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Angewandte
Eine Zeitschrift der Gesellschaft Deutscher Chemiker
Chemie
www.angewandte.de
Akzeptierter Artikel
Titel: Synthesis of Pyrrole-Fused Corannulenes via Unprecedented
1,3-Dipolar Cycloaddition of Azomethine Ylides to Corannulene
Autoren: Yuki Tokimaru, Shingo Ito, and Kyoko Nozaki
Dieser Beitrag wurde nach Begutachtung und Überarbeitung sofort als
"akzeptierter Artikel" (Accepted Article; AA) publiziert und kann unter
Angabe der unten stehenden Digitalobjekt-Identifizierungsnummer
(DOI) zitiert werden. Die deutsche Übersetzung wird gemeinsam mit der
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Für die AA-Fassung trägt der Autor die alleinige Verantwortung.
Zitierweise: Angew. Chem. Int. Ed. 10.1002/anie.201707087
Angew. Chem. 10.1002/ange.201707087
Link zur VoR: http://dx.doi.org/10.1002/anie.201707087
http://dx.doi.org/10.1002/ange.201707087
10.1002/ange.201707087
Angewandte Chemie
COMMUNICATION
Synthesis of Pyrrole-Fused Corannulenes via Unprecedented
1,3-Dipolar Cycloaddition of Azomethine Ylides to Corannulene
Abstract: In the long history of corannulene chemistry, the 1,3dipolar cycloaddition to corannulene is unprecedented. Herein, we
report the 1,3-dipolar cycloaddition of a polycyclic aromatic
azomethine ylide to corannulene, which occurs exclusively at the rim
bond of corannulene from the convex side in an exo fashion. The
cycloadducts could be successfully converted by successive
oxidative dehydrogenation to pyrrole-fused corannulenes, which
exhibited pronounced solvatofluorochromism.
Since its first synthesis in 1966, corannulene (1),[1,2] a C5vsymmetric polycyclic aromatic hydrocarbon (PAH) consisting of
a central pentagon surrounded by five fused hexagonal benzene
rings, has attracted much attention due to its unique structural
and electronic properties, e.g. its bowl-shaped structure,[3] its
dipole moment, which is oriented perpendicular relative to the πsurface,[4] and its high electron-accepting ability.[5] The
fascinating properties of 1 have led to much research on the
applications of 1 in e.g. organic electronics,[6] molecular
recognition,[7,8] and supramolecular polymerization,[9] whereby
attention has predominantly been focused on the
functionalization of 1.[2] Most methods available for such
functionalization rely on substitution reactions at the rim bond of
1 (Figure 1a), including electrophilic,[10–13] and radical
as
well
as
metal-catalyzed
C–H
substitutions,[14]
functionalization.[15,16] The rim bond of 1 is also amenable to
addition reactions with various reagents such as alkyllithium[17]
and alkylradical species (Figure 1b).[18] Conversely, addition
reactions of carbocations occur at the spoke bond of 1 and
afford
isolable
cationic
species
(Figure
1c).[19]
Cyclization/cycloaddition reactions represent another important
functionalization mode for 1. The spoke double bond can be
used for cycloaddition reactions such as the cyclopropanation
with dichlorocarbene species (Figure 1d).[20] Recently,
palladium-catalyzed annulative π-extensions of 1 have been
reported as a method to engage the rim double bond of 1 in a
one-step cyclization (Figure 1e).[21] However, to the best of our
knowledge, cycloadditions involving the rim bond of pristine 1
have not yet been demonstrated experimentally (Figure 1f),[20]
even though theoretical calculations have predicted that the rim
double bond of 1 may be reactive toward [4π+2π]-type
cyclizations.[22]
[a]
Mr. Y. Tokimaru, Dr. S. Ito, and Prof. Dr. K. Nozaki
Department of Chemistry and Biotechnology
Graduate School of Engineering
The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
E-mail: ito_shingo@chembio.t.u-tokyo.ac.jp, nozaki@chembio.t.utokyo.ac.jp
Supporting information for this article is given via a link at the end of
the document.
