Synthetic approaches to zigzag-shaped oligophenylene strands laterally decorated with hydroxy functions

Article abstract of DOI:10.1002/ejoc.201001058

Two nanosized zigzag-shaped oligophenylene strands incorporating 2,2′-biphenol units were prepared by Suzuki-Miyaura coupling methodology. The two strands are made up of ten and seven phenyl rings, respectively. Two synthetic pathways were evaluated. The

Full text of DOI:10.1002/ejoc.201001058

FULL PAPER
DOI: 10.1002/ejoc.201001058
Synthetic Approaches to Zigzag-Shaped Oligophenylene Strands Laterally
Decorated with Hydroxy Functions
Carine Diebold,[a] David Michael Weekes,[a] Maria Torres Navarrete,[a] Pierre Mobian,*[a]
Nathalie Kyritsakas,[b] and Marc Henry[a]
Keywords: Polyphenylene structure / Suzuki–Miyaura reaction / 2,2Ј-Biphenol / Cross-coupling / Multicomponent
reactions / Oligomerization
Two nanosized zigzag-shaped oligophenylene strands incor-
porating 2,2Ј-biphenol units were prepared by Suzuki–
Miyaura coupling methodology. The two strands are made
up of ten and seven phenyl rings, respectively. Two synthetic
pathways were evaluated. The first involved the preparation
of the target oligophenylene molecules by a sequential ap-
proach, whereas the second entailed the formation of the
precursors of the target compounds in a one-step fashion.
The efficiencies of these two approaches are discussed and
compared.
Introduction
In the field of organic materials, nanosized polyphenyl-
ene structures occupy a particular place.[1] The self-assemb-
ling,[2] photophysical,[3] conducting,[4] and mechanical
properties,[5] as well as the liquid-crystal behavior,[6] of this
very large family of thermally and photochemically stable
compounds have been intensively studied. In coordination
chemistry, oligophenylenes or oligophenylene backbones
substituted with coordinating atoms or groups are an im-
portant class of ligands.[7] A large variety of synthetic ap-
proaches to oligophenylene structures have been reported;
these include, for instance, reductive and oxidative cou-
pling,[1,8] thermolysis or aromatization of appropriate pre-
cursors,[1,9] and Diels–Alder cycloaddition.[1,10] Nowadays,
however, transition-metal-catalyzed aryl–aryl coupling re-
actions are certainly the most widely employed.[1,11] In par-
ticular, mild palladium(0)-catalyzed couplings of aryl-
boronic acids with aryl halides, known as Suzuki–Miyaura
cross-coupling reactions,[12] have allowed the preparation of
a large range of molecules containing polyphenylene back-
bones.[1,13]
Scheme 1.
Here we report two synthetic approaches leading to the
formation of the zigzag-shaped[15] polyhydroxyoligophenyl-
ene strand L(OH)4 and its longer analogue, the strand
L(OH)6 (Scheme 1). Both approaches reported here involve
the preparation of the nanosized oligophenylene structures
by application of Suzuki–Miyaura reactions. A complete
description of the procedure for preparing these strands is
presented, and the efficiencies of the two strategies are dis-
cussed and compared. Furthermore, the solid-state charac-
terization of some target strands and their synthetic inter-
mediates is reported.
Recently, our group has described the ability of a novel
tetrahydroxyheptaphenylene strand – L(OH)4 (Scheme 1) –
to complex a titanium(IV) center, leading to a non-centro-
symmetric double-stranded titanium(IV) helicate.[14]
Results and Discussion
The molecular strands L(OH)4 and L(OH)6, incorporat-
ing two and three 2,2Ј-biphenol units, respectively, are
shown in Scheme 1. The L(OH)4 molecule contains two 3-
phenyl-2,2Ј-biphenol entities linked together through a
para-phenylene spacer, whereas in L(OH)6 the central core
of the molecule is a 3,3Ј-diphenyl-2,2Ј-biphenol fragment.
Of the large variety of methods described for the prepara-
tion of oligophenylene structures, palladium-catalyzed
cross-coupling reactions looked the most suitable. Applica-
[a] Laboratoire de Chimie Moléculaire de l’Etat Solide, UMR
7140, Université de Strasbourg
67070 Strasbourg, France
E-mail: mobian@chimie.u-strasbg.fr
[b] Laboratoire de Chimie de Coordination Organique, UMR
7140, Université de Strasbourg
67070 Strasbourg, France
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tion of Suzuki–Miyaura condensation reactions to con- Path A
struct our target molecules by two synthetic pathways was
thus envisaged, as shown in Scheme 2.
The compound L(OH)4 was prepared in five steps by
starting from 2,2Ј-dimethoxybiphenyl as shown in
Scheme 3. The synthesis of L(OH)4 was performed by ap-
plication of ortho-metalation, metal-catalyzed cross-cou-
pling in the presence of the “classical” Pd(PPh3)4 catalyst,
and ether cleavage methodologies. 2,2Ј-Dimethoxybiphenyl
was first ortho-monolithiated and then quenched with
B(OMe)3 to give the corresponding monoboronic acid after
basic hydrolysis followed by acidification. However, to cir-
cumvent tedious characterization of the product due to the
possible formation of anhydride products, the boronic acid
was directly converted into the pinacol ester 2. Under Su-
zuki–Miyaura conditions, 2 was transformed in good yield
into the dissymmetric compound 3.
The chemical integrities of 2 and 3 were confirmed by
1
various analytical techniques including H and 13C NMR
spectroscopy and electrospray ionization mass spectrometry
(ESI-MS).
Scheme 2. Two synthetic approaches leading to L(OH)4 and
L(OH)6.
