Cascade reaction for the synthesis of polycyclic aromatic hydrocarbons via transient directing group strategy

Article abstract of DOI:10.1016/j.tet.2019.06.036

A Pd(II)-catalyzed cascade synthesis of diverse polycyclic aromatic hydrocarbons via transient directing group strategy has been developed, involving the consecutive arylation, cyclization and aromatization. The efficiency and practicality were demonstrated by wide substrate range, concise synthetic pathway and mild reaction conditions. The subsequent transformations of the benz[a]anthracene core accessed natural bioactive PAH molecules.

Full text of DOI:10.1016/j.tet.2019.06.036

Accepted Manuscript
Cascade reaction for the synthesis of polycyclic aromatic hydrocarbons via transient
directing group strategy
Ziqi Wang, Wendan Dong, Bing Sun, Qinqin Yu, Fang-Lin Zhang
PII:
S0040-4020(19)30708-2
https://doi.org/10.1016/j.tet.2019.06.036
TET 30428
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 11 April 2019
Revised Date: 14 June 2019
Accepted Date: 22 June 2019
Please cite this article as: Wang Z, Dong W, Sun B, Yu Q, Zhang F-L, Cascade reaction for the
synthesis of polycyclic aromatic hydrocarbons via transient directing group strategy, Tetrahedron (2019),
doi: https://doi.org/10.1016/j.tet.2019.06.036.
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Cascade Reaction for the Synthesis of
Polycyclic Aromatic Hydrocarbons via
Transient Directing Group Strategy
Leave this area blank for abstract info.
Ziqi Wang, Wendan Dong, Bing Sun, Qinqin Yu, and Fang-Lin Zhang
School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan
4
30070, PR China

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Cascade Reaction for the Synthesis of Polycyclic Aromatic Hydrocarbons via
Transient Directing Group Strategy
Ziqi Wang, Wendan Dong, Bing Sun, Qinqin Yu,∗ and Fang-Lin Zhang∗
a
School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, PR China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A Pd(II)-catalyzed cascade synthesis of diverse polycyclic aromatic hydrocarbons via transient
directing group strategy has been developed, involving the consecutive arylation, cyclization and
aromatization. The efficiency and practicality were demonstrated by wide substrate range,
concise synthetic pathway and mild reaction conditions. The subsequent transformations of the
benz[a]anthracene core accessed natural bioactive PAH molecules.
Available online
2
009 Elsevier Ltd. All rights reserved.
Keywords:
palladium
cascade
polycyclic aromatic hydrocarbons
transient directing group
bioactive molecules
1
. Introduction
Polycyclic aromatic hydrocarbons (PAHs) are privileged
1
scaffolds in a variety of useful organic functional molecules and
2
drug molecules . Specifically, benz[a]anthracenes, containing a
quinone moiety, constitute the core skeleton of an important class
of angucycline natural products (Scheme 1A), such as antibiotics
3
4
5
tetrangulol ,
anhydrolandomycinone ,
mayamycin ,
and
6
antitumor agents marmycin A and B . The synthetic value of
benz[a]anthracene and its derivatives to date has promoted
manifold synthetic strategies toward their facile and efficient
7
construction. Representatively, Zhou’s group unveiled a simple
one-pot synthesis of tetraphenes from propargylphosphonium
salts through sequential propargyl-allenyl isomerization,
phosphine addition, intramolecular Wittig reactions and Diels-
7e
Alder reactions (Scheme 1B) . Shi and co-workers developed a
gold-catalyzed tandem synthetic pathway, involving cyclization-
oxidation of alkylidenecyclopropane-containing 1,5-enynes with
3
,5-dibromo-pyridine N-oxide via a noncarbene model to access
the arylacetaldehyde derivatives, and followed by a further
7i
transformation to produce the tetraphenes . Despite these efforts,
the reported traditional strategies commonly suffer shortcomings
such as tedious synthetic process, the lack of availability of the
substrates and the weak tolerance. From a practical point of view,
a facile and efficient synthetic strategy is in great demand to
access this type of important tetraphene compounds.
Scheme 1. Examples of bioactive molecules bearing angular
tetracyclic skeleton (A) and the synthetic approaches (B-D).
In recent years, transition-metal-catalyzed direct C–H
functionalization via transient directing group (TDG) strategy has
8
emerged to be a powerful tool in the cleavage of C–H bond. Yu
∗
∗
Corresponding author. e-mail: green_lemon@whut.edu.cn (Q. Yu)
Corresponding author. e-mail: fanglinzhang@whut.edu.cn (F.-L. Zhang)

2
Tetrahedron
group pioneered that with amino acid as
A
TD
C
G
C
, t
E
hePTin
E
s
D
itu MAel
N
ect
U
ron
S
-
C
do
R
na
I
ti
P
ng group (3c, 3d, 3e, 3f, 3m and 3n) or electron-
T
formed reversible imine linkage as well as the palladacycle could
serve as bidentate directing species to realize sp C–H
functionalization. The synthetic utility of this strategy has been
demonstrated by various work from several groups for organic
synthesis . Recently, Jung and co-workers unveiled a one-pot
cascade sequence involving a Pd(II)-catalyzed C–H arylation via
phenylalanine-based TDG strategy and subsequent AgOTf
mediated electrophilic aromatic cyclization to construct
substituted anthracenes from o-tolualdehydes and aryl iodides
withdrawing group (3a, 3g, 3h, 3i, 3j and 3k) with different
positions or numbers were all transformed to the corresponding
product in moderate to good yields. According our observation,
the lower yields of a few cases were possibly attributed to the
easily happening self-coupling of the aryl iodides and the
oxidation of the generated arylated benzaldehydes under harsh
conditions. The augment of PAH by introducing thiophene ring
coupled with 2-iodonaphthalene was accomplished with 54%
yield (3p). Bromide-substituted iodonaphthalene was smoothly
coupled with fluorine-substituted substrates, giving good yields
of 3q and 3r. To the best of our knowledge, this is the first report
3
9
10
11
with low yields and limited range of substrates (Scheme 1C).
Then, we reported a two-step protocol to construct PAHs,
including a TDG enabled palladium-catalyzed ortho-C(sp )–H
3
3
using direct C(sp )–H functionalization strategy to construct this
arylation of benzaldehydes with aryl diiodides and subsequent
kind of valuable compounds. Moreover, tert-butyl-tetraphene
products 3s and 3t were also obtained, though with low yields,
12
TfOH-catalyzed cycloaromatization. Encouraged by all these
contributions, we envision that a cascade synthesis of this
tetracyclic structure could be achieved via this TDG strategy in
one pot, overcoming the major limitations of the traditional
methods. Herein, we reported a general and practical approach
for one-pot construction of diverse PAHs via TDG strategy,
involving consecutive arylation, cyclization, and aromatization
1
4
which can be potential synthon for special graphene synthesis .
We also examined the effect of an increased number of rings on
the synthetic efficiency by using iodonaphthalene as the coupling
partner. The corresponding benzo[a]naphthalene 3u was obtained
in a good yield of 69%, which is the skeleton of a series of
15
natural bioactive molecules. Notably, in our previous work the
construction of dibenzophenanthrene and trinaphthylene could be
achieved through a two-step protocol by coupling benzaldehydes
(Scheme 1D). The further transformations of these platform
molecules could access variety of benz[a]anthracene
a
12
derivatives including tetrangulol and other natural bioactive
molecules.
with aryl diiodide or aryl triiodide, however, these PAH product
were not observed under the present system, probably due to the
self-coupling of the aryl iodides to inhibit the desired arylation.
2
. Results and discussion
Table 2
We initiated our investigations by treating 4-chloro-2-
methylbenzaldehyde (1a) with 2-iodonaphthalene (2a) in the
Substrate scope screening
presence of Pd(OAc) (Table 1). After extensive screening, the
2
optimized conditions were obtained including 10 mol% of
Pd(OAc) , 1.2 equiv. of AgTFA, 50 mol% of TfOH and 50 mol%
2
of glycine as TDG. As a comparison, no product was detected
without TfOH. An appropriate amount of TfOH could give the
highest yield (entry 3). The more or less TfOH significantly
reduced the yields (entries 2, 4 and 5). Other Brønsted acids, p-
TsOH and MsOH, both gave lower yield (entries 6 and 7). The
promotion effect of Cu(OTf) as Lewis acid catalyst has been
2
13
proven previously, however, in our case, only 44% yield of
product could be reached (entry 8). Notably, all the reactions
were conducted under air, suggesting the excellent practicality
and robustness of this novel synthetic strategy.
Table 1
Control experiments for benz[a]anthracene synthesis
a
Entry
Brønsted acid (equiv.)
/
Yield (%)
1
/
2
3
4
5
6
7
8
TfOH (0.3)
TfOH (0.5)
TfOH (1.0)
TfOH (1.5)
p-TsOH (0.5)
MsOH (0.5)
68
86
56
18
79
62
44
a
The yield of 3i was obtained at a scale of 5 mmol.
Cu(OTf) (0.5)
2
Considering the medicinal value of anthracene, extensive
effort has been devoted to the synthesis of anthracenes and their
a
Isolated yield.
10b,13a
analogues.
We were also encouraged to examine the
With the optimized procedures in hand, the reactions of
applicability of our method in the anthracene synthesis.
Successfully, variously substituted iodobenzene underwent
cascade reactions, affording the corresponding anthracenes with
substituted o-tolualdehydes with various iodobenzenes were
investigated to probe the scope of this directed cascade process
(
Table 2). To our delight, tolualdehydes bearing different

3
yields from 30% to 95% (4a-4m, Table
A
3).
C
T
C
heEPco
T
up
E
li
D
ng MAan
N
tit
U
um
S
o
C
r a
R
ge
I
nt 5 was successfully accomplished with high
P
T
reactions of iodothiophene or iodofuran were also conducted,
giving yields from 24% to 62% (4n, 4o, 4p and 4q). Noteworthy,
the newly formed 4r from 2,3-dihydrobenzo[b][1,4]dioxine as
efficiency by two-step reaction utilizing Suzuki cross-coupling.
Meanwhile, analogue 6 was obtained through the same method
from 3ia in 75% yield. An intermediate 7 was also afforded via
the similar Suzuki cross-coupling from 3ba in 56% yield, which
16
coupling partner can be used for polymer fibre synthesis. 3-
Succinimide-substituted tolualdehyde was also converted to the
product 4s in 35% yield, which is potentially used for further
2
1
can be subsequently converted into anti-infective compound 9.
