Synthesis of a remarkably stable dehydro[14]annulene

Article abstract of DOI:10.1002/1521-3773(20010702)40:13<2509::AID-ANIE2509>3.0.CO;2-F

The substituents at the peri positions of dehydro[14]annulenes 1 have a dramatic effect on the stability of these macrocycles, and lead to derivatives that are stable even at elevated temperatures (up to 190°C).

Full text of DOI:10.1002/1521-3773(20010702)40:13<2509::AID-ANIE2509>3.0.CO;2-F

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of the (R1/Et)1,3-p interaction. The lower reactivity of dialkyl
and alkyl aryl acrylonitriles compared to monosubstituted
substrates is not unexpected considering the influence of the
substituents on the electronic density at the double bond. This
could also be responsible for the low reactivity of trisubsti-
tuted vinyl sulfoxide 8, but the (O/R3)gauche and (Tol/R3)gauche
interactions present when R3=H can also be involved in the
destabilization of both TSA and TSB.
Desulfinylation of the amides 15 ± 17 and 19 with Raney
nickel afforded the corresponding enantiopure amides 21 ± 24,
which were isolated in good yields (>70%, Scheme 3).[21]
In summary we have shown that the hydrocyanation of
alkenyl sulfoxides with Et2AlCN takes place in a completely
stereoselective manner. Taking into account the chemical
versatility of the cyano and sulfinyl groups, this reaction can
be considered as the key step in a short sequence that allows
the creation of optically pure molecules containing tertiary or
quaternary chiral centers from terminal alkynes, as illustrated
with the preparation of amides 21 ± 24.
Crystallographic Data Centre as supplementary publication no.
CCDC-154583 (16). Copies of the data can be obtained free of charge
on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK
(fax: (‡44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
[21] As the optical purity of the amides could not be established by chiral
shift reagents or chiral HPLC, the chemical correlation of 21 with
commercially availale (S)-2-methylbutanoic acid was neccesary. The
amides derived from (S)-2-methylbutanoic acid and from 21 by
desulfurization exhibited a specific rotation of the same value and
sign. Therefore, we can conclude that the configuration at C2 of 21
must be S, in complete agreement with the X-ray structure analysis.
Synthesis of a Remarkably Stable
Dehydro[14]annulene**
Grant J. Palmer, Sean R. Parkin, and John E. Anthony*
Received: December 22, 2000
Revised: March 26, 2001 [Z16322]
Dehydroannulenes are a fascinating class of carbon-rich
molecules which have been studied intensively.[1] With the
development of improved synthetic methodologies, these
macrocycles are now being exploited for their potential
material properties. Recent applications employ such annu-
lenes as conjugated scaffolds for nonlinear optical applica-
tions[2] and as precursors for carbon nanotube synthesis.[3] We
are currently exploring the use of fused dehydroannulenes as
components in conjugated ladder polymers (e.g. acynes 1 and
rylynes 2).
[1] G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann, Methods
Org. Chem. (Houben-Weyl), Vol. 21d, 1995.
[2] M. Hodgson, D. Parker, R. J. Taylor, G. Ferguson, Organometallics
1988, 7, 1761.
[3] a) P. S. Elmes, W. R. Jackson, J. Am. Chem. Soc. 1979, 101, 6128;
b) P. S. Elmes, W. R. Jackson, Ann. N. Y. Acad. Sci. 1980, 333, 225.
[4] R. Noyori, H. Takaya, Acc. Chem. Res. 1990, 23, 345.
[5] T. Horiuchi, E. Shirakawa, K. Nozaki, H. Takaya, Tetrahedron:
Asymmetry 1997, 8, 57.
[6] a) T. V. RajanBabu, A. L. Casalnuovo, J. Am. Chem. Soc. 1992, 114,
6265; b) A. L. Casalnuovo, T. V. RajanBabu, T. A. Ayers, T. H.
Warren, J. Am. Chem. Soc. 1994, 116, 9869.
R
[7] M. Yan, Q.-Y. Xu, A. S. C. Chan, Tetrahedron: Asymmetry 2000, 11,
845.