Formation of the key intermediate 4 was possible
Path A involves the preparation of L(OH)4 and L(OH)6 through ortho-lithiation of 3 and subsequent addition of
starting from the commercially available 2,2Ј-dimethoxybi- B(OMe)3, acidification, and esterification in the presence of
phenyl (1; Scheme 2) by a sequential approach. The key in- pinacol.
termediate is the dissymmetric boronic ester 4, obtained in
Compounds 2, 3, and 4 are crystalline materials. Crystals
three steps from 1. Compound 4 proved suitable, after Su- suitable for X-ray diffraction (XRD) were obtained by slow
zuki–Miyaura coupling with an appropriate spacer and diffusion of pentane in the case of 2 and of hexane in those
subsequent cleavage of the methoxy groups, for the pro- of 3 and 4 into CH2Cl2 solutions of these compounds. The
duction of L(OH)4 and L(OH)6. The second approach, structures of the dissymmetric compounds 2, 3, and 4 are
path B, is more straightforward. It consists first of the con- shown in Figure 1. Interestingly, these three compounds
version of 2,2Ј-dimethoxybiphenyl into the bis(boronic crystallized in the same crystal system and the same space
acid) adduct 6, followed by a one-pot Suzuki–Miyaura re- group (monoclinic and P21/c). Torsion angle measurements
action in the simultaneous presence of bromobenzene and between the phenyl rings bearing the methoxy groups indi-
1,4-dibromobenzene. The isolation of the desired com- cate synclinal conformations between two neighboring cy-
pounds was achieved by careful separation from a crude cles for 3 and 4, with angle values of 66° and 80°, respec-
material composed of a complex mixture of polyphenylene tively, whereas an anticlinal conformation was found in 2
molecules.
(measured torsion angle 117°).
Scheme 3. Synthesis of the tetrahydroxyheptaphenylene strand L(OH)4. (a) nBuLi, TMEDA, B(OMe)3, HCl; (b) 2,3-dimethylbutane-2,3-
diol, toluene, reflux, 34% (based on 1); (c) bromobenzene, Pd(PPh3)4, toluene/MeOH/water, 110 °C, Na2CO3, 89%; (d) nBuLi, TMEDA,
B(OMe)3, HCl; (e) 2,3-dimethylbutane-2,3-diol, toluene, reflux, 56% (based on 3); (f) 1,4-dibromobenzene, Pd(PPh3)4, toluene/MeOH/
water, 110 °C, Na2CO3, 75%; (g) BBr3, dichloromethane, quantitative.
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Zigzag Oligophenylene Strands Laterally Decorated with Hydroxy Functions
lar hydrogen bond between two neighboring hydroxy func-
tions (O(OH)···O 2.865 Å, O···H···O 130.4°) allowing a syn-
clinal arrangement of two phenol subunits (measured tor-
sion angle: 63°). Inspection of the monodimensional pack-
ing of L(OH)4 is also instructive. In the crystal, L(OH)4
interacts with two nearest neighbors through four intermo-
lecular hydrogen bonds (O(OH)···O 2.855 Å, O···H···O
149.9°). Each L(OH)4 molecule behaves both as a hydro-
gen-bond donor and as a hydrogen-bond acceptor, leading
to an infinite ladder-type structure as shown in Figure 3.
Figure 1. X-ray structures of 2, 3, and 4. Hydrogen atoms are omit-
ted for clarity.
Next, the palladium-catalyzed cross-coupling reaction
between 4 and 1,4-dibromobenzene (0.55 equiv.) led to the
formation of the tetramethoxyheptaphenylene derivative 5
in good yield (75%).
Finally, upon treatment with BBr3, 5 was quantitatively
1
deprotected to give the target strand L(OH)4. H and 13C
NMR spectroscopy, as well as elemental analysis and ES-
MS data, are in full accordance with the expected structure
of L(OH)4.
Figure 3. View along x of the monodimensional hydrogen-bond
networks in the crystal of L(OH)4 (O(OH)···O 2.855 Å, O···H···O
149.9°).
Crystals of L(OH)4 and of its methylated precursor 5
suitable for X-ray analysis were obtained by slow diffusion
of pentane into CH2Cl2 solutions. Figure 2 shows the X-ray
crystallographic structures of 5 and L(OH)4.
With the efficient synthetic route described in Scheme 3
to hand, the synthesis of a second polyphenylene derivative
composed of three biphenol units [i.e., L(OH)6] was tack-
led. The formation of L(OH)6 required the condensation of
4 (2 equiv.) with 7 as shown in Scheme 4, followed by cleav-
age of the methoxy groups.
Figure 2. (a) X-ray crystal structure of 5. (b) X-ray crystal structure
of L(OH)4. In both structures, the hydrogen atoms are omitted for
clarity except for [in (b)] the hydroxy functions involved in the in-
tramolecular hydrogen bonds (dotted line) (O(OH)···O 2.865 Å,
O···H···O 130.4°).
A slight size difference can be observed in these struc-
tures. In the solid state, lengths of 27.6 Å and 26.2 Å were
measured for 5 and L(OH)4, respectively. Another signifi-
cant difference between these two structures relates to the
torsion angles between the pairs of consecutive phenyl rings
bearing methoxy or hydroxy groups in 5 and in L(OH)4,
respectively. Because of the steric hindrance produced by
Scheme 4. Synthesis of the hexahydroxydecaphenylene strand
L(OH)6. (a) 1-Bromo-4-iodobenzene, Pd(PPh3)4, toluene/MeOH/
water, 110 °C, Na2CO3, 74%; (b) 4, Pd(PPh3)4, toluene/MeOH/
water, 110 °C, Na2CO3, 30%; (c) BBr3, dichloromethane, 76%.
The synthesis of 7 was first attempted through a conden-
two adjacent methoxy groups, the two phenyl rings adopt sation under Suzuki–Miyaura conditions between 1,4-di-
an anticlinal conformation (measured torsion angle: 99°). bromobenzene and 6, which could be easily obtained on a
For L(OH)4 the situation is different, with an intramolecu- large scale from the commercially available 2,2Ј-dimethoxy-
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P. Mobian et al.
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1,1Ј-biphenyl by a recently described procedure.[7f] In order
to disfavor the formation of polymeric species, a large ex-
cess of 1,4-dibromobenzene (10 equiv.) was used. However,
despite this precaution, 7 was isolated only in a poor yield
of 25%.