Compared with gold-catalyzed oxidative dehydrogenation
strategy to construct 7, the present method shows superior
efficiency and practicality. Meanwhile, the fluorine-containing
analogue 8 was also accessed in the same way from 3ia with a
yield of 44%.
17
18
7g
design for anticancer drugs and polymers . Furthermore, the
solubility of 4t can be remarkably improved by introducing long
alkyl chain, and the alkyl moieties in this type of skeleton has
19
proven to be crucial in solid-state light emitting device design.
Table 3
Substrate scope screening for anthracene synthesis
Scheme 2. Plausible mechanism for the synthesis of PAHs.
Scheme 3. Oxidation of 3q and 4o with CrO as oxidant.
3
9-10
In the light of the previously established knowledge,
plausible mechanism of this methodology was proposed (Scheme
). The initiative step starts with a reversible formation of the
a
2
linkage imine A between o-tolualdehyde and glycine (TDG),
which is consecutively chelated with Pd(II) in bidentate mode to
generate palladacycle B. By eliminating an AcOH, the activation
3
of C(sp )–H could be realized through proximity effect to form
Pd(II) complex C. The oxidative addition of aryl iodide gives
Pd(IV) complex D and followed by a reductive elimination to
produce an intermediate E. Further treatment with silver salt as
halogen scavenger allows Pd(II) to cleavage from the complex
and the arylated imine F is formed. The subsequent hydrolysis of
F releases the arylated benzaldehyde G and glycine which then
returns to the catalytic cycle. The cascade intramolecular
electrophilic aromatic cyclization of G gives the final PAHs.
Scheme 4. Diverse transformations of benz[a]anthracenes to
access bioactive molecules.
3
. Conclusions
In summary, we have developed a general and practical
3
transient directing group enabled C(sp )−H functionalization
strategy for the cascade construction of PAHs in a highly
efficient manner. The practicability and compatibility of this
method have been extensively demonstrated by the synthesis of
diverse PAH structures from a wide range of substrates under air.
The further transformation of the obtained PAH molecules could
access various natural bioactive molecules. This newly developed
To explore the practical value of PAHs, we performed the
further transformation to access the aromatic quinones, which are
the core skeletons of a variety of bioactive molecules. As shown
in Scheme 3, the oxidation of 3q and 4o were accomplished with
20
CrO as oxidant, giving the corresponding quinones 3qa and
3
strategy provides
a promising protocol for the efficient
4
oa in good yields.
construction of polycyclic molecules.
To further illustrate the synthetic value of this newly
4
. Experimental section
developed strategy, we attempted to synthesize bioactive
compounds through subsequent transformation of the platform
benz[a]anthracene molecules (Scheme 4). Delightedly, the
Unless otherwise stated, reagents were obtained from the
commercial sources and used directly without further

4
Tetrahedron
hyTE as MAN
purification. Analytical thin layer chro
A
ma
C
to
C
gr
E
ap
P
w
D
4
U
.2.2SCTe
R
tra
I
phene (3b). The compound 3b was prepared by
P
T
performed on 0.25 mm silica gel 60-F254. Visualization was
carried out with UV light. Column chromatography was carried
out using silica gel (200-300 mesh), eluting with a mixture of
reacting 2-methylbenzaldehyde (1b) with 2-iodonaphthalene (2a)
according to the general procedure in 5 mmol scale and purified
by column chromatography using PE as the eluent to give yellow
solid in 62% yield (706.8 mg). H NMR (500 MHz, CDCl ) δ =
9.17 (s, 1H), 8.84 (d, J = 8.1 Hz, 1H), 8.37 (s, 1H), 8.16 – 8.12
(m, 1H), 8.08 – 8.03 (m, 1H), 7.87 (d, J = 7.7 Hz, 1H), 7.80 (d, J
= 9.0 Hz, 1H), 7.70 (t, J = 7.5 Hz, 1H), 7.66 – 7.61 (m, 2H), 7.57
(p, J = 4.9 Hz, 2H). C NMR (126 MHz, CDCl ) δ = 132.01,
131.97, 130.68, 130.59, 128.91, 128.65, 128.48, 127.78, 127.37,
127.11, 126.87, 126.81, 125.83, 125.72, 122.98, 121.58; HRMS
1
petroleum ether (PE), ethyl acetate (EA) or dichloromethane
3
1
(DCM) at increased pressure. H NMR was recorded on Bruker
instrument (500 MHz). Chemical shifts were quoted in parts per
million (ppm) referenced to 0.0 ppm for tetramethylsilane. The
following abbreviations (or combinations thereof) were used to
explain multiplicities: s = singlet, d = doublet, t = triplet, q =
quartet, m = multiplet, br = broad. Coupling constants, J, were
reported in Hertz unit (Hz). C NMR spectra were recorded on
Bruker instrument (126 MHz), and were fully decoupled by
broad band proton decoupling. Chemical shifts were reported in
ppm referenced to the center line of a triplet at 77.0 ppm of
chloroform-d or referenced to the center line of a septet at 39.52
ppm of DMSO-d6.
13
3
13
+
+
(ESI): m/z calculated for C H [M+H] 229.1017, found
18 13
229.1015.
.2.3 8-Methyltetraphene (3c). The compound 3c was prepared
4
by reacting 2,3-dimethylbenzaldehyde (1c) with 2-
iodonaphthalene (2a) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
1
4
.1 General procedure for the preparation of substrates
the eluent to give yellow solid in 53% yield (25.7 mg). H NMR
(
500 MHz, CDCl ): δ = 9.16 (s, 1H), 8.84 (d, J = 8.1 Hz, 1H),
3
Most substrates are commercially available or prepared
11
8.49 (s, 1H), 8.00 (d, J = 8.3 Hz, 1H), 7.86 (t, J = 9.0 Hz, 2H),
7.70 (t, J = 7.6 Hz, 1H), 7.67 – 7.60 (m, 2H), 7.47 (t, J = 7.5 Hz,
1
according to the reported procedures . Representatively,
21
compound 2c was prepared with the following procedure:
13
H), 7.40 (d, J = 6.7 Hz, 1H), 2.86 (s, 3H). C NMR (126 MHz,
Methyl iodide (1.42 g 10 mmol) was added dropwise to a mixture
2
1
CDCl
128.60, 128.56, 127.72, 127.04, 126.99, 126.97, 126.83, 126.21,
25.52, 123.38, 122.96, 122.16, 19.62. HRMS (ESI): m/z
3
): δ = 134.14, 132.15, 132.03, 131.51, 130.49, 130.48,
of 7-iodo-3-methylnaphthalen-1-ol (0.57 g, 2 mmol) and K CO
(
2
3
o
1.38 g 10 mmol) in dry acetone (25 mL), stirring at 70 C,
overnight. After filtration the mixture was washed with water (3
10 mL). The combined organic extracts were then dried over
1
+
+
calculated for C H [M+H] 243.1174, found 243.1170.
19
15
×
MgSO . The residue was purified via column chromatography
with PE as eluent to afford the product 2c as yellow oil in 70%
yield.
4.2.4 11-Methyltetraphene (3d). The compound 3d was prepared
by reacting 2,6-dimethylbenzaldehyde (1d) with 2-
iodonaphthalene (2a) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
4
1
4
.1.1 7-Iodo-1-methoxy-3-methylnaphthalene (2c). H NMR (500
the eluent to give yellow solid in 41% yield (19.8 mg). Yield:
MHz, CDCl ): δ = 8.57 (s, 1H), 7.67 (dd, J = 8.6, 1.4 Hz, 1H),
1
3
4
1%; yellow solid. H NMR (500 MHz, CDCl ): δ = 9.33 (s, 1H),
3
7
2
1
5
2
.42 (d, J = 8.6 Hz, 1H), 7.14 (s, 1H), 6.65 (s, 1H), 3.97 (s, 3H),
13
8.88 (d, J = 8.1 Hz, 1H), 8.36 (s, 1H), 7.92 (d, J = 8.2 Hz, 1H),
.86 (d, J = 7.7 Hz, 1H), 7.80 (d, J = 9.0 Hz, 1H), 7.70 (t, J = 7.6
Hz, 1H), 7.67 – 7.59 (m, 2H), 7.48 – 7.43 (m, 1H), 7.40 (d, J =
.47 (s, 3H); C NMR (126 MHz, CDCl ): δ = 154.20, 136.64,
3
7
34.93, 133.28, 131.06, 128.44, 125.56, 119.04, 106.89, 89.42,
+
+
5.52, 22.26; HRMS (ESI): m/z calculated for C H IO [M+H]
13
12
12
6
1
.6 Hz, 1H), 2.94 (s, 3H). C NMR (126 MHz, CDCl ) δ =
3
98.9933; found: 298.9937.
34.55, 132.17, 132.06, 131.36, 130.83, 130.31, 128.69, 128.56,
4
.2 General procedure for the synthesis of polycyclic
aromatic hydrocarbons
127.40, 127.20, 127.07, 127.01, 126.81, 126.35, 126.25, 125.59,
122.86, 117.73, 19.83. HRMS (ESI): m/z calculated for
+
+
C H [M+H] 243.1174, found 243.1172.
19
15
A sealed tube with magnetic stir bar was charged with substrate 1
0.24 mmol), glycine (0.1 mmol, 7.5 mg), Pd(OAc) (0.02 mmol,
(
4
4.2.5 9,11-Dimethyltetraphene (3e). The compound 3e was
prepared by reacting 2,4,6-trimethylbenzaldehyde (1e) with 2-
iodonaphthalene (2a) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
2
.45 mg), AgTFA (0.24 mmol, 53.01 mg) and 2 (0.2 mmol)
under air. After addition of AcOH (2 mL) as solvent, TfOH (0.1
mmol, 15.0 mg) was added. The reaction mixture was allowed to
stir at 100 °C for 24 hours. Upon completion, the reaction
mixture was cooled to room temperature, diluted with DCM, and
1
the eluent to give yellow solid in 39% yield (20.0 mg). H NMR
(500 MHz, CDCl ) δ = 9.27 (s, 1H), 8.86 (d, J = 8.1 Hz, 1H),
3
then extracted with saturated NaHCO aqueous solution. The
8.26 (s, 1H), 7.85 (d, J = 7.7 Hz, 1H), 7.78 (d, J = 9.0 Hz, 1H),
3
organic layer was dried over anhydrous Na SO and concentrated
7.72 – 7.65 (m, 2H), 7.65 – 7.57 (m, 2H), 7.26 (s, 1H), 2.90 (s,
2
4
13
in vacuo. The crude residue was purified by column
chromatography on silica gel using PE as the eluent to afford the
desired products.
