Direct C–H Arylation as a Chemoselective Single-Step Access to π–Acceptor–π Type Building Blocks

Article abstract of DOI:10.1002/adsc.201700762

Different from the traditional multi-step synthesis, a chemoselective direct C–H arylation is reported for the single-step synthesis of various useful π–acceptor–π (π–A–π) type building blocks for use in organic electronics. This well-optimized C–H heteroarylation exhibits good product yields, broad substrate scope, and high functional group compatibility. Applications in the efficient synthesis of a new metal-free dye sensitizer for dye-sensitized solar cells (DSSCs) are also demonstrated. (Figure presented.).

Full text of DOI:10.1002/adsc.201700762

Title: Direct C-H Arylation as Chemoselective Single-Step Access to
Organic-Electronics-Versatile π-Acceptor-π Type Building Blocks
Authors: Kuan-Ming Lu, Wei-Ming Li, Po-Yu Lin, Kuan-Ting Liu, and
Ching-Yuan Liu
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700762
Link to VoR: http://dx.doi.org/10.1002/adsc.201700762

Advanced Synthesis & Catalysis
10.1002/adsc.201700762
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Direct C-H Arylation as Chemoselective Single-Step Access to
-Acceptor- Type Building Blocks

Kuan-Ming Lu, Wei-Ming Li, Po-Yu Lin, Kuan-Ting Liu, and Ching-Yuan Liu*
Department of Chemical and Materials Engineering, National Central University, Jhongli District, Taoyuan, Taiwan 320,
(
R.O.C)
Fax: (+886)-3-4252296; e-mail: cyliu0312@ncu.edu.tw
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######
Abstract: Different from the traditional multi-step
synthesis, a chemoselective direct C-H arylation is reported
for the single-step synthesis of various useful acceptor
(
A) type building blocks for use in organic
electronics. This well-optimized C-H heteroarylation
exhibits good product yields, broad substrate scope, and
high functional group compatibility. Application in the
efficient synthesis of a new metal-free dye sensitizer for
dye-sensitized solar cells (DSSCs) is also demonstrated.
Keywords: C-H Activation; Chemoselectivity; Dye-
Sensitized Solar Cells; Organic Electronics
Introduction
Over
the
last
decade,
has
C-H
bond
advanced
activation/functionalization
of electron-deficient heteroarenes under harsh
conditions as well as the use/treatment of toxic
significantly in the field of synthetic organic
chemistry.[ Coupling of two reaction substrates
without pre-functionalization steps makes this
approach synthetically attractive and it gradually
becomes the main stream in modern carbon-carbon or
carbon-heteroatom bond formations. Among various
types of C-H activations, facile construction of
1]
[10]
organotin reagents (Scheme 1). In contrast to the
traditional synthetic route, we demonstrate herein a
single-step synthesis of various usefulA type
building blocks via Pd-catalyzed C-H arylations in a
chemoselective manner while keeping two further
arylable C-H bonds at both ends (H , Scheme 1).
b
C
sp2Csp2 bonds via direct C-H cleavage occupies a
[2]
central place in not only synthetic methodology but
also in organic electronics[ bacause the resulting
3]
(
hetero)aryls usually exhibit prominent optoelectronic
properties. For example, -conjugated small
molecules[
4]
or polymers
[5]
prepared by step-
economical C-H arylations have been reported to
show remarkable semiconducting and photovoltaic
properties. More importantly, we found these organic
electronic materials were stepwise synthesized
starting mainly from a multi-function building block,
[
6]

acceptor (A), which could serve as core,
[7] [8] [9]
Scheme 1. -acceptor- building blocks accessed by
multi-step Stille coupling or single-step
chemoselective C-H arylation.
This report represents the substrate scope extension
end, -spacer, or monomers respectively (Figure
1).
However, all these versatile A structures were
synthesized by the multi-step Stille- or Suzuki
coupling reactions that must include the bromination
Figure 1. Versatile -acceptor- building blocks for
the organic optoelectronic materials.
[11]
from our previous work,
which a variety of
important thiopheneacceptorthiophenemolecular
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201700762
units can be straightforward prepared through one- Table 1. Optimization of the chemoselective C-H
step chemoselective direct heteroarylations.
heteroarylation using TPD (1a) and 2-bromothiophene
[
a]
(
2a).
Results and Discussion
For organic electronic materials, thieno[3,4-c]pyrrole-
4
,6-dione (TPD, 1a of Table 1) has been widely used
[12]
as electron-deficient unit
and thiophene also
regarded as one of the most important -bridges, we
therefore decided to connect 1a with 2-
bromothiophene (2a) via direct C-H bond cleavage to
facilely construct thiopheneTPDthiophene (3a) as
en-
try
1
2
3
4
5
6
7
time yield
(h) (%)
acid
ligand
base
solvent
[
b]
A1
A2
A3
A4
A5
A6
A7
AcOH
TFA
HCl
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L2
L3
L4
L5
L6
L7
L8
L9
L1
L1
L1
L1
L1
L1
L1
L1
L1
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
p-xylene
DMAc
NMP
6
6
6
6
6
6
6
6
6
6
6
6
3
12
24
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
50
62
64
53
66
23
70
81
13
52
34
0
11
40
47
84
37
46
83
62
45
trace
trace
79
trace
75
0
78
a
representative A building block. The
optimization of reaction conditions was summarized
in Table 1. Initially, the di-heteroarylation was
performed with a commonly used acid additive (A1:
PivOH), an inexpensive ligand (L1: PCy
3
), and
in toluene at 100 C for 6 h. The target
Amolecule (3a) was isolated in 50% yield
entry 1). In addition to PivOH, we screened a variety
of additives including aliphatic- and aromatic acids
8
9
o
Cs
2
CO
3

(
1
0
11
H
2
SO
---
4
1
1
1
1
1
1
2
3
4
5
6
7
AcOH
AcOH
AcOH
AcOH
AcOH
(
(
A2~A7), giving the desired product in 23-70% yield
entries 2-7). Interestingly, we found that abundant
and inexpensive acetic acid afforded 3a in a
promising yield (81%, entry 8). Other acid additives
such as TFA, HCl, or H
2
SO
4
gave unsatisfactory
18 AcOH
19 AcOH
Cs CO3
2
results (13-52%, entries 9-11). The C-H activation
did not occur in the absense of organic carboxylate
Cs
Cs
Cs
Cs
Cs
2
2
2
2
2
CO
CO
CO
CO
CO
3
3
3
3
3
2
2
2
2
2
2
0
1
2
3
4
5
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
(
entry 12). Subsequently, we tried to shorten (3 h) or
lengthen (12, 24 h) the reaction time. However, this
did not further improve the chemoselectivity or yield
because most starting materials were recovered in the
case of 3 h (entry 13) whereas a significant amount of
complex mixtures were formed when the reaction
time was extended to 12 or 24 h (entries 14, 15).
K
2
CO
CO
3
Na
2
3
26 AcOH
27 AcOH
K
3
PO
---
4
2
2
3
3
3
8
9
0
1
2
AcOH
AcOH
AcOH
AcOH
AcOH
Cs
Cs
Cs
Cs
Cs
2
2
2
2
2
CO
CO
CO
CO
CO
3
3
3
3
3
11
Under present optimal conditions (AcOH, PCy
3
, 6 h),
trace
trace
trace
we proceeded to examine different phosphine ligands
DMSO
DMPU
(
(
8
L2~L7). P(tBu)
L5) were shown to give better yields of 3a (84%,
3%; entries 16, 19). N,N-bidentate type ligands (L8,
3
•HBF
4
(L2) and tri-o-tolylphosphine
L9) were much less efficient and only a trace of 3a
was generated (entries 22, 23). Thus, we fixed on the
use of relatively cheaper PCy
3
as optimal ligand for
the following investigation of bases. It was found that
K
2
CO
3
and K
3
PO
4
were almost as effective as Cs
2
2
CO
CO
3
(
79%, 75%; entries 24, 26) while less basic Na
3
was inefficient in C-H activation reactions (trace,
entry 25). Under base-free condition, the
heteroarylation did not take place (entry 27). Finally,
solvent effect was studied. Like toluene, nonpolar p-
xylene gave good isolated yield of 3a (78%, entry 28).
In contrast, we found the reaction hardly proceeded in
polar aprotic solvents such as DMAc, NMP, DMSO,
and DMPU (entries 29-32).
[
a]
Unless specified, the reaction was conducted with TPD 1a (1.00
mmol) and 2-bromothiophene 2a (2.20 mmol) under N in the
presence of Pd(OAc) (0.10 mmol), ligand (0.20 mmol), acid
0.30 mmol), and base (2.40 mmol) in solvent (3 mL) at 100 C
2
2
o
(
[
b]
for 3-24 hrs. Isolated yields.
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201700762
As shown in Table 2, in order to explore the reaction Table 2. Reaction Scope: C-H heteroarylation of various
[
a]
scope, we tested the chemoselective C-H di- acceptors (1b-t) with 2-bromothiophene (2a).
heteroarylation with various acceptor type heteroaryls
(
1b-t), mainly under the optimum reaction conditions
obtained in entry 8 of Table 1 (PCy
3
, AcOH, Cs
2
CO ,
3
toluene). In certain cases, the ligand or acid additive
was further optimized to obtain the best isolated yield.