It is well known that the rate-determining step in the Su-
zuki reaction is the oxidative addition of the aryl halide to
the palladium complex, with a relative reactivity decrease
in the order I Ͼ Br Ͼ Cl.[16] Application of Suzuki condi-
tions to the synthesis of 7 from 6 and 1-bromo-4-iodo-
benzene (3 equiv.) instead of 1,4-dibromobenzene therefore
allowed the isolation of the desired dibromo derivative 7 in
good yield (74%). The structure of the expected compound
was confirmed by various analytical techniques including
XRD as shown in Figure 4.
Scheme 5. One-pot procedure allowing the isolation, in one step,
of
9 (3,3Ј-diphenyl-2,2Ј-dimethoxy-1,1Ј-biphenyl), 5, and 8.
(a) Pd(PPh3)4 (5 mol-%), bromobenzene (0.70 equiv.), 1,4-dibro-
mobenzene (0.33 equiv.).
Figure 4. X-ray crystal structure of 7. Hydrogen atoms are omitted
for clarity.
Under Suzuki–Miyaura conditions, 8 was then prepared
through the coupling of 2 equiv. of 4 with 7 (Scheme 4).
Compound 8 was isolated in modest yield (30%). Deprotec-
tion of 8 with BBr3 resulted in the formation of the strand
L(OH)6, poorly soluble in common organic solvents with
the exception of tetrahydrofuran.
The two sequential synthetic routes described above led
to the isolation of the target nanosized molecular strands
L(OH)4 and L(OH)6, incorporating seven and ten aromatic
units, respectively. Five synthetic steps starting from 2,2Ј-
dimethoxybiphenyl were necessary to isolate L(OH)4 with
an overall yield of 12%, whereas for the longer analogue
L(OH)6 seven steps were required. In both cases, the syn-
thetic pathways involve the tedious preparation of the dis-
symmetric compound 4. Therefore, in order to improve the
accessibility of L(OH)4 and L(OH)6, another protocol
based on a much more direct approach was developed.
mixture with chromatographic tools was necessary to iso-
late the target compounds. In an optimized procedure, bro-
mobenzene
(0.70 equiv.)
and
1,4-dibromobenzene
(0.33 equiv.) reacted with 6 at 50 °C over a period of 53 h
with catalysis by Pd(PPh3)4 (5 mol-%) in a triphasic mixture
(toluene/methanol/water). The composition of the reaction
mixture was evaluated by analytical silica gel thin layer
chromatography (TLC). Development by elution with n-
pentane/CH2Cl2 (50:50) revealed the presence of three
major round spots characterized by significant differences
in their Rf values (0.52, 0.37, and 0.33). These products
could easily be separated by chromatography [SiO2; n-pent-
ane/CH2Cl2 (50:50)]. It should be noted that TLC analysis
also revealed the presence of more polar products, which
could not be isolated as pure samples under our conditions.
Compounds 9, 5, and 8 were obtained in 19%, 11%, and
9% yields, respectively. These yields, although modest, are
satisfactory, especially for the longest rod 8, containing ten
aromatic rings, if we consider that six carbon–carbon bonds
were created in one step. It should be noted that slight
Path B
The synthesis of the precursors 5 and 8 (Scheme 5) of the modifications of the optimized protocol described above
target hydroxylated strands was envisaged as starting from have important consequences for the isolated yields, as re-
the readily available 2,2Ј-dimethoxy-1,1Ј-biphenyl-3,3Ј- ported in Table 1.
bis(boronic acid) (6) in a one-pot reaction. Compound 6
Finally, a similar synthetic route involving the condensa-
was engaged in a palladium(0)-catalyzed double C–C bond tion of benzeneboronic acid and 1,4-benzenediboronic acid
formation with bromobenzene and 1,4-dibromobenzene with 3,3Ј-dibromo-2,2Ј-dimethoxy-1,1Ј-biphenyl has also
simultaneously present in the reaction mixture in sub- been investigated.[17] In that case, only 5 could be isolated
stoichiometric amounts as shown in Scheme 5.
in a yield of 8% and as a sample contaminated by a large
The formation of several polyphenylene structures was amount of inseparable impurities (ca. 30% evaluated by 1H
indeed expected, and so a careful separation of the crude NMR spectroscopy).
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Zigzag Oligophenylene Strands Laterally Decorated with Hydroxy Functions
Table 1. Reaction conditions tested for the one-step synthesis of 9, 5, and 8 starting from 6. Entry 6 corresponds to the optimized
protocol.
Entry
6
Bromobenzene
[equiv.]
1,4-Dibromobenzene
[equiv.]
Procedure,[a]
temperature
Product,
yield[b]
[10–3 mol]
1
1.6
1.6
1.6
1.6
1.6
3.3
0.55
0.55
1.05
1.05
0.7
0.27
0.27
0.55
0.55
0.33
0.33
i, 50 °C
ii, 50 °C
ii, 50 °C
ii, 110 °C
ii, 110 °C
ii, 50 °C
9, 0%
5, 0%
8, 0%
9, 0%
5, 4%
8, 0%
9, 11%
5, 6%
8, 0%
9, 13%
5, 5%
8, 0%
9, 14%
5, 3%
8, 0%
9, 19%
5, 11%
8, 9%
2
3
4
5
6
0.7
[a] Procedure (i): Pd(PPh3)4 (5 mol-%), Na2CO3 (1 m), toluene, MeOH, 50 °C. Compound 6 was first treated with bromobenzene. After
24 h, 1,4-dibromobenzene was then added to the reaction mixture. Procedure (ii): Pd(PPh3)4 (5 mol-%), Na2CO3 (1 m), toluene, MeOH,
50 °C. Compound 6 was treated simultaneously with bromobenzene and 1,4-dibromobenzene. [b] Isolated yields obtained after purifica-
tion of the crude reaction on silica gel (CH2Cl2/pentane). For Entries 1, 2, 3, 4, and 5 undesired products corresponding, for instance, to
1 or to strands 5 and 8 with one or two phenyl rings missing were isolated.