[8] W. Nagata, M. Yoshiota, Org. React. 1977, 25, 255.
[9] D. N. Piatak, P.-F. L. Tang, Can. J. Chem. 1987, 65, 1327.
[10] K. Utimoto, Y. Wakabayashi, T. Horiie, M. Inoue, Y. Shishiyama, M.
Obayashi, H. Nozaki, Tetrahedron 1983, 39, 967.
R
acyne
n
1
R
R
R
R
Ä
[11] a) M. C. Carreno, Chem. Rev. 1995, 95, 1717; b) J. L. García Ruano, B.
Cid, Top. Curr. Chem. 1999, 204, 1 ± 126, and references therein.
[12] a) J. L. García Ruano, Phosphorus Sulfur Silicon Relat. Elem. 1993,
Â
Â
74, 233; b) R. Sanchez-Obregon, B. Ortiz, F. Walls, F.Yuste, J. L.
García Ruano, Tetrahedron: Asymmetry 1999, 10, 947, and references
therein.
rylyne
n
2
Ä
[13] a) A. B. Bueno, M. C. Carreno, J. L. García Ruano, An. Quim. Int. Ed.
1994, 90, 442; b) J. L. García Ruano, C. García Paredes, Tetrahedron
Lett. 2000, 41, 261.
[14] J. L. García Ruano, A. M. Martín Castro, J. H. Rodríguez, Recent Res.
Devel. Org. Chem. Part I 2000, 4, 261.
While the phenyldiacetylene macrocycles that comprise 1
are well-known compounds,[4] the class of dehydroannulenes
that make up the backbone of 2 is poorly understood. The
parent compound 3 was prepared in 1968 by Mitchell and
Sondheimer, who were unable to fully characterize this new
[15] J. L. García Ruano, A. Esteban Gamboa, A. M. Martín Castro, J. H.
Â
Rodríguez, M. I. Lopez Solera, J. Org. Chem. 1998, 63, 3324.
[16] H. Kosugi, M. Kitaota, K. Tagami, A. Takahashi, H. Uda, J. Org.
Chem. 1987, 52, 1078.
[*] Prof. J. E. Anthony, G. J. Palmer, Dr. S. R. Parkin
Department of Chemistry
[17] After the reaction mixture was heated for 24 h at reflux, we isolated an
unexpected compound (30% yield) which has not been identified yet.
[18] These conditions promote the conversion of sulfinyl nitriles into
sulfinyl amides with inversion of the configuration at sulfur (see
refs. [14c, 15]) The hydrolysis of nitrile 12 with KOH in refluxing
tBuOH (J. H. Hall, M. Gisler, J. Org. Chem. 1976, 41, 3769) afforded
diastereomer 18', an epimer at sulfur of 18, because under these
conditions neither the configuration at carbon or at sulfur is affected.
[19] Proper crystals of compunds 9 ± 13 could not be obtained.
[20] Crystallographic data (excluding structure factors) for the structure
reported in this paper have been deposited with the Cambridge
University of Kentucky
Lexington, KY, 40506-0055 (USA)
Fax : (‡1)859-323-1069
E-mail: anthony@pop.uky.edu
[**] The authors acknowledge the National Science Foundation (CHE-
9875123) and the Office of Naval Research (N00014-99-1-0859) for
support of this research. NMR spectroscopy facilities were enhanced
by the National Science Foundation CRIF program (CHE-997841)
and the Research Challenge Trust Fund of the University of Kentucky.
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formally antiaromatic, numerous other antiaromatic dehy-
droannulenes have been shown to be stable.[11] To prepare 8,
diethynylacenaphthylene 7 was synthesized by the oxidation
of acenaphthene 5. Desilylation followed by oxidative cycli-
zation led to a brilliant orange powder, which was sparingly
soluble in dichloromethane.