First, reaction of 2-ethylhexyl substituted thieno[3,4-
c]pyrrole-4,6-dione (TPD, 1b) with 2a afforded
desired product 3b in 77% yield. Benzo-dithiophene-
diones (BDD, 1c-1e), an important class of acceptor-
[13]
type monomer for polymer semiconductors,
underwent C-H arylations smoothly to give A
products in moderate to good yields (3c-3e, 61-91%).
In addition to alkyl BDD, we found the
phenothiazine-substituted BDD (1f) was also facilely
arylated to generate 3f in 53% yield. Traditionally, to
access these compounds must rely on the use of Stille
coupling reactions that
needed the pre-
functionalizations of both starintg materials. Likewise,
[14]
direct C-H arylation of naphtho-thiophene-diones
NaphTD, 1g-1h) with 2a was efficiently performed
to provide compounds 3g, 3h in good yields (78%,
5%). Thieno-isoindole-diones (1i-1j), another
popular acceptor-type monomers used in the synthesis
(
7
[15]
of functional -conjugated polymers, were shown
to undergo diarylations best with P(1-
adamantyl) (nBu), affording desired prodicts in 61-
0% yields (3i-3j). In addition, we examined a series
2
7
of 3,4-diester-substituted thiophenes (1k-1o) under
optimum reaction time (24h). The target products (3k-
3
o) were isolated in 35-88% yields. C-H arylation of
diester compounds with perfluoroalkyl chains (1p-1q)
also proceeded successfully to yield 3p, 3q (55%,
5
0%)
Interestingly, 3,4-dibromothiophene (1r) reacted with
-bromothiophene regioselectively to produce a
under
modified
reaction
conditions.
2
versatile synthetic intermediate 3r in 61% yield. Two
bromine atoms remaining on the middle thiophene
may undergo further cross couplings to extend
conjugation length. Finally, other acceptors including
dialdehyde (1s) or diester furan (1t) were also tested,
providing desired products 3s-3t, respectively (36%,
60%).
The synthetic application of present methodology was
realized by the use of 3b as key building block in the
facile preparation of DA type organic sensitizer
for dye-sensitized soalr cells (Scheme 2). One-pot
sequential C-H arylations of 3b with a triphenylamine
(
TPA)-based donor followed by a furan-containing
acceptor led to the formation of desired aldehyde-
terminated unsymmetrical oligoaryl 4, which was
further converted into cyanoacetic acid as required
anchoring group by Knoevenagel condensation. To
access compound 4 traditionally by Stille couplings
would take at least ten synthetic steps.
[
a]
Unless specified, the C-H heteroarylation was conducted with
acceptors 1b-1t (1.00 mmol) and 2-bromothiophene 2a (2.20
mmol) under N in the presence of Pd(OAc) (0.10 mmol), ligand
0.20 mmol), acid (0.30 mmol), and Cs CO (2.40 mmol) in
solvent (3 mL) at 100 C for 6 or 24 hrs. Isolated yields.
Obtained sensitizer (CYL-12) was fabricated as dye-
sensitized soalr cells (DSSCs, the detailed procedures
for device fabrication and characterization were
provided in Experimental Section).
2
2
(
2
3
o
[b]
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201700762
(
b)
Figure 2. Photovoltaic characteristics of CYL-12: (a)
photocurrent density vs. photovoltage; (b) incident photon-
to-current conversion efficiency (IPCE)
Conclusion
Scheme 2. Application of -acceptor- building block (3b)
in the facile synthesis of new organic sensitizer CYL-12.
In summary, this work demonstrated a single-step
access to a variety of useful acceptor (A)
type building blocks for use in organic -functional
Table 3 and Figure 2 showed the photovoltaic materials. Under optimized reaction parameters, the
parameters and characteristics of CYL-12. Compared direct C-H heteroarylation displayed promising
to
the
commercially
available
cis- isolated yields and tolerated important fuctional
bis(isothiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylato) groups such as ester, ketone, aldehyde, sulfide, and
[16]
[17]
(
4,4’-di-nonyl-2’-bipyridyl)ruthenium(II) (Z907),
the open-circuit photovoltage (Voc) and the fill factor heteroarylation was also achieved thus remaining two
FF) of CYL-12 were found to be slightly lower than further arylable C-H bonds on both ends of desired
bromide. In addition, good chemoselectivity of this
(
those of the metal-containg dye (Z907). The short- prodcuts, which enabled subsequent chemical
circuit photocurrent density (Jsc) of CYL-12, however, transformations/-extensions. To apply present
2
was only 8.51 mA/cm , much smaller than that of methodology in the facile preparation of photovoltaic
2
Z907 (Jsc = 14.75 mA/cm ) thus leading to a materials, a new organic dye sensitizer (CYL-12) was
relatively inferior power conversion efficiency (PCE) step-economically synthesized via sequential C-H
of 3.86%.
arylations starting from one of the obtained
Astructures. Preparation of small-molecule
photovoltaic organic materials by step-saving C-H

Table 3. Fabrication of DSSCs using CYL-12 as dye (hetero)arylations is currently ongoing in our
sensitizer: photovoltaic parameters.
[
a]
laboratory.
DSSCs
V
oc [V]
J
sc [mA/cm2] FF [%] PCE [%]
CYL-12
0.64
0.69
8.51
14.75
70.71
69.50
3.86
7.07
Z907[
b]
Experimental Section
[
a]
Chenodeoxycholic acid (CDCA) was added as co-
[
b]
General Information
Unless otherwise specified, all reactions were carried out with
magnetic stirring and in flame-dried glassware under nitrogen if
adsorbent
(5
mM
for
CYL-12).
cis-
Bis(isothiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylato)(4,4’-
di-nonyl-2’-bipyridyl)ruthenium(II).
2
air or moisture sensitive. Reagents including Pd(OAc) , ligands,
acids, and bases are commercially available. Anhydrous or
reagent-grade solvents such as toluene, p-xylene, 1,4-dioxane,
N,N-dimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP),
dimethyl sulfoxide (DMSO), and N,N′-dimethylpropylene urea
(
DMPU) were purchased from Sigma-Aldrich, Acros, or Alfa
Aesar and used directly without further purifications. Syringes
used to transfer reagents and solvents were purged with nitrogen
prior to use. Reactions were monitored by thin layer
chromatography (TLC, aluminum plates coated with silica gel,
Merck 60, F-254). The spots were visualized by UV light. Flash
column chromatography was performed using silica gel 60
(
a)
(spherical, 40-75 μm) from Japan. The diameters of the columns
and the amount of silica gel loaded were calculated according to
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201700762
the recommendation of W. C. Still.[18] Melting points were
measured on a Fargo MP-2D apparatus. NMR spectra were
c]pyrrole-4,6(5H)-dione (TPD, 1a) and 2-bromothiophene (2a)
To a solution of Pd(OAc) (0.10 mmol), ligand (0.20 mmol), acid
2
recorded on a Bruker Magnet System 300 or 500 MHz instrument. (0.30 mmol), and base (2.40 mmol) in solvent (3 mL) in a flame-
1
Chemical shifts were given relative to CDCl
3
(7.26 ppm for H
dried Schlenk tube were added TPD (1a) (1.00 mmol) and 2-
bromothiophene (2a) (2.20 mmol) under N . The reaction mixture
was then heated at 100 °C under N for 3~24 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),
1
3
1
NMR, 77.0 ppm for C NMR), CD
2
Cl
2
(5.32 ppm for H NMR,
(2.50 ppm for H NMR, 39.4
(2.04 ppm for H NMR, 29.3 ppm
for C NMR). For the characterization of the observed signal
multiplicities, the following abbreviations were applied:
singlet), d (doublet), dd (doublet of doublets), dt (doublet of
2
1
3
1
5
4.0 ppm for C NMR), DMSO-d
6
2
1
3
1
ppm for C NMR), acetone-d
6
1
3
s
(
2 4
dried (Na SO ) and concentrated in vacuo. Purification by flash
triplets), dm (doublet of multiplets), t (triplet), td (triplet of
doublets), q (quartet), quint (quintet), m (multiplet), comp
chromatography yielded the desired product 3a.
(
complex), app (apparent), and br (broad). Mass spectra were
5-Phenethyl-1,3-di(thiophen-2-yl)-4H-thieno[3,4-c]pyrrole-
4,6(5H)-dione (3a) was prepared from 1a (257 mg, 1.00 mmol),
recorded on a JEOL JMS-700 for electron impact ionization (EI)
and high resolution mass spectra (HRMS) on a JEOL JMS-700
spectrometers. Fast atom bombardment (FAB) samples were
2a (359 mg, 2.20 mmol), Pd(OAc)
tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid (18 mg,
0.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
2
(24 mg, 0.10 mmol),
recorded in
a
3-nitrobenzyl alcohol- or glycerine-matrix.
2
3
Absorption spectra were measured on a Hitachi U-4100 UV-Vis
according to the general procedure A and yielding after column
spectrophotometer, and the HOMO-LUMO optical band gap
chromatography (dichloromethane : hexanes = 50 : 50) the pure
opt
o
(
E
g
) was calculated according to the λonset obtained. The
product 3a (354 mg, 84 %). Yellow powder; m.p.: 175.1-178.0 C.