3H), 2.54 (s, 3H). C NMR (126 MHz, CDCl ) δ = 135.17,
3
134.30, 132.56, 131.93, 130.95, 130.45, 129.88, 129.03, 128.65,
127.91, 127.25, 126.91, 126.76, 126.73, 126.50, 124.77, 122.73,
1
17.55+, 21.88, 19.69. HRMS (ESI): m/z calculated for
4
.2.1 9-Chlorotetraphene (3a). The compound 3a was prepared
+
C H [M+H] 257.1330, found 257.1327.
20
17
by reacting 4-chloro-2-methylbenzaldehyde (1a) with 2-
iodonaphthalene (2a) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
4.2.6 9,10-Dimethyltetraphene (3f). The compound 3f was
prepared by reacting 2,4,5-trimethylbenzaldehyde (1f) with 2-
iodonaphthalene (2a) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
1
the eluent to give yellow solid in 86% yield (45.2 mg). H NMR
(
500 MHz, CDCl ) δ = 9.06 (s, 1H), 8.75 (d, J = 8.1 Hz, 1H),
3
1
8
7
.19 (s, 1H), 8.00 (d, J = 8.9 Hz, 1H), 7.97 (s, 1H), 7.84 (d, J =
.6 Hz, 1H), 7.72 (d, J = 9.0 Hz, 1H), 7.70 – 7.66 (m, 1H), 7.62
the eluent to give yellow solid in 58% yield (29.7 mg). H NMR
(
500 MHz, CDCl ) δ = 9.04 (s, 1H), 8.81 (d, J = 8.1 Hz, 1H),
13
3
(
dd, J = 7.5, 6.0 Hz, 2H), 7.46 (dd, J = 8.8, 1.8 Hz, 1H). C NMR
8
8
2
.23 (s, 1H), 7.87 (s, 1H), 7.85 (d, J = 8.2 Hz, 1H), 7.77 (d, J =
(
1
1
126 MHz, CDCl ) δ = 132.20, 131.96, 131.52, 131.32, 130.34,
3
.7 Hz, 2H), 7.68 (t, J = 7.2 Hz, 1H), 7.61 (t, J = 7.8 Hz, 2H),
30.06, 129.97, 129.02, 128.72, 127.77, 127.30, 127.03, 127.01,
26.75, 126.10, 125.83, 122.89, 121.60. HRMS (ESI): m/z
13
.52 (s, 3H), 2.50 (s, 3H). C NMR (126 MHz, CDCl ) δ =
3
+
+
135.94, 135.82, 131.92, 131.27, 131.25, 130.77, 130.17, 128.57,
28.30, 127.54, 127.53, 126.83, 126.76, 126.68, 126.44, 125.61,
calculated for C H Cl [M+H] 263.0628; found: 263.0631.
18
12
1

5
1
22.84, 120.34, 20.47, 20.44. HRMS (ESI): m
A
/z
C
c
C
al
E
cu
P
la
T
ted
E
f
D
or MA4.
N
2.1
prepared by reacting 5-bromo-2-methylbenzaldehyde (1k) with
-iodonaphthalene (2a) according to the general procedure in 0.2
U
1
S
1
C
0-
R
Br
I
o
P
m
T
otetraphene (3k). The compound 3k was
+
+
C H [M+H] 257.1330, found 257.1332.
20
17
2
4
.2.7 8-Fluorotetraphene (3g). The compound 3g was prepared
mmol scale and purified by column chromatography using PE as
the eluent to give yellow solid in 53% yield (32.5 mg). H NMR
500 MHz, CDCl ): δ = 8.98 (s, 1H), 8.75 (d, J = 8.1 Hz, 1H),
8.27 (s, 1H), 8.25 (s, 1H), 7.85 (t, J = 8.7 Hz, 2H), 7.73 (d, J =
.0 Hz, 1H), 7.70 – 7.66 (m, 1H), 7.66 – 7.61 (m, 2H), 7.57 (dd, J
8.8, 1.8 Hz, 1H). C NMR (126 MHz, CDCl ): δ = 132.67,
32.11, 130.85, 130.20, 130.11, 129.59, 129.39, 129.20, 128.69,
27.52, 127.44, 127.07, 127.02, 126.87, 122.99, 120.60, 119.67.
by reacting 3-fluoro-2-methylbenzaldehyde (1g) with 2-
iodonaphthalene (2a) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
1
(
3
1
the eluent to give yellow solid in 66% yield (32.5 mg). H NMR
9
=
1
1
(500 MHz, CDCl ) δ = 9.15 (s, 1H), 8.80 (d, J = 8.1 Hz, 1H),
13
3
3
8
7
2
1
1
.60 (s, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.86 (d, J = 7.6 Hz, 1H),
.82 (d, J = 9.0 Hz, 1H), 7.69 (t, J = 7.5 Hz, 1H), 7.68 – 7.61 (m,
H), 7.46 (dd, J = 13.3, 7.9 Hz, 1H), 7.20 (dd, J = 10.6, 7.5 Hz,
+
+
13
HRMS (ESI): m/z calculated for C18H12Br [M+H] 307.0122,
H). C NMR (126 MHz, CDCl ) δ = 158.81 (d, J = 253.0 Hz),
3
found 307.0120.
33.17 (d, J = 4.6 Hz), 132.16 (s), 130.72 (d, J = 1.3 Hz), 130.25
(
1
(
4
s), 129.60 (s), 128.70 (s), 127.61 (s), 127.45 (s), 127.38 (s),
27.00 (s), 125.13 (d, J = 8.2 Hz), 124.23 (d, J = 4.2 Hz), 122.98
s), 122.82 (d, J = 17.3 Hz), 121.30 (d, J = 3.3 Hz), 119.91 (d, J =
.2 Hz), 108.51 (d, J = 19.5 Hz). HRMS (ESI): m/z calculated for
4.2.12 9-Bromo-11-methyltetraphene (3l). The compound 3l was
prepared by reacting 4-bromo-2,6-dimethylbenzaldehyde (1l)
with 2-iodonaphthalene (2a) according to the general procedure
in 0.2 mmol scale and purified by column chromatography using
+
+
1
C H F [M+H] 247.0923, found 247.0927.
PE as the eluent to give yellow solid in 30% yield (19.3 mg). H
18
12
NMR (500 MHz, CDCl ): δ 9.23 (s, 1H), 8.82 (d, J = 8.1 Hz,
3
4
.2.8 9-Fluorotetraphene (3h). The compound 3h was prepared
1
=
H), 8.22 (s, 1H), 8.04 (s, 1H), 7.85 (d, J = 7.7 Hz, 1H), 7.75 (d, J
9.0 Hz, 1H), 7.69 (t, J = 7.6 Hz, 1H), 7.67 – 7.62 (m, 2H), 7.46
by reacting 4-fluoro-2-methylbenzaldehyde (1h) with 2-
iodonaphthalene (2a) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
13
(s, 1H), 2.88 (s, 3H). C NMR (126 MHz, CDCl ): δ 136.85,
3
1
132.93, 132.04, 130.99, 130.58, 129.65, 129.36, 128.79, 127.96,
the eluent to give yellow solid in 70% yield (34.4 mg). H NMR
1
1
3
27.77, 127.26, 127.00, 126.88, 126.44, 122.81, 119.51, 117.97,
(500 MHz, CDCl ): δ = 9.10 (s, 1H), 8.77 (d, J = 8.1 Hz, 1H),
+ +
3
9.51. HRMS (ESI): m/z calculated for C H Br [M+H]
19
14
8
1
.24 (s, 1H), 8.08 (dd, J = 9.0, 5.7 Hz, 1H), 7.85 (d, J = 7.7 Hz,
H), 7.73 (d, J = 9.0 Hz, 1H), 7.69 (t, J = 7.5 Hz, 1H), 7.64 (d, J
21.0279, found 321.0283.
=
5.1 Hz, 1H), 7.63 – 7.58 (m, 2H), 7.34 (td, J = 8.8, 2.3 Hz, 1H).
4.2.13 9-Methoxytetraphene (3m). The compound 3m was
prepared by reacting 4-methoxyl-2-methylbenzaldehyde (1m)
with 2-iodonaphthalene (2a) according to the general procedure
in 0.2 mmol scale and purified by column chromatography using
13
C NMR (126 MHz, CDCl ): δ = 160.53 (d, J = 247.1 Hz),
3
1
32.30 (d, J = 9.5 Hz), 131.83 (s), 131.32 (s), 131.05 (d, J = 9.1
Hz), 130.47 (s), 129.08 (s), 128.70 (s), 128.25 (d, J = 2.5 Hz),
27.74 (s), 127.11 (s), 127.00 (s), 126.91 (s), 125.97 (d, J = 6.6
Hz), 122.76 (s), 121.75 (d, J = 1.3 Hz), 116.96 (d, J = 26.8 Hz),
09.85 (d, J = 20.4 Hz). HRMS (ESI): m/z calculated for
1
1
PE as the eluent to give yellow solid in 72% yield (37.2 mg). H
NMR (500 MHz, CDCl ): δ = 9.05 (s, 1H), 8.75 (d, J = 8.1 Hz,
3
1
1H), 8.19 (s, 1H), 7.98 (d, J = 8.8 Hz, 1H), 7.81 (d, J = 7.7 Hz,
1H), 7.73 (d, J = 9.0 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 7.60 (d, J
+
+
C H F [M+H] 247.0923, found 247.0928.
18
12
=
9.0 Hz, 1H), 7.56 (t, J = 7.4 Hz, 1H), 7.24 – 7.20 (m, 2H), 3.95
4
.2.9 11-Fluorotetraphene (3i). The compound 3i was prepared
13
(s, 3H). C NMR (126 MHz, CDCl ): δ = 157.67, 133.12,
3
by reacting 6-fluoro-2-methylbenzaldehyde (1i) with 2-
iodonaphthalene (2a) according to the general procedure in 5
mmol scale and purified by column chromatography using PE as
the eluent to give yellow solid in 88% yield (1082.4 mg). H
NMR (500 MHz, CDCl ): δ = 9.41 (s, 1H), 8.86 (d, J = 8.2 Hz,
1
1
31.64, 131.14, 130.78, 130.07, 128.60, 128.13, 127.18, 127.14,
26.82, 126.62, 125.15, 122.64, 121.50, 120.06, 104.12, 55.35.
+
+
1
HRMS (ESI): m/z calculated for C19H15O [M+H] 259.1123,
found 259.1127.