HO
SiMe3
3.18Å
4
3
annulene because it decomposed rapidly, even in dilute
solution.[5] They postulated that this instability arose from
the proximity of the alkynes in the rigid macrocycle. Indeed,
the high reactivity of this structural motif has been exploited
in acyclic systems such as 4, which undergo facile intra-
molecular cyclization to form extended aromatic structures.[6]
Recently, several examples of unconjugated macrocyclic
butadiynes have been shown to be stable at room temper-
ature,[7] which has led us to revisit the chemistry of compounds
based on 3, the fundamental component of ladder polymer 2.
If the decomposition of 3 is in fact related to the proximity
of the two parallel butadiyne units (calculated distance:
3.18 Š),[8] substituents which increase the separation between
these units should stabilize the macrocycle. For example, it has
been shown that changes in alkyne terminus separation of as
small as 0.05 Š can have a significant effect on reactions such
as the Bergman cycloaromatization.[9] According to ab initio
calculations, the butadiyne units in acenaphthene derivative 6
are separated by 3.25 Š (Scheme 1), an increase of 0.07 Š
The UV/Vis spectrum of this new compound (Figure 1)
strongly resembles that reported for 3, with two characteristic
peaks at 455 and 485 nm (3 shows absorbances at 502 and
540 nm). This stable compound survived recrystallization
3.25Å
6
Figure 1. UV/Vis spectra of compounds 8, 10, and 14.
a
SiMe3
SiMe3
SiMe3
SiMe3
from o-dichlorobenzene (1808C) without decomposition.
High-resolution mass spectrometry and H NMR spectros-
b
1
copy support the structural assignment for 8. Unfortunately,
this compound proved to be too insoluble for further
characterization.
5
7
c
In an attempt to synthesize a more characterizable macro-
cycle, fluoranthene
9
was prepared[12] and alkynylated
3.26Å
(Scheme 2). Desilylation followed by oxidative cyclization
again led to a stable orange powder, which exhibited
characteristic absorbances at 480 and 515 nm. Surprisingly,
this compound was significantly less soluble than the ace-
8
Scheme 1. Synthesis of macrocycle 8. Reagents and conditions:
a) 1. K2CO3 in MeOH/THF; 2. CuCl/TMEDA in CH2Cl2; b) DDQ (2,3-
dichloro-5,6-dicyano-1,4-benzoquinone); c) 1. K2CO3 in MeOH/THF;
2. CuCl/TMEDA in CH2Cl2, 75%.
EtO2C
CO2Et
compared to 3. Thus, 5,6-diethynylacenaphthene[10] was sub-
jected to oxidative cyclization under high-dilution conditions.
Analysis of the resulting insoluble solid by high-resolution
LD-MS (laser desorption mass spectrometry) showed only
small amounts of both residual starting material and a
dimerized, acyclic species. Compound 6 could not be detected,
presumably as a result of the rapid decomposition of the
macrocycle.
Examination of the p-bond topology of 3 reveals that the
perimeter of that macrocycle is not fully conjugated, unlike
other stable dehydroannulenes. The acenaphthylene-derived
macrocycle 8 addresses this deficiency, leading to a fully-
conjugated 28 p-electron macrocycle. Although this cycle is
EtO2C
CO2Et
a–c
3.25 Å
Br Br
9
10
EtO2C
CO2Et
Scheme 2. Synthesis of 10. Reagents and conditions: a) Me3SiCCSnBu3/
[(Ph3P)2PdCl2]; b) K2CO3 in EtOH/THF; c) CuCl/TMEDA in CH2Cl2.
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naphthylene derivative 8. Although the high-resolution mass
spectrum and UV/Vis absorption spectrum supported the
assignment of macrocyclic structure 10, a species soluble
enough for more thorough characterization was still required.
A more aggressive solubilization strategy was utilized in the
preparation of 14 (Scheme 3). Beginning with quinone 11,
treatment with a Grignard reagent followed by reductive
lations, the central carbon atoms of the two butadiyne units
(C14 C1) are indeed splayed outward, separated by a
distance of 3.23 Š. Even with this distortion, the butadiyne
units are nearly linear, with the most extreme variation from
linearity a mere 78. As expected, the annulene backbone is
planar to within 0.05 Š.