1,3-Dipolar cycloadditions represent a powerful synthetic tool
to construct heterocyclic five-membered rings containing oxygen
or nitrogen atoms. Azomethine ylides, which are characterized
by a C=N+–C− moiety, are reactive and versatile 1,3-dipoles that
allow the construction of pyrrolidine or 2,5-dihydropyrrole
structures when treated with alkenes or alkynes. 1,3-Dipolar
cycloadditions involving azomethine ylides are widely used for
the functionalization of curved PAHs such as fullerenes[23] and
carbon nanotubes.[24] However, successful 1,3-dipolar
cycloadditions involving 1 remain elusive, although some
unsuccessful attempts have been reported.[20]
(a)
(f)
X
X
(b) spoke
This work
(e)
hub
X
(c)
Y
flank
rim
(d)
1
X
X
X
Figure 1. Functionalization of 1: (a) substitution at the rim bonds, (b) addition
to the rim bonds, (c) addition to the spoke bonds, (d) cycloaddition to the
spoke bonds, (e) substitutive cyclization at the rim bonds, and (f) cycloaddition
to the rim bonds.
The probability to engage 1 in unprecedented 1,3-dipolar
cycloadditions should be maximized when employing highly
reactive azomethine ylides. Previously, our group[25] and those of
Feng and Müllen[26] have independently developed polycyclic
aromatic azomethine ylide 3, which is generated in situ from
iminium salt 2, and can be used for 1,3-dipolar cycloadditions to
alkenes and alkynes to afford the corresponding pyrrolidines and
2,5-dihydropyrroles (Scheme 1). The most noteworthy feature of
3 is its high reactivity towards dipolarophiles, i.e., 3 even
converts sterically crowded 1,2-diarylethynes into the
corresponding cycloadducts.[27] Herein, we report unprecedented
1,3-dipolar cycloadditions of azomethine ylide 3 to the rim
double bond of 1, which affords the corresponding mono- and
diadducts 4 and 5, respectively. This reaction represents the first
example of a 1,3-dipolar cycloaddition to 1. Furthermore, upon
subsequent aromatizations, cycloadducts 4 and 5 could be
converted into pyrrole-fused corannulenes 6 and 7 (Scheme
1).[28,29]
This article is protected by copyright. All rights reserved.
Accepted Manuscript
Yuki Tokimaru,[a] Shingo Ito,*[a] and Kyoko Nozaki*[a]
10.1002/ange.201707087
Angewandte Chemie
tBu
H
H
N
H
1 (1.0 equiv)
+
Cl
N
iPr2NEt (8 equiv)
DMSO
120 ºC, 1 h
H
H
H
H
N
+
H
H
H
N
H
H
via
N
tBu
tBu
2 (4.0 equiv)
4 (46%)
tBu
5 (29%)
tBu
tBu
3
N
DDQ
(2.1 equiv)
DDQ
(4.2 equiv)
4
5
CH2Cl2
rt, 10 min
N
tBu
6 (99%)
CH2Cl2
rt, 14 h
N
tBu 7 (80%)
Scheme 1. 1,3-Dipolar cycloaddition of azomethine ylide 3 to corannulene 1
and subsequent dehydrogenation to form pyrrole-fused corannulenes 6 and 7.
