End-Capping Groups for Small-Molecule Organic Semiconducting Materials: Synthetic Investigation and Photovoltaic Applications through Direct C–H (Hetero)arylation

Article abstract of DOI:10.1002/ejoc.201601257

A Pd-catalyzed C–H (hetero)arylation methodology has been optimized for the efficient synthesis of various useful end-capping groups that are widely applied in small-molecule optoelectronic materials. We report herein the synthesis of a broad scope of target molecules ranging from donor-type through acceptor-type to hybrid-type end-capping groups. To demonstrate their application in dye-sensitized solar cells, we have designed two new D–A–π–A′-type organic sensitizers (CYL-3 and CYL-4), which were synthesized in a step-economic manner by sequential C–H arylations using the facilely obtained end-capping groups. The devices based on CYL-3 and CYL-4 give V_ocvalues of 0.67–0.71 V, J_scvalues of 10.07–11.63 mA cm^–2, and FF values of 70.6–72.9 %, which correspond to overall power conversion efficiencies of 4.76–6.02 %. This work is expected to become a practical synthetic alternative allowing materials scientists to access small-molecule organic materials in fewer synthetic transformations.

Full text of DOI:10.1002/ejoc.201601257

A Journal of
Accepted Article
Title: End-Capping Groups for Small-Molecule Organic Semiconducting Materials:
Synthetic Investigation and Photovoltaic Applications through Direct C-H (He-
tero)arylations
Authors: Te-Jui Lu; Po-Han Lin; Kun-Mu Lee; Ching-Yuan Liu
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201601257
Link to VoR: http://dx.doi.org/10.1002/ejoc.201601257
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European Journal of Organic Chemistry
10.1002/ejoc.201601257
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End-Capping Groups for Small-Molecule Organic Semiconducting
Materials: Synthetic Investigation and Photovoltaic Applications
through Direct C-H (Hetero)arylations
Te-Jui Lu,[a] Po-Han Lin,[a] Kun-Mu Lee,[a], [b] and Ching-Yuan Liu*[a]
Abstract: A Pd-catalyzed C-H (hetero)arylation methodology is well
optimized for the efficient synthesis of various useful end-capping
groups that are widely applied in small-molecule optoelectronic
materials. This report provides a broad substrate scope of target
molecules ranging from donor-type through acceptor-type to hybrid-
type end-capping groups. To demonstrate applications as dye-
sensitized solar cells (DSSCs), we design two new DAA’ type
organic sensitizers (CYL-3 and CYL-4) which are step-economically
synthesized via sequential C-H arylations using the facilely obtained
end-capping groups. The devices based on CYL-3~4 give a Voc of
0.67~0.71 V, a Jsc of 10.07~11.63 mA/cm2, and a FF of 70.6~72.9%,
corresponding to an overall power conversion efficiency (PCE) of
4.76~6.02%. This work is expected to become a practical synthetic
alternative aiming to guide material scientists to access small-
molecule organic materials with less synthetic transformations.
Introduction
Since
past
two
decades,
organic
molecule-based
semiconductors have shown their significance and broad
applicability in the fabrication of various optoelectronic devices
such as organic photovoltaic cells (OPVCs), organic field-effect
transistors (OFETs), and organic light-emitting diodes (OLEDs).[1]
These organic materials attracted considerable attention not
only in academic world but also in industry research because
they present distinguishing characteristics including lower cost,
simpler fabrication process, and higher mechanical flexibility.
Particularly, in contrast to -conjugated polymers, small-
molecule organic semiconductors are of unique importance in
modern organic electronics owing to their diverse molecular
design, well-defined conjugation lengths, and easier
modifications of functional groups.[2] As shown in Figure 1, we
listed a number of symmetrical and unsymmetrical small-
molecule semiconducting materials that possess three
representative molecular configurations of DAD (a[3], b[4]),
A’AA’ (c[5], d[6]), and DA types (e[7], f[8]), respectively.
In general, these materials were built by the assembly of an
appropriate core group with end groups through the mature and
reliable cross-coupling techniques such as Suzuki and Stille
reactions.[3-8] Moreover, we noted that material scientists have
Figure 1. The end groups of small-molecule organic semiconducting
materials.
devoted themselves to discovering new core groups in order to
improve device performances, focusing especially on the study
of electron-deficient ones. For instance, thienopyrrolediones
(TPD),[9] diketopyrrolopyrroles (DPP),[10] and thiazolothiazoles
(TzTz)[11] were often used as core-type building blocks in
functional materials. However, to the best of our knowledge,
synthetic studies concerning the design and economical
synthesis of the equally important end groups have yet
appeared to date. Taking N,N-diphenyl-4-(thiophen-2-yl)aniline
(3a) as example (Scheme 1), even though it has been shown to
be an efficient hole-transporting end unit for the photovoltaic
devices,[12] synthetic methods reported to date to access 3a
mainly relied on traditional cross-couplings, which cannot avoid
the preparation and treatment of air-sensitive or toxic
organometallic reagents.[12], [13] Therefore, we report herein an in-
[a]
Prof. Dr. C.-Y. Liu, T.-J. Lu, P.-H. Lin
Department of Chemical and Materials Engineering
National Central University
Jhongli District, Taoyuan City, Taiwan 320 (R.O.C)
TEL: (+886) 3-422-7151 ext.34217
E-mail: cyliu0312@ncu.edu.tw
depth
synthetic
investigation
of
Pd-catalyzed
C-H
(hetero)arylations[14] that targets on the efficient synthesis of
various useful end groups. This work includes the optimization of
reaction parameters as well as the exploration of a broad
substrate scope ranging from donor-type (D) through acceptor-
type (A) to hybrid-type (DD, DA, AA) end groups.
[b]
Prof. Dr. K.-M. Lee
Research Center for New Generation Photovoltaics
(RCNPV)
National Central University
Jhongli District, Taoyuan City, Taiwan 320 (R.O.C)
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European Journal of Organic Chemistry
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Table 1. Optimization of the Pd-catalyzed direct C-H monoarylation of
thiophene (1a) with 4-bromotriphenylamine (2a).[a]
Yield
entry
ligand
base
(%)[d]
71
51
58
56
57
24
54
59
58
51
50
52
trace
33
66
65
12
0
1
2
P(adamantyl)2(n-Bu)
P(t-Bu)3•HBF4
P(CH3)(t-Bu)2•HBF4
PCy3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
Cs2CO3
K3PO4
LiOt-Bu
─
3
Scheme 1. Accessing the versatile hole-transport material (3a) by Stille
4
reaction or direct C-H arylation.
5
PPh3
6
P(o-tolyl)3
7
P(p-tolyl)3
Results and Discussion
8
XPhos
9
SPhos
Firstly, optimization of reaction conditions was carried out using
thiophene (1a) and 4-bromotriphenylamine (2a) as C-H arylation
substrates (Table 1). Prior to the synthetic study shown in Table
1, we performed a pre-screening of ligands in nonpolar toluene.
Among various kinds of ligands, P(adamantyl)2(n-Bu) was
shown to be efficient and product 3a was isolated in 52% yield
(pre-screening results were summarized in Table S1 in
Supporting Information). More importantly, when the C-H
arylation was conducted in polar solvent (DMF) under identical
conditions, a promising yield of 3a was obtained (71%, Table 1,
entry 1). Therefore, we fixed on the use of DMF as primary
reaction solvent for subsequent ligand and base screenings.
From monodentate- through bidentate ligands, it appeared that
P(adamantyl)2(n-Bu) was still the most effective one for the
monoarylation of 1a (trace to 71%, entries 1-13). Less basic
Na2CO3 led to a low yield of 3a (33%, entry 14), while Cs2CO3
and K3PO4 gave the moderate yields (65-66%, entries 15-16).
Stronger base such as LiOt-Bu was inefficient for the C-H
arylation and a poor yield of 3a was obtained (12%, entry 17). In
the absence of base, no reaction occurred and both starting
materials were recovered (entry 18). Finally, even though the
amount of PivOH or K2CO3 was doubled, we found no
considerable alterations in the isolated yields (68-69%, entries
19-20, compared with the yield of entry 1). In each entry of Table
1, we observed the symmetrical byproduct (triphenylamine-
thiophene-triphenylamine) that has been generated via
diarylations of 1a. This side-reaction could be inhibited by an
excess loading of 1a (5 equiv.).
10
11
12
13
14
15
16
17
18
19[b]
20[b],[c]
dppe
dppf
bipyridyl
phenanthroline
P(adamantyl)2(n-Bu)
P(adamantyl)2(n-Bu)
P(adamantyl)2(n-Bu)
P(adamantyl)2(n-Bu)
P(adamantyl)2(n-Bu)
P(adamantyl)2(n-Bu)
P(adamantyl)2(n-Bu)
K2CO3
K2CO3
68
69
[a]
Unless otherwise noted, the monoarylation was conducted with
thiophene (1a) (5.0 mmol) and 4-bromotriphenylamine (2a) (1.0 mmol) in
the presence of Pd(OAc)2 (0.05 mmol), ligand (0.1 mmol), pivalic acid
(PivOH, 0.3 mmol), and base (1.5 mmol) in N,N-dimethylformamide
o
[b]
(DMF, 2 mL) at 110 C for 12 h. The amount of PivOH was doubled
[c]
(0.6 mmol). The amount of K2CO3 was doubled (3.0 mmol)
yields.
.
[d] Isolated
55% yield. C-H arylation with 1-bromopyrene (2i) also
proceeded smoothly to give 3i in 62% yield. In general, reaction
of thiophene with 2-bromo-5-alkyl(thio)thiophenes (2j-l) gave
relatively lower yields (40-45%, 3j-l). This is due to the formation
of undesired debromination byproducts[16] from bromothiophenes
2j-l.
Investigation of substrate scope with respect to the donor-type
(hetero)aryl bromides was carried out using the optimum
reaction conditions: Pd(OAc)2 (5 mol%), P(adamantyl)2(nBu) (10
mol%), PivOH (30 mol%), and K2CO3 (1.50 equiv.) in DMF at
110 oC for 12 h. As shown in Table 2, firstly we examined some
representative hole-transport materials (HTM)[15] including alkyl-
substituted triphenylamines (2b-c) and two different kinds of
carbazoles (2d-e, 2f-g), producing the desired donor-type end
groups in moderate to good isolated yields (43-78%, 3b-g).
(Diphenylamino)fluorene (2h), another important class of HTM,
was successfully coupled with thiophene to afford product 3h in
Subsequently, examination of the substrate scope was
extented to the electron-deficient (hetero)aryl bromides (4a-n)
(Table 3). Fluoro-substituted arenes have been proved essential
as electron-withdrawing end groups when designing N-channel
organic field-effect transistors (OFETs).[17] Under optimum
reaction conditions, we efficiently synthesized five acceptor-type
end
groups
that
own
monofluoro-,
trifluoromethyl-,
trifluoroacetyl-, or pentafluoro-benzene as electron-withdrawing
part (35-66%, 5a-e). Separation of the desired products 5d-e
from their corresponding diarylated adducts was found to be
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European Journal of Organic Chemistry
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Table 2. Substrate scope: synthesis of various donor-type end groups.[a]
Table 3. Substrate scope: synthesis of various acceptor-type end
groups.[a]
[a] Unless otherwise noted, the monoarylation was conducted under the
[b]
[c]
[a]
optimum reaction conditions shown in Table 2.
Isolated yields.
Unless otherwise noted, the monoarylation was conducted with
Reaction time: 6 h. [d] Reaction temperature: 80 oC.
thiophene (1a) (5.0 mmol) and (hetero)aryl bromides (2b-l) (1.0 mmol) in
the presence of Pd(OAc)2 (0.05 mmol), P(adamantyl)2(n-Bu) (0.1 mmol),
pivalic acid (PivOH, 0.3 mmol), and K2CO3 (1.5 mmol) in N,N-
dimethylformamide (DMF, 2 mL) at 110 oC for 12 h. [b] Isolated yields.
