 4F; o-F), À136.45 (dd, J1 =25.7 Hz, J2 =11.0 Hz, 4F;
o-F), À151.55 (m, 3F; p-F), and À1611.49 ppm (m, 6F; m-F). UV/Vis
(CH2Cl2): lmax [nm]=413, 505, and 585. HR ESI-TOF-MS (positive
mode): m/z 953.0317 [M+H]+, calcd for C44H14N4F15 =953.0351.
C84H22F30N8S2·ACTHNUTRGEN(UNG PhCl)3, Mr =2109.83, orthorhombic, space group C2221
(No. 20), a=7.9846(5), b=30.722(3), c=34.370(3) ꢂ, V=8431.0(11) ꢂ3,
Z=4, 1calcd =1.662 gcmÀ3, T=93 K, R1 =0.1534 [I>2s(I)], Rw =0.4309
(all data), GOF=1.173. Crystals were grown from PhCl/heptane.
Crystallographyic data: CCDC 853155 (8b), CCDC 853157 (10), and
CCDC 853156 (11) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif.
5,10,15-Tris(pentafluorophenyl)-20-phenyl porphyrin (9dH2): 1H NMR
(600 MHz, CDCl3, 298 K): d=8.97 (d, J=4.1 Hz, 2H; b-H), 8.89 (m, 4H;
b-H), 8.81 (d, J=4.1 Hz, 2H; b-H), 8.21 (d, J=7.3 Hz, 2H; o-H), 7.21 (d,
J=7.3 Hz, 1H; p-H), 7.79 (m, 2H; m-H), and À2.83 ppm (br s, 2H; inner
NH); 19F NMR (565 MHz, CDCl3): d=À136.43 (dd, J1 =24.9 Hz, J2 =
7.3 Hz, 2F; o-F), À136.55 (dd, J1 =25.7 Hz, J2 =7.3 Hz, 4F; o-F), À151.70
(m, 3F; p-F), and À161.55 ppm (m, 6F; m-F). UV/Vis (CH2Cl2): lmax
[nm]=413, 509, and 585. HR ESI-TOF-MS (positive mode): m/z
885.1108 [M+H]+, calcd for C44H16N4F15 =885.1130.
Acknowledgements
This work was supported by Grants-in-Aids for Scientific Research (No.
22245006 (A) and 20108001 “pi-Space”) from MEXT, Japan.
Singly N-thienyl fused [38]octaphyrin 10: A solution of 8a (36 mg, 20
mmol) in toluene (10 mL) was heated at reflux for 10 min. After removal
of the solvent by using a rotary evaporator, separation over a silica gel
column using CH2Cl2/hexane as an eluent gave singly thienyl-fused
[38]octaphyrin 10 (25 mg; 70% yield). 1H NMR (600 MHz, CDCl3,
298 K): d=11.10 (br s, 1H; NH), 10.06 (br s, 1H; NH), 9.89 (br s, 1H;
NH), 9.14 (br s, 1H; NH), 6.85 (br s, 1H; NH), 6.79 (m, 2H; b-H), 6.71
(d, J=4.6 Hz, 1H; b-H), 6.65 (d, J=5.0 Hz, 1H; b-H), 6.54 (d, J=4.6 Hz,
1H; b-H), 6.51 (m, 1H; b-H), 6.31 (d, J=5.0 Hz, 1H; b-H), 6.23 (m, 1H;
b-H), 6.04 (d, J=4.1 Hz, 1H; b-H), 5.89 (d, J=5.0 Hz, 1H; b-H), 5.66 (d,
J=4.1 Hz, 1H; b-H), 5.62 (d, J=4.1 Hz, 1H; b-H; b-H), 5.25 (d, J=
5.0 Hz, 1H; b-Hd), 5.15 (m, 2H; b-Hc), 4.77 (d, J=5.0 Hz, 1H; b-Hb),
4.37 (m, 1H; b-Ha), and 3.28 ppm (m, 1H; thienyl-H). Three thienyl pro-
tons were not detected, probably due to severe broadening both at room
temperature and at À608C.; 19F NMR (565 MHz, CDCl3): d=À135.34
(d, J=22.0 Hz, 2F; o-F), À135.84 (d, J=22.0 Hz, 2F; o-F), À136.61 (d,
J=22.0 Hz, 2F; o-F), À135.34 (d, J=25.7 Hz, 2F; o-F), À136.69 (d, J=
25.7 Hz, 2F; o-F), À137.13 (m, 4F; o-F), À137.29 (d, J=22.0 Hz, 2F; o-
F), À137.46 (dd, J1 =7.3 Hz, J2 =22.0 Hz, 2F; o-F), À137.91 (d, J=
22.0 Hz, 2F; o-F), À138.09 (d, J=22.0 Hz, 2F; o-F), À138.54 (m, 4F; o-
F), À150.59 (t, J=22.0 Hz, 2F; p-F), À151.08 (t, J=22.0 Hz, 2F; p-F),
À152.72 (t, J=22.0 Hz, 2F; p-F), À153.05 (t, J=22.0 Hz, 2F; p-F),
À153.29 (t, J=22.0 Hz, 2F; p-F), À153.67 (t, J=22.0 Hz, 2F; p-F),
À159.04 (m, 2F; m-F), À159.53 (m, 2F; m-F), À160.23 (m, 2F; m-F),
[1] a) A. Jasat, D. Dolphin, Chem. Rev. 1997, 97, 2267; b) H. Furuta, H.