We have demonstrated that with proper functionalization,
the preparation of stable naphthalene diacetylene macro-
cycles is possible. The distance between butadiyne units in
these systems has been found to be less important to stability
than conjugation. We are currently exploring the incorpora-
tion of these stabilized macrocycles into new carbon ladder
polymers based on 2.
Received: February 23, 2001 [Z16670]
[1] a) H. Meier, Synthesis 1972, 235; b) M. Nakagawa, Pure Appl. Chem.
1975, 44, 885; c) N. Huang, F. Sondheimer, Acc. Chem. Res. 1982, 15,
96; d) S. Akiyama, Anal. Sci. 1994, 10, 365; e) R. R. Tykwinski, F.
Diederich, Liebigs Ann. 1997, 649; f) W. J. Youngs, C. A. Tessier, J. D.
Bradshaw, Chem. Rev. 1999, 99, 3153; g) M. M. Haley, J. J. Pak, S. C.
Brand, Top. Curr. Chem. 1999, 201, 81.
[2] For example donor± acceptor substituted dehydroannulenes: J. J. Pak,
T. J. R. Weakley, M. M. Haley, J. Am. Chem. Soc. 1999, 121,
8182.
Scheme 3. Synthesis of 14. Reagents and conditions: a) 1. iPr3SiCCMgBr;
2. AcOH/SnCl2, 80%; b) Me3SiCCSnBu3, [(Ph3P)2PdCl2], 60%;
c) 1. K2CO3 in MeOH/THF; 2. CuCl/TMEDA in acetone, 88%.
[3] K. P. Baldwin, A. J. Matzger, D. A. Scheiman, C. A. Tessier, K. P. C.
Vollhardt, W. J. Youngs, Synlett 1995, 1215.
[4] a) O. M. Behr, G. Eglinton, A. R. Galbraith, R. A. Raphael, J. Chem.
Soc. 1960, 3614; b) U. H. F. Bunz, V. Enkelmann, Chem. Eur. J. 1999,
5, 263.
deoxygenation led to the very soluble enediyne 12.[13]
Alkynylation by Stille coupling[14] led to tetrayne 13, which
was selectively desilylated and oxidatively coupled to yield a
deep red solution of macrocycle 14. This soluble material
shows remarkable thermal and photochemical stability. So-
lutions of 14 were heated at >1908C for several hours, or left
in direct sunlight for a period of several weeks, without
noticeable decomposition. Examination of the 1H NMR
spectrum shows a slight paratropic shift of all of the aromatic
protons of the macrocycle with respect to the acyclic starting
material. The FTIR, 13C NMR, and mass spectral analyses all
support the structural assignment of 14.
[5] R. H. Mitchell, F. Sondheimer, Tetrahedron 1968, 24, 1397.
[6] a) K. Miyawaki, R. Suzuki, T. Kawano, I. Ueda, Tetrahedron Lett.
1997, 38, 3943; b) K. Miyawaki, T. Kawano, I. Ueda, Tetrahedron Lett.
2000, 41, 1447.
[7] a) R. Gleiter, R. Merger, J. Chavez, T. Oeser, H. Irngartinger, H.
Pritzkow, B. Nuber, Eur. J. Org. Chem. 1999, 2841; b) F. Sondheimer,
Y. Amid, R. Wolovsky, J. Am. Chem. Soc. 1957, 79, 6263.
[8] Distances reported in this paper were calculated by using ab initio HF
methods in Mac Spartan Plus (version 1.1.9): Wavefunction, Inc.,
18401 Von Karman Ave., Ste. 370, Irvine, CA 92612.
[9] a) K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew.
Chem. Int. Ed. Engl. 1991, 30, 1387; b) R. G. Bergman, Acc. Chem.
Res. 1973, 6, 25.
Slow evaporation of a 1,2-dichloroethane solution of
compound 14 led to dark purple crystals with a golden
metallic luster. The structure was determined by X-ray
crystallographic analysis (Figure 2).[15] Consistent with calcu-
Â
Â
[10] J. J. Gonzalez, A. Francesch, D. J. Cardenas, A. M. Echavarren, J. Org.