(EDOT) (1b), N-methyl pyrrole (1c), and selenophene (1d)
underwent C-H arylations with different kinds of (hetero)aryl
bromides respectively, producing the (DD)-type (6a, 6c, 6e)
and (DA)-type (6b, 6d, 6f) end groups in 51-71% yields. On the
other hand, the arylation was examined by the employment of
electron-deficient heteroarenes (thieno[3,4-c]pyrrole-4,6-dione:
1e; dimethyl thiophene-3,4-dicarboxylate: 1f). Recently, our
group[22] and Kanbara[23] et al. reported that the C-H arylations or
copolymerizations of electron-deficient heteroarenes were best
performed in low-polarity organic solvents. Therefore, the
following reactions were conducted both in polar DMF and
nonpolar toluene in order to investigate the solvent effect on the
direct C-H monoarylation of substrates 1e-f. Interestingly, we
found that there were no significant yield differences when the
electron-donating aryl bromides (2f, 2a) were used (6g: 75% in
DMF vs.78% in toluene; 6i: 65% in DMF vs. 77% in toluene),
whereas the C-H heteroarylation of 1e or 1f with electron-
deficient coupling partners (4d, 4g) was found inefficient in polar
solvent (DMF) thus leading to substaintial yield differences in the
cases of 6h and 6j (6h: trace in DMF vs.68% in toluene; 6j: 29%
in DMF vs. 63% in toluene).
inefficient thus leading to the unsatisfactory yields of 35-36%.[18]
Next on, the aldehyde-terminated end groups were obtained in
moderate yields (45-65%, 5f-i), in which case the –CHO
functionality of molecules 5f-i can be further converted into
cyanoacetic acid as anchoring group for TiO2 attachments in
dye-sensitized solar cells (DSSCs). Interestingly, the nitrogen-
containing end groups such as products 5j-l (68-77%) were also
employed as effective anchoring groups in DSSCs.[19] Finally,
end groups terminated with
a nitrile or 2-ethylhexyl 2-
cyanoacrylate were facilely prepared by present strategy (78%,
21%; 5m, 5n). These molecules were frequently applied in
small-molecule organic photovoltaic cells (OPVCs).[20] In the
case of 5n, we found a large amount of byproduct resulted from
the hydrolysis of the cyanoacrylate moiety (aldehyde group
obtained) thus leading to the poor yield of desired 5n.[21]
Therefore, the better way to access end group 5n would be
employing product 5f as starting material and transforming its
aldehyde group into alkyl 2-cyanoacrylate by condensation
reactions.
To shed light on the application of our methodology in dye-
sensitized solar cells (DSSCs), we designed two new DAA’
type sensitizers utilizing the facilely obtained end-capping
As shown in Table 4, we further extended the reaction scope
by testing various heteroarenes (1b-f) under optimum conditions.
Electron-rich heteroaryls such as 3,4-ethylenedioxythiophene
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European Journal of Organic Chemistry
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Table 4. Substrate scope: synthesis of various hybrid-type end groups.[a]
[a] Unless otherwise noted, the monoarylation was conducted under the
[b]
[c]
optimum reaction conditions shown in Table 2.
Isolated yields.
Reaction time: 6 h. [d] Reactions were conducted in toluene.
groups (Scheme 2). 2-Ethylhexyl-substituted TPD (7) was
employed as internal acceptor that underwent sequential C-H
heteroarylations with the donor- and acceptor-type end groups
respectively (8a/8b and 9a/9b obtained by NBS brominations)
under the optimum conditions shown in Table 2. This led to the
formation of the aldehyde-terminated oligoaryls 11a-b in 74-75%
yields (monoarylated intermediates 10a-b were isolated in 50-
52%). Traditionally, accessing these DSSCs-oriented aldehyde
precursors (11a-b) would take at least 14 synthetic
transformations including the preparation of both end-capping
groups. However, combining our previously reported step-saving
synthetic strategy involving C-H arylations as key steps for
DAA’ organic dyes[24] with present method for end-group
synthesis rendered the access to 11a-b much more succinct
(shortened to 6 steps). Conversion of the aldehydes into
anchoring groups by Knoevenagel condensations afforded
target sensitizers CYL-3~4 in 75-83% yields.
Scheme 2. Application of end-capping groups in DSSCs: facile synthesis
of new DAA’ organic sensitizers via sequential C-H heteroarylations.
The optical and electrochemical properties of CYL-3 and CYL-
4 were investigated and the results were summaried in Table 5.
In THF solutions, CYL-3 and CYL-4 exhibited similar molar
extinction coefficients (ɛ = 27299 M-1cm-1 for CYL-3; ɛ = 26880 M-
1cm-1 for CYL-4). When absorbed on TiO2 films, two sensitizers
were all blue-shifted by 19~25 nm (19 nm for CYL-3; 25 nm for
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European Journal of Organic Chemistry
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CYL-4). This result was attributable to the coordination of dye
molecules to titanium oxide. Both in solution and film states,
CYL-3 showed a more red-shifted maximum absorbance than
CYL-4 (In THF: λmax = 475 nm for CYL-3; λmax = 462 nm for
CYL-4 / On TiO2: λmax = 456 nm for CYL-3; λmax = 437 nm for
CYL-4), implying that the triphenylamine moiety of CYL-3 has
superior electron-donating ability than the carbazole unit of CYL-
4. In addition to the difference of λmax, CYL-3 also showed a
smaller optical band gap (Egopt = 1.85 eV for CYL-3; Egopt = 1.92
eV for CYL-4), indicating a more efficient intramolecular charge
transfer (ICT) was generated by triphenylamine in CYL-3.
Compared with CYL-3, CYL-4 was found to exhibit a lower-lying
HOMO energy level (EHOMO = -5.83 eV), probably owing to the
presence of the strong electron-withdrawing fluorine atom.
current conversion efficiency (IPCE) of both sensitizers, the
onset excitation wavelength of CYL-3 (>700 nm) was longer
than that of CYL-4, which was attributed to the more electron-
donating triphenylamine moiety, thus leading to a higher Jsc.
However, under visible light excitation wavelengths (400~700
nm), two sensitizers showed nearly identical IPCE. Based on
above DSSCs perfomance characterizations (summarized in
Table 6), CYL-3 gave a Voc of 0.71 V, a Jsc of 11.63 mA/cm2,
and a fill factor (FF) of 72.9%, corresponding to a superior power
conversion efficiency (PCE) of 6.02 %.
(2A)
Table 5. UV-Vis absorption and electrochemical properties of sensitizers
CYL
-
3
and CYL-4.
opt
λmax

λmax on TiO2 Eg
E1/2 EHOMO/ELUMO
[nm][a] [M-1cm-1][a]
[nm][a]
456
[eV][b] [V][c] [eV][d]
Dyes
CYL-3 475
CYL-4 462
27299
26880
1.85
1.92
1.07 -5.77/-3.92
1.13 -5.83/-3.90
437
[a] Measured in THF solutions (~10-5 M); : extinction coefficient. [b] The optical
band gap, Egopt, was calculated by 1240/λonset (dyes on TiO2 films). [c] The half-
wave potential, E1/2, was calculated by (Epa+Epc)/2, where Epa and Epc are the
potential energy of anodic and cathodic peaks, respectively; The
measurements are conducted in THF solutions (~10-4 M) containing (n-
C4H9)4NPF6 as a supporting electrolyte under a scan rate of 100 mVs-1. [d] The
(2B)
HOMO energy level, EHOMO, was calculated by –[(E1/2 + 0.197)vs.NHE + 4.500]
opt
eV; ELUMO = EHOMO + Eg
.
Subsequently, dye-sensitized solar cells were fabricated using
CYL-3 and CYL-4 as sensitizers (procedures for solar cells
fabrication and characterization were detailed in Supporting
Information). The photovoltaic parameters are summarized in
Table 6 and illustrated in Figure 2. As shown in Figure 2A
(photocurrent density vs. voltage), sensitizer CYL-3 displayed
higher short-circuit current (Jsc) and open-circuit voltage (Voc).
CYL-3 and CYL-4 possess identical alkyl chains (2-ethylhexyl
groups) to prevent aggregation on TiO2, thus leading to a little
difference in Voc. Figure 2B demonstrated the incident photon-to-
Figure 2. Photovoltaic characteristics of CYL-3 and CYL-4: (2A)
photocurrent density vs. photovoltage; (2B) incident photon-to-
current conversion efficiency (IPCE).
Table 6. Photovoltaic parameters of DSSCs fabricated using CYL-3
and CYL- .
Conclusions
4 [a], [b]
Voc [V]
Jsc [mA/cm2]
FF [%]
PCE [%]
DSSCs
CYL-3
CYL-4
In summary, we have developed a step-saving synthetic
approach for the facile preparation of various useful end-capping
groups that are essential components in small-molecule organic
semiconducting materials. Under optimum reaction conditions, a
broad range of target molecules including donor-type, acceptor-
type and hybrid-type end groups were successfully synthesized
in moderate to good isolated yields. Moreover, via using these
readily available end groups, we efficiently prepared new
DAA’ type organic sensitizers (CYL-3 & CYL-4) that were
fabricated as dye-sensitized solar cells (DSSCs). Photovoltaic
characterizations of the devices based on CYL-3 & CYL-4
demonstrated the power conversion efficiencies (PCEs) of
4.76%~6.02%. Design and efficient synthesis of new end-
0.71
0.67
0.69
11.63
10.07
14.75
72.9
70.6
69.5
6.02
4.76
7.90
Z907
[a]
Irradiation light source: AM 1.5G solar simulator (100 mW/cm2);
Photo-electrode (working electrode): TiO2 film was composed of 16 μm
thick mesoporous anatase-TiO2 nanoparticles with a diameter of 20 nm
and has an active area of 0.160 cm2; Electrolyte solution: a mixture of 0.6
M 1-butyl-3-methylimidazolium iodide ([bmim][I]), 0.1 M LiI, 0.05 M I2, 0.1
M guanidinium thiocyanate (GuNCS) and 0.5 M 4-t-butylpyridine (TBP)
[b]
in acetonitrile.
Chenodeoxycholic acid (CDCA) was added as co-
adsorbent (1.0 mM for CYL-3; 1.0 mM for CYL-4).
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European Journal of Organic Chemistry
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FULL PAPER
capping molecules via direct C-H (hetero)arylations and their
applications as optoelectronic devices are currently underway in
our laboratory.
mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according
to the general procedure B and yielding after column chromatography
(hexanes) the pure product 3c (330 mg, 75 %). A transparent viscous
1
liquid. H NMR (CD2Cl2, 300 MHz, ppm): δ 7.63-7.50 (comp, 2 H), 7.38-
7.25 (comp, 4 H), 7.24-7.05 (comp, 10 H), 2.64 (d, J = 7.0 Hz, 2 H), 1.77-
1.63 (m, 1 H), 1.53-1.36 (comp, 8 H), 1.15-0.94 (comp, 6 H); 13C NMR
(CD2Cl2, 75 MHz, ppm): δ 148.4, 148.2, 145.6, 145.0, 137.9, 130.8,
129.9, 128.71, 128.68, 127.2, 125.5, 124.7, 124.5, 123.8, 123.4, 122.8,
41.8, 40.2, 33.1, 29.6, 26.2, 23.8, 14.7, 11.4; MS (EI, 70 eV): 439 (M+,
55 %), 340 (100 %), 262 (4 %), 115 (4 %), 57 (8 %); HRMS (EI): calcd.
for C30H33NS: 439.2334, found: 439.2335.