NMR: CDCl3: δ = 77.23 ppm, CD2Cl2: δ = 54.00 ppm). Mass spec-
tra were obtained with a VG-BIOQ triple quadrupole in positive
Conclusions
Here we have described the synthesis of two new poly-
mode (ES-MS). Microanalyses were performed by the Service de
phenylene structures incorporating two or three 2,2Ј-bi- Microanalyses de la Fédération de Recherche de Chimie, Université
de Strasbourg, Strasbourg. Crystallography data were collected at
173(2) K with a Bruker APEX8 CCD diffractometer equipped with
an Oxford Cryosystem liquid N2 device, with use of graphite-mono-
chromated Mo-Kα (λ = 0.71073) radiation. For all structures, dif-
fraction data were corrected for absorption, and structural determi-
nation was achieved by using the APEX (1.022) package. The hy-
drogen atoms were introduced at calculated positions and not re-
fined (riding model). CCDC-783150 (2), -783151 (3), -783389 (4),
-783152(5), -783153 (6), and -783388 (7) contain the supplementary
crystallographic data for this paper. These data can be obtained
phenol moieties linked through para-phenylene spacers.
These two strands were obtained by application of Suzuki–
Miyaura C–C bond formation, once again highlighting the
crucial role of palladium cross-coupling methodologies in
the construction of polyphenylene nanostructures. Two syn-
thetic pathways were applied. The stepwise procedure,
which required the synthesis of an unsymmetrically ortho-
substituted 2,2Ј-dimethoxy-1,1Ј-biphenyl intermediate, al-
lowed the preparation of L(OH)4 and L(OH)6 in five and
seven steps, respectively. A second synthetic strategy based free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
on an efficient one-pot protocol was also evaluated. In the
particular case of the synthesis of our target compounds,
the use of the one-pot cross-coupling strategy represented
an efficient alternative to the stepwise procedure. We are
now focusing on the preparation of other polyphenylene
Compound 2: The reaction was conducted under nitrogen. 2,2Ј-Di-
methoxy-1,1Ј-biphenyl (5 g, 2.34ϫ10–2 mol) and freshly distilled
TMEDA (5.23 mL, 3.51ϫ10–2 mol) were dissolved in dry diethyl
ether. The resulting mixture was cooled to –78 °C, and nBuLi solu-
structures that incorporate biphenol units by a similar one- tion (1.35 m, 26 mL, 3.51ϫ10–2 mol) was added. The solution was
allowed to come to room temperature and stirred for 3 h. The re-
sulting milky solution was cooled again to –78 °C, and B(OMe)3
(22.3 mL, 1.96ϫ10–1 mol) was slowly added. After the mixture had
been stirred at room temperature overnight, an aqueous solution
of NaOH (6 n, 100 mL) was added. After 5 h, the white suspension
had disappeared, and the aqueous layer was extracted, washed with
CH2Cl2, and acidified with concentrated HCl to pH = 1. The re-
sulting yellowish aqueous layer was then washed with CH2Cl2, and
pot approach, for potential applications in coordination
chemistry and materials science.
Experimental Section
General: All chemicals were of the best commercially available
grade and were used without further purification. Column
chromatography was performed with silica gel 60 (Merck 9385, the isolated organic layer was dried with MgSO4 and concentrated
230–400 mesh) or aluminium oxide 90 (neutral, activity II–III,
Merck 1097). 1H and 13C NMR spectra were recorded with a
Bruker Avance 300 (300 MHz) spectrometer with use of a deuter-
ated solvent as the lock. The chemical shifts were referenced to
residual solvent protons as internal standards (1H NMR: CDCl3:
δ = 7.24 ppm, CD2Cl2: δ = 5.32 ppm, [D8]THF: δ = 3.31 ppm; 13C
under reduced pressure to yield a yellow oil. The monoboronic acid
was separated from the crude material by silica gel column
chromatography (Ø = 4.5 cm, l = 35 cm; CH2Cl2/MeOH, 99:1) to
yield a yellow oil (4.06 g). In order to facilitate the characterization,
the resulting product was used directly in the next step. The re-
sulting oil and pinacol (3.66 g, 3.10ϫ10–2 mol) were dissolved in
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P. Mobian et al.
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toluene (150 mL). Water formed during the reaction was removed
by use of a Dean–Stark apparatus. The mixture was heated to
110 °C, left overnight, and concentrated under reduced pressure.
Purification was performed by silica gel chromatography (Ø =
3.2 cm, l = 43 cm; CH2Cl2) and crystallization from CH2Cl2/pent-
ane to yield transparent crystals (2.74 g, 34% based on 1). M.p.
(0.52 mL, 3.51ϫ10–3 mol) were dissolved in dry diethyl ether
(10 mL). The resulting mixture was cooled to –78 °C, and nBuLi
solution (1.4 m, 3.3 mL, 4.13ϫ10–3 mol) was added. After 5 min at
–78 °C, the solution was allowed to come to room temperature and
stirred for 3 h. The resulting solution was cooled again to –78 °C,
and B(OMe)3 (4.3 mL, 0.037 mol) was slowly added. A white pre-
cipitate appeared and redissolved when the reaction mixture was
1
3
4
110 °C. H NMR (300 MHz, CDCl3): δ = 7.72 (dd, J = 7.3, J =
3
4
1.8 Hz, 1 H), 7.37 (dd, J = 7.4, J = 1.9 Hz, 1 H), 7.32 (complex, allowed to come to room temperature. After stirring at room tem-
3
3
2 H), 7.14 (t, J = 7.3 Hz, 1 H), 6.97 (td, J = 7.7 Hz, 2 H), 3.76
(s, 3 H, OMe), 3.49 (s, 3 H, OMe), 1.36 (s, 12 H, CH3) ppm. 13C
NMR (75 MHz, CDCl3): δ = 136.0, 135.1, 131.8, 131.7, 128.5,
perature overnight, the reaction was quenched by addition of water
(25 mL) at 0 °C. The mixture was then acidified with concentrated
HCl to pH = 1, and diethyl ether was added (55 mL). The organic
layer was isolated, dried with MgSO4, and concentrated under re-
duced pressure. The resulting oil (1.68 g) was used directly in the
next step without further characterization. The oil (1.68 g) and pin-
acol (1.19 g, 1.01ϫ10–2 mol) were dissolved in toluene (35 mL).
