Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

Article abstract of DOI:10.3762/bjoc.16.51

An efficient synthesis of tetrabenzo[a,d,j,m]coronene derivatives having alkyl and alkoxy substituents at the 3, 6, 13, and 16-posi-tions was achieved based on the ruthenium-catalyzed coupling reactions of anthraquinone derivatives with arylboronates via C–H and C–O bond cleavage. The reaction sequence involving the arylation, carbonyl methylenation, and oxidative cyclization effectively provided various tetrabenzo[a,d,j,m]coronenes in short steps from readily available starting materials. Tetra-benzo[a,d,j,m]coronenes possessing two different types of substituents were obtained selectively by sequential chemoselective C–O arylation and C–H arylation. The ¹H NMR spectra of the tetrabenzo[a,d,j,m]coronene product indicated its self-assembling behavior in CDCl₃

Full text of DOI:10.3762/bjoc.16.51

Efficient synthesis of 3,6,13,16-tetrasubstituted-
tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O
arylations of anthraquinone derivatives
Seiya Terai, Yuki Sato, Takuya Kochi and Fumitoshi Kakiuchi*
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2020, 16, 544–550.
Department of Chemistry, Faculty of Science and Technology, Keio
University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa
223-8522, Japan
doi:10.3762/bjoc.16.51
Received: 31 January 2020
Accepted: 16 March 2020
Published: 31 March 2020
Email:
Fumitoshi Kakiuchi* - kakiuchi@chem.keio.ac.jp
This article is part of the thematic issue "C–H functionalization for
materials science".
* Corresponding author
Keywords:
Guest Editor: K. Itami
C–H arylation; C–O arylation; oxidative cyclization; polycyclic
aromatic hydrocarbons; ruthenium catalyst
© 2020 Terai et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Abstract
An efficient synthesis of tetrabenzo[a,d,j,m]coronene derivatives having alkyl and alkoxy substituents at the 3, 6, 13, and 16-posi-
tions was achieved based on the ruthenium-catalyzed coupling reactions of anthraquinone derivatives with arylboronates via C–H
and C–O bond cleavage. The reaction sequence involving the arylation, carbonyl methylenation, and oxidative cyclization effec-
tively provided various tetrabenzo[a,d,j,m]coronenes in short steps from readily available starting materials. Tetra-
benzo[a,d,j,m]coronenes possessing two different types of substituents were obtained selectively by sequential chemoselective C–O
arylation and C–H arylation. The 1H NMR spectra of the tetrabenzo[a,d,j,m]coronene product indicated its self-assembling behav-
ior in CDCl3.
Introduction
Polycyclic aromatic hydrocarbons (PAHs) and their derivatives However, in search of more efficient synthetic routes, C–H
have attracted much attention from researchers due to their high arylation reactions have been increasingly utilized in recent
potential as organic optoelectronic materials [1-3] and great years for the rapid expansion of the aromatic frameworks [10-
efforts have been devoted to the development of their efficient 15].
synthetic methods [4]. One of the important steps in most
of the PAH syntheses is the construction of carbon–carbon We have been working on the efficient syntheses of PAH deriv-
bonds between aryl groups to form biaryl frameworks. atives based on the ruthenium-catalyzed C–H/C–O arylation
Traditionally, transition-metal-catalyzed cross-coupling reac- reactions developed in our group [16-33]. In the presence of ru-
tions of aryl halides or pseudohalides with arylmetal reagents thenium carbonyl phosphine complexes, the reaction of aromat-
have been employed for the connection of two aryl units [5-9]. ic ketones possessing C–H bonds or C–OR (R = alkyl) bonds
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Beilstein J. Org. Chem. 2020, 16, 544–550.
with arylboronates provided C–H or C–O arylation products dimethoxyanthraquinone followed by subsequent methylena-
[21-33]. Anthraquinone was chosen as a convenient template tion/cyclization would provide tetrabenzo[a,d,j,m]coronenes
for the PAH syntheses, because various anthraquinone deriva- having two different types of substituents.