3
1
1
7
7
2
H), 8.34 (s, 1H), 7.85 (d, J = 7.7 Hz, 1H), 7.80 (d, J = 8.4 Hz,
H), 7.76 (d, J = 9.0 Hz, 1H), 7.70 (t, J = 7.5 Hz, 1H), 7.67 –
.61 (m, 2H), 7.45 (td, J = 7.9, 5.5 Hz, 1H), 7.21 (dd, J = 10.8,
4.2.14 9-Methoxy-10-methyltetraphene (3n). The compound 3n
was prepared by reacting 4-methoxyl-2,5-dimethylbenzaldehyde
(1n) with 2-iodonaphthalene (2a) according to the general
procedure in 0.2 mmol scale and purified by column
13
.5 Hz, 1H). C NMR (126 MHz, CDCl ): δ = 159.10 (d, J =
3
53.0 Hz), 133.14 (d, J = 4.4 Hz), 132.05 (s), 131.28 (s), 130.52
chromatography using PE as the eluent to give yellow solid in
1
(
1
s), 129.05 (d, J = 1.3 Hz), 128.65 (s), 127.85 (s), 127.39 (s),
27.10 (s), 127.02 (s), 126.57 (d, J = 3.3 Hz), 125.22 (d, J = 8.4
Hz), 123.60 (d, J = 4.2 Hz), 123.19 (s), 122.68 (d, J = 16.4 Hz),
14.47 (d, J = 4.7 Hz), 108.44 (d, J = 19.8 Hz). HRMS (ESI): m/z
56% yield (30.5 mg). H NMR (500 MHz, CDCl ): δ 9.01 (s,
3
1H), 8.78 (d, J = 8.2 Hz, 1H), 8.20 (s, 1H), 7.84 (d, J = 8.4 Hz,
2H), 7.76 (d, J = 9.0 Hz, 1H), 7.69 – 7.64 (m, 1H), 7.63 – 7.56
13
1
(m, 2H), 7.22 (s, 1H), 4.00 (s, 3H), 2.47 (s, 3H). C NMR (126
+
+
calculated for C H Br [M+H] 307.0122, found 307.0119.
MHz, CDCl ): δ 157.19, 132.26, 131.64, 130.84, 130.44, 129.61,
18
12
3
1
1
29.00, 128.56, 128.14, 127.25, 127.07, 126.68, 126.62, 126.46,
4
.2.10 9-Bromotetraphene (3j). The compound 3j was prepared
24.74, 122.61, 120.44, 103.09, 55.37, 17.24. HRMS (ESI): m/z
by reacting 4-bromo-2-methylbenzaldehyde (1j) with 2-
iodonaphthalene (2a) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
+
+
calculated for C H O [M+H] 273.1279, found 273.1274.
20
17
4.2.15 8,11-Dimethoxytetraphene (3o). The compound 3o was
prepared by reacting 3,6-dimethoxyl-2-methylbenzaldehyde (1o)
with 2-iodonaphthalene (2a) according to the general procedure
according to the general procedure in 0.2 mmol scale and
purified by column chromatography using PE as the eluent to
1
the eluent to give yellow solid in 45% yield (27.6 mg). H NMR
(500 MHz, CDCl ): δ = 9.05 (s, 1H), 8.75 (d, J = 8.0 Hz, 1H),
3
8
7
7
.18 (s, 1H), 8.15 (s, 1H), 7.93 (d, J = 8.9 Hz, 1H), 7.84 (dd, J =
.8, 0.9 Hz, 1H), 7.72 (d, J = 9.0 Hz, 1H), 7.70 – 7.66 (m, 1H),
13
1
.65 – 7.61 (m, 2H), 7.58 (dd, J = 8.9, 1.9 Hz, 1H). C NMR
give yellow solid in 42% yield (24.2 mg). H NMR (500 MHz,
(
126 MHz, CDCl ): δ = 132.69, 131.97, 131.27, 130.31, 130.07,
CDCl ): δ = 9.57 (s, 1H), 8.92 (d, J = 7.5 Hz, 1H), 8.72 (s, 1H),
3
3
1
1
29.51, 129.12, 129.09, 128.72, 127.79, 127.34, 127.04, 127.01,
7.85 (d, J = 8.1 Hz, 2H), 7.64 (dt, J = 14.2, 6.0 Hz, 3H), 6.72 (s,
13
25.77, 122.90, 121.66, 119.84. HRMS (ESI): m/z calculated for
2H), 4.09 (s, 3H), 4.06 (s, 3H). C NMR (126 MHz, CDCl ): δ =
3
+
+
C H Br [M+H] 307.0122, found 307.0116.
149.74, 149.46, 132.12, 130.88, 130.44, 128.66, 128.50, 127.69,
18
12
1
27.09, 126.94, 126.74, 125.44, 125.31, 123.27, 121.30, 115.83,

6
Tetrahedron
1
01.98, 101.97, 55.76, 55.74. HRMS (ESI):
A
m/
C
z c
C
al
E
cu
P
la
T
ted
E
f
D
or MA4.
N
2.2
was prepared by reacting 3-chloro-1-methyl-2-naphthaldehyde
1t) with 4-(tert-butyl)-1-iodo-2-methylbenzene (2c) according to
U
0
S
9-
C
(T
R
er
I
t-
P
bu
T
tyl)-6-chlorotetraphene (3t). The compound 3t
+
+
C H O [M+H] 289.1229, found 289.1232.
20
17
2
(
4
.2.16 Phenanthro[3,2-b]thiophene (3p). The compound 3p was
the general procedure in 0.2 mmol scale and purified by column
chromatography using PE as the eluent to give yellow solid in
prepared by reacting 3-methylthiophene-2-carbaldehyde (1p)
with 2-iodonaphthalene (2a) according to the general procedure
in 0.2 mmol scale and purified by column chromatography using
PE as the eluent to give yellow solid in 54% yield (25.3 mg). H
NMR (500 MHz, CDCl ): δ = 9.20 (s, 1H), 8.73 (d, J = 8.1 Hz,
1
4
8% yield (30.6 mg). H NMR (500 MHz, CDCl ): δ = 9.08 (s,
3
1
1H), 8.82 (s, 1H), 8.75 (d, J = 8.1 Hz, 1H), 8.06 (d, J = 10.6 Hz,
2
1
H), 7.75 (s, 1H), 7.72 (d, J = 9.3 Hz, 2H), 7.66 (t, J = 7.4 Hz,
H), 7.59 (t, J = 7.3 Hz, 1H), 1.50 (s, 9H). C NMR (126 MHz,
3
13
1
1
5
H), 8.30 (s, 1H), 7.90 (d, J = 7.7 Hz, 1H), 7.80 (d, J = 8.9 Hz,
H), 7.68 (t, J = 8.0 Hz, 2H), 7.65 – 7.60 (m, 1H), 7.57 (d, J =
.5 Hz, 1H), 7.48 (d, J = 5.5 Hz, 1H). C NMR (126 MHz,
CDCl ): δ = 149.07, 132.13, 131.36, 130.84, 130.58, 129.88,
128.94, 127.97, 127.94, 127.85, 127.30, 127.07, 126.28, 126.00,
3
13
1
24.35, 122.93, 122.89, 121.41, 35.12, 31.14, 29.74. HRMS
CDCl ) δ = 139.02, 138.83, 132.01, 130.05, 129.59, 128.56,
+ +
3
(ESI): m/z calculated for C H Cl [M+H] 319.1254, found
22 20
1
1
2
28.04, 127.83, 127.44, 126.67, 126.31, 123.54, 122.69, 122.56,
16.15. HRMS (ESI): m/z calculated for C H S [M+H]
35.0581, found 235.0585.
+ +
319.1260.
16
11
4.2.21
1-Methoxy-3-methylbenzo[a]tetracene
(3u).
The
compound 3u was prepared by reacting 3-methyl-2-
naphthaldehyde (1u) with 7-iodo-1-methoxy-3-
methylnaphthalene (2d) according to the general procedure in 0.2
4
.2.17 3-Bromo-8-fluorotetraphene (3q). The compound 3q was
prepared by reacting 3-fluoro-2-methylbenzaldehyde (1g) with 2-
bromo-7-iodonaphthalene (2b) according to the general
procedure in 0.2 mmol scale and purified by column
chromatography using PE as the eluent to give yellow solid in
7
MHz, CDCl ): δ = 8.99 (s, 1H), 8.54 (d, J = 8.8 Hz, 1H), 8.53 (s,
1
=
1
mmol scale and purified by column chromatography using PE as
1
the eluent to give yellow solid in 69% yield (44.4 mg). H NMR
1
(500 MHz, CDCl
.44 (s, 1H), 8.06 (ddd, J = 9.6, 6.3, 3.8 Hz, 2H), 7.69 (d, J = 9.0
Hz, 1H), 7.45 (dd, J = 6.6, 3.2 Hz, 2H), 7.42 (d, J = 9.0 Hz, 1H),
3
): δ = 10.27 (s, 1H), 8.75 (s, 1H), 8.59 (s, 1H),
3% yield (47.5 mg). Yield: 73%; yellow solid. H NMR (500
8
3
H), 7.93 (d, J = 2.1 Hz, 1H), 7.83 (d, J = 8.4 Hz, 1H), 7.77 (d, J
9.0 Hz, 1H), 7.71 (dd, J = 8.7, 2.1 Hz, 1H), 7.49 (d, J = 9.0 Hz,
13
7
.22 (s, 1H), 7.04 (s, 1H), 4.23 (s, 3H), 2.55 (s, 3H). C NMR
(126 MHz, CDCl ): δ = 159.07, 137.46, 134.54, 131.65, 131.54,
31.41, 130.94, 129.56, 128.59, 128.35, 128.17, 128.00, 127.46,
27.44, 126.04, 125.22, 125.04, 124.83, 121.84, 117.87, 111.09,
13
3
H), 7.47 – 7.42 (m, 1H), 7.19 (dd, J = 10.6, 7.5 Hz, 1H).
C
1
1
5
3
NMR (126 MHz, CDCl ): δ = 158.73 (d, J = 253.4 Hz), 133.60
3
(
s), 133.22 (d, J = 4.5 Hz), 130.84 (s), 130.28 (d, J = 1.2 Hz),
29.90 (s), 128.91 (d, J = 3.1 Hz), 128.64 (s), 126.26 (s), 125.50
s), 125.43 (s), 124.62 (s), 124.16 (d, J = 4.2 Hz), 122.90 (d, J =
7.3 Hz), 121.40 (s), 121.18 (d, J = 3.2 Hz), 120.19 (d, J = 4.3
Hz), 108.76 (d, J = 19.5 Hz). HRMS (ESI): m/z calculated for
+
+
5.80, 29.72. HRMS (ESI): m/z calculated for C H O [M+H]
24
19
1
(
1
23.1436, found 323.1432.