Water formed during the reaction was removed by use of a Dean–
Stark apparatus. The mixture was heated to 110 °C, left overnight,
and concentrated under reduced pressure. Purification was per-
formed by silica gel chromatography (Ø = 3.2 cm, l = 21 cm; pen-
tane/CH2Cl2, 70:30). Compound 4 was isolated as a yellowish solid
(814 mg, 56% based on 3). M.p. 169 °C. 1H NMR (300 MHz,
123.0, 120.1, 110.7, 83.5, 61.8, 55.5, 24.8 ppm. IR: ν = 3069, 2995,
˜
2978, 2969, 2932, 1591, 1496, 1470, 1458, 1412, 1389, 1371, 1309,
1298, 1273, 1254, 1236, 1224, 1200, 1165, 1148, 1134, 1120, 1078,
1057, 1036, 1024, 1008 cm–1. C20H25BO4 (340.18): calcd. C 70.61,
H 7.41; found C 70.43, H 7.41. MS (ES): calcd. for [M + Li]+
347.200, found 347.200. Crystals were obtained by slow diffusion
of pentane into a CH2Cl2 solution of 2. X-ray data for 2: empirical
formula: C20H25BO4; formula mass: 340.21; crystal system: mono-
clinic; space group: P21/c; unit cell dimensions: a = 11.0075(5) Å,
b = 11.3215(5) Å, c = 15.5545(12) Å; V = 1867.85(15) Å3; Z = 4;
density (calcd.): 1.201 Mgm–3; crystal size: 0.18ϫ0.14ϫ0.12 mm;
θ range for data collection: 2.88–27.59°; reflections collected:
16537; independent reflections: 4320 [R(int) = 0.0451]; refinement
method: full-matrix least squares on F2; data/restraints/parameters:
4320/0/232; goodness-of-fit on F2: 1.025; final R indices [IϾ2σ(I)]:
R1 = 0.0425, wR2 = 0.0952; R indices (all data): R1 = 0.0759, wR2
= 0.1106.
3
4
CDCl3): δ = 7.74 (dd, J = 7.3, J = 1.9 Hz, 1 H), 7.61 (complex,
3
4
2 H), 7.50 (dd, J = 7.6, J = 1.9 Hz, 1 H), 7.44–7.30 (complex, 5
H), 7.18 (t, 1 H), 7.16 (t, 1 H), 3.60 (s, 3 H, OMe), 3.16 (s, 3 H,
OMe), 1.37 (s, 12 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
136.3, 135.1, 134.9, 131.3, 130.4, 129.2, 128.2, 128.1, 127.0, 123.5,
123.1, 83.6, 62.0, 60.4, 24.9 ppm. IR: ν = 2977, 2930, 1592, 1497,
˜
1461, 1413, 1389, 1358, 1306, 1263, 1226, 1142, 1114, 1078, 1044,
1004 cm–1. MS (ES): calcd. for [M + Li]+ 423.232, found 423.229.
C26H29BO4 (416.21): calcd. C 75.01, H 7.02; found C 75.03, H 7.34.
Crystals were obtained by slow diffusion of hexane into a CH2Cl2
solution of 4. X-ray data for 4: empirical formula: C26H29BO4; for-
mula mass: 416.30; crystal system: monoclinic; space group: P21/
c; unit cell dimensions: a = 7.1425(3) Å, b = 10.3652(4) Å, c =
31.1487(12) Å; V = 2303.17(16) Å3; Z = 4; density (calcd.):
1.201 Mgm–3; crystal size: 0.11ϫ0.10ϫ0.09 mm; θ range for data
collection: 2.07–27.06°; reflections collected: 16081; independent
reflections: 5297 [R(int) = 0.0412]; refinement method: full-matrix
least squares on F2; data/restraints/parameters: 5297/0/286; good-
ness-of-fit on F2: 1.030; final R indices [IϾ2σ(I)]: R1 = 0.0688,
wR2 = 0.1467; R indices (all data): R1 = 0.0985, wR2 = 0.1600.