tives possessing zero to four oxygen substituents at the ortho-
positions are readily available and the regioselective arylation at Coronene derivatives such as hexabenzocoronenes and ovalenes
the positions of either C–H or C–O bonds provided a variety of have been extensively studied because of their optoelectronic
multiarylated anthraquinone derivatives [16-20]. Using this and self-assembling properties [34-44]. Various synthetic
method, we have synthesized various π-extended aromatic methods have been developed for coronene derivatives in
compounds such as multiarylated acenes [16,18,20], general [34-37], however, only a few strategies have been re-
dibenzo[h,rst]pentaphenes and dibenzo[fg,qr]pentacenes [19]. ported for the syntheses of tetrabenzo[a,d,j,m]coronenes
[43,44]. Wu and co-workers reported the synthesis of 2,7,12,17-
In the course of our reaction development, it was found that an tetrasubstituted tetrabenzo[a,d,j,m]coronenes by using the
introduction of two different aryl groups at the ortho-positions Barton–Kellogg reaction, followed by dehydrogenative photo-
can be achieved by chemoselective C–O arylation of aromatic cyclization, and FeCl3-mediated oxidative cyclization
ketones possessing both C–H and C–O bonds and subsequent (Scheme 2a) [43]. Tao, Chao, and co-workers succeeded in the
C–H arylation. We envisioned that the application of this preparation of similar tetrasubstituted tetrabenzocoronenes by a
strategy to the anthraquinone template would provide its Corey–Fuchs reaction, followed by a Suzuki–Miyaura cross-
derivatives possessing two different types of aryl groups in coupling, and a two-step dehydrogenative cyclization using
a designed manner and lead to the preparation of DDQ and FeCl3 (Scheme 2b) [44]. However, 3,6,13,16-tetra-
tetrabenzo[a,d,j,m]coronenes having two different types of sub- substituted tetrabenzo[a,d,j,m]coronenes have not been re-
stituents (Scheme 1). While 1,4,5,8-tetraarylanthraquinones ported using these reported methods.
prepared by the ruthenium-catalyzed C–H arylation of
anthraquinone with a para-substituted arylboronate may be con- Here, we describe a convenient method for the synthesis of
verted to 3,6,13,16-tetrasubstituted tetrabenzo[a,d,j,m]coron- 3,6,13,16-tetrasubstituted tetrabenzo[a,d,j,m]coronenes based
enes via carbonyl methylenation and oxidative cyclization, the on a ruthenium-catalyzed C–O/C–H multiarylation of
two-step sequential C–O and C–H arylation of 1,4- anthraquinone and its derivatives.
Scheme 1: Projected synthetic routes for 3,6,13,16-tetrasubstituted tetrabenzo[a,d,j,m]coronenes.
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Beilstein J. Org. Chem. 2020, 16, 544–550.
Scheme 2: Reported syntheses of 2,7,12,17-tetrasubstituted tetrabenzo[a,d,j,m]coronenes.
Results and Discussion
we examined the synthesis of a tetraarylanthraquinone
Our efforts toward the synthesis of tetrabenzo[a,d,j,m]coron- possessing four hexyloxy groups. When the reaction of 1 with
enes started with the preparation of tetraarylanthraquinones. 4-hexyloxyphenylboronate 2a was carried out in the presence of
Previously, we reported the synthesis of anthraquinone deriva- 20 mol % of RuH2(CO)(PPh3)3 (3) in refluxing pinacolone, the
tives possessing four aryl groups at the 1, 4, 5, and 8-positions corresponding tetraarylation product 4aa was obtained in 57%
through a RuH2(CO)(PPh3)3-catalyzed C–H arylation of yield (Scheme 3). Tetrakis(4-hexylphenyl)anthraquinone (4bb),
anthraquinone (1) with arylboronates 2 [16]. Using this method, the synthesis of which has been described in the above-
Scheme 3: C–H tetraarylation of anthraquinone (1).
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Beilstein J. Org. Chem. 2020, 16, 544–550.
mentioned publication [16], was also prepared using dration. Thus, the reaction of 4aa with methyllithium and
4-hexylphenylboronate (2b) accordingly and used for further subsequent treatment of the crude diol with NaH2PO2·H2O
transformations. The reaction of 1 with 2b was also attempted and NaI in refluxing acetic acid gave the corresponding
using 10 mol % of 3, however, it only gave mono-, di- and dimethylenation product 6aa in 96% yield (Table 1, entry 1).
triarylation products, and the tetraarylation product 4bb was not The oxidative cyclization of 6aa by treatment with 12 equiv of
detected.
FeCl3 at 35 °C for 0.5 h provided the desired tetra-
benzo[a,d,j,m]corronene derivative 7aa in 37% yield. This
Tetraarylanthraquinones containing two different aryl groups method was also applicable to the conversion of tetrakis(4-
were also prepared via the above-mentioned chemoselective hexylphenyl)anthraquinone 4bb as well as the tetraarylan-
C–O arylation and subsequent C–H arylation. The chemoselec- thraquinones containing two different aryl groups, 4ac and 4ba,
tive C–O diarylation of 1,4-dimethoxyanthraquinone to form leading to the corresponding tetrabenzo[a,d,j,m]corronene de-
1,4-diarylanthraquinones has been previously reported by our rivatives, 7bb, 7ac, and 7ba, respectively (Table 1, entries 2–4).