Chem. 1998, 63, 2854.
[11] A. J. Matzger, K. P. C. Vollhardt, Tetrahedron Lett.
1998, 39, 6791, and references therein.
[12] L. T. Scott, P.-C. Cheng, M. M. Hashemi, M. S.
Bratcher, D. T. Meyer, H. B. Warren, J. Am. Chem.
Soc. 1997, 119, 10963.
[13] W. Baidossi, H. Schumann, J. Blum, Tetrahedron 1996,
52, 8349.
[14] J. K. Stille, Angew. Chem. 1986, 98, 504; Angew.
Chem. Int. Ed. Engl. 1986, 25, 508.
[15] Data for the X-ray structure analysis: Crystals from
1,2-dichloroethane, C76H92Si4 (Mr ˆ 1117.86); crystal
size 0.26 Â 0.20 Â 0.08 mm3; monoclinic, space group
I2/a, a ˆ 21.717(3), b ˆ 13.8940(10), c ˆ 22.961(2) Š,
b ˆ 101.235(10)8, Z ˆ 4, Vˆ 6795.4(12) Š3, 1calcd
ˆ
1.093 gcm 3, Tˆ 173(1) K, 2q ˆ 50, 11692 reflections
measured, 5980 were unique (Rint ˆ 0.0372), and 4831
were observed (I > 2s(I)), MoKa radiation (l ˆ
0.71073 Š), graphite monochromated, data were
corrected for Lorentz and polarization effects. The
structure was solved by direct methods and refined
with the full-matrix, least-squares method; R1 ˆ
0.0561, wR2 ˆ 0.1080 (for 4831 reflections with
Figure 2. Molecular structure of 14 (ORTEP plot) in the crystal. Selected bond lengths [Š]
and angles [8]: C1'-C14 1.371(3), C14-C13 1.201(3), C13-C12 1.430(3), C12-C15 1.441(3), C15-
C3 1.439(3), C3-C2 1.428(3), C2-C1 1.202(3), C1-C14' 1.371(3), C12-C11 1.389(3), C11-C10
1.407(3), C10-C9 1.370(3), C9-C8 1.474(3), C8-C7 1.379(3), C7-C6 1.472(3), C6-C5 1.369(3),
C5-C4 1.402, C4-C3 1.398(3), C15-C16 1.394(3), C9-C16 1.411(3), C16-C6 1.413(3); C1'-C14-
C13 173.6(2), C14-C13-C12 176.3(2), C13-C12-C15 121.34(19), C12-C15-C3 129.65(18), C15-
C3-C2 123.26(19), C3-C2-C1 178.0(2), C2-C1-C14' 172.7(2).
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I > 2s(I)), R1 ˆ 0.0768, wR2 ˆ 0.1153 (for all data); data-to-parameter
ratio 16.52; residual electron density ‡0.302/ 0.260 eŠ 3. Crystallo-
graphic data (excluding structure factors) for the structure reported in
this paper have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-158650. Copies
of the data can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB21EZ, UK (fax: (‡44)1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk).
circuit containing several connected logic gates as a (logic)
equivalent of the intramolecular dynamics of a single
molecule. The experimental demonstration of such a scheme
is presented herein.
A molecule in a molecular logic gate scheme[11] becomes a
vehicle for information processing, where the input is optical
excitation. In the experiment discussed below the resonance
requirement is paramount, and an intramolecular motion is
essential for the logic action. We discuss time-resolved
measurements because one advantage of our gates is that
they can be ultrafast, as reported for a number of other
systems.[11] With our device we get the output as an optical
signal. However, the recent experiments of Crim and co-
workers[13] suggest that the logic of the present approach can
be probed by chemical means.