The 1,3-dipolar cycloaddition of 1 with 3 generated in situ
from iminium salt 2 was carried out under the conditions outlined
in Scheme 1.[30] As a result, mono- (4) and diadducts (5) were
obtained in 46% and 29% isolated yield, respectively. Singlecrystal X-ray diffraction analyses of 4 and 5 (vide infra) revealed
that 3 was added to the rim C=C bond of 1 from the convex side
in an exo fashion to give 4. The addition of a second molecule of
3 proceeded in a similar manner to give cis diadduct 5. It should
be noted that other regio- and stereoisomers, which could be
formed by a cycloaddition to the rim C=C bond in an endo
fashion, or by a cycloaddition to a spoke C=C bond, were not
detected. In sharp contrast, other typical azomethine ylides such
as CH2=N+MeCH2− and CH2=N+BnCH−CO2Me[23] as well as other
aromatic azomethine ylides did not provide any cycloadducts
under similar reaction conditions (Scheme S1). These results
are consistent with the report by Scott et al., who examined 1,3dipolar cycloadditions involving 1.[20] Subsequently, we treated
cycloadducts 4 and 5 with 2,3-dichloro-5,6-dicyano-pbenzoquinone (DDQ) to afford dehydrogenated pyrroles 6 and 7
in good yields (Scheme 1).
Single-crystal X-ray diffraction analyses on 4, 5, and 6 were
conducted using crystals grown by slow diffusion of
hexane/pentane into a dichloromethane solution (4 and 5) or a
carbon disulfide solution (6) of the target compounds, whereas
no single crystal of 7 suitable for structural determination could
be obtained. As shown in Figure 2, the polycyclic cores of 4 and
6 exhibit a Cs-symmetric structure due to the attachment of a
fused pyrrolidine and a fused pyrrole ring to the rim bond of C5vsymmetric 1. The structure of the corannulene core was slightly
distorted due to the ring fusion. For example, the C2–C3 single
bond in 4 [1.608(9) Å], i.e., the rim bond of 1 that is fused with
the pyrrolidine ring, is even longer than typical Csp3–Csp3 single
bonds (~1.54 Å). This elongation is presumably due to the strain
of the corannulene moiety that arises from the elongation of the
C–C single bond. The pyrrole-fused rim bond of 6 [1.472(5) Å] is
also significantly elongated compared to the other rim bonds
(1.37–1.39 Å) and the rim bonds of 1 (1.38 Å), as well as the
C2–C3 bond of pyrrole (1.43 Å).[31] Considering the shorter
length of the rim bond in a porphyrin-fused corannulene (1.40
Å),[12a] this elongation could be attributed to the larger
contribution of a single bond to the bond alternation caused by
fusion of a pyrrole ring. This notion is supported by the
decreased aromaticity of the pyrrole-fused six-membered ring,
which can be estimated by NICS calculations conducted at the
B3LYP/6-31G(d) level of theory. The NICS(0) values of the
pyrrole-fused six-membered ring of 6 (−2.6 ppm) and 7 (−2.4
ppm) are significantly higher than those of the other sixmembered rings in the corannulene moiety (Figure S16). The
perpendicular distance between the center of the central fivemembered ring of the corannulene core and the parallel plane
containing the middle points of each rim bond were calculated
for 4 (0.70, 0.88, and 0.84 Å) and 6 (0.70, 0.95, and 0.86 Å). The
elongation of the rim bond that carries the pyrrolidine and pyrrole
rings leads to a release of bowl strain and shallower bowl depths
compared to 1 (0.87 Å). Moreover, the comparatively longer
distance to the plane containing C24–C25(C33–C34) in 6 (0.95
Å) should be noted, and probably be attributed to the repulsion
of hydrogen atoms attached to C6(C21) and C24(C34), i.e., the
repulsion between the annulated dibenzoullazine cores and the
corannulene moiety.
Figure 2. Single-crystal X-ray diffraction structures of (a) 4 and (b) 6 with
thermal ellipsoids set to 50 % probability. Solvent molecules, tert-butyl groups,
and hydrogen atoms except for those on the pyrrolidine ring of 4 (side view)
were omitted for clarity.