Experimental Section
General procedure B for Table 2: Substrate scope of the donor-type
aryl bromides
To a solution of Pd(OAc)2 (0.05 mmol), P(adamantyl)2(n-Bu) (0.10 mmol),
PivOH (0.30 mmol), and K2CO3 (1.50 mmol) in DMF (2 mL) in a flame-
dried Schlenk tube were added thiophene (1a) (5.00 mmol) and the
corresponding aryl bromides (2b-l) (1.00 mmol) under N2. The reaction
mixture was then heated at 110 °C under N2 for 12 h. After the reaction
mixture had cooled to room temperature, water (10 mL) was added. The
mixture was extracted with ethyl acetate (2 × 20 mL), and the combined
organic layers were washed with brine (50 mL), dried (Na2SO4) and
concentrated in vacuo. Purification by flash chromatography (ethyl
acetate/hexanes) yielded the desired products 3b-l.
Synthesis and characterization of (2c): To a solution of 4-(2-ethylhexyl)-
N,N-diphenylaniline (358 mg, 1.00 mmol) in CHCl3 (10 mL), N-
bromosuccinimide (180 mg, 1.01 mmol) was added portionwise. The
reaction mixture was then stirred at room temperature for 12 h before it
was diluted with water (10 mL). The mixture was extracted with
dichloromethane (2 × 20 mL), and the combined organic layers were
washed with aqueous NaHSO3 (30 mL) and brine (30 mL), dried
(Na2SO4) and concentrated in vacuo. Purification by flash
chromatography (hexanes) yielded the desired product 2c. A transparent
viscous liquid. 1H NMR (CDCl3, 300 MHz, ppm): δ 7.40-7.24 (comp, 4 H),
7.18-6.90 (comp, 9 H), 2.54 (d, J = 7.0 Hz, 2 H), 1.67-1.56 (m, 1 H), 1.46-
1.23 (comp, 8 H), 0.93 (app t, J = 7.2 Hz, 6 H); 13C NMR (CDCl3, 75 MHz,
ppm): δ 147.5, 147.2, 144.8, 137.3, 132.0, 130.1, 129.2, 124.7, 124.6,
124.0, 122.8, 114.2, 41.0, 39.5, 32.3, 28.8, 25.5, 23.0, 14.1, 10.8; MS (EI,
70 eV): 435 (M+, 33 %), 336 (100 %), 257 (12 %), 180 (9 %), 57 (9 %);
HRMS (EI): calcd. for C26H30BrN: 435.1562, found: 435.1557.
4-Dodecyl-N-phenyl-N-(4-(thiophen-2-yl)phenyl)aniline
(3b)
was
prepared from 1a (420 mg, 5.00 mmol), 4-bromo-N-(4-dodecylphenyl)-N-
phenylaniline (2b) (492 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol),
P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol),
K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the general
procedure B and yielding after column chromatography (hexanes) the
pure product 3b (298 mg, 60 %). A transparent viscous liquid. 1H NMR
(CD2Cl2, 300 MHz, ppm): δ 7.57-7.49 (comp, 2 H), 7.37-7.24 (comp, 4 H),
7.22-7.14 (comp, 4 H), 7.13-7.03 (comp, 6 H), 2.66 (t, J = 7.7 Hz, 2 H),
1.79-1.63 (comp, 2 H), 1.50-1.32 (comp, 18 H), 0.99 (t, J = 6.6 Hz, 3 H);
13C NMR (CD2Cl2, 125 MHz, ppm): δ 148.4, 148.2, 145.7, 145.0, 139.0,
130.0, 129.9, 128.73, 128.68, 127.2, 125.7, 124.8, 124.5, 123.8, 123.4,
122.8, 36.1, 32.7, 32.3, 30.5, 30.48, 30.46, 30.42, 30.35, 30.3, 30.2, 23.5,
14.7; MS (EI, 70 eV): 495 (M+, 100 %), 340 (40 %), 333 (27 %), 262
(28 %), 97 (10 %); HRMS (EI): calcd. for C34H41NS: 495.2960, found:
495.2965. Synthesis and characterization of (2b): To a solution of 4-
dodecyl-N,N-diphenylaniline (413 mg, 1.00 mmol) in CHCl3 (10 mL), N-
bromosuccinimide (180 mg, 1.01 mmol) was added portionwise. The
reaction mixture was then stirred at room temperature for 12 h before it
was diluted with water (10 mL). The mixture was extracted with
dichloromethane (2 × 20 mL), and the combined organic layers were
washed with aqueous NaHSO3 (30 mL) and brine (30 mL), dried
(Na2SO4) and concentrated in vacuo. Purification by flash
chromatography (hexanes) yielded the desired product 2b. A transparent
viscous liquid. 1H NMR (CDCl3, 300 MHz, ppm): δ 7.38-7.23 (comp, 4 H),
7.17-6.90 (comp, 9 H), 2.60 (t, J = 7.8 Hz, 2 H), 1.71-1.58 (comp, 2 H),
1.46-1.25 (comp, 18 H), 0.93 (t, J = 6.7 Hz, 3 H); 13C NMR (CDCl3, 125
MHz, ppm): δ 147.5, 147.2, 144.8, 138.4, 132.0, 129.3, 129.2, 124.8,
124.6, 124.0, 122.8, 114.2, 35.4, 31.9, 31.5, 29.68, 29.67, 29.65, 29.60,
29.5, 29.38, 29.35, 22.7, 14.1; MS (EI, 70 eV): 493 (M+, 92 %), 336
(100 %), 258 (14 %), 167 (10 %), 153 (8 %); HRMS (EI): calcd. for
C30H38BrN: 491.2188, found: 491.2195.
3,6-Di-t-butyl-9-(4-(thiophen-2-yl)phenyl)-9H-carbazole[25] (3d) was
prepared from 1a (420 mg, 5.00 mmol), 9-(4-bromophenyl)-3,6-di-t-butyl-
9H-carbazole (2d) (434 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol),
P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol),
K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the general
procedure B and yielding after column chromatography (hexanes) the
1
pure product 3d (342 mg, 78 %). A white solid; m.p.: 204.8-205.5 oC. H
NMR (CDCl3, 300 MHz, ppm): δ 8.20 (d, J = 1.7 Hz, 2 H), 7.84 (d, J = 8.4
Hz, 2 H), 7.60 (d, J = 8.4 Hz, 2 H), 7.52 (dd, J = 8.7, 1.7 Hz, 2 H), 7.45-
7.39 (comp, 3 H), 7.36 (d, J = 5.1 Hz, 1 H), 7.16 (dd, J = 5.1, 3.6 Hz, 1 H),
1.52 (s, 18 H); 13C NMR (CDCl3, 75 MHz, ppm):
143.5, 142.9, 139.1,
137.3, 133.0, 128.2, 127.1, 127.0, 125.1, 123.6, 123.4, 116.2, 109.2,
34.7, 32.0.
9-([2,2'-Bithiophen]-5-yl)-3,6-di-t-butyl-9H-carbazole[26]
(3e)
was
prepared from 1a (420 mg, 5.00 mmol), 9-(5-bromothiophen-2-yl)-3,6-di-
t-butyl-9H-carbazole (2e) (440 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05
mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30
mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the
general procedure
B and yielding after column chromatography
(hexanes) the pure product 3e (191 mg, 43 %). A white solid; m.p.:
1
188.6-190.8 oC. H NMR (CD2Cl2, 300 MHz, ppm): δ 8.16 (s, 2 H), 7.61-
7.45 (comp, 4 H), 7.30 (d, J = 5.0 Hz, 1 H), 7.25 (d, J = 3.7 Hz, 2 H),
7.19-7.03 (comp, 2 H), 1.48 (s, 18 H); 13C NMR (CD2Cl2, 75 MHz, ppm):
δ 144.4, 140.7, 138.5, 137.7, 135.7, 128.5, 125.45, 125.38, 124.6, 124.5,
124.1, 123.0, 116.9, 110.2, 35.3, 32.3
4-(2-Ethylhexyl)-N-phenyl-N-(4-(thiophen-2-yl)phenyl)aniline (3c) was
prepared from 1a (420 mg, 5.00 mmol), 4-bromo-N-(4-(2-
ethylhexyl)phenyl)-N-phenylaniline (2c) (436 mg, 1.00 mmol), Pd(OAc)2
(12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31
9-Hexyl-3-(thiophen-2-yl)-9H-carbazole (3f) was prepared from 1a (420
mg, 5.00 mmol), 3-bromo-9-hexyl-9H-carbazole (2f) (330 mg, 1.00 mmol),
This article is protected by copyright. All rights reserved

European Journal of Organic Chemistry
10.1002/ejoc.201601257
FULL PAPER
Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol),
PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2
mL) according to the general procedure B and yielding after column
chromatography (hexanes) the pure product 3f (210 mg, 63 %). A
transparent viscous liquid. 1H NMR (CD2Cl2, 300 MHz, ppm): δ 8.44 (d, J
= 1.8 Hz, 1 H), 8.22 (d, J = 7.3 Hz, 1 H), 7.80 (dd, J = 8.5, 1.8 Hz, 1 H),
7.61-7.40 (comp, 4 H), 7.39-7.26 (comp, 2 H), 7.18 (dd, J = 5.0, 3.6 Hz, 1
H), 4.29 (t, J = 7.2 Hz, 2 H), 1.99-1.80 (comp, 2 H), 1.49-1.30 (comp, 6
H), 0.95 (t, J = 6.9 Hz, 3 H); 13C NMR (CD2Cl2, 75 MHz, ppm): δ 146.4,
141.6, 140.6, 128.7, 126.6, 126.1, 124.7, 124.1, 123.8, 123.3, 122.6,
121.1, 119.6, 118.2, 109.7, 109.6, 43.6, 32.2, 29.5, 27.5, 23.2, 14.5; MS
(EI, 70 eV): 333 (M+, 88 %), 262 (100 %), 248 (12 %), 217 (6 %), 131
(5 %); HRMS (EI): calcd. for C22H23NS: 333.1551, found: 333.1550.
127.86, 127.7, 127.4, 127.3, 126.15, 126.07, 125.3, 125.0, 124.9, 124.7,
124.5.
5-Decyl-2,2'-bithiophene[29] (3j) was prepared from 1a (420 mg, 5.00
mmol), 2-bromo-5-decylthiophene (2j) (303 mg, 1.00 mmol), Pd(OAc)2
(12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31
mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according
to the general procedure B and yielding after column chromatography
(hexanes) the pure product 3j (123 mg, 40 %). A transparent liquid. 1H
NMR (CDCl3, 300 MHz, ppm): δ 7.18 (dd, J = 5.1, 1.0 Hz, 1 H), 7.13 (d, J
= 3.6 Hz, 1 H), 7.05-6.97 (comp, 2 H), 6.70 (d, J = 3.6 Hz, 1 H), 2.81 (t, J
= 7.6 Hz, 2 H), 1.78-1.65 (comp, 2 H), 1.41-1.27 (comp, 14 H), 0.93 (t, J
= 6.6 Hz, 3 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 145.3, 138.0, 134.7,
127.6, 124.6, 123.6, 123.3, 122.9, 31.9, 31.6, 30.1, 29.6, 29.5, 29.4, 29.3,
29.1, 22.7, 14.1.