2Ј,2ЈЈ-Dimethoxy-1,1Ј:3Ј,1ЈЈ-triphenyl (3): Under nitrogen, an aque-
ous solution of Na2CO3 (1 m, 15 mL) was transferred by cannula
to toluene (40 mL) containing bromobenzene (2.79 mL,
2.65ϫ10–2 mol) and tetrakis(triphenylphosphane)palladium(0)
(70 mg, 0.06 mmol). After addition of an MeOH solution of 2
(1.5 g, 4.41ϫ10–3 mol), the mixture was heated overnight at
110 °C. After cooling, the aqueous phase was extracted with
CH2Cl2 (3ϫ). The combined organic phases were dried with
MgSO4, concentrated under reduced pressure, and purified by silica
gel chromatography (Ø = 3.2 cm, l = 24.5 cm; n-pentane/CH2Cl2,
1
50:50) to yield a white solid (1.14 g, 89%). M.p. 70 °C. H NMR
(300 MHz, CDCl3): δ = 7.63–7.59 (complex, 2 H), 7.45–7.26 (com-
plex, 7 H), 7.25–7.18 (complex, 2 H), 7.05–6.97 (complex, 2 H),
3.81 (s, 3 H, OMe), 3.18 (s, 3 H, OMe) ppm. 13C NMR (75 MHz,
CDCl3): δ = 157.0, 155.5, 139.1, 135.0, 132.6, 131.4, 131.0, 130.4,
129.2, 128.7, 128.3, 128.0, 127.1, 123.7, 120.5, 111.1, 60.4,
2Ј,2ЈЈ,2ЈЈЈЈ,2ЈЈЈЈЈ-Tetramethoxy-1,1Ј:3Ј,1ЈЈ:3ЈЈ,1ЈЈЈ:4ЈЈЈ,1ЈЈЈЈ:3ЈЈЈЈ,
1ЈЈЈЈЈ:3ЈЈЈЈЈ,1ЈЈЈЈЈЈ-heptaphenyl (5): The reaction was conducted un-
der nitrogen. An aqueous solution of Na2CO3 (1 m, 15 mL) was
first transferred by cannula into a degassed solution of 1,4-dibro-
mobenzene (86 mg, 3.65ϫ10–4 mol) and Pd(PPh3)4 (37 mg) in tolu-
ene (20 mL), followed by 4 (0.304 g, 7.30ϫ10–4 mol) dissolved in
MeOH (5 mL). The resulting mixture was then heated to 100 °C
and left overnight. After cooling, the solution was filtered through
Celite. The collected organic layers were combined, dried with
MgSO4, and concentrated under reduced pressure. The crude prod-
uct was purified by silica gel chromatography (Ø = 3.2 cm, l =
23 cm; CH2Cl2) to afford 5 as a white solid (177 mg, 75%). M.p.
55.6 ppm. IR: ν = 3050, 3037, 2985, 2952, 2929, 2895, 2833, 1599,
˜
1581, 1495, 1465, 1459, 1434, 1410, 1331, 1297, 1282, 1272, 1256,
1238, 1221, 1174, 1131, 1104, 1082, 1071, 1053, 1021, 1014,
1005 cm–1. MS (ES): calcd. for [M + Li]+ 297.146, found 297.145.
C20H18O2 (290.13): calcd. C 82.73, H 6.25; found C 80.66, H 6.25.
Crystals were obtained by slow diffusion of pentane into a CH2Cl2
solution of 3 at +4 °C. X-ray data for 3: empirical formula:
C20H18O2; formula mass: 290.34; crystal system: monoclinic; space
group: P21/c; unit cell dimensions:
a = 14.071(4) Å, b =
7.2788(19) Å, c = 15.767(5) Å; V = 1576.6(7) Å3; Z = 4; density
(calcd.): 1.223 Mgm–3; crystal size: 0.06ϫ0.04ϫ0.03 mm; θ range
for data collection: 2.65–27.51°; reflections collected: 10524; inde-
pendent reflections: 3583 [R(int) = 0.0862]; refinement method:
full-matrix least squares on F2; data/restraints/parameters: 3583/0/
201; goodness-of-fit on F2: 1.246; final R indices [IϾ2σ(I)]: R1 =
0.1005, wR2 = 0.1644; R indices (all data): R1 = 0.1500, wR2 =
0.1934.
1
230 °C. H NMR (300 MHz, CDCl3): δ = 7.70 (s, 4 H), 7.63 (dd,
3J = 8.1, 4J = 1.2 Hz, 4 H), 7.46–7.32 (complex, 7 H), 7.27–7.20
(complex, 4 H), 3.32 (s, 6 H, OMe), 3.27 (s, 6 H, OMe) ppm. 13C
NMR (75 MHz, CDCl3): δ = 155.6, 155.5, 139.0, 137.7, 135.3,
134.9, 133.1, 131.0, 130.7, 129.4, 129.2, 128.3, 127.2, 123.8, 60.7,
38.4 ppm. IR: ν = 2932, 1560, 1509, 1459, 1410, 1226, 1079,
˜
1002 cm–1. MS (MALDI-TOF): calcd. for [M]+ 654.277, found
654.282. C46H38O4 (654.27): calcd. C 84.38, H 5.85; found C 83.01,
H 5.59. X-ray data for 5: empirical formula: C46H38O4; formula
Compound 4: The reaction was conducted under nitrogen. Com-
pound 3 (1 g, 3.44ϫ10–3 mol) and freshly distilled TMEDA
¯
mass: 654.76; crystal system: triclinic; space group: P1; unit cell
6954
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 6949–6956

Zigzag Oligophenylene Strands Laterally Decorated with Hydroxy Functions
dimensions: a = 7.2091(3) Å, b = 13.1829(4) Å, c = 19.46625(8) Å; c; unit cell dimensions: a = 30.8980(11) Å, b = 7.7851(4) Å, c =
V = 1711.78(18) Å3; Z = 2; density (calcd.): 1.270 Mgm–3; crystal
size: 0.20 ϫ 0.15 ϫ 0.14 mm; θ range for data collection: 1.65–
29.91°; reflections collected: 17330; independent reflections: 9789
[R(int) = 0.0306]; refinement method: full-matrix least squares on
F2; data/restraints/parameters: 9789/0/455; goodness-of-fit on F2:
23.5903(15); V = 4423.4(4) Å3 ; Z = 4; density (calcd.):
1.574 Mgm–3; crystal size: 0.12ϫ0.06ϫ0.06 mm; θ range for data
collection: 2.75–27.54°; reflections collected: 17316; independent
reflections: 5032 [R(int) = 0.0607]; refinement method: full-matrix
least squares on F2; data/restraints/parameters: 5032/0/273; good-
1.082; final R indices [IϾ2σ(I)]: R1 = 0.0580, wR2 = 0.1155; R ness-of-fit on F2: 1.005; final R indices [IϾ2σ(I)]: R1 = 0.0433,
indices (all data): R1 = 0.1183, wR2 = 0.1251.
wR2 = 0.0788; R indices (all data): R1 = 0.1054, wR2 = 0.0962.