In order to elucidate the reason for the observed high regioand stereoselectivity of this 1,3-dipolar cycloaddition, DFT
calculations were performed at the B3LYP-D3/6-31G(d) level of
theory.[32] In order to simplify the calculations, the t-butyl group of
3 and the cycloadducts were replaced with hydrogen atoms, and
only concerted mechanisms were considered, while stepwise or
radical addition mechanisms were disregarded in conformity with
the results of previous calculations.[22] We calculated the relative
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COMMUNICATION
10.1002/ange.201707087
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COMMUNICATION
Figure 3. Energy profiles for the 1,3-dipolar cycloaddition of azomethine ylide
3’, in which the t-butyl group of 3 was replaced with a hydrogen atom, to 1,
calculated at the B3LYP-D3/6-31G(d) level of theory: (a) convex-rim-exoaddition, (b) convex-rim-endo-addition, (c) convex-spoke-addition, (d)
concave-rim-exo-addition, and (e) concave-rim-endo-addition.
The conformation and the bowl inversion behavior of 6’, in
which the t-butyl group of 6 was replaced with a hydrogen atom,
was also investigated by DFT calculations at the B3LYP-D3/631G(d) level of theory (Figure 4). The butterfly-shaped
conformation A, which was observed experimentally in the
single-crystal X-ray diffraction analysis of 6 (Figure 2b), was
identified as the most stable conformer, including twisted
conformation B (∆G = 5.1 kcal/mol) and another butterfly-shaped
conformation (A*; ∆G = 9.5 kcal/mol). Among TSAA*, TSAB, and
TSBB, i.e., the calculated TSs between each conformer, TSAA*
(11.1 kcal/mol) is the highest pathway. The calculated barrier is
comparable to the bowl inversion barrier of 1 (experimental
value: 10–11 kcal/mol;[34] theoretical value: 10.4 kcal/mol[35]) and
those of similar phenanthrene-annulated corannulenes (11.0
kcal/mol).[21]
Figure 4. Interconversion pathways of 6’ calculated at the B3LYP-D3/631G(d) level of theory. Pink highlights indicate transition states that involve a
bowl inversion of the corannulene core, while blue highlights indicate transition
states that involve a flipping of the ortho-fused helicene structure.
Finally, the optical properties of pyrrole-fused corannulenes
6 and 7 were evaluated by UV-vis absorption and fluorescence
spectroscopy (Figures 5 and Table S3). The UV-vis absorption
spectra of solutions of 6 and 7 in cyclohexane, benzene, THF,
CH2Cl2, and DMSO exhibited broad peaks, whose absorption
edges (6: ~490 nm; 7: ~540 nm) and absorption spectra were
virtually inert to the polarity of solvents. The observed absorption
wavelengths are bathochromically shifted relative to those of 1[36]
and similar to those of related molecules bearing an ullazine
structure.[26,27] The HOMO and LUMO energies of 6 and 7 were
estimated by combining the results of UV absorption analysis
and the oxidation potentials of 6 and 7 measured by cyclic
voltammetry (Figure S14 and Table S4). The emission spectra
of 6 and 7 exhibited remarkable solvatofluorochromism.
Characteristic vibronic emission bands with small Stokes shifts
were observed in non-polar solvents (6: 470, 503, and 540 nm;
7: 487, 522, and 562 nm; both in cyclohexane), whereas broad
emission bands with large Stokes shifts were observed in polar
solvents. These phenomena are consistent with a radiative
deactivation from locally excited states in non-polar solvents,
and an emission from a low-lying charge-transfer state by
intramolecular charge transfer (ICT) in polar solvents.[37]
Considering that the LUMOs of 6 and 7 are mainly located on
the corannulene core (Figures S17 and S18), the ICT may occur
from the ullazine moiety to the corannulene core in polar
solvents. Notably, the highest quantum yield was observed in
DMSO (6: 34%, 7: 33%; Table S3). These results stand in sharp
contrast to the typical behavior of solvatofluorochromic
molecules, whose fluorescence quantum yields decrease with
increased polarity of the solvent. To the best of our knowledge,
this is the first example of a solvatofluorochromic molecule that
bears a corannulene moiety.