9-(2-Ethylhexyl)-3-(thiophen-2-yl)-9H-carbazole (3g) was prepared
from 1a (420 mg, 5.00 mmol), 3-bromo-9-(2-ethylhexyl)-9H-carbazole
(2g) (358 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol),
P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol),
K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the general
procedure B and yielding after column chromatography (hexanes) the
pure product 3g (249 mg, 69 %). A transparent viscous liquid. 1H NMR
(CD2Cl2, 300 MHz, ppm): δ 8.40 (d, J = 1.9 Hz, 1 H), 8.19 (d, J = 7.7 Hz,
1 H), 7.78 (dd, J = 8.5, 1.9 Hz, 1 H), 7.59-7.38 (comp, 4 H), 7.34-7.24
(comp, 2 H), 7.16 (dd, J = 5.1, 3.6 Hz, 1 H), 4.18 (d, J = 7.6 Hz, 2 H),
2.20-2.02 (m, 1 H), 1.50-1.26 (comp, 8 H), 1.01-0.88 (comp, 6 H); 13C
NMR (CD2Cl2, 75 MHz, ppm): δ 146.3, 142.0, 141.1, 128.6, 126.5, 126.1,
124.6, 124.1, 123.7, 123.2, 122.5, 120.9, 119.6, 118.1, 110.0, 109.9,
48.0, 40.0, 31.6, 29.4, 25.0, 23.7, 14.4, 11.3; MS (EI, 70 eV): 361 (M+,
47 %), 262 (100 %), 248 (6 %), 228 (4 %), 207 (7 %); HRMS (EI): calcd.
for C24H27NS: 361.1864, found: 361.1861.
5-(2-Ethylhexyl)-2,2'-bithiophene (3k) was prepared from 1a (420 mg,
5.00 mmol), 2-bromo-5-(2-ethylhexyl)thiophene (2k) (275 mg, 1.00 mmol),
Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol),
PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2
mL) according to the general procedure B and yielding after column
chromatography (hexanes) the pure product 3k (125 mg, 45 %). A
1
transparent liquid. H NMR (CDCl3, 300 MHz, ppm): δ 7.18 (dd, J = 5.1,
1.0 Hz, 1 H), 7.14 (dd, J = 3.5, 1.0 Hz, 1 H), 7.06-6.99 (comp, 2 H), 6.70
(d, J = 3.5 Hz, 1 H), 2.77 (d, J = 6.7 Hz, 2 H), 1.70-1.57 (m, 1 H), 1.47-
1.31 (comp, 8 H), 1.01-0.90 (comp, 6 H); 13C NMR (CDCl3, 75 MHz,
ppm): δ 143.8, 138.0, 134.9, 127.6, 125.7, 123.6, 123.2, 122.9, 41.3,
34.1, 32.3, 28.8, 25.5, 23.0, 14.1, 10.8; MS (EI, 70 eV): 278 (M+, 98 %),
180 (100 %), 147 (28 %), 135 (34 %), 121 (26 %); HRMS (EI): calcd. for
C16H22S2: 278.1163, found: 278.1166.
9,9-Dihexyl-N,N-diphenyl-7-(thiophen-2-yl)-9H-fluoren-2-amine[27]
(3h) was prepared from 1a (420 mg, 5.00 mmol), 7-bromo-9,9-dihexyl-
N,N-diphenyl-9H-fluoren-2-amine (2h) (581 mg, 1.00 mmol), Pd(OAc)2
(12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31
mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according
to the general procedure B and yielding after column chromatography
(hexanes) the pure product 3h (321 mg, 55 %). A pale green solid; m.p.:
5-(Dodecylthio)-2,2'-bithiophene[30] (3l) was prepared from 1a (420 mg,
5.00 mmol), 2-bromo-5-(dodecylthio)thiophene (2l) (363 mg, 1.00 mmol),
Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol),
PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2
mL) according to the general procedure B and yielding after column
chromatography (hexanes) the pure product 3l (154 mg, 42 %). A white
1
solid; m.p.: 47.0-47.8 oC. H NMR (CDCl3, 500 MHz, ppm): δ 7.21 (dd, J
o
100.5-102.0 C. 1H NMR (CDCl3, 300 MHz, ppm): δ 7.72-7.52 (comp, 4
= 5.1, 1.0 Hz, 1 H), 7.14 (dd, J = 3.5, 1.0 Hz, 1 H), 7.07-6.98 (comp, 3 H),
2.81 (t, J = 7.4, 2 H), 1.71-1.60 (comp, 2 H), 1.42-1.22 (comp, 18 H), 0.89
(t, J = 6.9 Hz, 3 H); 13C NMR (CDCl3, 125 MHz, ppm): δ 140.4, 137.1,
134.1, 134.0, 127.8, 124.5, 123.75, 123.73, 38.9, 31.9, 29.63, 29.62,
29.57, 29.5, 29.4, 29.3, 29.1, 28.4, 22.7, 14.1. Synthesis and
characterization of (2l): To a solution of 2-(dodecylthio)thiophene (1425
mg, 5.00 mmol) in the cosolvent of CH2Cl2 (15 mL) and AcOH (10 mL),
N-bromosuccinimide (890 mg, 5.00 mmol) was added portionwise. The
reaction mixture was then stirred at room temperature for 12 h before it
was diluted with water (30 mL). The mixture was extracted with
dichloromethane (2 × 50 mL), and the combined organic layers were
washed with aqueous NaHSO3 (100 mL) and brine (100 mL), dried
(Na2SO4) and concentrated in vacuo. Purification by flash
chromatography (hexanes) yielded the desired product 2l. A transparent
liquid. 1H NMR (CDCl3, 300 MHz, ppm): δ 6.92 (d, J = 3.8 Hz, 1 H), 6.88
(d, J = 3.8 Hz, 1 H), 2.75 (t, J = 7.3 Hz, 2 H), 1.66-1.55 (comp, 2 H), 1.41-
1.23 (comp, 18 H), 0.89 (t, J = 6.7 Hz, 3 H); 13C NMR (CDCl3, 125 MHz,
ppm): δ 136.3, 134.1, 130.3, 113.7, 39.1, 31.9, 29.61, 29.55, 29.5, 29.34,
29.33, 29.1, 28.3, 22.7, 14.1; MS (EI, 70 eV): 364 (M+, 21 %), 196 (55 %),
H), 7.40 (d, J = 2.9 Hz, 1 H), 7.36-7.25 (comp, 5 H), 7.25-7.12 (comp, 6
H), 7.12-6.99 (comp, 3 H), 1.92 (d, J = 9.2 Hz, 4 H), 1.26-1.00 (comp, 12
H), 0.90-0.58 (comp, 10 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 152.3,
151.4, 148.0, 147.2, 145.3, 140.5, 135.8, 132.4, 129.1, 128.0, 124.9,
124.3, 123.8, 123.6, 122.6, 122.5, 120.4, 120.0, 119.4, 119.3, 55.1, 40.3,
31.5, 29.6, 23.7, 22.5, 14.0.
2-(Pyren-1-yl)thiophene[28] (3i) was prepared from 1a (420 mg, 5.00
mmol), 1-bromopyrene (2i) (281 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05
mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30
mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the
general procedure
B and yielding after column chromatography
(hexanes) the pure product 3i (176 mg, 62 %). A pale yellow solid; m.p.:
o
69.5-72.0 C. 1H NMR (CDCl3, 300 MHz, ppm): δ 8.53 (d, J = 9.3 Hz, 1
H), 8.25-7.99 (comp, 8 H), 7.55 (dd, J = 5.1, 1.1 Hz, 1 H), 7.41 (dd, J =
3.5, 1.1 Hz, 1 H), 7.29 (dd, J = 5.1, 3.5 Hz, 1 H); 13C NMR (CDCl3, 75
MHz, ppm): δ 142.5, 131.4, 130.95, 130.90, 129.7, 129.1, 128.4, 127.90,
This article is protected by copyright. All rights reserved

European Journal of Organic Chemistry
10.1002/ejoc.201601257
FULL PAPER
114 (41 %), 71 (52 %), 57 (100 %); HRMS (EI): calcd. for C16H27BrS2:
362.0738, found: 362.0740.
mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the
general procedure C and yielding after column chromatography (ethyl
acetate : hexanes = 20 : 80) the pure product 5d (92 mg, 36 %). A pale
yellow solid; m.p.: 92.5-94.0 oC. 1H NMR (CDCl3, 300 MHz, ppm): δ 8.07
(d, J = 8.3 Hz, 2 H), 7.75 (d, J = 8.3 Hz, 2 H), 7.49 (d, J = 3.7 Hz, 1 H),
7.43 (dd, J = 5.1, 0.6 Hz, 1 H), 7.15 (dd, J = 5.1, 3.7 Hz, 1 H); 13C NMR
(CDCl3, 75 MHz, ppm): δ 179.5 (q, 2JC-F = 34.8 Hz), 142.0, 141.0, 130.9,
128.6, 128.2, 127.6, 125.8, 125.6, 116.7 (q, 1JC-F = 289.5 Hz); MS (EI, 70
eV): 256 (M+, 40 %), 187 (100 %), 159 (18 %), 115 (93 %), 69 (34 %);
HRMS (EI): calcd. for C12H7F3OS: 256.0170, found: 256.0174.
General procedure C for Table 3: Substrate scope of the acceptor-
type aryl bromides
To a solution of Pd(OAc)2 (0.05 mmol), P(adamantyl)2(n-Bu) (0.10 mmol),
PivOH (0.30 mmol), and K2CO3 (1.50 mmol) in DMF (2 mL) in a flame-
dried Schlenk tube were added thiophene (1a) (5.00 mmol) and the
corresponding aryl bromides (4a-n) (1.00 mmol) under N2. The reaction
mixture was then heated at 110 °C under N2 for 6-12 h. After the reaction
mixture had cooled to room temperature, water (10 mL) was added. The
mixture was extracted with ethyl acetate (2 × 20 mL), and the combined
organic layers were washed with brine (50 mL), dried (Na2SO4) and
concentrated in vacuo. Purification by flash chromatography (ethyl
acetate/hexanes) yielded the desired products 5a-n.
2-(Pentafluorophenyl)thiophene[33] (5e) was prepared from 1a (420 mg,
5.00 mmol), 1-bromo-2,3,4,5,6-pentafluorobenzene (4e) (247 mg, 1.00
mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10
mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and
DMF (2 mL) according to the general procedure C and yielding after
column chromatography (hexanes) the pure product 5e (88 mg, 35 %). A
2-(4-Fluorophenyl)thiophene[31] (5a) was prepared from 1a (420 mg,
5.00 mmol), 1-bromo-4-fluorobenzene (4a) (175 mg, 1.00 mmol),
Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol),
PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2
mL) according to the general procedure C and yielding after column
chromatography (hexanes) the pure product 5a (103 mg, 58 %). A white
solid; m.p.: 55.0-56.0 oC. 1H NMR (CDCl3, 300 MHz, ppm): δ 7.62-7.54
(comp, 2 H), 7.28 (dd, J = 5.1, 0.9 Hz, 1 H), 7.25 (dd, J = 3.5, 0.9 Hz, 1
H), 7.13-7.03 (comp, 3 H); 13C NMR (CDCl3, 125 MHz, ppm): δ 162.3 (d,
1
white solid; m.p.: 42.0-44.0 oC. H NMR (CDCl3, 300 MHz, ppm): δ 7.60-
7.51 (comp, 2 H), 7.24-7.15 (m, 1 H); 13C NMR (CDCl3, 75 MHz, ppm): δ
144.0 (dm, 1JC-F = 249.9 Hz), 139.9 (dm, 1JC-F = 254.6Hz), 138.0 (dm, 1JC-
3
4
= 252.5 Hz), 130.1 (t, JC-F = 5.0 Hz), 128.2 (t, JC-F = 3.4 Hz), 127.3,
F
126.3 (d, 5JC-F = 2.3 Hz), 110.0 (td, 2J = 15.4 Hz, 3J = 4.2 Hz).