Maeda, A. Osuka, Chem. Commun. 2002, 1795; c) J. L. Sessler, D.
Seidel, Angew. Chem. 2003, 115, 5292; Angew. Chem. Int. Ed. 2003,
42, 5134; d) T. K. Chandrashekar, S. Venkatraman, Acc. Chem. Res.
2003, 36, 676; e) Z. S. Yoon, A. Osuka, D. Kim, Nat. Chem. 2009, 1,
´
´
113; f) M. Ste˛pien, N. Sprutta, L. Latos-Graz˙ynski, Angew. Chem.
2011, 123, 4376; Angew. Chem. Int. Ed. 2011, 50, 4288; g) S. Saito,
A. Osuka, Angew. Chem. 2011, 123, 4432; Angew. Chem. Int. Ed.
2011, 50, 4342; h) A. Osuka, S. Saito, Chem. Commun. 2011, 47,
4330.
[2] a) J.-Y. Shin, H. Furuta, A. Osuka, Angew. Chem. 2001, 113, 639;
Angew. Chem. Int. Ed. 2001, 40, 619; b) J.-Y. Shin, H. Furuta, K.
Yoza, S. Igarashi, A. Osuka, J. Am. Chem. Soc. 2001, 123, 7190.
[3] a) T. K. Ahn, J. H. Kwon, D. Y. Kim, D. W. Cho, D. H. Jeong, S.
Keun, M. Suzuki, S. Shimizu, A. Osuka, D. Kim, J. Am. Chem. Soc.
2005, 127, 12856; b) Z. S. Yoon, J. H. Kwon, M.-C. Yoon, M. K. Koh,
S. B. Noh, J. L. Sessler, J. T. Lee, D. Seidel, A. Aguilar, S. Shimizu,
M. Suzuki, A. Osuka, D. Kim, J. Am. Chem. Soc. 2006, 128, 14128.
[4] a) S. Shimizu, V. G. Anand, R. Taniguchi, K. Furukawa, T. Kato, T.
Yokoyama, A. Osuka, J. Am. Chem. Soc. 2004, 126, 12280; b) S.
Mori, A. Osuka, J. Am. Chem. Soc. 2005, 127, 8030; c) S. Shimizu,
A. Osuka, Eur. J. Inorg. Chem. 2006, 1319.
&
&
&6
&
www.chemasianj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!

Synthesis of A2B6-Type [36]Octaphyrins
[5] a) E. Vogel, M. Michels, L. Zander, J. Lex, N. S. Tuzun, K. N. Houk,
Angew. Chem. 2003, 115, 2964; Angew. Chem. Int. Ed. 2003, 42,
2857; b) S. Saito, K. S. Kim, Z. S. Yoon, D. Kim, A. Osuka, Angew.
Chem. 2007, 119, 5687; Angew. Chem. Int. Ed. 2007, 46, 5591; c) R.
Sakamoto, S. Saito, S. Shimizu, Y. Inokuma, N. Aratani, A. Osuka,
Chem. Lett. 2010, 39, 439; d) K. Moriya, S. Saito, A. Osuka, Angew.
Chem. 2010, 122, 4393; Angew. Chem. Int. Ed. 2010, 49, 4297; e) T.