4.2.22 Anthracene (4a). The compound 4a was prepared by
reacting 2-methylbenzaldehyde (1b) with iodobenzene (2e)
according to the general procedure in 0.2 mmol scale and
purified by column chromatography using PE as the eluent to
+
+
C H BrF [M+H] 325.0028, found 325.0032.
18
11
4
.2.18 3-Bromo-11-fluorotetraphene (3r). The compound 3r was
give white solid in 78% yield (27.8 mg). Yield: 78%; white solid.
prepared by reacting 6-fluoro-2-methylbenzaldehyde (1i) with 2-
bromo-7-iodonaphthalene (2b) according to the general
procedure in 0.2 mmol scale and purified by column
chromatography using PE as the eluent to give yellow solid in
5
1
1
H NMR (500 MHz, CDCl ): δ = 8.44 (s, 2H), 8.02 (dd, J = 6.4,
.2 Hz, 4H), 7.48 (dd, J = 6.6, 3.1 Hz, 4H). C NMR (126 MHz,
3
13
3
CDCl ): δ = 131.72, 128.20, 126.25, 125.37. HRMS (ESI): m/z
3
+
+
1
calculated for C14H11 [M+H] 179.0861, found 179.0864.
6% yield (36.4 mg). H NMR (500 MHz, CDCl ): δ = 9.12 (s,
3
H), 8.49 (d, J = 8.7 Hz, 1H), 8.18 (s, 1H), 7.85 (s, 1H), 7.71 (d,
4.2.23 1-Methylanthracene (4b). The compound 4b was prepared
by reacting 2,3-dimethylbenzaldehyde (1c) with iodobenzene
(2e) according to the general procedure in 0.2 mmol scale and
purified by column chromatography using PE as the eluent to
J = 8.4 Hz, 1H), 7.67 – 7.61 (m, 2H), 7.44 – 7.38 (m, 2H), 7.16
13
(dd, J = 10.5, 7.7 Hz, 1H). C NMR (126 MHz, CDCl ) δ =
3
1
1
58.91 (d, J = 253.2 Hz), 133.40 (s), 133.11 (d, J = 4.2 Hz),
30.76 (s), 130.71 (s), 129.90 (s), 129.07 (s), 128.25 (s), 128.19
1
give white solid in 46% yield (17.7 mg). H NMR (500 MHz,
(s), 126.70 (d, J = 3.3 Hz), 126.40 (s), 125.42 (d, J = 8.3 Hz),
CDCl ): δ = 8.55 (s, 1H), 8.43 (s, 1H), 8.08 – 8.03 (m, 1H), 8.03
3
1
1
24.72 (s), 123.58 (d, J = 4.2 Hz), 122.70 (d, J = 16.3 Hz),
21.29 (s), 114.27 (d, J = 4.6 Hz), 108.66 (d, J = 19.8 Hz).
– 7.98 (m, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.48 (dd, J = 6.4, 3.0
Hz, 2H), 7.40 – 7.35 (m, 1H), 7.31 (d, J = 6.6 Hz, 1H), 2.83 (s,
+
+
13
HRMS (ESI): m/z calculated for C H BrF [M+H] 325.0028,
4H). C NMR (126 MHz, CDCl ) δ = 134.28, 131.91, 131.58,
18
11
3
found 325.0026.
131.42, 131.38, 128.53, 127.95, 126.80, 126.74, 125.62, 125.39,
1
25.32, 125.17, 122.80, 19.79. HRMS (ESI): m/z calculated for
4
.2.19 9-(Tert-butyl)tetraphene (3s). The compound 3s was
+ +
C H [M+H] 193.1017, found 193.1021.
15
13
prepared by reacting 1-methyl-2-naphthaldehyde (1s) with 4-
tert-butyl)-1-iodo-2-methylbenzene (2c) according to the general
(
4.2.24 2-Methylanthracene (4c). The compound 4c was prepared
by reacting 2,4-dimethylbenzaldehyde (1v) with iodobenzene
(2e) according to the general procedure in 0.2 mmol scale and
purified by column chromatography using PE as the eluent to
procedure in 0.2 mmol scale and purified by column
chromatography using PE as the eluent to give yellow solid in
2
1
0% yield (11.4 mg). Yield: 20%; yellow solid. H NMR (500
1
MHz, CDCl ): δ = 9.13 (s, 1H), 8.83 (d, J = 8.1 Hz, 1H), 8.34 (s,
give white solid in 80% yield (30.7 mg). H NMR (500 MHz,
3
1
1
H), 8.08 (d, J = 8.8 Hz, 1H), 7.95 (s, 1H), 7.85 (d, J = 7.7 Hz,
H), 7.79 (d, J = 9.0 Hz, 1H), 7.70 – 7.65 (m, 2H), 7.64 – 7.58
CDCl ): δ = 8.39 (s, 1H), 8.32 (s, 1H), 7.99 (d, J = 9.1 Hz, 2H),
3
7.92 (d, J = 8.6 Hz, 1H), 7.76 (s, 1H), 7.45 (p, J = 7.0 Hz, 2H),
13
13
(m, 2H), 1.48 (d, J = 6.1 Hz, 9H). C NMR (126 MHz, CDCl ) δ
7.32 (d, J = 8.6 Hz, 1H), 2.56 (s, 3H). C NMR (126 MHz,
3
=
148.44, 132.06, 131.89, 130.72, 130.70, 130.42, 128.57,
CDCl ): δ = 134.95, 132.03, 131.88, 131.26, 130.37, 128.28,
3
1
1
28.44, 128.11, 127.43, 126.85, 126.81, 126.75, 126.71, 125.16,
128.21, 128.08, 127.99, 126.35, 125.97, 125.26, 125.19, 124.94,
+
+
22.87, 122.21, 120.98, 35.03, 31.14, 29.71. HRMS (ESI): m/z
22.02. HRMS (ESI): m/z calculated for C H [M+H] 193.1017,
15 13
+
+
calculated for C H [M+H] 285.1643, found 285.1647.
found 193.1014.
22
21

7
4
.2.25 2-Fluoroanthracene (4d). The compoun
A
d 4
C
d
C
wa
E
s
P
pr
T
ep
E
ar
D
ed MA4.
N
2.3
U
0
S
1
C
-C
R
hloro-3-methylanthracene (4i). The compound 4i
I
P
T
by reacting 5-fluoro-2-methylbenzaldehyde (1w) with
iodobenzene (2e) according to the general procedure in 0.2 mmol
scale and purified by column chromatography using PE as the
was prepared by reacting 6-chloro-2,4-dimethylbenzaldehyde
(1x) with iodobenzene (2e) according to the general procedure in
0.2 mmol scale and purified by column chromatography using PE
1
1
eluent to give white solid in 84% yield (32.9 mg). H NMR (500
as the eluent to give white solid in 89% yield (40.4 mg). H NMR
MHz, CDCl ): δ = 8.43 (s, 1H), 8.35 (s, 1H), 8.00 (dd, J = 16.9,
(500 MHz, CDCl ): δ = 8.78 (s, 1H), 8.31 (s, 1H), 8.06 (d, J = 6.2
3
3
8
–
2
.4 Hz, 3H), 7.58 (d, J = 10.0 Hz, 1H), 7.51 – 7.44 (m, 2H), 7.31
Hz, 1H), 7.98 (d, J = 8.6 Hz, 1H), 7.66 (s, 1H), 7.51 – 7.46 (m,
13
13
7.26 (m, 1H). C NMR (126 MHz, CDCl ): δ = 160.15 (d, J =
2H), 7.44 (s, 1H), 2.52 (s, 3H). C NMR (126 MHz, CDCl ) δ =
3
3
47.3 Hz), 132.23 (s), 131.80 (d, J = 9.4 Hz), 131.13 (d, J = 2.1
134.70, 132.57, 132.19, 131.69, 131.59, 128.71, 128.02, 127.82,
127.69, 126.07, 125.84, 125.82, 125.60, 123.38, 21.70. HRMS
Hz), 130.95 (d, J = 9.2 Hz), 129.03 (s), 128.29 (s), 127.75 (s),
26.68 (d, J = 1.7 Hz), 126.01 (s), 125.41 (d, J = 7.4 Hz), 125.29
d, J = 1.1 Hz), 117.30 (d, J = 27.7 Hz), 109.71 (d, J = 20.4 Hz).
+
+
1
(
(ESI): m/z calculated for C H Cl [M+H] 227.0628, found
15 12
227.0627.
.2.31 2-Methoxyanthracene (4j). The compound 4j was
+
+
HRMS (ESI): m/z calculated for C H F [M+H] 197.0767,
found 197.0769.
14
10
4
prepared by reacting 2-methylbenzaldehyde (1b) with 1-iodo-4-
methoxybenzene (2f) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
4
.2.26 1-Fluoroanthracene (4e). The compound 4e was prepared
by reacting 6-fluoro-2-methylbenzaldehyde (1i) with
iodobenzene (2e) according to the general procedure in 0.2 mmol
1
the eluent to give white solid in 45% yield (18.7 mg). H NMR
scale and purified by column chromatography using PE as the
eluent to give white solid in 90% yield (35.3 mg). H NMR (500
(500 MHz, CDCl ) δ = 8.35 (s, 1H), 8.27 (s, 1H), 7.96 (t, J = 9.2
3
1
Hz, 2H), 7.90 (d, J = 9.1 Hz, 1H), 7.43 (dt, J = 14.7, 6.8 Hz, 2H),
1
3
MHz, CDCl ): δ = 8.69 (s, 1H), 8.45 (s, 1H), 8.06 (dd, J = 6.1,
7.20 (s, 1H), 7.17 (d, J = 9.2 Hz, 1H), 3.97 (s, 3H). C NMR
3
3
1
1
.1 Hz, 1H), 8.01 (dd, J = 6.1, 3.1 Hz, 1H), 7.80 (d, J = 8.6 Hz,
H), 7.51 (dd, J = 6.5, 3.0 Hz, 2H), 7.37 (dd, J = 13.6, 7.7 Hz,
H), 7.11 (dd, J = 10.8, 7.5 Hz, 1H). C NMR (126 MHz,
(126 MHz, CDCl ): δ = 157.19, 132.72, 132.21, 130.36, 129.85,
3
128.30, 128.25, 127.59, 126.24, 125.54, 124.44, 124.18, 120.57,
13
+
+
103.58, 55.28. HRMS (ESI): m/z calculated for C H O [M+H]
15 13
CDCl ): δ = 158.90 (d, J = 253.5 Hz), 132.77 (d, J = 4.5 Hz),
209.0966, found 209.0968.