2Ј,2ЈЈ,2ЈЈЈЈ,2ЈЈЈЈЈ-Tetrahydroxy-1,1Ј:3Ј,1ЈЈ:3ЈЈ,1ЈЈЈ:4ЈЈЈ,1ЈЈЈЈ:3ЈЈЈЈ,
1ЈЈЈЈЈ:3ЈЈЈЈЈ,1ЈЈЈЈЈЈ-heptaphenyl [L(OH)4]: The reaction was con-
ducted under nitrogen. Compound 5 (167 mg, 2.55ϫ10–4 mol) was
dissolved in anhydrous CH2Cl2 (20 mL). At –78 °C, BBr3 (1 m in
CH2Cl2, 1.32 mL) was added to the solution. The resulting mixture
was allowed to come to room temperature and stirred for 12 h.
Water (60 mL) was then added, and the organic layer was isolated,
dried with MgSO4, and concentrated under reduced pressure. The
product was obtained as a yellowish solid (157 mg, quantitative).
M.p. Ͼ270 °C. 1H NMR (300 MHz, CDCl3): δ = 7.68 (s, 4 H),
7.58–7.34 (complex, 18 H), 7.15 (td, J = 5.3, J = 2.4 Hz, 4 H), 5.92
(s, 2 H, OH), 5.83 (s, 2 H, OH) ppm. 13C NMR (75 MHz, CD2Cl2):
δ = 150.0, 149.7, 137.4, 136.9, 131.1, 138.7, 129.7, 129.5, 129.5,
2Ј,2ЈЈ,2ЈЈЈЈ,2ЈЈЈЈЈ,2ЈЈЈЈЈЈЈ,2ЈЈЈЈЈЈЈЈ-Hexamethoxy-1,1Ј:3Ј,1ЈЈ:3ЈЈ,
1ЈЈЈ:4ЈЈЈ,1ЈЈЈЈ:3ЈЈЈЈ,1ЈЈЈЈЈ:3ЈЈЈЈЈ,1ЈЈЈЈЈЈ:4ЈЈЈЈЈЈ,1ЈЈЈЈЈЈЈ:3ЈЈЈЈЈЈЈ,
1ЈЈЈЈЈЈЈЈ:3ЈЈЈЈЈЈЈЈ,1ЈЈЈЈЈЈЈЈЈ-decaphenyl (8): The reaction was con-
ducted under nitrogen. Pd(PPh3)4 (26 mg) and an aqueous solution
of Na2CO3 (6 mL, 1 m) was added to a degassed toluene solution
of 7. The resulting mixture was stirred for 30 min, and compound
4 dissolved in a degassed mixture of toluene/MeOH (5:3, 8 mL),
was added. The reaction mixture was heated at 90 °C for 24 h, and
a further addition of Pd(PPh3)4 catalyst (20 mg) was performed.
The mixture was heated for an additional 12 h. The reaction mix-
ture was then cooled to room temperature, and then water and
dichloromethane were added. The organic layer was isolated, dried
with MgSO4 and concentrated under reduced pressure. The crude
material was purified on silica gel (pentane/CH2Cl2, 70:30) to yield
129.3, 129.1, 128.8, 127.7, 125.2, 124.8, 121.4 ppm. IR: ν = 3521,
˜
1444, 1427, 1325, 1217, 1166, 1071 cm–1. MS (MALDI-TOF):
calcd. for [M]+ 598.214, found 598.208. C42H30O4 (598.21)·CH3OH
(analyzed sample was obtained by crystallization from MeOH):
calcd. C 81.35, H 5.17; found C 81.88, H 5.43. Crystals were ob-
tained by slow diffusion of pentane into a CH2Cl2 solution of
L(OH)4. X-ray data for L(OH)4: empirical formula: C42H30O4; for-
1
a white solid (30%). M.p. Ͼ270 °C. H NMR (300 MHz, CDCl3):
δ = 7.70–7.21 (complex), 3.33 (s, 3 H, OMe), 3.32 (s, 3 H, OMe),
3.27 (s, 3 H, OMe) ppm. 13C NMR (75 MHz, CDCl3): δ = 155.5,
155.4, 138.8, 137.6, 135.1, 134.8, 133.0, 132.9, 130.9, 130.6, 129.2,
129.1, 128.2, 127.0, 123.6, 60.6 ppm. IR: ν = 3054, 3025, 2933,
˜
2820, 1463, 1455, 1410, 1392, 1386, 1227, 1078, 1013, 1003 cm–1.
MS (MALDI-TOF): calcd. for [M]+ 942.392, found 942.345.
C66H54O6 (942.39): calcd. C 84.05, H 5.77; found C 84.30, H 8.40.
¯
mula mass: 598.66; crystal system: triclinic; space group: P1; unit
cell dimensions: a = 5.6618(8) Å, b = 10.7721(15) Å, c =
12.4561(16) Å; V = 742.36(18) Å3; Z = 1; density (calcd.):
1.339 Mgm–3; crystal size: 0.05ϫ0.03ϫ0.03 mm; θ range for data
collection: 2.36–27.06°; reflections collected: 8356; independent re-
flections: 3199 [R(int) = 0.0358]; refinement method: full-matrix
least squares on F2; data/restraints/parameters: 3199/0/211; good-
ness-of-fit on F2: 1.039; final R indices [IϾ2σ(I)]: R1 = 0.1100,
wR2 = 0.2404; R indices (all data): R1 = 0.1625, wR2 = 0.2814.
2Ј,2ЈЈ,2ЈЈЈЈ,2ЈЈЈЈЈ,2ЈЈЈЈЈЈЈ,2ЈЈЈЈЈЈЈЈ-Hexahydroxy-1,1Ј:3Ј,1ЈЈ:3ЈЈ,
1ЈЈЈ:4ЈЈЈ,1ЈЈЈЈ:3ЈЈЈЈ,1ЈЈЈЈЈ:3ЈЈЈЈЈ,1ЈЈЈЈЈЈ:4ЈЈЈЈЈЈ,1ЈЈЈЈЈЈЈ:3ЈЈЈЈЈЈЈ,
1ЈЈЈЈЈЈЈЈ:3ЈЈЈЈЈЈЈЈ,1ЈЈЈЈЈЈЈЈЈ-decaphenyl [L(OH)6]: The reaction was
conducted under nitrogen. Compound 8 (41 mg, 4.35ϫ10–5 mol)
was dissolved in anhydrous CH2Cl2 (10 mL). At –78 °C, BBr3 (1 m
in CH2Cl2, 0.4 mL) was added to the solution. The resulting mix-
ture was allowed to come to room temperature and stirred for 54 h.
