Rhodium-catalyzed dehydrogenative coupling of phenylheteroarenes with alkynes or alkenes

Article abstract of DOI:10.1021/acs.joc.5b00155

Benzo-fused tri- to heptacyclic heteroarenes were effectively constructed by the rhodium-catalyzed dehydrogenative coupling of phenylheteroarenes with alkynes. Using alkenes as coupling partners, dehydrogenative alkenylation took place selectively on the

Full text of DOI:10.1021/acs.joc.5b00155

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Article
Rhodium-Catalyzed Dehydrogenative Coupling
of Phenylheteroarenes with Alkynes or Alkenes
Tomonori Iitsuka, Koji Hirano, Tetsuya Satoh, and Masahiro Miura
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b00155 • Publication Date (Web): 16 Feb 2015
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The Journal of Organic Chemistry
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Rhodium-Catalyzed Dehydrogenative Coupling of
Phenylheteroarenes with Alkynes or Alkenes
Tomonori Iitsuka,† Koji Hirano,† Tetsuya Satoh, *,†,‡ and Masahiro Miura*,†
†Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871,
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Japan
‡JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
satoh@chem.eng.osaka-u.ac.jp; miura@chem.eng.osaka-u.ac.jp
RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required)
R3
R4
Z
37 examples
13-98% yield
R4
!
Y
R3
Rh(III)-cat.
Cu salt
Z
H
H
H
R5
Y
!
Z
14 examples
45-65% yield
R5
H
Y
Abstract: Benzo-fused tri- to hepta-cyclic heteroarenes were effectively constructed by the rhodium-
catalyzed dehydrogenative coupling of phenylheteroarenes with alkynes. Using alkenes as coupling
partners, dehydrogenative alkenylation took place selectively on the phenyl moiety of
phenylheteroarenes. Several experiments with deuterium-labeled substrates indicated that double C–H
bond cleavages take place even in the reaction with alkenes.
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Introduction
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Benzo-fused heteroarene frameworks can be seen in various fine chemicals including organic
materials1 and pharmaceuticals.2 Therefore, the development of simple and straightforward synthetic
methods for constructing the fused compounds has attracted much attention. One of the most promising
procedures is the transition-metal-catalyzed dehydrogenative coupling of aromatic substrates possessing
an hetero atom containing directing group with internal alkynes involving regioselective C–H bond
cleavage at the ortho-position of the directing group.3 So far, numerous reports for constructing benzo-
fused oxygen-, nitrogen-, phosphorous-, and sulfur-containing heterocycles have been disclosed
(Scheme 1a). Besides such σ-coordinating directing groups, π-electron units such as alkenyl, alkynyl,
aryl, and cyano functions have been found to act as directing groups for ortho C–H functionalization.4
We conceived that more highly fused polycyclic heteroarenes can be easily prepared if heteroaryl
groups can be employed as directing groups in the dehydrogenative coupling with alkynes.5 Indeed,
tricyclic naphthothiophene structures could be constructed by a single treatment of 3-phenylthiophenes
with alkynes under rhodium catalysis.6,7 This reaction seems to proceed via π-electron directed C–H
bond cleavage to form a rhodacycle intermediate, alkyne insertion, and reductive elimination (Scheme
1b, Y = S, Z = CH). We succeeded in applying this procedure to constructing tri- to hepta-cyclic benzo-
fused heteroarene derivatives 3 and 4 from readily available phenyl- or diphenylheteroarenes 1 and
alkynes 2. The oxidative coupling of 3-phenylthiophene with alkenes 5 also proceeded smoothly in the
presence of a same catalyst system to form the corresponding 2’-alkenylated product 6 (Scheme 1c).
New mechanistic insights were obtained for the latter reaction by some deuterium-labeling experiments.
The detailed results obtained for these reactions are described herein.
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Scheme 1. Dehydrogenative Coupling of Arenes Possessing a Directing Group
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The Journal of Organic Chemistry
a. Previous Work: Synthesis of Benzo-Fused Heterocycles
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R
H
R
R
cat
H
+
Y
Y
oxidant
R
4
Y = CO2, CR'2O, CONR', NR', POR'2O, etc.