3
1
32.17 (s), 131.61 (s), 128.60 (s), 128.14 (s), 126.14 (d, J = 3.5
Hz), 126.10 (s), 125.91 (s), 124.64 (d, J = 8.2 Hz), 124.05 (d, J =
.4 Hz), 122.95 (d, J = 17.6 Hz), 119.62 (d, J = 4.2 Hz), 107.63
d, 19.6 Hz). HRMS (ESI): m/z calculated for
C H F [M+H] 197.0767, found 197.0771.
4
.2.32 2-Chloro-6-methoxyanthracene (4k). The compound 4k
was prepared by reacting 4-chloro-2-methylbenzaldehyde (1a)
with 1-iodo-4-methoxybenzene (2f) according to the general
procedure in 0.2 mmol scale and purified by column
chromatography using PE as the eluent to give white solid in
48% yield (23.3 mg). H NMR (500 MHz, CDCl ): δ = 8.23 (s,
4
(
J =
+
10
+
14
1
4
.2.27 2-Bromoanthracene (4f). The compound 4f was prepared
3
by reacting 4-bromo-2-methylbenzaldehyde (1j) with
iodobenzene (2e) according to the general procedure in 0.2 mmol
2H), 7.93 (s, 1H), 7.87 (d, J = 9.0 Hz, 2H), 7.36 (dd, J = 9.0, 1.5
Hz, 1H), 7.18 (d, J = 8.8 Hz, 2H), 3.96 (s, 3H). C NMR (126
13
scale and purified by column chromatography using PE as the
eluent to give white solid in 71% yield (36.5 mg). H NMR (500
MHz, CDCl ): δ = 157.43, 132.84, 130.47, 130.24, 130.02,
129.71, 129.31, 128.81, 126.71, 126.43, 125.38, 124.41, 121.23,
3
1
MHz, CDCl ): δ = 8.39 (s, 1H), 8.31 (s, 1H), 8.17 (s, 1H), 7.99
103.66, 55.31. + HRMS (ESI):
m/z
calculated
for
3
13
+
(s, 2H), 7.87 (d, J = 8.8 Hz, 1H), 7.50 (s, 3H). C NMR (126
C H ClO [M+H] 243.0577, found 243.0579.
15
12
MHz, CDCl ) δ = 132.32, 132.17, 131.82, 129.89, 129.85,
3
4
.2.33 6-Chloro-1,3-dimethylanthracene (4l). The compound 4l
1
1
2
29.80, 128.88, 128.24, 128.13, 126.59, 126.06, 125.79, 125.38,
+ +
was prepared by reacting 4-chloro-2-methylbenzaldehyde (1a)
with 1-iodo-3,5-dimethylbenzene (2g) according to the general
procedure in 0.2 mmol scale and purified by column
19.46. HRMS (ESI): m/z calculated for C H Br [M+H]
14
10
56.9966, found 256.9969.
4
.2.28 3-Bromo-1-methylanthracene (4g). The compound 4g was
chromatography using PE as the eluent to give white solid in
1
prepared by reacting 4-bromo-2,6-dimethylbenzaldehyde (1l)
with iodobenzene (2e) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
63% yield (30.3 mg). H NMR (500 MHz, CDCl ): δ = 8.43 (s,
3
1H), 8.17 (s, 1H), 7.94 (d, J = 9.4 Hz, 2H), 7.58 (s, 1H), 7.35 (dd,
13
J = 8.9, 1.8 Hz, 1H), 7.17 (s, 1H), 2.76 (s, 3H), 2.51 (s, 3H).
C
1
the eluent to give white solid in 37% yield (20.1 mg). H NMR
NMR (126 MHz, CDCl ): δ = 135.43, 134.10, 132.86, 131.70,
3
(
500 MHz, CDCl ): δ = 8.49 (s, 1H), 8.31 (s, 1H), 8.03 (d, J = 9.1
130.97, 130.25, 130.10, 129.13, 128.93, 126.05, 126.04, 124.86,
3
Hz, 2H), 8.01 – 7.96 (m, 1H), 7.50 (dd, J = 6.3, 2.8 Hz, 2H), 7.38
124.76, 122.83, 21.93, 19.54. HRMS (ESI): m/z calculated for
C H Cl [M+H] 241.0784, found 241.0783.
16 14
13
+
+
(
s, 1H), 2.79 (s, 3H). C NMR (126 MHz, CDCl ): δ = 136.64,
3
1
1
32.56, 131.94, 131.64, 129.63, 128.86, 128.57, 128.24, 127.89,
4
.2.34 2-Chloro-6-ethylanthracene (4m). The compound 4m was
26.06, 125.96, 125.74, 123.25, 119.15, 19.45. HRMS (ESI): m/z
+
+
prepared by reacting 4-chloro-2-methylbenzaldehyde (1a) with 1-
ethyl-4-iodobenzene (2h) according to the general procedure in
0.2 mmol scale and purified by column chromatography using PE
as the eluent to give white solid in 30% yield (14.4 mg). H NMR
(500 MHz, CDCl ): δ = 8.32 (s, 1H), 8.28 (s, 1H), 7.95 (s, 1H),
calculated for C H Br [M+H] 271.0122, found 271.0126.
15
12
4
.2.29 2-Chloroanthracene (4h). The compound 4h was prepared
1
by reacting 4-chloro-2-methylbenzaldehyde (1a) with
iodobenzene (2e) according to the general procedure in 0.2 mmol
scale and purified by column chromatography using PE as the
3
7.92 (d, J = 8.9 Hz, 2H), 7.75 (s, 1H), 7.40 – 7.32 (m, 2H), 2.85
(q, J = 7.5 Hz, 2H), 1.37 (t, J = 7.6 Hz, 3H). C NMR (126
1
13
eluent to give white solid in 95% yield (40.4 mg). H NMR (500
MHz, CDCl ): δ = 8.40 (s, 1H), 8.32 (s, 1H), 8.00 (s, 1H), 7.98
MHz, CDCl ): δ = 141.58, 132.12, 131.38, 131.12, 130.60,
3
3
(
s, 2H), 7.94 (d, J = 9.0 Hz, 1H), 7.49 (p, J = 5.9 Hz, 2H), 7.39
129.88, 129.79, 127.97, 126.45, 126.36, 125.69, 125.10, 125.02,
13
+
+
(dd, J = 9.0, 1.2 Hz, 1H). C NMR (126 MHz, CDCl ): δ =
29.19, 15.07. HRMS (ESI): m/z calculated for C H Cl [M+H]
3
16 14
1
1
32.22, 131.79, 131.75, 131.10, 129.91, 129.73, 128.24, 128.08,
26.62, 126.53, 126.36, 126.04, 125.71, 125.40. HRMS (ESI):
241.0784, found 241.0787.
+
+
4.2.35 3-Chloronaphtho[2,3-b]thiophene (4n). The compound 4n
was prepared by reacting 4-chloro-2-methylbenzaldehyde (1a)
with 2-iodothiophene (2i) according to the general procedure in
m/z calculated for C H Cl [M+H] 213.0471, found 213.0469.
14
10

8
Tetrahedron
1
0
.2 mmol scale and purified by column chro
A
ma
C
to
C
gr
E
ap
P
hy
T
u
E
si
D
ng MAel
NU
uen
t
S
to
C
gi
R
ve
I
white solid in 35% yield (22.2 mg). H NMR (500
P
T
1
PE as the eluent to give white solid in 55% yield (24.1 mg). H
MHz, CDCl ): δ = 8.36 (s, 1H), 8.24 (s, 1H), 7.96 (dd, J = 16.9,
3
NMR (500 MHz, CDCl ): δ 8.28 (d, J = 6.1 Hz, 2H), 7.90 (d, J =
7.9 Hz, 2H), 7.72 (s, 1H), 7.47 (p, J = 7.0 Hz, 2H), 7.10 (s, 1H),
4.81 (dd, J = 9.1, 4.5 Hz, 1H), 3.78 (q, J = 7.1 Hz, 2H), 3.43 (dd,
J = 18.4, 9.7 Hz, 1H), 2.86 (dd, J = 18.4, 4.5 Hz, 1H), 2.51 (s,
3
13
9
.5 Hz, 2H), 7.52 (d, J = 5.6 Hz, 1H), 7.43 – 7.36 (m, 2H).
C
NMR (126 MHz, CDCl ): δ = 139.38, 139.09, 131.23, 130.89,
3
13
1
29.86, 129.07, 128.63, 126.01, 125.73, 123.44, 121.86, 119.82.
3H), 1.36 (t, J = 7.1 Hz, 3H). C NMR (126 MHz, CDCl ): δ =
3
+
+
HRMS (ESI): m/z calculated for C H ClS [M+H] 219.0035,
177.97, 175.95, 134.17, 133.64, 132.61, 131.76, 131.42, 128.38,
128.15, 127.83, 127.24, 126.75, 125.85, 125.60, 121.31, 43.48,
12
8
found 219.0030.
3
7.68, 34.22, 29.71, 21.86, 13.19. HRMS (ESI): m/z calculated
4
.2.36 3-Chloro-2-methylnaphtho[2,3-b]thiophene (4o). The
+ +
for C H NO [M+H] 318.1494, found 318.1497.
21
20
2
compound 4o was prepared by reacting 4-chloro-2-
methylbenzaldehyde (1a) with 2-iodo-5-methylthiophene (2j)
according to the general procedure in 0.2 mmol scale and
purified by column chromatography using PE as the eluent to
4.2.41 6-(Anthracen-2-yl)-2-(tridecan-7-yl)isoindoline-1,3-dione
(4t). The compound 4t was prepared by reacting 3-(1,3-dioxo-2-
(tridecan-7-yl)isoindolin-5-yl)benzaldehyde
iodobenzene (2e) according to the general procedure in 0.2 mmol
(1z)
with
1
give white solid in 62% yield (28.9 mg). H NMR (500 MHz,
CDCl ): δ = 8.12 (s, 1H), 8.07 (s, 1H), 7.84 (d, J = 8.9 Hz, 2H),
scale and purified by column chromatography using PE as the
eluent to give white solid in 53% yield (53.5 mg). H NMR (500
3
13
1
7
.36 (dd, J = 8.9, 1.7 Hz, 1H), 7.03 (s, 1H), 2.62 (s, 3H).