1
experiments of cyclic voltammetry were carried out with an
Autolab electrochemical analyzer using a Pt working electrode, a
Pt wire counter electrode, and a Ag/AgCl reference electrode. The
measurements were conducted in dry THF solution containing 0.1
M tetra-n-butylammonium hexafluorophosphate as a supporting
3
H NMR (CDCl , 300 MHz, ppm): δ 7.99 (dd, J = 3.8, 0.8 Hz, 2
H), 7.43 (dd, J = 5.0, 0.8 Hz, 2 H), 7.19-7.36 (comp, 5 H), 7.12
(dd, J = 5.0, 3.8 Hz, 2 H), 3.83-3.94 (comp, 2 H), 2.94-3.04
1
3
3
(comp, 2 H); C NMR (CDCl , 75 MHz, ppm): δ 162.3, 138.2,
136.7, 132.4, 129.9, 128.9, 128.7, 128.6, 128.5, 128.3, 126.6, 39.9,
-
1
+
electrolyte under a scan rate of 100 mVs . The half-wave
34.7; MS (EI, 70 eV): 421 (M , 47 %), 384 (100 %), 330 (91 %);
potential, E1/2, was calculated by (Epa+Epc)/2, where Epa and Epc
2 3
HRMS (EI): calcd. for C22H15NO S : 421.0265, found: 421.0258.
are the potential energy of anodic and cathodic peaks, respectively. Synthesis and characterization of (1a): starting material 1a was
The HOMO energy level, EHOMO, was calculated by -(E1/2 + 0.197
prepared according to the procedures reported in RSC Adv. 2014,
opt
o
1
+
4.500) eV (vs. Ag/AgCl and NHE); ELUMO = EHOMO + E
g
.
4, 35868-35878. Pale yellow solid; m.p.: 154.3-155.2 C.
NMR (CDCl , 300 MHz, ppm): δ 7.80 (s, 2 H), 7.19-7.35 (comp,
5 H), 3.82-3.92 (comp, 2 H), 2.92-3.02 (comp, 2 H); C NMR
(CDCl , 75 MHz, ppm): δ 162.4, 138.0, 136.5, 128.9, 128.6,
H
3
1
3
Procedures for the fabrication and performance characterization
of dye-sensitized solar cells (DSSCs): The DSSCs were fabricated
3
+
using CYL-12 as sensitizers. The TiO
prepared according to the methods described in the literature.
Photo-electrode (working electrode): TiO screen printing was
carried out on a piece of fluorine-doped tin oxide glass (FTO,
2
paste and TiO
2
film were
126.7, 125.7, 39.7, 39.5; MS (EI, 70 eV): 257 (M , 17 %), 166
(100 %), 139 (78 %), 91 (79 %); HRMS (EI): calcd. for
[
19]
2
14 2
C H11NO S: 257.0510, found: 257.0507.
sheet resistivity of 7 Ω/square). The TiO
6 μm thick mesoporous anatase-TiO
diameter of 20 nm and a 4 μm thick TiO
2
film was composed of
nanoparticles with a
scattering layer with a
General procedure B for Table 2: Exploration of the substrate
scope
1
2
2
To a solution of Pd(OAc) (0.10 mmol), ligand (0.20 mmol), acid
2
diameter of 400 nm. After sintered at 350 °C for 15 mins and at
00 °C for 30 mins, the TiO photo-electrode that has an active
(0.30 mmol), and Cs CO (2.40 mmol) in toluene (3 mL) in a
2
3
5
2
flame-dried Schlenk tube were added the corresponding substrates
(1b-t) (1.00 mmol) and 2-bromothiophene (2a) (2.20 mmol)
2
2
area of 0.160 cm was immersed in the freshly prepared dye
solution (anhydrous THF) at 40 °C for 24 hours. Counter
electrode: another piece FTO glass coated with Pt was used as
counter electrode. The electrolyte solution was prepared via
mixing 0.6 M 1-butyl-3-methylimidazolium iodide ([bmim][I]),
under N . The reaction mixture was then heated at 100 °C under
N for 6~24 h. After the reaction mixture had cooled to room
2
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 (Na SO ) and
0
.1 M LiI, 0.05 M I
2
, 0.1 M GuNCS, and 0.5 M 4-t-butylpyridine
2
4
-
4
(TBP) in acetonitrile. To the dye solution containing 2.0 x 10
M
concentrated in vacuo. Purification by flash chromatography
yielded the desired products 3b-t.
of CYL-12 in THF, chenodeoxycholic acid (CDCA, 1.0~10 mM
in anhydrous THF) was added as co-adsorbent to see if the
performance of DSSCs was improved (A CDCA-free dye solution
was also prepared for the comparative experiment during the
optimization of device performance of DSSCs). An IPCE
spectrometer (EQE-R-3011, ENLI Technology Co. Ltd., Taiwan)
calibrated with a single-crystal silicon reference cell for each
measurement was used for the incident monochromatic photon-to-
current conversion efficiency (IPCE) measurements. An AM 1.5G
solar simulator (Yamashita Denso Corporation, YSS-50A) was
used as the irradiation light source for the characteristic current
density-voltage (J-V) measurements. The intensity of the
5
-(2-Ethylhexyl)-1,3-di(thiophen-2-yl)-4H-thieno[3,4-
[20]
c]pyrrole-4,6(5H)-dione
ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (1b) (265 mg,
.00 mmol), 2a (359 mg, 2.20 mmol), Pd(OAc) (24 mg, 0.10
mmol), tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid
(3b) was prepared from 5-(2-
1
2
2 3
(18 mg, 0.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene
(3 mL) according to the general procedure B and yielding after
column chromatography (ethyl acetate : hexanes = 5 : 95) the pure
o
product 3b (330 mg, 77 %). Yellow powder; m.p.: 126.0-126.3 C.
1
3
H NMR (CDCl , 300 MHz, ppm): δ 8.01 (dd, J = 3.8, 1.2 Hz, 2
2
simulated sunlight was calibrated to 100 mW/cm . The J-V
H), 7.42 (dd, J = 5.1, 1.2 Hz, 2 H), 7.11 (dd, J = 5.1, 3.8 Hz, 2 H),
characteristics of the cell under an illumination of AM 1.5G
simulated sunlight were obtained by applying the external
potential bias to the cell and measuring the photocurrent output
with a Keithley model 2400 digital source meter (Keithley, USA).
3
8
1
3
.55 (d, J = 7.2 Hz, 2 H), 1.77-1.93 (m, 1 H), 1.20-1.46 (comp,
H), 0.82-1.05 (comp, 6 H); C NMR (CDCl , 75 MHz, ppm): δ
3
62.8, 136.4, 132.5, 129.9, 128.6, 128.4 (two peaks), 42.5, 38.3,
0.6, 28.6, 23.9, 23.1, 14.1, 10.5.
13
General procedure A for Table 1: Optimization of the
regioselective C-H arylation using 5-phenethyl-4H-thieno[3,4-
2
4
-Heptyl-5,7-di(thiophen-2-yl)benzo[1,2-b:4,5-c']dithiophene-
,8-dione (3c) was prepared from 2-heptylbenzo[1,2-b:4,5-
5
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.201700762
c']dithiophene-4,8-dione (1c) (318 mg, 1.00 mmol), 2a (359 mg,
100 %), 234 (69 %), 149 (57 %); HRMS (EI): calcd. for
2
.20
tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid (18 mg,
.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
mmol),
Pd(OAc)
2
(24
mg,
0.10
mmol),
20 24 2 2
C H O S : 360.1218, found: 360.1219.
0
2
3
2-(2-Ethylhexyl)-5,7-di(thiophen-2-yl)benzo[1,2-b:4,5-
according to the general procedure B and yielding after column
c']dithiophene-4,8-dione (3e) was prepared from 2-(2-
chromatography (dichloromethane : hexanes = 50 : 50) the pure
ethylhexyl)benzo[1,2-b:4,5-c']dithiophene-4,8-dione (1e) (332 mg,
o
product 3c (313 mg, 65 %). Dark red solid; m.p.: 117.9-118.6 C.
1.00 mmol), 2a (359 mg, 2.20 mmol), Pd(OAc)
mmol), tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid
(18 mg, 0.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene
2
(24 mg, 0.10
1
H NMR (CDCl
app d, 2 H), 7.24 (s, 1 H), 7.06 (app t, 2 H), 2.81 (t, J = 7.5 Hz, 2
H), 1.59-1.79 (comp, 2 H), 1.20-1.42 (comp, 8 H), 0.89 (t, J = 6.9
3
, 300 MHz, ppm): δ 7.71-7.82 (comp, 2 H), 7.47
(
2
3
(3 mL) according to the general procedure B and yielding after
1
3
Hz, 3 H); C NMR (CDCl
3
, 125 MHz, ppm): δ 175.8, 174.2,
column chromatography (dichloromethane : hexanes = 60 : 40)
1
1
1
3
3
4
56.6, 145.2, 144.3, 143.9, 143.6, 132.8, 132.7, 131.3, 131.2,
the pure product 3e (303 mg, 61 %). Red liquid. H NMR (CDCl
3
,
30.1, 129.97, 129.96, 129.8, 127.33, 127.28, 123.4, 37.7, 31.0,
300 MHz, ppm): δ 7.71-7.86 (comp, 2 H), 7.47 (app dd, 2 H),
7.25 (s, 1 H), 7.00-7.14 (comp, 2 H), 2.77 (d, J = 6.6 Hz, 2 H),
1.55-1.71 (m, 1 H), 1.20-1.42 (comp, 8 H), 0.89 (app dd, 6 H);
+
0.8, 28.97, 28.96, 22.6, 14.1; MS (EI, 70 eV): 482 (M , 100 %),
68 (54%), 71 (51%); HRMS (EI): calcd. for C25
82.0503, found: 482.0500.