5
b. This Work: Synthesis of Naphtho-Fused Heterocycles
R
6
7
8
9
R
R
R
H
H
R
R
Y
Cp*RhIII-cat
oxidant
R
2
+
Y
Z = C–Ph
R
Y
Z
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R
Z
R
Cp*RhX2
–2HX
4
R
R
Cp*
Rh
R
–Cp*Rh
R
Rh Cp*
Y
Y
Z
Z
Y = S, O; Z = CR, N; R = aryl, alkyl
c. This Work: Synthesis of 2'-Alkenylated 3-Phenylthiophenes
H
R
Cp*RhIII-cat
+
R
oxidant
S
S
1
5
6
R = EWG, aryl
Results and Discussion
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The reaction of 3-phenylthiophene (1a) with diphenylacetylene (2a) was explored to screen the
reaction conditions, as shown in Table S1 (see the Supporting Information). The desired
dehydrogenative coupling product, 4,5-diphenylnaphtho[2,1-b]thiophene (3aa), was obtained in 84%
yield by treatment of 1a (0.2 mmol) with 2a (0.1 mmol) in the presence of [Cp*RhCl2]2 (0.005 mmol),
Cu(OAc)2•H2O (0.2 mmol), and Cs2CO3 (0.03 mmol), as catalyst, oxidant, and additive, respectively, in
o
toluene (1 mL) at 125 C for 7 h under N2 (entry 1 in Table 1). Doubling of the reaction scale did not
affect the reaction efficiency (entry 2). Under the optimized conditions, bis(4-substituted
phenyl)acetylenes possessing electron-donating (2b-e) and –withdrawing (2f-h) groups also underwent
coupling with 1a to give the corresponding naphthothiophenes 3ab-ah in 54-86% yields (entries 3-9).
The reaction of 1a with di(2-naphthyl)acetylene (2i) proceeded efficiently to produce 4,5-di(2-
naphthyl)naphtho[2,1-b]thiophene (3ai) in 75% yield (entry 10). Besides diarylacetylenes,
dialkylacetylenes such as 4-octyne (2j) and 8-hexadecyne (2k) also coupled with 1a smoothly to afford
dialkylnaphthothiophenes 3aj and 3ak (entries 11 and 12). The latter reaction could be readily scaled up
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to a gram scale. Thus, from 1a (10 mmol) and 2k (5 mmol), 3ak was obtained in 56% yield (1.07 g,
entry 13). Contrastingly, more functionalized alkynes, such as 2,5-dimethyl-3-hexyne-2,5-diol (2l) and
dimethyl acetylenedicarboxylate (2m), did not react with 1a at all (entries 14 and 15). It is possible that
these alkynes deactivate the catalyst. The reaction of 1a with an unsymmetrical alkyne, 1-phenyl-1-
propyne (2n), produced 5-methyl-4-phenylnaphthothiophene derivative 3an predominantly, along with
a minor amount of its 4-methyl-5-phenyl derivative 3an’ (entry 16).
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Table 1. Reaction of 3-Phenylthiophene (1a) with Alkynes 2a
[Cp*RhCl2]2
Cu(OAc)2•H2O
Cs2CO3
R4
+
H
R3
refluxing toluene
R4
H
S
S
2
R3
1a
3
entry
time (h)
2
product(s), % yield
R
R
S
R
R
1b
2
3
4
5
7
2a: R = H
2a: R = H
3aa: R = H, 84 (90)c
3aa: R = H, (90)c
3ab: R = Me, 86
3ac: R = But, 65
3ad: R = OMe, 76
3ae: R = NMe2, 71
3af: R = Br, 54
10
10
24
7
7
7
2b: R = Me
2c: R = But
2d: R = OMe
2e: R = NMe2
2f: R = Br
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7
8
9
7
7
2g: R = Ac
2h: R = CF3
3ag: R = Ac, 62
3ah: R = CF3, 76
S
10
2i
3ai, 75
7
R
R
R
S
R
11b
12b
13d
14
7
7
24
7
7
2j: R = Prn
2k: R = n-C7H15
2k: R = n-C7H15
2l: R = C(OH)Me2
2m: R = CO2Me
3aj: R = Prn, 79
3ak: R = n-C7H15, 85
3ak: R = n-C7H15, 56
3al: R = C(OH)Me2, 0
3am: R = CO2Me, 0
15
Me
+
Me
Ph
Ph
S
S
Ph
Me
16b
7
2n
3an, 50
3an', 12
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The Journal of Organic Chemistry
a
Reaction conditions: 1a (0.4 mmol), 2 (0.2 mmol), [Cp*RhCl2]2 (0.01 mmol), Cu(OAc)2•H2O (0.4
mmol), Cs2CO3 (0.06 mmol) in toluene (2 mL) at 125 oC under N2, unless otherwise noted. b Using 1a
(0.2 mmol), 2 (0.1 mmol), [Cp*RhCl2]2 (0.005 mmol), Cu(OAc)2•H2O (0.2 mmol), Cs2CO3 (0.03 mmol)
in toluene (1 mL). c Determined by GC. d Using 1a (10 mmol), 2 (5 mmol), [Cp*RhCl2]2 (0.25 mmol),
Cu(OAc)2•H2O (10 mmol), Cs2CO3 (1.5 mmol) in toluene (30 mL).