C
NMR (126 MHz, CDCl ): δ = 143.28, 140.19, 139.98, 130.84,
MHz, CDCl ): δ = 8.49 (s, 1H), 8.45 (s, 1H), 8.26 (s, 1H), 8.21
3
3
1
1
2
30.40, 129.67, 129.19, 125.78, 125.69, 120.89, 120.31, 119.18,
(d, J = 0.9 Hz, 1H), 8.12 (d, J = 8.9 Hz, 1H), 8.06 (dt, J = 6.0, 3.0
Hz, 1H), 8.05 – 7.99 (m, 2H), 7.93 (d, J = 7.7 Hz, 1H), 7.74 (dd,
J = 8.8, 1.7 Hz, 1H), 7.53 – 7.47 (m, 2H), 4.25 (tt, J = 10.1, 5.2
+
+
6.68. HRMS (ESI): m/z calculated for C H ClS [M+H]
13
10
33.0192, found 233.0195.
Hz, 1H), 2.19 – 2.06 (m, 2H), 1.74 (qd, J = 10.0, 5.0 Hz, 2H),
4
.2.37 3,7-dimethylnaphtho[2,3-b]thiophene-2-carbaldehyde
13
1
.35 – 1.22 (m, 16H), 0.86 (t, J = 7.0 Hz, 6H). C NMR (126
(4p). The compound 4p was prepared by reacting 2,4-
MHz, CDCl ): δ = 168.81, 168.75, 147.10, 135.72, 132.86,
3
dimethylbenzaldehyde (1v) with 5-iodo-3-methylthiophene-2-
carbaldehyde (2k) according to the general procedure in 0.2
mmol scale and purified by column chromatography using PE as
1
1
32.47, 132.29, 132.23, 131.45, 131.03, 130.31, 129.43, 128.24,
27.17, 126.94, 126.22, 125.93, 125.86, 124.49, 123.63, 121.83,
1
52.48, 32.57, 31.76, 29.03, 26.73, 22.61, 14.08. HRMS (ESI):
the eluent to give white solid in 45% yield (21.6 mg). H NMR
+ +
m/z calculated for C H NO [M+H] 506.3059, found
35
40
2
(500 MHz, CDCl ): δ = 10.40 (s, 1H), 8.32 (s, 1H), 8.27 (s, 1H),
3
5
06.3053.
7
2
1
1
.81 (d, J = 8.5 Hz, 1H), 7.76 (s, 1H), 7.39 (d, J = 8.5 Hz, 1H),
13
22
.87 (s, 3H), 2.55 (s, 3H). C NMR (126 MHz, CDCl ): δ =
4.3 3-Bromo-8-fluorotetraphene-7,12-dione (3qa)
3
84.10, 143.14, 139.58, 138.53, 137.53, 135.20, 131.95, 131.14,
29.75, 127.31, 127.06, 122.61, 121.14, 21.76, 12.26. HRMS
To a solution of 3-bromo-8-fluorotetraphene 3q (0.163 g, 0.5
mmol) in glacial acetic acid (10 mL) was added with stirring at
+
+
(ESI): m/z calculated for C H OS [M+H] 241.0687, found
15 13
room temperature, dropwise over 1 h, a solution of CrO (0.2 g, 2
3
2
41.0683.
.2.38 7-Chloronaphtho[2,3-b]furan-2-carbaldehyde (4q). The
mmol) in glacial acetic acid (5 mL) and water (5 mL). The
solution was stirred for an additional 60 min at rt, poured into
water (100 mL), and extracted with CH Cl (3 × 50 mL). The
4
compound 4q was prepared by reacting 4-chloro-2-
methylbenzaldehyde (1a) with 5-iodofuran-2-carbaldehyde (2l)
according to the general procedure in 0.2 mmol scale and
purified by column chromatography using PE as the eluent to
2
2
combined organic phase was washed with a saturated solution of
NaCl (2 × 50 mL), dried over Na SO , concentrated, and purified
2
4
by chromatography to afford yellow crystals: 76% yield (134.9
1
1
give white solid in 24% yield (11.8 mg). H NMR (500 MHz,
mg). H NMR (500 MHz, CDCl ): δ = 9.50 (d, J = 9.3 Hz, 1H),
3
CDCl ): δ = 9.95 (s, 1H), 8.27 (s, 1H), 7.95 (s, 1H), 7.92 (d, J =
8.36 (d, J = 8.6 Hz, 1H), 8.13 (d, J = 7.7 Hz, 1H), 8.09 (d, J = 8.6
3
13
8
.2 Hz, 2H), 7.68 (s, 1H), 7.41 (d, J = 8.8 Hz, 1H). C NMR
Hz, 1H), 8.07 (s, 1H), 7.82 – 7.74 (m, 2H), 7.50 – 7.43 (m, 1H).
13
(
126 MHz, CDCl ): δ = 179.94, 154.62, 154.46, 134.41, 132.71,
C NMR (126 MHz, CDCl ): δ = 183.11 (d, J = 417.7 Hz),
3
3
1
30.11, 129.05, 127.40, 126.52, 126.09, 123.08, 117.32, 107.61.
160.96 (d, J = 269.1 Hz), 137.55 (s), 136.55 (s), 135.56 (d, J =
9.8 Hz), 134.72 (s), 134.48 (s), 133.37 (s), 130.75 (s), 130.26 (s),
128.65 (d, J = 4.5 Hz), 123.75 (s), 123.66 (d, J = 3.6 Hz), 122.44
+
+
HRMS (ESI): m/z calculated for C H ClO [M+H] 231.0213,
found 231.0216.
13
8
2
(
d,
J = 21.7 Hz). HRMS (ESI): m/z calculated for
4
.2.39 7-Chloro-2,3-dihydroanthra[1,2-b][1,4]dioxine (4r). The
+ +
C H BrFO [M+H] 354.9770, found 354.9773.
18
9
2
compound 4r was prepared by reacting 4-chloro-2-
methylbenzaldehyde (1a) with 6-iodo-2,3-
dihydrobenzo[b][1,4]dioxine (2m) according to the general
4.4 7-Chloro-2-methylnaphtho[2,3-b]thiophene-4,9-dione
22
(4oa)
procedure in 0.2 mmol scale and purified by column
To a solution of 6-chloro-2-methylnaphtho[2,3-b]thiophene 4o
(0.12 g, 0.5 mmol) in glacial acetic acid (10 mL) was added with
stirring at room temperature, dropwise over 1 h, a solution of
chromatography using PE as the eluent to give yellow solid in
1
7
1
2
5% yield (40.6 mg). H NMR (500 MHz, CDCl ): δ = 8.18 (s,
3
H), 8.10 (s, 1H), 7.87 (s, 1H), 7.83 (d, J = 9.0 Hz, 1H), 7.37 (s,
H), 7.28 (dd, J = 9.0, 1.7 Hz, 1H), 4.39 (s, 4H). C NMR (126
13
CrO (0.2 g, 2 mmol) in glacial acetic acid (5 mL) and water (5
3
mL). The solution was stirred for an additional 60 min at rt,
poured into water (100 mL), and extracted with CH Cl (3 × 50
MHz, CDCl ): δ = 145.02, 144.75, 130.93, 130.23, 129.50,
3
2
2
1
1
29.36, 128.87, 128.84, 125.94, 125.79, 124.42, 123.28, 111.30,
mL). The combined organic phase was washed with a saturated
solution of NaCl (2 × 50 mL), dried over Na SO , concentrated,
11.13, 64.55, 64.54. HRMS (ESI): m/z calculated for
+
+
2
4
C H ClO [M+H] 271.0526, found 271.0529.
16
12
2
and purified by chromatography to afford yellow crystals: 83%
1
4
(
.2.40 1-Ethyl-3-(3-methylanthracen-1-yl)pyrrolidine-2,5-dione
4s). The compound 4s was prepared by reacting 2-(1-ethyl-2,5-
dioxopyrrolidin-3-yl)-4-methylbenzaldehyde (1y) with
yield (109.2 mg). H NMR (500 MHz, CDCl ): δ = 8.16 – 8.10
3
(m, 2H), 7.67 (dd, J = 8.3, 2.2 Hz, 1H), 7.36 (s, 1H), 2.62 (s, 3H).
13
C NMR (126 MHz, CDCl ): δ = 178.52, 176.60, 151.29,
3
iodobenzene (2e) according to the general procedure in 0.2 mmol
143.39, 143.20, 140.61, 135.01, 133.53, 131.50, 128.83, 126.84,
scale and purified by column chromatography using PE as the

9
1
25.09, 16.22. HRMS (ESI):
m/z
A
c
C
alc
C
ul
E
at
P
edTE
f
D
or MAan
N
d
U
(4
S
-m
C
or
R
ph
I
o
P
li
T
nophenyl)boronic acid (0.42 g, 2 mmol) in
+
+
o
C H ClO S [M+H] 262.9934, found 262.9932.
DME (10 mL) and H O (4 mL) was stirred at 100 C under N for
13
8
2
2
2
23
24h. After filtration and extraction with water/dichloromethane,
the organic phase was dried over Na SO and evaporated to
4
.5 7-Bromotetraphene (3ba)
2
4
To a solution of tetraphene 3b (0.11 g, 0.5 mmol) in CH CN (10
dryness. The residue was purified via column chromatography
3
mL) was added N-bromosuccinimide (0.13 g, 0.75 mmol) at
room temperature. The progress of the reaction was monitored by
TLC. Once the starting material was totally consumed, water was
added and the organic materials were extracted with CH Cl (3 ×
with PE/EA (20:1) as eluent to afford the product 6 as yellow
1
solid in 75% yield (305 mg). H NMR (500 MHz, CDCl
): δ =
3
9.52 (s, 1H), 8.94 (d, J = 8.2 Hz, 1H), 7.82 (d, J = 7.6 Hz, 1H),
7.72 (t, J = 7.1 Hz, 1H), 7.63 (t, J = 7.2 Hz, 1H), 7.58 – 7.50 (m,
3H), 7.36 – 7.30 (m, 3H), 7.20 (dd, J = 10.6, 7.4 Hz, 1H), 7.12
2
2
1
0 mL). The combined organic extracts were then dried over
1
3
MgSO . Evaporation of the solvent gave a crude product that was
(d, J = 8.6 Hz, 2H), 4.00 – 3.92 (m, 4H), 3.38 – 3.29 (m, 4H).