22 2 4
H O S :
1
3
3
C NMR (CDCl , 75 MHz, ppm): δ 175.9, 174.3, 155.4, 145.5,
Synthesis and characterization of (1c): (i) To a solution of 3,4-
thiophenedicarboxylic acid (516 mg, 3.00 mmol) in anhydrous
144.3, 143.9, 143.6, 132.8, 132.7, 131.3, 131.2, 130.2, 130.0,
129.9 (two peaks), 127.4, 127.3 124.5, 41.4, 34.8, 32.4, 28.8, 25.5,
23.0, 14.1, 10.8 ; MS (EI, 70 eV): 497 ([M+1] , 5 %), 149 (47 %),
+
CH
2
Cl
2
(4.5 mL), oxalyl chloride (1.5 mL) was added. Few drops
of N,N-dimetheylformamide was added to the mixture till it
produced bubbles. The reaction mixture was then stirred at room
temperature for 12 h before the solvent was distilled off under
ambient pressure. The crude product (di-acid chloride) was used
directly for the next step without further purification; (ii) To a
solution of the di-acid chloride and aluminium chloride (1596 mg,
97 (68 %), 71 (93 %), 57 (100 %); HRMS (EI): calcd. for
C H O S : 496.0659, found: 496.0667.
26 24 2 4
Synthesis and characterization of (1e): compound 1e was prepared
under the same reaction conditions as described for 1c. Pale
o
1
brown solid; m.p.: 104.1-104.7 C. H NMR (CDCl
3
, 300 MHz,
ppm): δ 8.15 (app s, 2 H), 7.26 (s, 1 H), 2.77 (d, J = 6.6 Hz, 2 H),
1
3
1
2.0 mmol) in anhydrous CH
2
Cl
2
(3 mL), 2-heptylthiophene (601
Cl (3 mL) was added
1.49-1.73 (m, 1 H), 1.10-1.42 (comp, 8 H), 0.86 (app t, 6 H);
C
mg, 3.30 mmol) diluted in anhydrous CH
2
2
NMR (CDCl , 75 MHz, ppm): δ 175.4, 173.7, 155.7, 145.2, 144.5,
3
dropwise at 0 ˚C for a period of 0.5 h. The reaction mixture was
then stirred at room temperature for 12 h before it was quenched
with 1M HCl(aq). The mixture was extracted with dichloromethane
137.8, 137.6, 132.3, 131.9, 124.7, 41.4, 34.7, 32.3, 28.8, 25.5,
22.9, 14.1, 10.8; MS (EI, 70 eV): 333 ([M+1] , 24 %), 234 (100
+
%), 207 (77 %); HRMS (EI): calcd. for C18
found: 332.0908.
20 2 2
H O S : 332.0905,
(
2 × 30 mL), and the combined organic layers were washed with
brine (50 mL), dried (Na SO ) and concentrated in vacuo.
Purification by flash chromatography (dichloromethane : hexanes
60 : 40) yielded the desired staring material 1c. Pale yellow
2
4
2-(10-Hexyl-10H-phenothiazin-3-yl)-5,7-di(thiophen-2-
yl)benzo[1,2-b:4,5-c']dithiophene-4,8-dione (3f) was prepared
=
o
1
solid; m.p.: 169.9-171.4 C. H NMR (CDCl
3
, 300 MHz, ppm): δ
.19 (app s, 2 H), 7.33 (s, 1 H), 2.87 (t, J = 7.6 Hz, 2 H), 1.62-
.85 (comp, 2 H), 1.14-1.48 (comp, 8 H), 0.77-0.98 (app s, 3 H);
from
c']dithiophene-4,8-dione (1f) (501 mg, 1.00 mmol), 2a (359 mg,
2.20 mmol), Pd(OAc) (24 mg, 0.10 mmol),
tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid (18 mg,
0.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
2-(10-hexyl-10H-phenothiazin-3-yl)benzo[1,2-b:4,5-
8
1
2
1
3
C NMR (CDCl
3
, 75 MHz, ppm): δ 175.6, 174.0, 157.0, 145.1,
1
44.7, 137.9, 137.7, 132.3, 131.9, 123.8, 31.7, 31.1, 30.8, 28.9
2
3
+
(two peaks), 22.6, 14.0; MS (EI, 70 eV): 318 (M , 20 %), 234
100 %), 205 (40 %), 177 (22 %); HRMS (EI): calcd. for
according to the general procedure B and yielding after column
(
chromatography (dichloromethane : hexanes = 40 : 60) the pure
o
1
C
17
H
18
2
O S
2
: 318.0748, found: 318.0745.
product 3f (352 mg, 53 %). Red solid; m.p.: 154.1-154.5 C. H
NMR (CDCl , 300 MHz, ppm): δ 7.71-7.81 (comp, 2 H), 7.52-
3
2
4
-Decyl-5,7-di(thiophen-2-yl)benzo[1,2-b:4,5-c']dithiophene-
,8-dione (3d) was prepared from 2-decylbenzo[1,2-b:4,5-
7.57 (m, 1 H), 7.44.-7.51 (comp, 2 H), 7.27-7.36 (m, 1 H), 7.19-
7.26 (m, 1 H), 7.12-7.18 (m, 1 H), 7.04-7.11 (comp, 3 H), 6.93
(app t, 1 H), 6.81 (app d, 1 H), 6.67-6.74 (m, 1 H), 3.76 (app s, 2
H), 1.71-1.83 (comp, 2 H), 1.24-1.48 (comp, 6 H), 0.91 (t, J = 6.7
c']dithiophene-4,8-dione (1d) (360 mg, 1.00 mmol), 2a (359 mg,
.20 mmol), Pd(OAc) (24 mg, 0.10 mmol),
tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid (18 mg,
.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
2
2
1
3
3
Hz, 3 H); C NMR (CDCl , 75 MHz, ppm): δ 175.6, 174.0, 152.5,
0
2
3
146.3, 145.0, 144.6, 144.1, 143.5, 132.8, 132.7, 131.31, 131.28,
130.03, 129.85, 127.4, 127.34, 127.31, 126.7, 125.5, 125.4, 125.3,
124.6, 123.6, 122.9, 120.3, 115.4, 115.2, 47.7, 31.4, 26.7, 26.6,
according to the general procedure B and yielding after column
chromatography (dichloromethane : hexanes = 60 : 40) the pure
product 3d (478 mg, 91 %). Red liquid. H NMR (CDCl
1
+
3
, 300
22.6, 14.0; MS (FAB): 665 (M , 5 %), 95 (100 %); HRMS (FAB):
MHz, ppm): δ 7.70-7.84 (comp, 2 H), 7.47 (app d, 2 H), 7.25 (s, 1
H), 7.03-7.12 (comp, 2 H), 2.81 (t, J = 7.5 Hz, 2 H), 1.61-1.77
2 5
calcd. for C36H27NO S : 665.0645, found: 665.0639.
Synthesis and characterization of (1f): compound 1f was prepared
under similar reaction conditions described for 1c. Orange solid;
1
3
(comp, 2 H), 1.45-1.66 (comp, 14 H), 0.81-0.96 (comp, 3 H) ; C
o
1
NMR (CDCl
3
3
, 75 MHz, ppm): δ 175.9, 174.3, 156.6, 145.2, 144.4, m.p.: 206.1-206.8 C. H NMR (CDCl , 300 MHz, ppm): δ 8.21
1
1
2
43.9, 143.6, 132.8, 132.7, 131.3, 131.2, 130.2, 130.0 (two peaks), (d, J = 3.0 Hz, 1 H), 8.19 (d, J = 3.0 Hz, 1 H), 7.68 (s, 1 H), 7.37-
29.8, 127.3, 127.3, 123.5, 31.9, 31.0, 30.8, 29.6, 29.5, 29.34,
9.30, 29.0, 22.7, 14.2; MS (EI, 70 eV): 525 [(M+1) , 1 %], 436
21 %), 421 (24 %), 71 (100 %), 57 (95 %); HRMS (EI): calcd.
7.48 (comp, 2 H), 7.09-7.20 (comp, 2 H), 6.89-6.99 (m, 1 H),
+
6.79-6.89 (comp, 2 H), 3.84 (t, J = 7.2 Hz, 2 H), 1.73-1.89 (comp,
1
3
(
2 H), 1.25-1.53 (comp, 6 H), 0.88 (t, J = 6.9 Hz, 3 H); C NMR
(CDCl , 75 MHz, ppm): δ 175.5, 173.8, 153.0, 146.6, 145.4,
for C28
H O
28 2
S
4
: 524.0972, found: 524.0965.
3
Synthesis and characterization of (1d): compound 1d was
prepared under the same reaction conditions as described for 1c.
144.4, 144.1, 137.73, 137.70, 132.6, 131.9, 127.5, 126.6, 125.6,
125.5, 124.9, 123.6, 123.0, 120.7, 115.6, 115.4, 47.7, 31.5, 26.8,
26.6, 22.6, 14.0; MS (EI, 70 eV): 501 (M , 3 %), 111 (35 %), 83
o
1
+
Red solid; m.p.: 197.6-198.0 C. H NMR (CDCl
3
, 300 MHz,
ppm): δ 8.22 (app s, 2 H), 7.36 (s, 1 H), 2.88 (t, J = 6.5 Hz, 2 H),
(50 %), 71 (65 %), 57 (100 %); HRMS (EI): calcd. for
1
.81-1.86 (comp, 2 H), 1.15-1.45 (comp, 14 H), 0.87 (app s, 3 H);
C NMR (CDCl , 75 MHz, ppm): δ 175.5, 173.9, 157.0, 145.1,
3
28 2 3
C H23NO S : 501.0891, found: 501.0894.