group [19], and 1,4-bis(4-hexyloxyphenyl)anthraquinone (5a)
and 1,4-bis(4-hexylphenyl)anthraquinone (5b) were prepared Next, the effect of the substituents in compounds 7 on their
accordingly. When the reaction of 5a with 4-methylphenyl- optical properties was studied by UV–vis spectroscopy
boronate 2c was conducted in the presence of 40 mol % of 3 (Figure 1). The UV–vis spectra of 7aa, 7bb, and 7ba were
in refluxing pinacolone, the ortho-C–H diarylation occurred measured in chloroform, and the normalized UV–vis spectra are
giving the 1,4-bis(4-hexyloxyphenyl)-5,8-bis(4-methyl- shown in Figure 1. These compounds showed similar peak
phenyl)anthraquinone (4ac) in 91% yield. The C–H diarylation patterns between 300 and 500 nm, and the π–π* transitions
of 5b with 2a also proceeded smoothly to provide the corre- (p-band) for 7aa, 7bb, and 7ba were observed at 426 nm [11].
sponding tetraarylanthraquinone 4ba in 94% yield (Scheme 4). The peaks corresponding to n–π* transitions (α-band) were ob-
served at 456–469 nm and were red-shifted with growing inten-
Next, the conversion of tetraarylanthraquinones 4 to sity as the number of hexyloxy groups increases.
tetrabenzo[a,d,j,m]coronenes was investigated. After exam-
ining various carbonyl methylenation methods, we found that The self-assembling property of tetrabenzo[a,d,j,m]coronene
the dimethylenation products 6 can be obtained in high yields 7aa was also examined (Figure 2), as Wu and co-workers
through methylation of the carbonyl groups, followed by dehy- have studied the self-assembling property of the tetra-
Scheme 4: C–H diarylation of 1,4-diarylanthraquinones 5.
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Table 1: Synthesis of 3,6,13,16-tetrasubstituted tetrabenzo[a,d,j,m]coronenes.
entry
R1
R2
yield of 6 (%)a
yield of 7 (%)b
1
2
3
4
n-hexO
n-hex
n-hexO
n-hex
n-hexO
n-hex
Me
6aa: 96
6bb: 85
6ac: 78
6ba: 85
7aa: 37
7bb: 73
7ac: 48
7ba: 48
n-hexO
aReaction conditions: 1) 4 (0.2 mmol), MeLi (2 mmol), THF (10 mL), −78 °C to rt, 2 h; 2) NaH2PO2·H2O (2 mmol), NaI (2 mmol), AcOH (6 mL), reflux,
2 h; breaction conditions: 6 (0.02 mmol), FeCl3 (0.24 mmol), MeNO2 (1 mL), CH2Cl2 (5 mL), gentle N2 bubbling, 35 °C, 0.5 h.
Figure 1: Normalized UV–vis absorption spectra of 7aa, 7bb, and 7ba.
Figure 2: Effects of the concentration and the temperature on the
1H NMR spectra of 7aa.
benzo[a,d,j,m]coronene derivative possessing n-octyl groups at
the 2, 7, 12, and 17-positions by 1H NMR spectroscopy and
suggested its intermolecular π–π interaction in solution [10]. Conclusion
When the 1H NMR spectrum of 7aa was measured at The synthesis of a new class of tetrabenzo[a,d,j,m]coronene de-
2 × 10−3 M at rt, a considerable broadening of the signals in the rivatives having alkyl and alkoxy-substituents at the 3, 6, 13,
aromatic region was observed. By increasing the temperature and 16-positions was achieved based on a ruthenium-catalyzed
from rt to 60 °C, all signals in the aromatic region became coupling reaction of anthraquinone derivatives with aryl-
sharper and low-field shifted. The dilution of the solution to boronates via a C–H or/and C–O bond cleavage. The reaction
5 × 10−4 M at rt also led to a downfield shift and sharpening of sequence involving the arylation, carbonyl methylenation, and
the signals. These observations suggest that 7aa assembles by oxidative cyclization effectively provided various 3,6,13,16-
intermolecular π–π interaction in CDCl3 as was seen by Wu and tetrasubstituted tetrabenzo[a,d,j,m]coronenes in short steps
co-workers for their compound possessing substituents at differ- from readily available starting materials. The tetra-
ent positions.
benzo[a,d,j,m]coronenes possessing two different types of sub-
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Supporting Information
Supporting Information File 1
General experimental procedures, characterization data and
NMR spectra of new compounds.
[https://www.beilstein-journals.org/bjoc/content/
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This work was supported, in part, by a Grant-in-Aid for Scien-
tific Research on Innovative Areas 2707 “Middle molecule
strategy” from the Ministry of Education, Culture, Sports,
Science and Technology, Japan and by the Research Program of
“Five-star Alliance” in “NJRC Mater. & Dev.”. T.K. is grateful
for financial support provided by JSPS KAKENHI Grant Num-
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