C
4
purified by preparative TLC with hexane as eluent to give yellow
NMR (126 MHz, CDCl ): δ = 159.10 (d, J = 252.6 Hz), 150.53
3
1
crystals in 77% yield (118.2 mg). H NMR (500 MHz, CDCl ): δ
(s), 137.59 (d, J = 3.1 Hz), 132.59 (d, J = 3.8 Hz), 131.98 (s),
131.67 (s), 130.57 (s), 129.77 (s), 129.68 (s), 128.83 (d, J = 1.2
Hz), 128.49 (s), 127.42 (d, J = 2.2 Hz), 127.12 (s), 125.59 (s),
124.75 (d, J = 8.5 Hz), 123.35 (s), 122.86 (d, J = 4.1 Hz), 122.40
(d, J = 16.1 Hz), 115.24 (s), 113.96 (d, J = 5.7 Hz), 108.13 (d, J =
19.8 Hz), 67.02 (s), 49.15 (s). HRMS (ESI): m/z calculated for
3
=
9.10 (s, 1H), 8.76 (d, J = 8.1 Hz, 1H), 8.53 (d, J = 8.6 Hz, 1H),
8
7
.35 (d, J = 9.4 Hz, 1H), 8.06 (d, J = 8.3 Hz, 1H), 7.85 (dd, J =
.7, 0.9 Hz, 1H), 7.71 (d, J = 9.4 Hz, 1H), 7.68 (dd, J = 8.2, 1.2
13
Hz, 1H), 7.67 – 7.60 (m, 2H), 7.60 – 7.55 (m, 1H). C NMR
126 MHz, CDCl ): δ = 132.24, 131.50, 130.94, 130.13, 129.58,
(
3
+
+
1
1
29.44, 129.01, 128.82, 128.67, 127.59, 127.54, 127.37, 127.33,
C H23FNO [M+H] 408.1764, found 408.1761.
28
26.22, 126.08, 123.27, 123.03, 121.89. HRMS (ESI): m/z
+
+
4.9 Methyl 4-(tetraphen-7-yl)benzoate (7)
calculated for C H Br [M+H] 307.0122, found 307.0124.
18
12
To a solution of 7-bromotetraphene 3ba (307 mg, 1 mmol),
4
.6 4-(4-(Tetraphen-7-yl)phenyl)morpholine (5)
Pd(PPh ) (0.012 g, 0.01 mmol), K CO (0.28 g, 2 mmol) and (4-
3
4
2
3
To a solution of 7-bromotetraphene 3ba (307 mg, 1 mmol),
(methoxycarbonyl)phenyl)boronic acid (0.36 g, 2 mmol) in DME
o
Pd(PPh ) (0.012 g, 0.01 mmol), K CO (0.28 g, 2 mmol) and (4-
(10 mL) and H
After filtration and extraction with water/dichloromethane, the
organic phase was dried over Na SO and evaporated to dryness.
2
O (4 mL) was stirred at 100 C under N for 24h.
2
3
4
2
3
morpholinophenyl)boronic acid (0.42 g, 2 mmol) in DME (10
o
mL) and H O (4 mL) was stirred at 100 C under N for 24h.
2
4
2
2
After filtration and extraction with water/dichloromethane, the
organic phase was dried over Na SO and evaporated to dryness.
The residue was purified via column chromatography with
PE/EA (10:1) as eluent to afford the product 7 as yellow solid in
2
4
1
The residue was purified via column chromatography with
56% yield (202.7 mg). H NMR (500 MHz, CDCl
3
) δ 9.26 (s,
PE/EA (20:1) as eluent to afford the product 5 as yellow solid in
1H), 8.88 (d, J = 8.2 Hz, 1H), 8.30 (d, J = 8.1 Hz, 2H), 8.17 (d, J
= 8.3 Hz, 1H), 7.82 (d, J = 7.6 Hz, 1H), 7.71 (t, J = 7.1 Hz, 1H),
7.65 – 7.59 (m, 2H), 7.58 – 7.52 (m, 3H), 7.51 (d, J = 9.4 Hz,
1H), 7.47 – 7.43 (m, 1H), 7.41 (d, J = 9.4 Hz, 1H), 4.04 (s, 3H).
1
6
1
7% yield (260.6 mg). H NMR (500 MHz, CDCl ): δ = 9.24 (s,
H), 8.90 (d, J = 8.2 Hz, 1H), 8.17 (d, J = 8.3 Hz, 1H), 7.82 (d, J
3
=
–
6.9 Hz, 1H), 7.75 (d, J = 8.6 Hz, 1H), 7.72 – 7.68 (m, 1H), 7.64
7.59 (m, 1H), 7.58 (d, J = 9.4 Hz, 1H), 7.57 – 7.53 (m, 1H),
13
C NMR (126 MHz, CDCl ) δ 167.08, 144.20, 136.20, 131.53,
3
7
2
.50 (d, J = 9.4 Hz, 1H), 7.45 – 7.41 (m, 1H), 7.37 – 7.32 (m,
H), 7.12 (d, J = 8.6 Hz, 2H), 3.99 – 3.93 (m, 4H), 3.36 – 3.30
131.48, 130.50, 130.45, 129.74, 129.52, 128.75, 128.58, 128.57,
128.42, 127.35, 127.30, 127.11, 126.23, 126.08, 125.63, 125.02,
123.11, 122.14, 52.26, 29.76. HRMS (ESI): m/z calculated for
13
(m, 4H). C NMR (126 MHz, CDCl ): δ = 150.42, 137.60,
3
+
+
1
1
1
32.10, 131.64, 131.61, 131.31, 130.58, 130.11, 129.06, 128.64,
28.60, 128.47, 127.13, 126.90, 126.87, 126.67, 125.84, 125.61,
25.46, 123.11, 121.35, 115.27, 67.04, 49.22. HRMS (ESI): m/z
C
26
H
19
O
2
[M+H] 363.1385, found 363.1389.
.10 Methyl 4-(11-fluorotetraphen-7-yl)benzoate (8)
To a solution of 7-bromo-11-fluorotetraphene 3ia (0.32 g, 1
4
+
+
calculated for C H NO [M+H] 390.1858, found 390.1856.
28
24
2
3
mmol), Pd(PPh (0.012 g, 0.01 mmol), K CO (0.28 g, 2 mmol)
3
)
4
2
3
4
.7 7-bromo-11-fluorotetraphene (3ia)
and (4-(methoxycarbonyl)phenyl)boronic acid (0.36 g, 2 mmol)
o
To a solution of 10-fluorotetraphene 3i (0.13 g, 0.5 mmol) in
CH CN (10 mL) was added N-bromosuccinimide (0.13 g, 0.75
mmol) at room temperature. The progress of the reaction was
monitored by TLC. Once the starting material was totally
consumed, water was added and the organic materials were
extracted with CH Cl (3 × 10 mL). The combined organic
in DME (10 mL) and H
for 24 h. After
water/dichloromethane, the organic phase was dried over Na
2
O (4 mL) was stirred at 100 C under N
filtration and extraction with
SO
4
2
3
2
and evaporated to dryness. The residue was purified via column
chromatography with PE/EA (10:1) as eluent to afford the
1
product 8 as yellow solid in 44% yield (167 mg). H NMR (500
2
2
extracts were then dried over MgSO . Evaporation of the solvent
MHz, CDCl ): δ = 9.54 (s, 1H), 8.91 (d, J = 8.2 Hz, 1H), 8.28 (d,
3
4
gave a crude product that was purified by preparative TLC with
J = 8.2 Hz, 2H), 7.81 (d, J = 7.3 Hz, 1H), 7.72 (t, J = 8.2 Hz,
1H), 7.64 (t, J = 7.5 Hz, 1H), 7.55 – 7.48 (m, 3H), 7.39 – 7.29
(m, 3H), 7.23 – 7.18 (m, 1H), 4.03 (s, 3H). C NMR (126 MHz,
hexane as eluent to give yellow crystals in 82% yield (133 mg).
1
13
H NMR (500 MHz, CDCl ): δ = 9.20 (s, 1H), 8.73 (d, J = 8.2
3
Hz, 1H), 8.31 (s, 1H), 7.89 (d, J = 7.6 Hz, 1H), 7.81 (d, J = 8.9
Hz, 1H), 7.71 – 7.65 (m, 2H), 7.62 (t, J = 7.3 Hz, 1H), 7.57 (d, J
CDCl ): δ = 166.99 (s), 159.09 (d, J = 253.3 Hz), 143.81 (s),
3
136.18 (d, J = 3.2 Hz), 131.72 (d, J = 3.9 Hz), 131.55 (s), 131.32
(s), 130.43 (s), 129.76 (s), 129.68 (s), 129.05 (s), 128.76 (s),
128.59 (s), 128.08 (s), 127.48 (d, J = 31.3 Hz), 125.31 (d, J = 8.5
Hz), 124.77 (s), 123.32 (s), 122.34 (d, J = 16.3 Hz), 122.21 (d, J
= 4.2 Hz), 114.78 (d, J = 5.6 Hz), 108.34 (d, J = 19.8 Hz), 52.27
13
=
5.5 Hz, 1H), 7.48 (d, J = 5.5 Hz, 1H). C NMR (126 MHz,
CDCl ): δ = 138.92 (d, J = 23.5 Hz), 131.99 (s), 129.80 (d, J =
3
5
8.1 Hz), 128.55 (s), 128.05 (s), 127.82 (s), 127.43 (s), 126.67
(
s), 126.30 (s), 123.53 (s), 122.62 (d, J = 16.1 Hz), 116.14 (s).
+
+
HRMS (ESI): m/z calculated for C H BrF [M+H] 325.0038,
(s), 29.7+0 (s). HRMS (ESI): m/z calculated for
18
11
+
found 325.0031.
C
26
H18FO
2
[M+H] 381.1291, found 381.1291.
4
.8 4-(4-(11-fluorotetraphen-7-yl)phenyl)morpholine (6)
Acknowledgments
To a solution of 7-bromo-11-fluorotetraphene 3ia (0.32 g, 1
mmol), Pd(PPh ) (0.012 g, 0.01 mmol), K CO (0.28 g, 2 mmol)
3
4
2
3

1
0
Tetrahedron
TED
9
.
Zhang, F.-L.; Hong, K.; Li, T.-J.; Park, H.; Yu, J.-Q. Science 2016,
3
We thank the National Natural Scien
A
ce
C
F
C
ou
E
nd
P
at
io
n
of MANUSCRIPT
51, 252.
0. (a) Yang, K.; Li, Q.; Liu, Y.; Li, G.; Ge, H. J. Am. Chem. Soc.
016, 138, 12775; (b) Chen, X.-Y.; Ozturk, S.; Sorensen, E. J. Org.
China (grant no. 21703162) for financial support.
1
2
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