1
3
1
2
44.7, 137.9, 137.7, 132.4, 131.9, 123.8, 31.9, 31.1, 30.8, 29.6,
9.5, 29.30, 29.25, 29.0, 22.7, 14.1; MS (EI, 70 eV): 360 (M ,
6-Hexyl-1,3-di(thiophen-2-yl)naphtho[2,3-c]thiophene-4,9-
dione (3g) was prepared from 6-hexylnaphtho[2,3-c]thiophene-
+
6
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.201700762
4
,9-dione (1g) (298 mg, 1.00 mmol), 2a (359 mg, 2.20 mmol),
Pd(OAc) (24 mg, 0.10 mmol), tricyclohexylphosphine (56 mg,
.20 mmol), acetic acid (18 mg, 0.30 mmol), Cs CO (782 mg,
.40 mmol), and toluene (3 mL) according to the general
and yielding after column chromatography
dichloromethane : hexanes = 30 : 70) the pure product 3g (360
1.16-1.44 (comp, 10 H), 0.87 (t, J = 6.6 Hz, 3 H); 13C NMR
(CDCl , 75 MHz, ppm): δ 167.6, 135.3, 133.7, 132.5, 128.3,
3
2
0
2
2
3
127.3, 127.2, 126.8, 119.1, 38.5, 31.8, 29.2, 28.5, 26.9, 22.6, 14.1;
+
MS (EI, 70 eV): 479 (M , 18 %), 414 (21 %), 305 (14 %), 84 (69
procedure
(
B
%), 57 (100 %); HRMS (EI): calcd. for C26
found: 479.1049.
2 3
H25NO S : 479.1047,
1
mg, 78 %). Red liquid. H NMR (CDCl
d, J = 8.0 Hz, 1 H), 8.06 (d, J = 1.6 Hz, 1 H), 7.80 (app d, J = 3.8
Hz, 2 H), 7.45-7.55 (comp, 3 H), 7.09-7.12 (comp, 2 H), 2.72 (t, J
7.7 Hz, 2 H), 1.62-1.71 (comp, 2 H), 1.23-1.41 (comp, 6 H),
3
, 300 MHz, ppm): δ 8.15
(
6-(2-Ethylhexyl)-1,3-di(thiophen-2-yl)-5H-thieno[3,4-
f]isoindole-5,7(6H)-dione (3j) was prepared from 6-(2-
[
21]
=
ethylhexyl)-5H-thieno[3,4-f]isoindole-5,7(6H)-dione
(1j) (315
(24 mg, 0.10
(nBu) (72 mg, 0.20 mmol), acetic acid
(18 mg, 0.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene
1
3
0
1
1
2
%
4
.86-0.90 (comp, 3 H); C NMR (CDCl
3
, 75 MHz, ppm): δ 179.9, mg, 1.00 mmol), 2a (359 mg, 2.20 mmol), Pd(OAc)
2
79.5, 149.7, 143.8, 143.6, 134.6, 134.0, 132.9, 132.6, 131.0,
30.9, 129.9, 129.8, 129.7, 127.4, 127.3, 126.8, 36.1, 31.6, 30.7,
mmol), P(1-adamantyl)
2
2
3
+
8.8, 22.5, 14.0; MS (FAB): 462 (M , 3 %), 249 (40 %), 228 (90
(3 mL) according to the general procedure B and yielding after
column chromatography (ethyl acetate : hexanes = 8 : 92) the pure
product 3j (335 mg, 70 %). Orange/red solid; m.p.: 152.2-154.4
), 77 (60 %), 51 (100 %); HRMS (FAB): calcd. for C26
22 2 3
H O S :
62.0782, found: 462.0777.
o
1
Synthesis and characterization of (1g): compound 1g was
prepared under the same reaction conditions as described for 1c.
3
C. H NMR (CDCl , 300 MHz, ppm): δ 8.33 (s, 2 H), 7.45 (dd, J
= 5.1, 1.2 Hz, 2 H), 7.35 (dd, J = 3.6, 1.2 Hz, 2 H), 7.16 (dd, J =
5.1, 3.6 Hz, 2 H), 3.60 (d, J = 7.2 Hz, 2 H), 1.79-1.97 (m, 1 H),
o
1
White solid; m.p.: 77.4-78.3 C. H NMR (CDCl
ppm): δ 8.33 (d, J = 3.1 Hz, 1 H), 8.31 (d, J = 3.1 Hz, 1 H), 8.19
d, J = 8.0 Hz, 1 H), 8.08 (d, J = 1.7 Hz, 1 H), 7.56 (dd, J = 8.0,
3
, 300 MHz,
1
3
3
1.22-1.46 (comp, 8 H), 0.80-1.12 (comp, 6 H); C NMR (CDCl ,
(
75 MHz, ppm): δ 167.8, 135.3, 133.7, 132.4, 128.3, 127.3, 127.2,
1
1
7
1
2
.7 Hz, 1 H), 2.75 (t, J = 7.7 Hz, 2 H), 1.58-1.79 (comp, 2 H),
126.7, 119.1, 42.3, 38.2, 30.6, 28.5, 23.9, 23.0, 14.1, 10.5; MS (EI,
70 eV): 479 (M , 29 %), 380 (11 %), 263 (100 %), 234 (96 %),
1
3
+
.21-1.49 (comp, 6 H), 0.81-0.97 (comp, 3 H); C NMR (CDCl
3
,
5 MHz, ppm): δ 179.5, 179.1, 150.2, 137.4, 134.8, 134.3, 132.7,
218 (48 %); HRMS (EI): calcd. for C26
found: 479.1044.
2 3
H25NO S : 479.1047,
32.6, 132.4, 127.9, 127.3, 36.1, 28.9, 22.5, 14.0; MS (EI, 70 eV):
+
99 ([M+1] , 4 %), 109 (66 %), 95 (46 %), 81 (72 %), 69 (100 %);
HRMS (EI): calcd. for C18
H
18
O
2
S: 298.1028, found: 298.1029.
Dimethyl [2,2':5',2''-terthiophene]-3',4'-dicarboxylate (3k)
[
22]
was prepared from dimethyl thiophene-3,4-dicarboxylate
(200 mg, 1.00 mmol), 2a (359 mg, 2.20 mmol), Pd(OAc)
0.10 mmol), tricyclohexylphosphine (56 mg, 0.20 mmol), acetic
acid (18 mg, 0.30 mmol), Cs CO (782 mg, 2.40 mmol), and
(1k)
6
-(2-Ethylhexyl)-1,3-di(thiophen-2-yl)naphtho[2,3-
2
(24 mg,
c]thiophene-4,9-dione (3h) was prepared from 6-(2-
ethylhexyl)naphtho[2,3-c]thiophene-4,9-dione (1h) (326 mg, 1.00
2
3
mmol), 2a (359 mg, 2.20 mmol), Pd(OAc)
tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid (18 mg,
.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
2
(24 mg, 0.10 mmol),
toluene (3 mL) according to the general procedure B (reaction
time: 24 h) and yielding after column chromatography (ethyl
0
2
3
acetate : hexanes = 30 : 70) the pure product 3k (320 mg, 88 %).
1
according to the general procedure B and yielding after column
Yellow liquid. H NMR (CDCl
3
, 300 MHz, ppm): δ 7.40 (dd, J =
chromatography (ethyl acetate: hexanes = 20 : 80) the pure
5.2, 1.2 Hz, 2 H), 7.34 (dd, J = 3.6, 1.2 Hz, 2 H), 7.07 (dd, J = 5.2,
3.6 Hz, 2 H), 3.84 (s, 6 H); C NMR (CDCl , 75 MHz, ppm): δ
3
1
13
product 3h (367 mg, 75 %). Red liquid. H NMR (CDCl
3
, 300
MHz, ppm): δ 8.14 (d, J = 7.9 Hz, 1 H), 8.03 (s, 1 H), 7.75-7.84
164.1, 138.2, 132.5, 129.4, 128.7, 128.0, 127.7, 52.5; MS (FAB):
364 ([M+1] , 4 %), 249 (25 %), 280 (50 %), 51 (100 %); HRMS
+
(
comp, 2 H), 7.43-7.53 (comp, 3 H), 7.05-7.13 (comp, 2 H), 2.64
(
d, J = 7.2 Hz, 2 H), 1.57-1.76 (m, 1 H), 1.16-1.36 (comp, 8 H),
.87 (app t, 6 H); C NMR (CDCl , 75 MHz, ppm): δ 179.6,
3
12 4 3
(FAB): calcd. for C16H O S : 363.9898, found: 363.9901.