IR-UV Double-Resonance Photodissociation
of Nitric Acid (HONO2) Viewed as Molecular
Information Processing**
A conventional logic circuit is built from connected
switches. The advantage of the approach we follow is that
by operating a single molecule as a logic circuit one avoids the
need to connect switches. The circuit reported here is already
equivalent to several switches, and this, we hope, is only the
beginning. The logic gate that we describe is completely
irreversible since the molecule is destroyed. This dissociation
is not an essential aspect and we have discussed[11] other
molecules where this need not be the case, and where the
initial state can be recovered as quickly as one picosecond.
The power of organic synthesis to design molecules should
not be overlooked. What one wants is a circuit that is operable
over many cycles. The first step is the need to regenerate the
ground state. In some systems, for example, the photoinduced
keto ± enol tautomerism, this requirement is inherently sat-
isfied. In other systems, such as electrocyclic ring openings,
the photoprocess generates more than one possible product,
and this can be used to advantage. In essence what we look for
is a prompt intramolecular response to an optical excitation.
Typically, such a response involves a rotation of part of a
molecule relative to another to bring about a recoupling of the
electronic orbitals.
Since the 1970s great advances have been made possible by
combining laser spectroscopy and reaction dynamics. The
double-resonance experiment that we discuss falls into this
class. The principles[14±16] are understood and the application
to the HONO2 system has been previously studied.[17, 18] What
is new and interesting is the hitherto unknown effect
determined by the order of the two ultrafast UV and IR
pulses. Still, it can be asked if what we are discussing is little
more than a semantic rephrasing of an experiment. What we
actually do is to explore the implications of a spectroscopic
experiment from a new point of view, which opens up options
and possibilities that are not evident without it. It also raises
new questions of principle. For the moment, however, we just
want to highlight a cross-disciplinary study involving modern
chemical physics and Boolean logic. We are aware that one
can carry our ideas into the non-Boolean (that is, quantal)
regime, but for now we will view the experiment in chemical
kinetic, that is, classical, terms.
Thomas Witte, Christine Bucher, Françoise Remacle,
Detlev Proch, Karl L. Kompa, and R. D. Levine*
One route to nanoscale computing is to make single
molecules that can mimic the function of conventional
components of electronic logic circuits, such as switches or
wires. There is therefore increasing activity in producing
molecules that can conduct electrical current or can be
instructed to turn it on or off when placed within a suitable
support. This field of activity, sometimes known as molecular
electronics[1] or molecular scale electronics,[2] is a major
current research area. Now that several groups[2±4] have
demonstrated that a molecule can act as a switch,[5] it is
possible to begin thinking about replacing transistors by single
molecules within larger digital devices. The chemical pumping
of molecules in solution that induces changes that can be
optically detected has also been been studied for some
time[6±8] as a possible route to logic gates. More generally, the
progress in supramolecular chemistry towards the construc-
tion of molecular machines[9, 10] opens up many possibilities
for an induced response.
An alternative to the approach in which a molecule acts as a
single switch is a scheme where the function of an entire logic
circuit is performed by a single isolated molecule.[11, 12]
A
particular molecular coordinate, which could be a reactive
one, acts as the bus for information transfer. This alternative
route has the distant goal of incorporating the logic capa-
bilities of a complete integrated circuit on a single molecule. A
more modest goal is the experimental demonstration of a
[*] Prof. Dr. R. D. Levine
The Fritz Haber Research Center for Molecular Dynamics
The Hebrew University, Jerusalem 91904 (Israel)
Fax : (‡972)2-651-3742
E-mail: rafi@fh.huji.ac.il
Prof. Dr. R. D. Levine, T. Witte, Dr. C. Bucher, Dr. F. Remacle,
Dr. D. Proch, Prof. Dr. K. L. Kompa
Max-Planck-Institute of Quantum Optics
85740 Garching (Germany)
Dr. F. Remacle
Permanent address:
To introduce the subject we begin with the IR-UV double-
resonance experiment of Crim and co-workers (Fig-
ure 1).[14, 17±19] An IR photon generates a vibrationally excited
state (OH stretch overtone) of the ground electronic state of
Â
Departement de Chimie, B6
Â
Á
Á
Universite de Liege, 4000 Liege (Belgium)
[**] This work was supported by the James Franck Program for Laser-
Matter Interaction.
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