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Accepted Manuscript
G [kcal/mol]
Gibbs energies for the starting materials, transition state (TS),
and products for all the possible regioisomers arising from: (a)
convex-rim-exo-addition, (b) convex-rim-endo-addition, (c)
convex-spoke-addition, (d) concave-rim-exo-addition, and (e)
concave-rim-endo-addition (Figure 3).[33] Among all calculated
TSs, the TS of the rim-exo addition (12.8 kcal/mol) is the lowest
and affords the most stable product (−12.8 kcal/mol). In other
words, the convex-rim-exo pathway (a) is thermodynamically
and kinetically the most favourable pathway. The preference of
the convex addition of 3 to 1 should be interpreted in terms of
the larger coefficients of the lowest-unoccupied molecular
orbitals (LUMOs) at the convex side relative to those at the
concave side, considering that in typical 1,3-dipolar
cycloadditions, the highest-occupied molecular orbital (HOMO)
of the 1,3-dipole interacts with the LUMO of the dipolarophile. As
the LUMO of 1 is mainly located at the rim bonds, the 1,3-dipolar
cycloaddition of 3 should occur there, and this preference is
consistent with the experimental results, i.e., that only cis adduct
5 was obtained. Nevertheless, the high selectivity toward the rim
addition stands in sharp contrast to the spoke-selectivity of the
addition of carbene species to 1, in which the LUMO of the
electrophilic carbene species reacts with the HOMO of 1.[20]
10.1002/ange.201707087
Angewandte Chemie
[6]
[7]
[8]
Figure 5. Absorption (dashed lines: 5.0 × 10−6 M) and emission spectra (solid
lines: 5.0 × 10−7 M; λex = 350 nm) of (a) 6 and (b) 7 at room temperature;
purple: cyclohexane; blue: benzene; yellow: THF; green: CH2Cl2; red:
[37]
DMSO.
[9]
[10]
In summary, we have developed a new method for
synthesizing pyrrole-fused corannulenes 6 and 7 in a 2-step
procedure involving an unprecedented 1,3-dipolar cycloaddition
of azomethine ylide 3 to corannulene. The cycloaddition to
corannulene occurs selectively at one of the rim C=C bonds,
from its convex side in an exo fashion. The results of theoretical
calculations strongly support the observed selectivity. Pyrrolefused corannulenes 6 and 7 exhibited bathochromically shifted
absorption spectra relative to that of pristine corannulene, and a
remarkable solvatofluorochromism. We believe that this novel πextension method, based on the 1,3-dipolar cycloaddition to
corannulene, should become a useful tool for the development
of highly desirable corannulene-based functional materials.
[11]
[12]
[13]
[14]
Acknowledgements
This work was supported by JSPS KAKENHI No. 16H06030,
Japan. A part of this work was conducted at the Research Hub
for Advanced Nano Characterization, The University of Tokyo,
supported by MEXT, Japan. The theoretical calculations were
performed using computational resources provided by Research
Center for Computational Science, National Institutes of Natural
Sciences, Okazaki, Japan. Y.T. is grateful to the Japan Society
for the Promotion of Science (JSPS) for a Research Fellowship
for Young Scientists.
[15]
[16]
[17]
[18]
[19]
Keywords: corannulene • azomethine ylide • 1,3-dipolar
cycloaddition • polycyclic aromatic hydrocarbon • nitrogen atom
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This article is protected by copyright. All rights reserved.
Accepted Manuscript
COMMUNICATION
10.1002/ange.201707087
Angewandte Chemie
[23]
[24]
[25]
[26]
[27]
[28]
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For the details of optical properties of 6 and 7, see Table S3.
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Here we report the 1,3-dipolar cycloaddition of a polycyclic aromatic azomethine
ylide to corannulene, which occurs exclusively at the rim bond of corannulene from
the convex side in an exo fashion. The cycloadducts could be converted by
oxidative dehydrogenation to pyrrole-fused corannulenes, which exhibited
pronounced solvatofluorochromism.
Synthesis of Pyrrole-Fused
Corannulenes via Unprecedented 1,3Dipolar Cycloaddition of Azomethine
Ylides to Corannulene
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