4-(Thiophen-2-yl)benzaldehyde[34] (5f) was prepared from 1a (420 mg,
5.00 mmol), 4-bromobenzaldehyde (4f) (185 mg, 1.00 mmol), Pd(OAc)2
(12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31
mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according
to the general procedure C and yielding after column chromatography
(ethyl acetate : hexanes = 5 : 95) the pure product 5f (122 mg, 65 %). A
1JC-F = 247.0 Hz), 143.3, 130.7 (d, 4JC-F = 3.3 Hz), 128.0, 127.6 (d, 3JC-F
8.0 Hz), 124.8, 123.1, 115.8 (d, 2JC-F = 21.8
=
2-(4-(Trifluoromethyl)phenyl)thiophene[32] (5b) was prepared from 1a
(420 mg, 5.00 mmol), 1-bromo-4-(trifluoromethyl)benzene (4b) (225 mg,
1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg,
0.10 mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol),
and DMF (2 mL) according to the general procedure C and yielding after
column chromatography (hexanes) the pure product 5b (150 mg, 66 %).
o
1
white solid; m.p.: 68.5-70.5 C. H NMR (CDCl3, 300 MHz, ppm): δ 9.99
(s, 1 H), 7.88 (d, J = 8.4 Hz, 2 H), 7.75 (d, J = 8.4 Hz, 2 H), 7.46 (dd, J =
3.7, 1.1 Hz, 1 H), 7.39 (dd, J = 5.1, 1.1 Hz, 1 H), 7.13 (dd, J = 5.1, 3.7 Hz,
1 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 191.4, 142.6, 140.0, 135.0,
130.4, 128.4, 126.8, 125.9, 125.0.
o
1
A white solid; m.p.: 119.4-121.0 C. H NMR (CDCl3, 300 MHz, ppm): δ
7.72 (d, J = 8.7 Hz, 2 H), 7.63 (d, J = 8.7 Hz, 2 H), 7.40 (dd, J = 3.7, 1.1
Hz, 1 H), 7.37 (dd, J = 5.1, 1.1 Hz, 1 H), 7.12 (dd, J = 5.1, 3.7 Hz, 1 H);
2-Fluoro-4-(thiophen-2-yl)benzaldehyde[35] (5g) was prepared from 1a
(420 mg, 5.00 mmol), 4-bromo-2-fluorobenzaldehyde (4g) (203 mg, 1.00
mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10
mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and
DMF (2 mL) according to the general procedure C and yielding after
column chromatography (hexanes) the pure product 5g (113 mg, 55 %).
A white solid; m.p.: 72.8-74.0 oC. 1H NMR (CDCl3, 500 MHz, ppm): δ
10.32 (s, 1 H), 7.85 (dd, J = 7.9, 7.6 Hz, 1 H), 7.49 (dd, J = 8.2, 1.1 Hz, 1
H), 7.45 (dd, J = 3.7, 1.1 Hz, 1 H), 7.42 (dd, J = 5.1, 1.1 Hz, 1 H), 7.37
(dd, J = 11.6, 1.6 Hz, 1 H), 7.13 (dd, J = 5.1, 3.7 Hz, 1 H); 13C NMR
2
13C NMR (CDCl3, 125 MHz, ppm): δ 142.6, 137.7, 129.2 (q, JC-F = 32.5
Hz), 128.3, 126.2, 125.92, 125.87 (q, 3JC-F = 3.8 Hz), 124.4, 124.2 (q, 1JC-
F = 272.0 Hz).
2-(3,5-Bis(trifluoromethyl)phenyl)thiophene[32] (5c) was prepared from
1a (420 mg, 5.00 mmol), 1-bromo-3,5-bis(trifluoromethyl)benzene (4c)
(293 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-
Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg,
1.50 mmol), and DMF (2 mL) according to the general procedure C and
yielding after column chromatography (hexanes) the pure product 5c
3
1
(CDCl3, 125 MHz, ppm): δ 186.3 (d, JC-F = 6.0 Hz), 165.0 (d, JC-F
=
3
4
258.4 Hz), 142.4 (d, JC-F = 9.4 Hz), 141.5, 129.3 (d, JC-F = 1.1 Hz),
o
1
3
4
(151 mg, 51 %). A white solid; m.p.: 62.0-63.5 C. H NMR (CDCl3, 300
MHz, ppm): δ 8.00 (s, 2 H), 7.78 (s, 1 H), 7.48-7.38 (comp, 2 H), 7.15 (dd,
J = 5.0, 3.8 Hz, 1 H); 13C NMR (CDCl3, 125 MHz, ppm): δ 140.9, 136.5,
128.6, 127.6, 125.7, 122.6 (d, JC-F = 8.5 Hz), 121.7 (d, JC-F = 2.3 Hz),
112.9 (d, 2JC-F = 22.3 Hz).
2
1
132.3 (q, JC-F = 33.3 Hz), 128.5, 127.0, 125.6, 125.2, 123.2 (q, JC-F
=
[2,2'-Bithiophene]-5-carbaldehyde[36] (5h) was prepared from 1a (420
mg, 5.00 mmol), 5-bromothiophene-2-carbaldehyde (4h) (191 mg, 1.00
mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10
mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and
DMF (2 mL) according to the general procedure C and yielding after
column chromatography (ethyl acetate : hexanes = 8 : 92) the pure
272.8 Hz), 120.7
2,2,2-Trifluoro-1-(4-(thiophen-2-yl)phenyl)ethanone
(5d)
was
prepared from 1a (420 mg, 5.00 mmol), 1-(4-bromophenyl)-2,2,2-
trifluoroethanone (4d) (253 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05
mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30
o
product 5h (101 mg, 52 %). A yellow solid; m.p.: 57.0-57.8 C. 1H NMR
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European Journal of Organic Chemistry
10.1002/ejoc.201601257
FULL PAPER
(CDCl3, 300 MHz, ppm): δ 9.86 (s, 1 H), 7.66 (d, J = 3.9 Hz, 1 H), 7.36
(dd, J = 2.0, 1.1 Hz, 1 H), 7.35 (s, 1 H), 7.25 (d, J = 3.9 Hz, 1 H), 7.07 (dd,
J = 4.7, 4.1 Hz, 1 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 182.5, 147.1,
141.7, 137.3, 136.0, 128.3, 127.1, 126.1, 124.2.
white solid; m.p.: 94-94.5 oC. 1H NMR (CDCl3, 300 MHz, ppm): δ 7.69 (d,
J = 8.7 Hz, 2 H), 7.64 (d, J = 8.7 Hz, 2 H), 7.45-7.36 (comp, 2 H), 7.13
(dd, J = 5.0, 3.7 Hz, 1 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 142.0,
138.6, 132.7, 128.5, 127.0, 126.0, 125.1, 118.8, 110.5.
5-(Thiophen-2-yl)furan-2-carbaldehyde[36] (5i) was prepared from 1a
(420 mg, 5.00 mmol), 5-bromofuran-2-carbaldehyde (4i) (175 mg, 1.00
mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10
mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and
DMF (2 mL) according to the general procedure C and yielding after
column chromatography (ethyl acetate : hexanes = 10 : 90) the pure
product 5i (80 mg, 45 %). A brownish red liquid. 1H NMR (CDCl3, 300
MHz, ppm): δ 9.61 (s, 1 H), 7.52 (dd, J = 3.7, 1.1 Hz, 1 H), 7.40 (dd, J =
5.0, 1.1 Hz, 1 H), 7.28 (d, J = 3.8 Hz, 1 H), 7.10 (dd, J = 5.0, 3.7 Hz, 1 H),
6.67 (d, J = 3.8 Hz, 1 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 176.8, 154.8,
151.3, 131.5, 128.1, 127.5, 126.2, 123.8, 107.4.
(E)-2-Ethylhexyl 2-cyano-3-(4-(thiophen-2-yl)phenyl)acrylate (5n)
was prepared from 1a (420 mg, 5.00 mmol), (E)-2-ethylhexyl 3-(4-
bromophenyl)-2-cyanoacrylate (4n) (364 mg, 1.00 mmol), Pd(OAc)2 (12
mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg,
0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to
the general procedure C and yielding after column chromatography (ethyl
acetate : hexanes = 5 : 95) the pure product 5n (77 mg, 21 %). A
yellowish green solid; m.p.: 64.0-66.0 oC. 1H NMR (CDCl3, 300 MHz,
ppm): δ 8.20 (s, 1 H), 8.01 (d, J = 8.4 Hz, 2 H), 7.73 (d, J = 8.4 Hz, 2 H),
7.46 (d, J = 3.7 Hz, 1 H), 7.39 (d, J = 4.9 Hz, 1 H), 7.13 (dd, J = 4.9, 3.7
Hz, 1 H), 4.24 (d, J = 5.8 Hz, 2 H), 1.80-1.65 (m, 1 H), 1.51-1.28 (comp, 8
H), 1.00-0.85 (comp, 6 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 162.8,
153.9, 142.6, 139.0, 131.9, 130.2, 128.5, 127.0, 126.1, 125.0, 115.6,
102.0, 69.0, 38.7, 30.3, 28.9, 23.7, 22.9, 14.0, 11.0; MS (EI, 70 eV): 367
(M+, 7 %), 255 (56 %), 210 (32 %), 115 (25 %), 57 (100 %); HRMS (EI):
calcd. for C22H25NO2S: 367.1606, found: 367.1604.
2-(4-Nitrophenyl)thiophene[32] (5j) was prepared from 1a (420 mg, 5.00
mmol), 1-bromo-4-nitrobenzene (4j) (202 mg, 1.00 mmol), Pd(OAc)2 (12
mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg,
0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to
the general procedure C and yielding after column chromatography
(hexanes) the pure product 5j (154 mg, 75 %). A yellowish green solid;
m.p.: 141.5-143.0 oC. 1H NMR (CDCl3, 300 MHz, ppm): δ 8.23 (d, J = 9.0
Hz, 2 H), 7.73 (d, J = 9.0 Hz, 2 H), 7.47 (dd, J = 3.7, 1.1 Hz, 1 H), 7.44
(dd, J = 5.1, 1.1 Hz, 1 H), 7.15 (dd, J = 5.1, 3.7 Hz, 1 H); 13C NMR
(CDCl3, 75 MHz, ppm): δ 146.5, 141.5, 140.5, 128.6, 127.6, 125.9, 125.6,
124.3.
General procedure
heteroarenes
D for Table 4: Substrate scope of the
To a solution of Pd(OAc)2 (0.05 mmol), P(adamantyl)2(n-Bu) (0.10 mmol),
PivOH (0.30 mmol), and K2CO3 (1.50 mmol) in DMF or toluene (2 mL) in
a flame-dried Schlenk tube were added the corresponding heteroarenes
(1b-f) (5.00 mmol) and aryl bromides (1.00 mmol) under N2. The reaction
mixture was then heated at 110 °C under N2 for 6-12 h. After the reaction
mixture had cooled to room temperature, water (10 mL) was added. The
mixture was extracted with ethyl acetate (2 × 20 mL), and the combined
organic layers were washed with brine (50 mL), dried (Na2SO4) and
concentrated in vacuo. Purification by flash chromatography yielded the
desired product 6a-j.
2-Chloro-5-(thiophen-2-yl)pyridine[37] (5k) was prepared from 1a (420
mg, 5.00 mmol), 5-bromo-2-chloropyridine (4k) (192 mg, 1.00 mmol),
Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol),
PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2
mL) according to the general procedure C and yielding after column
chromatography (ethyl acetate : hexanes = 5 : 95) the pure product 5k
(133 mg, 68 %). A transparent liquid. 1H NMR (CDCl3, 300 MHz, ppm): δ
8.62 (d, J = 2.5 Hz, 1 H), 7.81 (dd, J = 8.3, 2.5 Hz, 1 H), 7.46-7.29 (comp,
3 H), 7.11 (dd, J = 5.0, 3.7 Hz, 1 H); 13C NMR (CDCl3, 75 MHz, ppm): δ
149.9, 146.5, 138.9, 135.7, 129.4, 128.4, 126.4, 124.6, 124.2.