Yoneda, S. Saito, H. Yorimitsu, A. Osuka, Angew. Chem. 2011, 123,
3537; Angew. Chem. Int. Ed. 2011, 50, 3475; f) Y. Tanaka, H. Mori,
T. Koide, H. Yorimitsu, N. Aratani, A. Osuka, Angew. Chem. 2011,
123, 11662; Angew. Chem. Int. Ed. 2011, 50, 11460.
[11] a) S. Shimizu, Y. Tanaka, K. Youfu, A. Osuka, Angew. Chem. 2005,
117, 3792; Angew. Chem. Int. Ed. 2005, 44, 3726; b) J. M. Lim, J.-Y.
Shin, Y. Tanaka, S. Saito, A. Osuka, D. Kim, J. Am. Chem. Soc.
2010, 132, 3105; c) H. Hata, Y. Kamimura, H. Shinokubo, A. Osuka,
Org. Lett. 2006, 8, 1169.
[12] a) R. Taniguchi, S. Shimizu, M. Suzuki, J.-Y. Shin, H. Furuta, A.
Osuka, Tetrahedron Lett. 2003, 44, 2505; b) Y. Tanaka, J.-Y. Shin, A.
Osuka, Eur. J. Org. Chem. 2008, 1341; c) Y. Kamimura, S. Shimizu,
A. Osuka, Chem. Eur. J. 2007, 13, 1620; d) M. Suzuki, A. Osuka,
Org. Lett. 2003, 5, 3943.
[13] C.-H. Lee, J. S. Lindsey, Tetrahedron 1994, 50, 11427.
[14] T. Rohand, E. Dolusic, T. H. Ngo, W. Maes, W. Dehaen, ARKIVOC
2007, 307.
[15] J.-W. Ka, W.-S. Cho, C.-H. Lee, Tetrahedron Lett. 2000, 41, 8121.
[16] a) P. D. Rao, B. J. Littler, G. R. Geier III, J. S. Lindsey, J. Org.
Chem. 2000, 65, 1084; b) P. D. Rao, S. Dhanalekshmi, B. J. Littler,
J. S. Lindsey, J. Org. Chem. 2000, 65, 7323.
[6] a) M. Suzuki, A. Osuka, J. Am. Chem. Soc. 2007, 129, 464; b) M.
Suzuki, A. Osuka, Angew. Chem. 2007, 119, 5263; Angew. Chem.
Int. Ed. 2007, 46, 5171.
´
´
[7] a) M. Ste˛pien, L. Latos-Graz˙ynski, N. Sprutta, P. Chwalisz, L. Szter-
enberg, Angew. Chem. 2007, 119, 8015; Angew. Chem. Int. Ed. 2007,
46, 7869; b) E. Pacholska-Dudziak, J. Skonieczny, M. Pawlicki, L.
´
Szterenberg, Z. Ciunik, L. Latos-Graz˙ynski, J. Am. Chem. Soc. 2008,
[17] S. Saito, A. Osuka, Chem. Eur. J. 2006, 12, 9095.
´
´
130, 6182; c) M. Ste˛pien, B. Szysko, L. Latos-Graz˙ynski, J. Am.
[18] D. K. Dogutan, D. K. Bediako, T. S. Teets, M. Schwalbe, D. G.
Nocera, Org. Lett. 2010, 12, 1036.
Chem. Soc. 2010, 132, 3140.
[8] a) Y. Tanaka, S. Saito, S. Mori, N. Aratani, H. Shinokubo, N. Shiba-
ta, Y. Higuchi, Z. S. Yoon, K. S. Kim, S. B. Noh, J. K. Park, D. Kim,
A. Osuka, Angew. Chem. 2008, 120, 693; Angew. Chem. Int. Ed.
2008, 47, 681; b) J. K. Park, Z. S. Yoon, M.-C. Yoon, K. S. Kim, S.
Mori, J.-Y. Shin, A. Osuka, D. Kim, J. Am. Chem. Soc. 2008, 130,
1824; c) J. Sankar, S. Mori, S. Saito, H. Rath, M. Suzuki, Y. Inoku-
ma, H. Shinokubo, K. S. Kim, Z. S. Yoon, J.-Y. Shin, J. M. Lim, Y.
Matsuzaki, O. Matsushita, A. Muranaka, N. Kobayashi, D. Kim, A.