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Next, we examined the reactions of variously substituted 3-phenylthiophenes 1b-i with alkyne 2a or
2j (Scheme 2). Methyl, methoxy, chloro, phenyl, fluoro, and methoxycarbonyl substituents on either the
phenyl ring or the thiophene ring were tolerated under standard conditions to furnish 3ba-3da, 3ej, and
3fa-3ia. It is noted that the reaction of 3-[(1,1’-biphenyl)-4-yl]thiophene (1e) was conducted using 2j,
because the coupling product of 1e with 2a was less soluble in usual organic solvents to make its
isolation difficult. Tetracyclic anthrathiophene 3ja and benzonaphthothiophene 3ka frameworks could
be readily constructed in the annulations of 3-(2-naphthyl)thiophene (1j) and 3-phenylbenzothiophene
(1k), respectively. In the latter case, a better product yield was obtained at 120 oC rather than that at 125
oC. In contrast to 1k, its regioisomer, 2-phenylbenzothiophene (1l), did not show any reactivity toward
2a, resulting in no formation of 3la. Treatment of p-di(thiophen-3-yl)benzene (1m) with 2j in a 2:1 ratio
gave 1:1 coupling product 3mj in 57% yield, along with a minor amount of 1:2 coupling product 4mj.
The use of 1m and 2j in a 1:2 ratio afforded 4mj exclusively, albeit with a moderate yield. The reactions
of m-isomer 1n with 2j gave similar results, providing 3nj and 4nj. A mixture of regioisomers 3oa and
3oa’ was formed in the reaction of 3,3’-bithiophene with 2a. 3,4-Diphenylthiophene (1p) reacted with
2a in a 1:1 manner under standard conditions to produce 3pa quantitatively. Even under conditions
using excess 2a, 3pa was formed predominantly, along with a minor amount of 1:2 coupling product
4pa. The reaction using 1p and 2j in a 2:1 ratio similarly gave 3pj almost quantitatively. In contrast,
3,6-diphenylthieno[3,2-b]thiophene (3q) reacted with 2k efficiently in a 1:2 manner to selectively form
hexacyclic 4qk. 3-Phenylbenzofuran (1r) coupled with 2a efficiently to form 3ra in 90% yield, while
the reaction of 2-phenyl isomer 1s did not give 3sa at all. The reactions of 2- (1t), 3- (1u), and 4- (1v)
(thiophen-3-yl)pyridines were next examined. Although 1t did not react with 2a, 1u and 1v underwent
the annulation. In the case with 1u, a mixture of regioisomers 3ua and 3ua’ was formed. 6-(Thiophen-3-
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yl)quinoline (1w) could also be employed for the annulation with 2a to selectively form tetracyclic
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2
3
4
5
product 3wa. 4-Phenylthiazoles 1x and 1y coupled with 2a smoothly, in contrast to 5-phenyl isomers 1z
and 1aa. Similar results were obtained in the reactions of phenyloxazoles 1bb-ee.
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Scheme 2. Reaction of (Hetero)arylheteroarenes 1 with Alkyne 2a, 2j, or 2ka
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W
[Cp*RhCl2]2
Cu(OAc)2•H2O
Cs2CO3
W
X
X
R
+
Z
H
Z
R
refluxing toluene
R
H
Y
Y
2
R
2a: R = Ph, 2j: R = Prn, 2k: R = n-C7H15
1
3 or 4
Me
Ph
OMe