1
3
0
1
1
1
79.2, 149.5, 137.5, 135.4, 134.63, 134.55, 132.7, 132.6, 132.4,
29.4, 129.1, 128.1, 127.6, 41.0, 40.4, 32.3, 28.8, 25.5, 23.0, 14.1,
Diisopropyl [2,2':5',2''-terthiophene]-3',4'-dicarboxylate (3l)
was prepared from diisopropyl thiophene-3,4-dicarboxylate (1l)
+
0.8; MS (FAB): 491 ([M+1] , 6 %), 228 (31 %), 107 (62 %), 77
(256 mg, 1.00 mmol), 2a (359 mg, 2.20 mmol), Pd(OAc)
0.10 mmol), tricyclohexylphosphine (56 mg, 0.20 mmol), acetic
acid (18 mg, 0.30 mmol), Cs CO (782 mg, 2.40 mmol), and
2
(24 mg,
26 2 3
(100 %); HRMS (FAB): calcd. for C28H O S : 490.1095, found:
4
90.1089.
2
3
Synthesis and characterization of (1h): compound 1h was
prepared under the same reaction conditions as described for 1c.
toluene (3 mL) according to the general procedure B (reaction
time: 24 h) and yielding after column chromatography (ethyl
o
1
Pale yellow solid; m.p.: 59.0-60.8 C. H NMR (CDCl
3
, 300 MHz, acetate : hexanes = 30 : 70) the pure product 3l (273 mg, 65 %).
1
ppm): δ 7.23-7.31 (comp, 2 H), 7.12-7.22 (comp, 3 H), 2.53 (d, J
5.4 Hz, 2 H), 1.47-1.65 (m, 1 H), 1.14-1.45 (comp, 8 H), 0.88
Yellow liquid. H NMR (CDCl
3
, 300 MHz, ppm): δ 7.39 (dd, J =
=
5.1, 1.2 Hz, 2 H), 7.29 (dd, J = 3.6, 1.2 Hz, 2 H), 7.05 (dd, J = 5.1,
3.6 Hz, 2 H), 5.16 (septet, J = 6.3 Hz, 2 H), 1.25 (d, J = 6.3 Hz,
1
3
(
3
app, t, 6 H); C NMR (CDCl , 75 MHz, ppm): δ 179.6, 179.2,
1
3
1
4
5
3
49.5, 137.5, 135.0, 134.7, 132.7, 132.6, 132.4, 128.1, 127.8, 41.0, 12 H); C NMR (CDCl , 75 MHz, ppm): δ 163.3, 137.6, 132.6,
+
+
0.4, 32.3, 28.8, 25.5, 23.0, 14.1, 10.8; MS (FAB): 327 ([M+1] ,
4 %), 229 (29 %), 217 (32 %), 67 (100 %); HRMS (FAB): calcd.
130.8, 128.7, 127.7, 127.4, 69.5, 21.6; MS (EI, 70 eV): 420 (M ,
18 %), 336 (28 %), 127 (100 %), 111 (61 %); HRMS (EI): calcd.
for C20
H O
22 2
S: 326.1341, found: 326.1342.
20 4 3
for C20H O S : 420.0524, found: 420.0515.
Synthesis and characterization of (1l): compound 1l was prepared
5
6
5
-Octyl-1,3-di(thiophen-2-yl)-5H-thieno[3,4-f]isoindole-
,7(6H)-dione (3i) was prepared from 6-octyl-5H-thieno[3,4-
under the same reaction conditions as reported in literature. Pale
1
yellow liquid. H NMR (CDCl
3
, 300 MHz, ppm): δ 7.79 (s, 2 H),
[
21]
13
f]isoindole-5,7(6H)-dione
mg, 2.20 mmol), Pd(OAc)
adamantyl) (nBu) (72 mg, 0.20 mmol), acetic acid (18 mg, 0.30
mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
(1i) (315 mg, 1.00 mmol), 2a (359
5.19 (septet, J = 6.3 Hz, 2 H), 1.34 (d, J = 6.3 Hz, 12 H);
NMR (CDCl , 75 MHz, ppm): δ 162.7, 134.2, 131.1, 68.9, 21.8;
MS (EI, 70 eV): 256 (M , 1 %), 155 (100 %), 128 (25 %), 59 (25
C
2
(24 mg, 0.10 mmol), P(1-
3
+
2
2
3
%); HRMS (EI): calcd. for
256.0774.
12 16 4
C H O S: 256.0769, found:
according to the general procedure B and yielding after column
chromatography (ethyl acetate : hexanes = 10 : 90) the pure
product 3i (292 mg, 61 %). Orange/red solid; m.p.: 143.1-144.3
Bis(2-ethylhexyl) [2,2':5',2''-terthiophene]-3',4'-dicarboxylate
(3m) was prepared from bis(2-ethylhexyl) thiophene-3,4-
dicarboxylate (1m) (397 mg, 1.00 mmol), 2a (359 mg, 2.20
o
1
C. H NMR (CDCl
5.1, 1.2 Hz, 2 H), 7.18 (dd, J = 3.6, 1.2 Hz, 2 H), 7.18 (dd, J =
.1, 3.6 Hz, 2 H), 3.70 (t, J = 7.2 Hz, 2 H), 1.60-1.78 (comp, 2 H),
3
, 300 MHz, ppm): δ 8.35 (s, 2 H), 7.47 (dd, J
=
5
mmol), Pd(OAc)
2
(24 mg, 0.10 mmol), tricyclohexylphosphine
7
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.201700762
(
56 mg, 0.20 mmol), acetic acid (18 mg, 0.30 mmol), Cs
2
CO
3
mg, 2.20 mmol), Pd(OAc)
2
(24 mg, 0.10 mmol),
(
782 mg, 2.40 mmol), and toluene (3 mL) according to the general
tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid (18 mg,
0.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
according to the general procedure B (reaction time: 24 h) and
yielding after column chromatography (dichloromethane
hexanes = 40 : 60)z the pure product 3o (155 mg, 35 %). Brown
procedure B (reaction time: 24 h) and yielding after column
chromatography (dichloromethane : hexanes = 30 : 70) the pure
product 3m (398 mg, 71 %). Brown liquid. H NMR (CDCl
2
3
1
3
, 300
:
MHz, ppm): δ 7.35 (dd, J = 5.1, 1.2 Hz, 2 H), 7.28 (dd, J = 3.6,
.2 Hz, 2 H), 7.02 (dd, J = 5.1, 3.6 Hz, 2 H), 4.10-4.24 (comp, 4
H), 1.51-1.64 (comp, 2 H), 1.18-1.40 (comp, 16 H), 0.79-0.97
1
1
3
liquid. H NMR (CDCl , 300 MHz, ppm): δ 7.39-7.43 (comp, 2
H), 7.25-7.39 (comp, 10 H), 7.19-7.24 (comp, 2 H), 7.05-7.10
1
3
(comp, 12 H); C NMR (CDCl
3
, 75 MHz, ppm): δ 164.0, 137.7,
(comp, 2 H), 4.38 (t, J = 7.2 Hz, 4 H), 3.13 (t, J = 7.2 Hz, 4 H);
1
3
1
2
7
5
32.6, 130.5, 128.5, 127.7, 127.6, 68.2, 38.6, 30.1, 28.9, 23.5,
C NMR (CDCl
3
, 75 MHz, ppm): δ 163.3, 138.5, 134.9, 132.3,
+
3.0, 14.1, 10.9; MS (EI, 70 eV): 561 ([M+1] , 73 %), 319 (19 %), 129.8, 129.4, 129.2, 128.9, 128.0, 127.7, 126.7, 63.9, 31.8; MS
+
1 (61 %), 57 (100 %); HRMS (EI): calcd. for C30
60.2089, found: 560.2087.
H
40
O
4
S
3
:
(EI, 70 eV): 608 (M , 66 %), 524 (74 %), 336 (86 %), 137 (80 %),
109 (100 %); HRMS (EI): calcd. for C30
608.0277.
24 4 5
H O S : 608.0278, found:
Synthesis and characterization of (1m): compound 1m was
prepared under the same reaction conditions as reported in
Synthesis and characterization of (1o): compound 1o was
[
22]
1
literature. Yellow liquid. H NMR (CDCl
7
1
3
, 300 MHz, ppm): δ
.81 (s, 2 H), 4.11-4.29 (comp, 4 H), 1.57-1.77 (comp, 2 H), 1.19-
.52 (comp, 16 H), 0.91 (app t, 12 H); 13C NMR (CDCl
synthesized according to the procedures described for 1n. Yellow
1
liquid. H NMR (CDCl
3
, 300 MHz, ppm): δ 7.78 (s, 2 H), 7.20-
3
, 75 MHz, 7.51 (comp, 10 H), 4.46 (t, J = 6.9 Hz, 4 H), 2.26 (t, J = 6.9 Hz, 4
1
3
ppm): δ 163.2, 133.8, 131.5, 67.8, 38.8, 30.4, 28.9, 23.8, 23.0,
3
H); C NMR (CDCl , 75 MHz, ppm): δ 162.5, 135.1, 132.9,
+
+
1
%
4.1, 11.0; MS (EI, 70 eV): 396 (M , 1 %), 173 (68 %), 155 (80
), 57 (100 %); HRMS (EI): calcd. for C22 S: 396.2334,
132.4, 129.9, 129.2, 126.7, 63.8, 32.3; MS (EI, 70 eV): 444 (M ,
9 %), 136 (100 %), 109 (26 %) ; HRMS (EI): calcd. for
36 4
H O
found: 396.2336.
22 20 4 3
C H O S : 444.0524, found: 444.0527.