3,6-Di-t-butyl-9-(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)phenyl)-
9H-carbazole (6a) was prepared from 2,3-dihydrothieno[3,4-
b][1,4]dioxine (1b) (710 mg, 5.00 mmol), (9-(4-bromophenyl)-3,6-di-t-
butyl-9H-carbazole (2d) (434 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05
mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30
mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the
general procedure D (reaction time = 6 h) and yielding after column
chromatography (dichloromethane : hexanes = 40 : 60) the pure product
6a (351 mg, 71 %). A pale yellow solid; m.p.: 245.0-246.5 oC. 1H NMR
(CDCl3, 300 MHz, ppm): δ 8.16 (d, J = 1.6 Hz, 2 H), 7.93 (d, J = 8.5 Hz, 2
H), 7.56 (d, J = 8.5 Hz, 2 H), 7.48 (dd, J = 8.7, 1.6 Hz, 2 H), 7.39 (d, J =
8.7 Hz, 2 H), 6.37 (s, 1 H), 4.42-4.34 (comp, 2 H), 4.33-4.24 (comp, 2 H),
1.48 (s, 18 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 142.8, 142.3, 139.2,
138.4, 136.3, 131.9, 127.1, 126.8, 123.6, 123.4, 116.7, 116.2, 109.3,
98.0, 64.9, 64.5, 34.7, 32.0; MS (EI, 70 eV): 495 (M+, 17 %), 480 (14 %),
177 (70 %), 84 (60 %), 54 (100 %); HRMS (EI): calcd. for C32H33NO2S:
495.2232, found: 495.2224.
5-(Thiophen-2-yl)pyrimidine[38] (5l) was prepared from 1a (420 mg,
5.00 mmol), 5-bromopyrimidine (4l) (159 mg, 1.00 mmol), Pd(OAc)2 (12
mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg,
0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to
the general procedure C and yielding after column chromatography (ethyl
acetate : hexanes = 20 : 80) the pure product 5l (125 mg, 77 %). A pale
yellow solid; m.p.: 77.0-79.0 oC. 1H NMR (CDCl3, 300 MHz, ppm): δ 9.10
(s, 1 H), 8.93 (s, 2 H), 7.43 (dd, J = 5.1, 1.1 Hz, 1 H), 7.40 (dd, J = 3.7,
1.1 Hz, 1 H), 7.15 (dd, J = 5.1, 3.7 Hz, 1 H); 13C NMR (CDCl3, 75 MHz,
ppm): δ 157.2, 153.4, 136.2, 128.6, 128.5, 127.2, 125.2.
4-(Thiophen-2-yl)benzonitrile[39] (5m) was prepared from 1a (420 mg,
5.00 mmol), 4-bromobenzonitrile (4m) (182 mg, 1.00 mmol), Pd(OAc)2
(12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31
mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according
to the general procedure C and yielding after column chromatography
(ethyl acetate : hexanes = 5 : 95) the pure product 5m (144 mg, 78 %). A
4-(2,3-Dihydrothieno[3,4-b][1,4]dioxin-5-yl)benzaldehyde[40] (6b) was
prepared from 2,3-dihydrothieno[3,4-b][1,4]dioxine (1b) (710 mg, 5.00
mmol), 4-bromobenzaldehyde (4f) (185 mg, 1.00 mmol), Pd(OAc)2 (12
mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg,
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European Journal of Organic Chemistry
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FULL PAPER
0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to
the general procedure D (reaction time = 6 h) and yielding after column
chromatography (ethyl acetate : hexanes = 30 : 70) the pure product 6b
(150 mg, 61 %). A yellow solid; m.p.: 133.0-134.0 oC. 1H NMR (CDCl3,
300 MHz, ppm): δ 9.95 (s, 1 H), 7.87 (d, J = 8.9 Hz, 2 H), 7.83 (d, J = 8.9
K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the general
procedure
D (reaction time = 12 h) and yielding after column
chromatography (ethyl acetate : hexanes = 8 : 92) the pure product 6f
(133 mg, 55 %). A bright yellow solid; m.p.: 62.0-63.5 oC. 1H NMR (CDCl3,
300 MHz, ppm): δ 9.84 (s, 1 H), 8.03 (dd, J = 5.6, 1.1 Hz, 1 H), 7.64 (d, J
= 4.0 Hz, 1 H), 7.51 (dd, J = 3.9, 1.1 Hz, 1 H), 7.29 (dd, J = 5.6, 3.9 Hz, 1
H), 7.18 (d, J = 4.0 Hz, 1 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 182.5,
149.2, 141.7, 140.9, 137.3, 132.7, 130.7, 128.4, 124.9; MS (EI, 70 V):
242 (M+, 100 %), 169 (35 %), 134 (30 %), 89 (38 %), 63 (33 %); HRMS
(EI): calcd. for C9H6OSSe: 241.9305, found: 241.9306.
Hz, 2 H), 6.42 (s, 1 H), 4.39-4.30 (comp, 2 H), 4.29-4.21 (comp, 2 H); 13
C
NMR (CDCl3, 75 MHz, ppm): δ 191.5, 142.4, 140.1, 139.3, 134.0, 130.1,
125.7, 116.1, 100.1, 64.9, 64.3.
4-(1-Methyl-1H-pyrrol-2-yl)-N,N-diphenylaniline[41] (6c) was prepared
from 1-methyl-1H-pyrrole (1c) (405 mg, 5.00 mmol), 4-
bromotriphenylamine (2a) (324 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05
mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30
mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2 mL) according to the
general procedure D (reaction time = 6 h) and yielding after column
chromatography (ethyl acetate : hexanes = 2 : 98) the pure product 6c
5-Hexyl-1-(9-hexyl-9H-carbazol-3-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-
dione (6g) was prepared from 5-hexyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-
dione (1e) (1185 mg, 5.00 mmol), 3-bromo-9-hexyl-9H-carbazole (2f)
(330 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-
Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg,
1.50 mmol), and DMF or toluene (2 mL) according to the general
1
(204 mg, 63 %). A transparent viscous liquid. H NMR (CDCl3, 300 MHz,
ppm): δ 7.40-7.27 (comp, 6 H), 7.23-7.03 (comp, 8 H), 6.75 (s, 1 H), 6.25
(d, J = 1.9 Hz, 2 H), 3.72 (s, 3 H); 13C NMR (CDCl3, 75 MHz, ppm): δ
147.6, 146.5, 134.3, 129.3, 129.2, 127.3, 124.4, 123.29, 123.26, 122.9,
108.2, 107.6, 35.0.
procedure
D (reaction time = 12 h) and yielding after column
chromatography (ethyl acetate : hexanes = 10 : 90) the pure product 6g
o
1
(75-78 %). An orange solid; m.p.: 145.0-146.0 C. H NMR (CD2Cl2, 300
MHz, ppm): δ 8.88 (d, J = 1.7 Hz, 1 H), 8.23 (dd, J = 8.2, 1.7 Hz, 1 H),
8.17 (d, J = 8.2 Hz, 1 H), 7.63 (s, 1 H), 7.58-7.39 (comp, 3 H), 7.34-7.22
(m, 1 H), 4.29 (t, J = 7.2 Hz, 2 H), 3.63 (t, J = 7.3 Hz, 2 H), 1.96-1.80
(comp, 2 H), 1.77-1.63 (comp, 2 H), 1.47-1.24 (comp, 12 H), 0.97-0.79
(comp, 6 H); 13C NMR (CD2Cl2, 75 MHz, ppm): δ 163.9, 161.3, 150.0,
141.8, 141.6, 138.6, 127.7, 126.9, 126.3, 123.5, 123.3, 122.35, 122.27,
121.1, 120.8, 120.1, 109.8, 109.5, 43.8, 38.9, 32.1, 32.0, 29.4, 29.0, 27.4,
27.2, 23.14, 23.11, 14.4, 14.3; MS (EI, 70 eV): 486 (M+, 59 %), 149
(25 %), 97 (36 %), 71 (63 %), 57 (100 %); HRMS (EI): calcd. for
C30H34N2O2S: 486.2341, found: 486.2345.
4-(1-Methyl-1H-pyrrol-2-yl)benzaldehyde (6d) was prepared from 1-
methyl-1H-pyrrole (1c) (405 mg, 5.00 mmol), 4-bromobenzaldehyde (4f)
(185 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-
Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg,
1.50 mmol), and DMF (2 mL) according to the general procedure D
(reaction time = 6 h) and yielding after column chromatography (ethyl
acetate : hexanes = 10 : 90) the pure product 6d (94 mg, 51 %). A
brownish red liquid. 1H NMR (CDCl3, 300 MHz, ppm): δ 10.02 (s, 1 H),
7.90 (d, J = 8.4 Hz, 2 H), 7.57 (d, J = 8.4 Hz, 2 H), 6.84-6.75 (m, 1 H),
6.39 (dd, J = 3.7, 1.8 Hz, 1 H), 6.24 (dd, J = 3.7, 2.7 Hz, 1 H), 3.74 (s, 3
H); 13C NMR (CDCl3, 75 MHz, ppm): δ 191.7, 139.2, 134.2, 133.2, 129.9,
128.2, 125.7, 110.7, 108.5, 35.5; MS (EI, 70 eV): 185 (M+, 100 %), 184
(28 %), 156 (16 %), 128 (6 %), 115 (10 %); HRMS (EI): calcd. for
C12H11NO: 185.0841, found: 185.0843.
5-Hexyl-1-(4-(2,2,2-trifluoroacetyl)phenyl)-4H-thieno[3,4-c]pyrrole-
4,6(5H)-dione (6h) was prepared from 5-hexyl-4H-thieno[3,4-c]pyrrole-
4,6(5H)-dione (1e) (1185 mg, 5.00 mmol), 1-(4-bromophenyl)-2,2,2-
trifluoroethanone (4d) (253 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05
mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30
mmol), K2CO3 (207 mg, 1.50 mmol), and DMF or toluene (2 mL)
according to the general procedure D (reaction time = 12 h) and yielding
after column chromatography (ethyl acetate : hexanes = 15 : 85) the pure
product 6h (trace-68 %). A pale yellow solid; m.p.: 106.0-107.5 oC. 1H
NMR (CDCl3, 300 MHz, ppm): 8.29 (d, J = 8.4 Hz, 2 H), 8.13 (d, J = 8.4
Hz, 2 H), 7.84 (s, 1H), 3.64 (t, J = 7.4 Hz, 2 H), 1.71-1.58 (comp, 2 H),
1.40-1.24 (comp, 6 H), 0.86 (t, J = 6.8 Hz, 3 H); 13C NMR (CDCl3, 125
3,6-Di-t-butyl-9-(4-(selenophen-2-yl)phenyl)-9H-carbazole (6e) was
prepared from selenophene (1d) (655 mg, 5.00 mmol), (9-(4-
bromophenyl)-3,6-di-t-butyl-9H-carbazole (2d) (434 mg, 1.00 mmol),
Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol),
PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF (2
mL) according to the general procedure D (reaction time = 12 h) and
yielding after column chromatography (hexanes) the pure product 6e
(340 mg, 70 %). A white solid; m.p.: 204.5-205.5 oC. 1H NMR (CDCl3,
300 MHz, ppm): δ 8.18 (d, J = 1.8 Hz, 2 H), 8.01 (dd, J = 5.6, 1.0 Hz, 1
H), 7.78 (d, J = 8.5 Hz, 2 H), 7.62-7.55 (comp, 3 H), 7.50 (dd, J = 8.7, 1.8
Hz, 2 H), 7.44-7.36 (comp, 3 H), 1.50 (s, 18 H); 13C NMR (CDCl3, 75
MHz, ppm): δ 149.8, 143.0, 139.1, 137.4, 135.0, 130.8, 130.4, 127.5,
127.0, 125.6, 123.6, 123.4, 116.2, 109.2, 34.7, 32.0; MS (EI, 70 eV): 485
(M+, 33 %), 470 (40 %), 251 (27 %), 136 (100 %), 91 (71 %); HRMS (EI):
calcd. for C30H31NSe: 485.1622, found: 485.1626.