Osuka, J. Am. Chem. Soc. 2008, 130, 13568; d) S. Saito, J.-Y. Shin,
J. M. Lim, K. S. Kim, D. Kim, A. Osuka, Angew. Chem. 2008, 120,
9803; Angew. Chem. Int. Ed. 2008, 47, 9657; e) T. Higashino, J. M.
Lim, T. Miura, S. Saito, J.-Y. Shin, D. Kim, A. Osuka, Angew. Chem.
2010, 122, 5070; Angew. Chem. Int. Ed. 2010, 49, 4950.
[19] a) S. Mori, J.-Y. Shin, S. Shimizu, F. Ishikawa, H. Furuta, A. Osuka,
Chem. Eur. J. 2005, 11, 2417; b) S. Shimizu, J.-Y. Shin, H. Furuta, R.
Ismael, A. Osuka, Angew. Chem. 2003, 115, 82; Angew. Chem. Int.
Ed. 2003, 42, 78; c) M. Suzuki, R. Taniguchi, A. Osuka, Chem.
Commun. 2004, 2682; d) C.-H. Hung, J.-P. Jong, M.-Y. Ho, G.-H.
Lee, S.-M. Peng, Chem. Eur. J. 2002, 8, 4542; e) A. Srinivasan, T.
Ishizuka, H. Furuta, Angew. Chem. 2004, 116, 894; Angew. Chem.
Int. Ed. 2004, 43, 876; f) A. Srinivasan, H. Furuta, Acc. Chem. Res.
2005, 38, 10–20; g) S. Tokuji, J.-Y. Shin, K. S. Kim, J. M. Lim, K.
Youfu, S. Saito, D. Kim, A. Osuka, J. Am. Chem. Soc. 2009, 131,
7240; h) M. Inoue, K. S. Kim, M. Suzuki, J. M. Lim, J.-Y. Shin, D.
Kim, A. Osuka, Angew. Chem. 2009, 121, 6815; Angew. Chem. Int.
Ed. 2009, 48, 6687.
[9] a) T. Koide, G. Kashiwazaki, M. Suzuki, K. Furukawa, M.-C. Yoon,
S. Cho, D. Kim, A. Osuka, Angew. Chem. 2008, 120, 9807; Angew.
Chem. Int. Ed. 2008, 47, 9661; b) T. Koide, K. Furukawa, H. Shino-
kubo, J.-Y. Shin, K. S. Kim, D. Kim, A. Osuka, J. Am. Chem. Soc.
2010, 132, 7246.
[10] a) Y. Tanaka, W. Hoshino, S. Shimizu, K. Youfu, N. Aratani, N. Mar-
uyama, S. Fujita, A. Osuka, J. Am. Chem. Soc. 2004, 126, 3046; b) Y.
Tanaka, H. Shinokubo, Y. Yoshimura, A. Osuka, Chem. Eur. J. 2009,
15, 5674.
[20] A similar set of conformers in a ratio of 20:1 was detected in the
1H NMR spectrum of 8d.
[21] a) P. v. R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao, N. J. R. v. E.
Hommes, J. Am. Chem. Soc. 1996, 118, 6317; b) Z. Chen, C. S. Wan-
nere, C. Corminboeuf, R. Puchta, P. v. R. Schleyer, Chem. Rev. 2005,
105, 3842.
Received: November 10, 2011
Published online: && &&, 0000
Chem. Asian J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
7
&
&
&
These are not the final page numbers! ÞÞ

FULL PAPERS
Porphyrinoids
H. Mori, N. Aratani,
A. Osuka*
&&& — &&&
Synthesis of A2B6-Type [36]Octa-
phyrins: Copper(II)-Metalation-
Induced Fragmentation Reactions to
Porphyrins and N-Fusion Reactions of
meso-(3-Thienyl) Substituents
Make ꢀem and break ꢀem: A2B6-type
[36]octaphyrins were prepared in mod-
erate yields by the cross condensation
of tetrapyrromethane with aryl alde-
hydes. Compounds bearing 2,4,6-tri-
fluorophenyl, 2,6-dichlorophenyl, and
phenyl substituents underwent CuII-
metalation-induced fragmentation to
give AB3-type CuII porphyrins, while
that bearing a 3-thienyl substituent
underwent N-thienyl fusion to provide
a modestly aromatic [38]octaphyrin
(see scheme).
&
&
&8
&
www.chemasianj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!