Bis(6-ethoxy-6-oxohexyl)
dicarboxylate (3n) was prepared from bis(6-ethoxy-6-oxohexyl)
[2,2':5',2''-terthiophene]-3',4'-
Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)
terthiophene]-3',4'-
[2,2':5',2''-
thiophene-3,4-dicarboxylate (1n) (456 mg, 1.00 mmol), 2a (359
dicarboxylate
bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)
dicarboxylate (1p) (864 mg, 1.00 mmol), 2a (359 mg, 2.20 mmol),
Pd(OAc) (24 mg, 0.10 mmol), P(tBu) (Me)•HBF (50 mg, 0.20
mmol), p-anisic acid (46 mg, 0.30 mmol), Cs CO (782 mg, 2.40
(3p)
was
prepared
from
mg, 2.20 mmol), Pd(OAc)
tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid (18 mg,
.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
2
(24 mg, 0.10 mmol),
thiophene-3,4-
0
2
3
2
2
4
according to the general procedure B (reaction time: 24 h) and
2
3
yielding after column chromatography (ethyl acetate : hexanes =
mmol), and toluene (3 mL) according to the general procedure B
(reaction time: 24 h) and yielding after column chromatography
(ethyl acetate : dichloromethane : hexanes = 5 : 15 : 80) the pure
1
3
0 : 70) the pure product 3n (260 mg, 42 %). Yellow liquid. H
NMR (CDCl
7
4
3
, 300 MHz, ppm): δ 7.38 (dd, J = 5.1, 1.1 Hz, 2 H),
.28 (dd, J = 3.7, 1.1 Hz, 2 H), 7.04 (dd, J = 5.1, 3.7 Hz, 2 H),
.20 (t, J = 6.6 Hz, 4 H), 4.10 (q, J = 7.1 Hz, 4 H), 2.24 (t, J = 7.5
o
product 3p (565 mg, 55 %). Yellow solid; m.p.: 102.6-103.3 C.
1
H NMR (CDCl , 300 MHz, ppm): δ 7.43 (dd, J = 5.1, 1.2 Hz, 2
3
1
3
Hz, 4 H), 1.51-1.68 (comp, 8 H), 1.18-1.36 (comp, 10 H);
C
H), 7.27-7.30 (comp, 2 H), 7.00-7.14 (comp, 2 H), 4.51 (t, J = 6.6
1
3
NMR (CDCl
3
, 75 MHz, ppm): δ 173.4, 163.6, 137.8, 132.4, 130.0, Hz, 4 H), 2.45 (tt, J = 18.3, 6.3 Hz, 4 H); C NMR (CDCl , 125
3
1
28.6, 127.7, 127.4, 65.4, 60.1, 34.0, 28.0, 25.3, 24.5, 14.2; MS
MHz, ppm): δ 163.1, 139.0, 132.0, 129.1, 129.0, 128.1, 127.6,
+
1
2
(
(
6
EI, 70 eV): 621 ([M+1] , 21 %), 430 (91 %), 143 (57 %), 69
100 %); HRMS (EI): calcd. for C30 : 620.1572, found:
20.1572.
117.4 (q, J = 255 Hz), 108.6 (t, J = 33.3 Hz), 57.3, 30.2 (t,
C-F
C-F
+
2
H
36
O
8
S
3
JC-F = 21.8 Hz); MS (FAB): 1027 (M , 18 %), 746 (6 %), 654 (15
30 14 26 4 3
%), 69 (100 %); HRMS (FAB): calcd. for C H F O S :
1027.9639, found: 1027.9637.
Synthesis and characterization of (1p): compound 1p was
Synthesis and characterization of (1n): (i) To a solution of 3, 4-
thiophenedicarboxylic acid (516 mg, 3.00 mmol) in anhydrous
CH
2
Cl
2
(4.5 mL), oxalyl chloride (1.5 mL) was added. Few drops
prepared under the same reaction conditions as reported in
[
23]
1
of N, N-dimetheylformamide were added to the mixture till it
produced bubbles. The reaction mixture was then stirred at room
temperature for 12 h before the solvent was distilled off under
ambient pressure. The crude product (di-acid chloride) was used
directly for the next step without further purification; (ii) To a
solution of the corresponding R-OH (1200 mg, 7.5 mmol) in
literature.
3
Transparent liquid. H NMR (CDCl , 300 MHz,
ppm): δ 7.87 (s, 2 H), 4.56 (t, J = 6.5 Hz, 4 H), 2.55 (tt, J = 18.3,
1
3
6.3 Hz, 4 H); C NMR (CDCl , 125 MHz, ppm): δ 162.1, 132.62,
3
1
2
132.58, 117.5 (q, J = 152.6 Hz), 112.9 (t, J = 19.9 Hz),
108.3 (t, J = 3.0 Hz), 57.0, 30.3 (t, J = 13.1 Hz); MS (FAB):
864 ([M+1] , 16 %), 501 (80 %), 155 (100 %), 69 (61 %); HRMS
(FAB): calcd. for C H F O S: 863.9885, found: 863.9889.
C-F
C-F
3
2
C-F
+
C-F
2 2
anhydrous CH Cl (4 mL), pyridine (711 mg, 9.0 mmol) was
2
2
10 26
4
added dropwise at ice-bath temperature. The reaction mixture was
then stirred at room temperature for 6 h before it was quenched
with water. The mixture was extracted with dichloromethane (2 ×
Bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl)[2,2':5',2''-
terthiophene]-3',4'-dicarboxylate (3q) was prepared from
3
0 mL), and the combined organic layers were washed with brine
bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl)
dicarboxylate (1q) (799 mg, 1.00 mmol), 2a (359 mg, 2.20 mmol),
Pd(OAc) (24 mg, 0.10 mmol), P(tBu) (Me)•HBF (50 mg, 0.20
mmol), PivOH (31 mg, 0.30 mmol), Cs CO (782 mg, 2.40
mmol), and toluene (3 mL) according to the general procedure B
thiophene-3,4-
(
50 mL), dried (Na SO ) and concentrated in vacuo. Purification
2
4
by flash chromatography (ethyl acetate : hexanes = 30 : 70)
2
2
4
1
yielded the desired staring material 1n. Yellow liquid. H NMR
2
3
3
(CDCl , 300 MHz, ppm): δ 7.82 (s, 2 H), 4.25 (t, J = 6.6 Hz, 4 H),
4
.10 (q, J = 7.2 Hz, 4 H), 2.30 (t, J = 7.5 Hz, 4 H), 1.60-1.82
(
(
reaction time: 24 h) and yielding after column chromatography
ethyl acetate : dichloromethane : hexanes = 5 : 15 : 80) the pure
1
3
(comp, 8 H), 1.37-1.50 (comp, 4 H), 1.22 (t, J = 7.2 Hz, 6 H) ; C
NMR (CDCl
3
, 75 MHz, ppm): δ 173.5, 163.1, 133.5, 131.6, 65.2,
o
1
product 3q (482 mg, 50 %). Yellow solid; m.p.: 79.9-80.6 C. H
+
6
0.3, 34.2, 28.3, 25.5, 24.6, 14.2; MS (EI, 70 eV): 457([M+1] , 2
NMR (CDCl
3
, 300 MHz, ppm): δ 7.45 (dd, J = 5.1, 1.2 Hz, 2 H),
%), 183 (50 %), 155 (100 %), 142 (65 %); HRMS (EI): calcd. for
7
6
.35 (dd, J = 3.6, 1.2 Hz, 2 H), 7.09 (dd, J = 5.1, 3.6 Hz, 2 H),
.03 (tt, J = 51.9, 5.1 Hz, 2 H), 4.68 (t, J = 14.0 Hz, 4 H);
C
22
H
32
8
O S: 456.1818, found: 456.1814.
13
C
NMR (CDCl
3
, 125 MHz, ppm): δ 161.8, 140.4, 131.3, 129.4,
Bis(2-(phenylthio)ethyl)
dicarboxylate (3o) was prepared from bis(2-(phenylthio)ethyl)
thiophene-3,4-dicarboxylate (1o) (445 mg, 1.00 mmol), 2a (359
[2,2':5',2''-terthiophene]-3',4'-
2
2
1
28.5, 127.8, 127.5, 112.9 (t, JC-F = 31.3 Hz), 60.6 (t, JC-F = 25
+
Hz); MS (FAB): 963 (M , 100 %), 632 (85 %), 127 (52 %), 111
12 24 4 3
40 %), 51 (70 %); HRMS (FAB): calcd. for C28H F O S :
(
8
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.201700762
9
63.9514, found: 963.9509.
mixture was then heated again to 100 °C under N
2
and kept at the
Synthesis and characterization of (1q): compound 1q was
same temperature for 24 hours. After the reaction mixture had
cooled to room temperature, water (10 mL) was added. The
mixture was extracted with dichloromethane (2 × 30 mL), and the
combined organic layers were washed with brine (50 mL), dried
(Na SO ) and concentrated in vacuo. Purification by column
2 4
chromatography (hexane : ethyl acetate = 85 : 15) afforded the
prepared under the same reaction conditions as reported in
[
23]
1
literature.