2
MHz, ppm): δ 179.6 (q, JC-F = 35.2 Hz), 162.7, 162.1, 144.4, 138.4,
1
136.9, 131.5, 130.7, 130.3, 128.2, 124.9, 116.5 (q, JC-F = 289.4 Hz),
38.7, 31.3, 28.3, 26.5, 22.4, 13.9; MS (EI, 70 eV): 409 (M+, 52 %), 338
(100 %), 256 (33 %), 185 (41 %), 113 (46 %); HRMS (EI): calcd. for
C20H18F3NO3S: 409.0959, found: 409.0965.
Dimethyl
2-(4-(diphenylamino)phenyl)thiophene-3,4-dicarboxylate
(6i) was prepared from dimethyl thiophene-3,4-dicarboxylate (1f) (1000
mg, 5.00 mmol), 4-bromotriphenylamine (2a) (324 mg, 1.00 mmol),
Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol),
PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF or
toluene (2 mL) according to the general procedure D (reaction time = 12
h) and yielding after column chromatography (dichloromethane) the pure
5-(Selenophen-2-yl)thiophene-2-carbaldehyde (6f) was prepared from
selenophene (1d) (655 mg, 5.00 mmol), 5-bromothiophene-2-
carbaldehyde (4g) (191 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol),
P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol),
product 6i (65-77 %). A pale yellow solid; m.p.: 184.0-186.0 oC. H NMR
1
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European Journal of Organic Chemistry
10.1002/ejoc.201601257
FULL PAPER
(CDCl3, 300 MHz, ppm): δ 7.97 (s, 1 H), 7.41-7.27 (comp, 6 H), 7.22-7.02
(comp, 8 H), 3.90 (s, 3 H), 3.89 (s, 3 H); 13C NMR (CDCl3, 125 MHz,
ppm): δ 166.6, 162.1, 148.5, 147.0, 144.3, 132.2, 131.3, 129.3, 128.8,
125.02, 125.00, 123.6, 122.1, 52.7, 52.0; MS (EI, 70 eV): 443 (M+, 22 %),
105 (36 %), 91 (70 %), 61 (79 %), 57 (100 %); HRMS (EI): calcd. for
C26H21NO4S: 443.1191, found: 443.1184.
(comp, 8 H), 1.01 (app t, 6 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 147.9,
147.6, 146.1, 144.9, 137.4, 130.9, 130.2, 129.4, 127.2, 126.4, 125.0,
124.4, 123.1, 122.2, 110.3, 41.2, 39.7, 32.5, 29.0, 25.7, 23.2, 14.3, 11.0;
MS (EI): 519 ([M+2]+, 13 %), 517 (M+, 12 %), 487 (100 %), 420 (21 %);
HRMS (EI): calcd. for C30H32BrNS: 517.1439, found: 517.1439.
5-(2-Ethylhexyl)-1-(5-(9-hexyl-9H-carbazol-3-yl)thiophen-2-yl)-4H-
thieno[3,4-c]pyrrole-4,6(5H)-dione (10b) was prepared from 7[22] (1325
mg, 5.00 mmol), 3-(5-bromothiophen-2-yl)-9-hexyl-9H-carbazole (8b)
(412 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-
Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg,
1.50 mmol), and toluene (2 mL) according to the general procedure D
(reaction time = 12 h) and yielding after column chromatography
(dichloromethane : hexanes = 50 : 50) the pure product 10b (312 mg,
50 %). A yellow solid; m.p.: 84.9-86.6 oC. 1H NMR (CDCl3, 500 MHz,
ppm): δ 8.30 (d, J = 1.3 Hz, 1 H), 8.15 (d, J = 7.6 Hz, 1 H), 7.99 (d, J =
3.9 Hz, 1 H), 7.70 (dd, J = 8.5, 1.8 Hz, 1 H), 7.47-7.53 (comp, 2 H), 7.39
(d, J = 8.2 Hz, 1 H), 7.32 (d, J = 8.5 Hz, 1 H), 7.26-7.30 (comp, 2 H),
4.05-4.18 (comp, 2 H), 3.52 (d, J = 7.4 Hz, 2 H), 2.01-2.11 (m, 1 H), 1.81-
1.94 (m, 1 H), 1.24-1.48 (comp, 16 H), 0.86-1.02 (comp, 12 H); 13C NMR
(CDCl3, 125 MHz, ppm): δ 163.0, 162.6, 149.2, 141.2, 140.8, 140.3,
137.2, 131.0, 130.3, 126.6, 126.0, 124.2, 123.8, 123.1, 122.8, 122.6,
121.3, 120.4, 119.2, 117.7, 109.2, 109.1, 47.3, 42.2, 39.3, 38.1, 30.9,
30.5, 28.7, 28.5, 24.3, 23.8, 23.0, 22.9, 14.0, 13.9, 10.8, 10.4; MS (FAB):
624 ([M]+, 60 %), 525 (40 %), 413 (8 %), 77 (100 %); HRMS (FAB): calcd.
for C38H44N2O2S2: 624.2844, found: 624.2850.
Dimethyl 5'-formyl-[2,2'-bithiophene]-3,4-dicarboxylate (6j) was
prepared from dimethyl thiophene-3,4-dicarboxylate (1f) (1000 mg, 5.00
mmol), 5-bromothiophene-2-carbaldehyde (4g) (191 mg, 1.00 mmol),
Pd(OAc)2 (12 mg, 0.05 mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol),
PivOH (31 mg, 0.30 mmol), K2CO3 (207 mg, 1.50 mmol), and DMF or
toluene (2 mL) according to the general procedure D (reaction time = 12
h) and yielding after column chromatography (ethyl acetate : hexanes =
30 : 70) the pure product 6j (29-63 %). A yellow solid; m.p.: 117.0-118.5
1
oC. H NMR (CDCl3, 300 MHz, ppm): δ 9.88 (s, 1 H), 8.05 (s, 1 H), 7.69
(d, J = 4.0 Hz, 1 H), 7.33 (d, J = 4.0 Hz, 1 H), 3.93 (s, 3 H), 3.86 (s, 3 H);
13C NMR (CDCl3, 75 MHz, ppm): δ 182.6, 165.5, 161.6, 144.2, 142.3,
136.5, 135.2, 133.2, 132.8, 132.0, 127.8, 53.2, 52.4; MS (EI, 70 eV): 310
(M+, 90 %), 279 (100 %), 249 (10 %), 192 (10 %), 119 (13 %); HRMS
(EI): calcd. for C13H10O5S2: 309.9970, found: 309.9970.
Synthesis and characterization of compounds 8a-b, 9a-b, 10a-b,
11a-b, and CYL-3~4 (Scheme 2):
5-(2-Ethylhexyl)-1-(5-(4-((4-(2-
ethylhexyl)phenyl)(phenyl)amino)phenyl)thiophen-2-yl)-4H-
thieno[3,4-c]pyrrole-4,6(5H)-dione (10a) was prepared from 7[22] (1325
mg, 5.00 mmol), 4-(5-bromothiophen-2-yl)-N-(4-(2-ethylhexyl)phenyl)-N-
phenylaniline (8a) (518 mg, 1.00 mmol), Pd(OAc)2 (12 mg, 0.05 mmol),
P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol),
K2CO3 (207 mg, 1.50 mmol), and toluene (2 mL) according to the general
Synthesis and characterization of (8b): compound 8b was prepared
under the same reaction conditions used in the synthesis of 8a. A
1
transparent viscous liquid. H NMR (CDCl3, 300 MHz, ppm): δ 8.27 (d, J
= 1.7 Hz, 1 H), 8.18 (d, J = 7.5 Hz, 1 H), 7.63 (dd, J = 8.4, 1.7 Hz, 1 H),
7.60-7.53 (m, 1 H), 7.45 (d, J = 8.4 Hz, 1 H), 7.39-7.30 (comp, 2 H), 7.11
(d, J = 3.8 Hz, 1 H), 7.10 (d, J = 3.8 Hz, 1 H), 4.13 (d, J = 2.1 Hz, 1 H),
4.10 (d, J = 2.7 Hz, 1 H), 2.20-2.03 (m, 1 H), 1.53-1.31 (comp, 8 H), 1.05-
0.94 (comp, 6 H); 13C NMR (CDCl3, 75 MHz, ppm): δ 147.2, 141.2, 140.4,
130.7, 125.9, 124.6, 123.5, 123.0, 122.5, 121.8, 120.3, 119.0, 117.2,
109.5, 109.15, 109.08, 47.2, 39.2, 30.9, 28.7, 24.3, 23.0, 14.0, 10.8.
procedure
D (reaction time = 12 h) and yielding after column
chromatography (ethyl acetate : hexanes = 5 : 95) the pure product 10a
(366 mg, 52 %). A red viscous liquid. 1H NMR (CDCl3, 300 MHz, ppm): δ
8.00 (d, J = 3.9 Hz, 1 H), 7.56 (s, 1 H), 7.43-7.53 (comp, 2 H), 7.26-7.34
(m, 1 H), 7.23-7.26 (m, 1 H), 7.20 (d, J = 3.9 Hz, 1 H), 6.95-7.18 (comp, 9
H), 3.54 (d, J = 7.3 Hz, 2 H), 2.51 (d, J = 6.9 Hz, 2 H), 1.78-1.95 (m, 1 H),
1.50-1.60 (m, 1 H), 1.22-1.41 (comp, 16 H), 0.70-1.10 (comp, 12 H); 13C
NMR (CDCl3, 75 MHz, ppm): δ 163.3, 162.8, 148.4, 147.8, 147.4, 144.6,
140.3, 137.6, 137.4, 131.1, 130.7, 130.2, 129.3, 127.1, 126.8, 126.5,
125.1, 124.5, 123.2, 123.1, 122.5, 121.8, 42.4, 41.1, 39.6, 38.2, 32.4,
30.6, 29.7, 28.9, 28.6, 25.5, 23.9, 23.1, 14.2, 14.1, 10.8, 10.5; MS (FAB):
703 ([M+1]+, 3 %), 538 (100 %), 426 (40 %), 269 (50 %); HRMS (FAB):
calcd. for C44H50N2O2S2: 702.3314, found: 702.3311.
4-(5-(5-(2-Ethylhexyl)-3-(5-(4-((4-(2-
ethylhexyl)phenyl)(phenyl)amino)phenyl)thiophen-2-yl)-4,6-dioxo-
5,6-dihydro-4H-thieno[3,4-c]pyrrol-1-yl)thiophen-2-yl)benzaldehyde
(11a) was prepared from 10a (703 mg, 1.00 mmol), 4-(5-bromothiophen-
2-yl)benzaldehyde (9a) (400 mg, 1.50 mmol), Pd(OAc)2 (12 mg, 0.05
mmol), P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30
mmol), K2CO3 (207 mg, 1.50 mmol), and toluene (2 mL) according to the
general procedure D (reaction time = 16 h) and yielding after column
Synthesis and characterization of (8a): To a solution of 4-(2-ethylhexyl)-
N-phenyl-N-(4-(thiophen-2-yl)phenyl)aniline (3c) (2200 mg, 5.00 mmol) in
the cosolvent of DMF (15 mL) and AcOH (10 mL), N-bromosuccinimide
(890 mg, 5.00 mmol) was added portionwise. The reaction mixture was
then stirred at 30 oC for 24 h before it was diluted with water (30 mL). The
mixture was extracted with dichloromethane (2 × 50 mL), and the
combined organic layers were washed with aqueous NaHSO3 (100 mL)
and brine (100 mL). The organic phase was dried over Na2SO4 and then
concentrated in vacuo. Purification by flash chromatography (hexanes)
yielded the desired product 8a (2024 mg, 78 %). An orange viscous liquid.