Water (30 mL) and dichloromethane (60 mL) were then added. The
organic layer was isolated, dried with MgSO4, and concentrated
under reduced pressure. The resulting solid was then taken up with
THF and precipitated with pentane to afford a poorly soluble com-
pound as yellowish solid. L(OH)6 was obtained in 76% yield. M.p.
4,4ЈЈЈ-Dibromo-2Ј,2ЈЈ-dimethoxy-1,1Ј:3Ј,1ЈЈ:3ЈЈ,1ЈЈЈ-tetraphenyl (7):
The reaction was conducted under nitrogen. A degassed toluene
solution (8 0 mL) of 1- brom o- 4- io do be nz en e ( 5. 62 g,
19.8ϫ10–3 mmol) was placed in a 250 mL two-necked round-bot-
tomed flask. Pd(PPh3)4 (3.6 mol-%) was then added, and a de-
gassed aqueous solution of Na2CO3 (15 mL, 1 m) and a degassed
solution of 2,2Ј-dimethoxy-1,1Ј-biphenyl-3,3Ј-bis(boronic acid)
(0.5 g, 1.66 mmol) in methanol (30 mL) were transferred into the
mixture by cannula. The resulting solution was heated to 120 °C
and left for 22 h. After 6 h of heating, a further quantity of
Pd(PPh3)4 (1.4 mol-%) was added to the reaction mixture. The
solution was cooled to room temperature, and then water (150 mL)
and dichloromethane (150 mL) were added. The organic layer was
isolated, dried with MgSO4, and concentrated under reduced pres-
sure. The crude product was purified on silica gel (Ø = 3.5 cm, l =
30 cm; pentane/CH2Cl2, 70:30) to yield a white solid (59%). M.p.
177 °C. 1H NMR (300 MHz, CDCl3): δ = 7.61–7.49 (complex, 8
H), 7.37–7.32 (complex, 4 H), 7.23–7.20 (complex, 2 H), 3.25 (s, 6
H, OMe) ppm. 13C NMR (75 MHz, CDCl3): δ = 137.7, 134.1,
133.0, 131.5, 131.4, 131.0, 130.5, 124.0, 121.5, 60.8, 29.9 ppm. IR:
1
Ͼ270 °C. H NMR (400 MHz, [D8]THF): δ = 7.90 (2 br. s, 4 H),
7.78 (br. s, 2 H), 7.73 (s, 8 H), 7.66 (multiplet, 4 H), 7.4 (complex,
8 H), 7.25 (complex, 10 H), 7.15 (complex, 6 H) ppm. 13C NMR
(75 MHz, [D8]THF): δ = 149.8, 135.3, 129.2, 128.3, 127.6, 127.3,
126.0, 125.9, 125.5, 125.4, 125.4, 124.6, 123.1, 118.6 ppm. IR: ν =
˜
3496, 3375, 2956, 2926, 1440, 1426, 1359, 1247, 1214, 1181, 1172,
1130, 1086 cm–1. HRMS (ESI): calcd. for C60H42NaO6 [M]+
881.287, found 881.291. C60H42O6 (858.30)·2CH2Cl2: calcd. C
72.38, H 4.51; found C 73.44, H 6.17.
Optimized One-Pot Procedure: The reaction was conducted under
nitrogen. 1,4-Dibromobenzene (260 mg, 1.1 10–3 mol) and bromo-
benzene (0.240 mL, 2.27 10–3 mol) in toluene (80 mL) were placed
in a three-necked flask (250 mL), followed by Pd(PPh3)4 (140 mg).
An aqueous solution of Na2CO3 (30 mL, 1 m) and a solution of 6
(1 g, 0.003 mol) in methanol (60 mL) were then transferred into the
mixture by cannula. The reaction mixture was heated at 50 °C for
5 h, and further Pd(PPh3)4 (70 mg) was added. The reaction was
monitored by TLC analysis (SiO2; n-pentane/CH2Cl2,50:50), and
after a total of 48 h, the mixture was allowed to come to room
temperature and filtered through Celite. Next, dichloromethane
ν = 2931, 1490, 1454, 1415, 1385, 1227, 1173, 1075, 1009 cm–1. MS
˜
(ES): calcd. for [M + H]+ 524.988, found 525.030; calcd. for [M +
Na]+ 546.970, found 547.014; calcd. for [M + K]+ 562.944, found
563.229. C26H20Br2O2 (521.98): calcd. C 59.57, H 3.85; found C
60.11, H 3.83. X-ray data for 7: empirical formula: C26H20Br2O2;
formula mass: 524.24; crystal system: monoclinic; space group: C2/
Eur. J. Org. Chem. 2010, 6949–6956
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6955

P. Mobian et al.
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(50 mL) and methanol (60 mL) were added. The organic layer was
isolated, dried with Na2CO3, and concentrated under reduced pres-
sure. Compounds 9, 5, and 8 were isolated by purification by silica
gel chromatography (Ø
=
5.5 cm,
l
=
25 cm; pentane/
CH2Cl2,50:50). 9: 19% yield, Rf
=
0.52 (SiO2; pentane/
CH2Cl2,50:50); 5: 11%, Rf = 0.37 (SiO2; pentane/CH2Cl2, 50:50);
8: 9%, Rf = 0.33 (SiO2; pentane/CH2Cl2,50:50).
Acknowledgments
This work was done at the Université de Strasbourg with public
funds allocated by the Centre National de la Recherche Scientifique
and the French government.
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Received: July 26, 2010
Published Online: October 29, 2010
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