3
Transparent liquid. H NMR (CDCl , 300 MHz,
ppm): δ 8.02 (s, 2 H), 6.04 (tt, J = 51.9, 5.1 Hz, 2 H), 4.77 (t, J =
1
3
1
1
(
3.5 Hz, 4 H); C NMR (CDCl
3
, 125 MHz, ppm): δ 160.4, 134.2,
2
2
31.2, 104.2 (t, JC-F = 53.1 Hz), 60.1 (t, JC-F = 45 Hz) ; MS
+
FAB): 799 (M , 5 %), 469 (100 %), 157 (12 %), 110 (16 %);
pure product 4a (286 mg, 28 %). Dark red solid; m.p.: 36.1-38.1
1
HRMS (FAB): calcd. for S: 799.9760, found:
C
20
H
8
F
24
O
4
˚C. H NMR (CDCl
3
, 300 MHz, ppm): δ 9.63 (s, 1 H), 7.97 (dd, J
7
99.9761.
= 21.0, 4.0 Hz, 2 H), 7.47 (d, J = 4.0 Hz, 1 H), 7.41 (d, J = 8.7 Hz,
H), 7.29 (d, J = 3.8 Hz, 1 H), 7.16 (d, J = 4.0 Hz, 1 H), 7.07 (d,
2
3
',4'-Dibromo-2,2':5',2''-terthiophene[24] (3r) was prepared
J = 8.9 Hz, 4 H), 6.78-6.96 (comp, 6 H), 6.75 (d, J = 3.7 Hz, 1 H),
3.94 (t, J = 6.5 Hz, 4 H), 3.56 (d, J = 7.2 Hz, 2 H), 1.72-1.89
(comp, 5 H), 1.23-1.50 (comp, 28 H), 0.80-1.04 (comp, 12 H).;
from 3,4-dibromothiophene (1r) (242 mg, 1.00 mmol), 2a (359
mg, 2.20 mmol), Pd(OAc) (24 mg, 0.10 mmol),
tricyclohexylphosphine (56 mg, 0.20 mmol), benzoic acid (37 mg,
.30 mmol), K CO (331 mg, 2.40 mmol), and toluene (3 mL)
2
1
3
3
C NMR (CDCl , 75 MHz, ppm): δ 162.9, 162.8, 155.9, 154.9,
0
2
3
154.3, 153.6, 151.9, 149.3, 148.9, 140.2, 140.0, 137.7, 134.3,
134.1, 133.6, 131.8, 130.4, 129.7, 127.0, 126.7, 124.6, 122.8,
119.6, 115.4, 108.9, 68.3, 38.3, 31.9, 31.8, 30.6, 30.1, 29.7, 29.4,
29.3, 28.6, 26.1, 23.9, 23.1, 22.7, 14.1, 10.5; MS (FAB): 1022
according to the general procedure B (reaction time: 24 h) and
yielding after column chromatography (hexanes) the pure product
o
1
3
(
(
r (248 mg, 61 %). Yellow solid; m.p.: 101.5-102.6 C. H NMR
CDCl , 300 MHz, ppm): δ 7.44-7.55 (comp, 2 H), 7.34-7.43
comp, 2 H), 7.05-7.19 (comp, 2 H); C NMR (CDCl
+
3
(M , 21 %), 909 (8 %), 51 (100 %); HRMS (FAB): calcd. for
1
3
3
, 75 MHz,
61 70 2 6 3
C H N O S : 1022.4396, found: 1022.4398.
ppm): δ 134.0, 131.0, 112.4, 77.3, 77.1, 76.8.
Knoevenagel condensations:
[
2,2':5',2''-Terthiophene]-3',4'-dicarbaldehyde
prepared from thiophene-3,4-dicarbaldehyde (1s) (140 mg, 1.00
mmol), 2a (359 mg, 2.20 mmol), Pd(OAc) (24 mg, 0.10 mmol),
P(o-tolyl) (61 mg, 0.20 mmol), acetic acid (18 mg, 0.30 mmol),
Cs CO (782 mg, 2.40 mmol), and toluene (3 mL) according to
(3s)
was
(E)-3-(5-(5-(3-(5-(4-(Bis(4-
(octyloxy)phenyl)amino)phenyl)thiophen-2-yl)-5-(2-
ethylhexyl)-4,6-dioxo-5,6-dihydro-4H-thieno[3,4-c]pyrrol-1-
yl)thiophen-2-yl)furan-2-yl)-2-cyanoacrylic acid (CYL-12): To
a solution of the aldehyde (4a) (255 mg, 0.25 mmol) in
chloroform (5 mL) were added cyanoacetic acid (10.0 mmol) and
piperidine (0.5 mL) at room temperature. The reaction mixture
2
3
2
3
the general procedure B (reaction time: 24 h) and yielding after
column chromatography (ethyl acetate : dichloromethane :
hexanes = 10 : 15 : 75) the pure product 3s (104 mg, 36 %).
Yellow solid; m.p.: 107.6-108.1 C. H NMR (CDCl
ppm): δ 10.27 (s, 2 H), 7.40-7.80 (comp, 4 H), 7.06-7.23 (comp, 2
2
was then heated at reflux under N for 12 h. After the reaction
o
1
, 300 MHz,
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 (Na SO ) and concentrated in vacuo. Purification by
2 4
column chromatography (using the eluent with a gradient polarity:
from dichloromethane : methanol = 95 : 5 to dichloromethane :
3
1
3
H); C NMR (CDCl
31.3, 130.7, 129.6, 128.2; MS (EI, 70 eV): 303 (M , 3 %), 220
13 %), 154 (100 %), 89 (49 %), 77 (49 %); HRMS (EI): calcd.
: 303.9686, found: 303.9693.
3
, 75 MHz, ppm): δ 186.7, 144.9, 135.3,
+
1
(
8 2 3
for C14H O S
methanol = 85 : 15) gave the pure product CYL-12 (232 mg, 85
1
%). Dark red solid; m.p.: 139.1-141.8 ˚C. H NMR (CDCl
3
and
Diethyl 2,5-di(thiophen-2-yl)furan-3,4-dicarboxylate (3t) was
prepared from diethyl furan-3,4-dicarboxylate (1t) (212 mg, 1.00
few drops of CD
.26-7.46 (comp, 4 H), 7.06-7.18 (comp, 2 H), 6.90-7.04 (comp, 4
H), 6.69-6.87 (comp, 5 H), 6.59-6.67 (m, 1 H), 3.85 (t, J = 6.4 Hz,
3
OD, 300 MHz, ppm): δ 7.63-7.96 (comp, 3 H),
7
mmol), 2a (359 mg, 2.20 mmol), Pd(OAc)
tricyclohexylphosphine (56 mg, 0.20 mmol), acetic acid (18 mg,
.30 mmol), Cs CO (782 mg, 2.40 mmol), and toluene (3 mL)
2
(24 mg, 0.10 mmol),
4
1
H), 3.28 (dt, J = 3.2, 1.6 Hz, 2 H), 1.61-1.82 (comp, 5 H), 1.14-
0
2
3
.41 (comp, 28 H), 0.67-0.95 (comp, 12 H); MS (FAB): 1090
according to the general procedure B (reaction time: 24 h) and
yielding after column chromatography (ethyl acetate : hexanes =
+
(
[M+1] , 5 %), 654 (3 %), 77 (100 %); HRMS (FAB): calcd. for
1
64 71 3 7 3
C H N O S : 1089.4454, found: 1089.4456.
1
0 : 90) the pure product 3t (226 mg, 60 %). Green liquid. H
NMR (CDCl , 300 MHz, ppm): δ 7.79 (dd, J = 3.9, 1.0 Hz, 2 H),
.44 (dd, J = 5.1, 1.0 Hz, 2 H), 7.11 (dd, J = 5.1, 3.9 Hz, 2 H),
.37 (q, J = 7.2 Hz, 4 H), 1.37 (t, J = 7.2 Hz, 6 H); 13C NMR
, 75 MHz, ppm): δ 163.2, 148.8, 130.2, 128.3, 128.2,
3
7
4
Acknowledgements
(CDCl
3
+
Financial support provided by the Ministry of Science and
Technology (MOST), Taiwan (MOST 105-2113-M-008-005) and
the National Central University (NCU) are gratefully
acknowledged. Mr. Kuan-Ming Lu and Mr. Wei-Ming Li
contributed equally to this work.
1
%
3
27.7, 113.8, 61.5, 14.2; MS (EI, 70 eV): 376 (M , 7 %), 203 (11
), 111 (100 %), 83 (12 %); HRMS (EI): calcd. for C18
76.0439, found: 376.0446.
16 5 2
H O S :
Synthesis and characterization of compounds 4a and CYL-12
Scheme 2):
(
5
2
-(5-(3-(5-(4-(Bis(4-(octyloxy)phenyl)amino)phenyl)thiophen-
-yl)-5-(2-ethylhexyl)-4,6-dioxo-5,6-dihydro-4H-thieno[3,4-
References
c]pyrrol-1-yl)thiophen-2-yl)furan-2-carbaldehyde (4a): To a
solution of Pd(OAc)
mg, 10 mol%), PivOH (31 mg, 30 mol%), and Cs
2
(12 mg, 5 mol%), P(1-adamantyl)
CO
2
(nBu) (36
(391 mg,
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Advanced Synthesis & Catalysis
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0
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Advanced Synthesis & Catalysis
10.1002/adsc.201700762
FULL PAPER
Direct C-H Arylation as
Chemoselective Single-Step Access to
Organic-Electronics-Versatile -
Acceptor- Type Building Blocks
Adv. Synth. Catal. Year, Volume, Page
–
Page
Kuan-Ming Lu, Wei-Ming Li, Po-Yu
Lin, Kuan-Ting Liu, and Ching-Yuan
Liu*
1
1
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