1H NMR (CDCl3, 300 MHz, ppm): δ 7.39-7.50 (comp, 2 H), 7.29-7.39
(comp, 2 H), 7.07-7.29 (comp, 9 H), 7.05 (d, J = 3.9 Hz, 1 H), 7.00 (d, J =
3.9 Hz, 1 H), 2.62 (d, J = 6.9 Hz, 2 H), 1.61-1.78 (m, 1 H), 1.30-1.55
chromatography (using the eluent with
a gradient polarity: from
dichloromethane : hexanes = 40 : 60 to dichloromethane : hexanes = 70 :
30) the pure product 11a (658 mg, 74 %). A dark red viscous liquid. 1H
NMR (CDCl3, 300 MHz, ppm): δ 9.84 (s, 1 H), 7.77 (dd, J = 8.4, 3.9 Hz, 2
H), 7.69 (d, J = 8.1 Hz, 2 H), 7.52 (d, J = 8.1 Hz, 2 H), 7.22-7.38 (comp, 4
H), 7.01-7.20 (comp, 8 H), 6.82-7.01 (comp, 3 H), 3.43 (d, J = 6.9 Hz, 2
H), 2.55 (d, J = 6.9 Hz, 2 H), 1.75-1.94 (m, 1 H), 1.52-1.70 (m, 1 H), 1.19-
1.49 (comp, 16 H), 0.64-1.12 (comp, 12 H); 13C NMR (CDCl3, 75 MHz,
ppm): δ 190.9, 162.44, 162.40, 148.3, 148.0, 147.2, 144.7, 144.5, 138.5,
137.7, 136.7, 135.3, 134.3, 133.7, 131.6, 130.7, 130.2, 130.1, 129.4,
129.0, 127.6, 126.5, 126.0, 125.7, 125.3, 124.7, 123.3, 122.9, 121.9,
42.4, 41.1, 39.7, 38.3, 32.4, 30.7, 29.7, 28.9, 28.6, 25.6, 23.9, 23.2, 23.1,
This article is protected by copyright. All rights reserved

European Journal of Organic Chemistry
10.1002/ejoc.201601257
FULL PAPER
14.2, 10.9, 10.5; MS (FAB): 889 ([M+1]+, 6 %), 538 (100 %), 426 (50 %),
269 (60 %); HRMS (FAB): calcd. for C55H56N2O3S3: 888.3453, found:
888.3444.
acid (CYL-3) was prepared from 11a (444 mg, 0.50 mmol), cyanoacetic
acid (1700 mg, 20.0 mmol), piperidine (1.0 mL), and chloroform (7 mL)
according to the general procedure
E and yielding after column
Synthesis and characterization of (9a): compound 9a was prepared
chromatography (using the eluent with a gradient polarity: from 100 %
dichloromethane to dichloromethane : methanol = 90 : 10) the pure
product CYL-3 (358 mg, 75 %). A dark red solid; m.p.: 189.0-192.3 oC.
1H NMR (CDCl3 and few drops of CD3OD, 500 MHz, ppm): δ 7.84 (d, J =
8.9 Hz, 1 H), 7.67-7.75 (m, 1 H), 7.52-7.62 (comp, 2 H), 7.28-7.36 (comp,
2 H), 7.08-7.17 (comp, 4 H), 6.81-7.01 (comp, 12 H), 3.25-3.26 (comp, 2
H), 2.40 (d, J = 6.4 Hz, 2 H), 1.67-1.73 (m, 1 H), 1.49-1.52 (m, 1 H), 1.18-
1.29 (comp, 16 H), 0.76-0.83 (comp, 12 H); MS (FAB): 955 ([M]+, 20 %),
856 (12 %), 469 (27 %), 77 (100%); HRMS (FAB): calcd. for
C58H57N3O4S3: 955.3511, found: 955.3516.
under the same reaction conditions used in the synthesis of 8a. Light
o
1
yellow powders; m.p.: 122.0-123.5 C. H NMR (CDCl3, 300 MHz, ppm):
δ 9.99 (s, 1 H), 7.86 (d, J = 8.4 Hz, 2 H), 7.64 (d, J = 8.4 Hz, 2 H), 7.19 (d,
J = 4.0 Hz, 1 H), 7.07 (d, J = 4.0 Hz, 1 H); 13C NMR (CDCl3, 75 MHz,
ppm): δ 191.2, 144.0, 139.0, 135.3, 131.3, 130.5, 125.6, 125.1, 113.9.
4-(5-(5-(2-Ethylhexyl)-3-(5-(9-(2-ethylhexyl)-9H-carbazol-3-
yl)thiophen-2-yl)-4,6-dioxo-5,6-dihydro-4H-thieno[3,4-c]pyrrol-1-
yl)thiophen-2-yl)-2-fluorobenzaldehyde (11b) was prepared from 10b
(625 mg, 1.00 mmol), 4-(5-bromothiophen-2-yl)-2-fluorobenzaldehyde
(9b) (428 mg, 1.50 mmol), Pd(OAc)2 (12 mg, 0.05 mmol),
P(adamantyl)2(n-Bu) (36 mg, 0.10 mmol), PivOH (31 mg, 0.30 mmol),
K2CO3 (207 mg, 1.50 mmol), and toluene (2 mL) according to the general
(E)-2-Cyano-3-(4-(5-(5-(2-ethylhexyl)-3-(5-(9-(2-ethylhexyl)-9H-
carbazol-3-yl)thiophen-2-yl)-4,6-dioxo-5,6-dihydro-4H-thieno[3,4-
c]pyrrol-1-yl)thiophen-2-yl)-2-fluorophenyl)acrylic acid (CYL-4) was
prepared from 11b (386 mg, 0.50 mmol), cyanoacetic acid (1700 mg,
20.0 mmol), piperidine (1.0 mL), and chloroform (7 mL) according to the
general procedure E and yielding after column chromatography (using
the eluent with a gradient polarity: from 100 % dichloromethane to
dichloromethane : methanol = 90 : 10) the pure product CYL-4 (371 mg,
83 %). A dark red solid; m.p.: 157.0-160.0 oC. 1H NMR (DMSO-d6, 300
MHz, ppm): δ 8.31 (s, 1 H), 8.16 (d, J = 7.6 Hz, 1 H), 7.95-8.07 (comp, 2
H), 7.83-7.93 (m, 1 H), 7.56-7.63 (m, 1 H), 7.32-7.49 (comp, 4 H), 7.09-
7.29 (comp, 5 H), 2.92-2.96 (comp, 2 H), 2.76-2.80 (comp, 2 H), 2.28-
2.30 (m, 1 H), 1.93-1.96 (m, 1 H), 1.16-1.28 (comp, 16 H), 0.70-0.90
(comp, 12 H); MS (FAB): 895 ([M]+, 4 %), 796 (6 %), 107 (50 %), 77
(100%); HRMS (FAB): calcd. for C52H50FN3O4S3: 895.2947, found:
895.2947.
procedure
D (reaction time = 16 h) and yielding after column
chromatography (dichloromethane : hexanes = 50 : 50) the pure product
11b (613 mg, 75 %). A dark red solid; m.p.: 159.9-161.0 oC. 1H NMR
(CDCl3, 500 MHz, ppm): δ 10.03 (s, 1 H), 7.91-8.01 (comp, 2 H), 7.80 (d,
J = 3.9 Hz, 1 H), 7.67 (d, J = 3.9 Hz, 1 H), 7.50-7.59 (m, 1 H), 7.46 (dd, J
= 8.4, 1.7 Hz, 1 H), 7.36-7.42 (m, 1 H), 7.21-7.25 (m, 1 H), 7.08-7.20
(comp, 3 H), 6.94-7.06 (comp, 3 H), 3.88-4.00 (comp, 2 H), 3.41-3.48
(comp, 2 H), 1.91-2.01 (m, 1 H), 1.79-1.90 (m, 1 H), 1.20-1.45 (comp, 16
H), 0.80-1.02 (comp, 12 H); 13C NMR (CDCl3, 125 MHz, ppm): δ 185.7,
165.4, 163.4, 162.4, 149.43, 149.40, 143.0, 141.1, 140.7, 137.0, 134.3,
133.6, 131.6, 130.3, 129.6, 129.2, 128.8, 127.1, 126.0, 123.8, 123.43,
123.39, 123.0, 122.4, 121.0, 120.9, 120.3, 119.2, 117.2, 112.2, 112.1,
109.1, 108.9, 47.3, 42.4, 39.3, 38.3, 30.9, 30.6, 28.7, 28.6, 24.3, 23.9,
23.1, 23.0, 14.1, 14.0, 10.8, 10.4; MS (FAB): 828 ([M]+, 10 %), 469
(60 %), 89 (100 %), 77 (95 %); HRMS (FAB): calcd. for C49H49N2O3S3:
828.2889, found: 828.2898.
Acknowledgements
Synthesis and characterization of (9b): compound 9b was prepared
under the same reaction conditions used in the synthesis of 8a. Pale
green solid; m.p.: 108.4-109.7 oC. 1H NMR (CDCl3, 500 MHz, ppm): δ
10.30 (d, J = 0.3 Hz, 1 H), 7.85 (dd, J = 8.1, 7.5 Hz, 1 H), 7.37 (dd, J =
8.1, 1.1 Hz, 1 H), 7.26 (dd, J = 11.4, 1.6 Hz, 1 H), 7.18 (d, J = 3.9 Hz, 1
H), 7.07 (d, J = 3.9 Hz, 1 H); 13C NMR (CDCl3, 125 MHz, ppm): δ 186.1
Financial support provided by the Ministry of Science and
Technology (MOST), Taiwan (MOST 103-2113-M-008-009-MY2)
and the National Central University (NCU) are gratefully
acknowledged. We thank Prof. Chun-Guey Wu and Dr. Kuo-
Yuan Chiu (Research Center for New Generation Photovoltaics,
NCU) for giving helpful advices and guidance on the fabrication
and characterization of dye-sensitized solar cells.
3
1
3
(d, JC-F = 5.9 Hz), 164.9 (d, JC-F = 259 Hz), 142.7, 141.2 (d, JC-F = 9.4
4
3
Hz), 131.4, 129.5 (d, JC-F = 1.4 Hz), 125.8, 122.9 (d, JC-F = 8.6 Hz),
121.3 (d, 4JC-F = 2.4 Hz), 114.8, 112.6 (d, 2JC-F = 22.5 Hz).
Keywords: End-Capping Groups • Organic Semiconducting
Materials • Direct C-H Arylations • DAA’ Organic Dyes •
Dye-Sensitized Solar Cells
General procedure E for sensitizers CYL-3 and CYL-4 (Knoevenagel
condensations): To a solvent of chloroform (7 mL) were added the
corresponding aldehyde (11a or 11b) (0.50 mmol), cyanoacetic acid
(20.0 mmol), and piperidine (1.0 mL) at room temperature. The reaction
mixture was then heated at reflux under N2 for 12 h. After the reaction
mixture had cooled to room temperature, water (10 mL) was added. The
mixture was extracted with dichloromethane (2 × 20 mL), and the
combined organic layers were washed with brine (50 mL), dried (Na2SO4)
and concentrated in vacuo. Purification by flash chromatography yielded
the desired products CYL-3 or CYL-4.
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10.1002/ejoc.201601257
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Entry for the Table of Contents (Key Topic: Direct C-H Arylations)
FULL PAPER
Te-Jui Lu,[a] Po-Han Lin,[a] Kun-Mu
Lee,[a], [b] and Ching-Yuan Liu*[a]
Page No. – Page No.
End-Capping Groups for Small-
Molecule Organic Semiconducting
Materials: Synthetic Investigation and
Photovoltaic Applications through
Direct C-H (Hetero)arylations
End group synthesis was previously limited to traditional cross-coupling reactions.
This work demonstrates a step-economical new access to a variety of useful end-
capping groups. Incoporation of appropriate end groups into D-A--A’-shaped
oligoaryls allows a facile preparation of new organic dye sensitizers that exhibit
good power conversion efficiency (PCE) up to 6.02% when fabricated as dye-
sensitized solar cells.
This article is protected by copyright. All rights reserved