Cl
Ph
F
Me
Me
Ph
Ph
Prn
Ph
Ph
Ph
Me
S
S
S
S
S
S
S
Ph
Ph
Ph
Prn
Ph
Ph
Ph
3ba, 85% (10 h) 3ca, 66% (24 h)
3da, 98% (7 h) 3ej, 76% (7 h)
3fa, 87% (7 h)
3ga, 98% (10 h)
3ha, 97% (10 h)
Prn
Prn
Ph
S
+
S
Ph
S
Prn
S
Ph
Ph
Ph
MeO2C
S
S
S
S
Prn
Prn
Prn
Ph
Ph
Ph
3ia, 81% (7 h)
3ja, 93% (7 h)
3ka, 70% (24 h)b
3la, 0% (7 h)
3mj, 57% + 4mj, 14% (7 h)c
4mj, 40% (48 h)d
S
S
Prn
S
S
S
+
+
S
S
S
+
Ph
Ph
Ph
Prn
Prn
S
S
Ph
Ph
Prn
Prn
Ph
Ph
Ph
Ph
Ph
Prn
3nj, 28% + 4nj, 35% (10 h)e
3nj, 9% + 4nj, 48% (24 h)d
3oa, 9% + 3oa', 13% (10h)
3pa, 99% (7 h)
3pa, 75% + 4pa, 13% (48 h)f
n-C7H15
Ph
Ph
N
S
n-C7H15
n-C7H15
n-C7H15
Prn
S
Ph
Ph
S
O
O
S
Prn
Ph
Ph
3pj, 98% (10 h)g
4qk, 85% (7 h)e
3ra, 90% (24 h)h
3sa, 0% (7 h)
3ta, 0% (7 h)
N
N
N
N
N
N
+
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Me
S
S
S
S
S
S
Ph
Ph
Ph
Ph
Ph
Ph
3ua, 47% + 3ua', 27% (7 h)
3va, 86% (7 h)
3wa, 70% (7 h)
3xa, 75% (7 h)
3ya, 78% (7 h)
Ph
N
Ph
Ph
Ph
Ph
Ph
Ph
Ph
N
N
N
N
N
Ph
Ph
Ph
O
Me
Ph
O
Me
Ph
Me
O
O
S
S
Ph
Ph
3za, 0% (7 h)
3aaa, 0% (7 h)
3bba, 76% (24 h)
3cca, 44% (24 h)
3dda, 0% (7 h)
3eea, 0% (7 h)
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The Journal of Organic Chemistry
a
Reaction conditions: 1 (0.4 mmol), 2 (0.2 mmol), [Cp*RhCl2]2 (0.01 mmol), Cu(OAc)2•H2O (0.4
mmol), Cs2CO3 (0.06 mmol) in toluene (2 mL) at 125 oC under N2, unless otherwise noted. b At 120 oC. c
1
2
3
4
5
6
7
8
d
Using Cu(OAc)2•H2O (0.8 mmol). Using 1 (0.2 mmol), 2 (0.4 mmol), [Cp*RhCl2]2 (0.02 mmol),
Cu(OAc)2•H2O (0.8 mmol), and Cs2CO3 (0.12 mmol). e Using 1 (0.2 mmol), 2 (0.4 mmol), [Cp*RhCl2]2
(0.01 mmol), Cu(OAc)2•H2O (0.8 mmol), and Cs2CO3 (0.12 mmol). f Using 1 (0.2 mmol), 2 (0.4 mmol),
[Cp*RhCl2]2 (0.01 mmol), Cu(OAc)2•H2O (0.8 mmol), and Cs2CO3 (0.06 mmol). g Using 1 (2 mmol), 2
(1 mmol), [Cp*RhCl2]2 (0.05 mmol), Cu(OAc)2•H2O (2 mmol), Cs2CO3 (0.3 mmol) in toluene (10 mL).
h
Using 1 (0.2 mmol), 2 (0.1 mmol), [Cp*RhCl2]2 (0.005 mmol), Cu(OAc)2•H2O (0.2 mmol), and
Cs2CO3 (0.03 mmol) in toluene (1 mL).
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We also examined the construction of a molecule possessing a further expanded π-conjugated
system. Thus, benzonaphthothiophene 3ko, prepared by the annulative coupling of 1k with bis(3,4-
dimethoxyphenyl)acetylene (2o), was treated in the presence of an excess amount of FeCl3 in
CH2Cl2/CH3NO2 (2:1) at room temperature for 24 h (Scheme 3).8 As a result, dehydrogenative
cyclization took place to produce heptacyclic 7.
Scheme 3. Reaction of 1k with 2o and Further Cyclization
MeO
MeO
OMe
OMe
2o (1 mmol)
OMe
OMe
[Cp*RhCl2]2 (0.05 mmol)
Cu(OAc)2•H2O (2 mmol)
Cs2CO3 (0.3 mmol)
S
toluene (10 mL)
120 oC, 24 h
S
MeO
1k (2 mmol)
OMe
3ko, 50%
OMe
OMe
OMe
FeCl3 (0.33 mmol)
S
OMe
S
CH2Cl2 (1.2 mL)
CH3NO2 (0.6 mL)
rt, 24 h
MeO
MeO
OMe
OMe
3ko (0.05 mmol)
7, 59%
Under similar catalytic conditions, 1a also underwent the dehydrogenative coupling with alkenes in
place of alkynes. As shown in Table 2, treatment of 1a (0.4 mmol) with various acrylates 5a-e (0.2
mmol) in the presence of [Cp*RhCl2]2 (0.01 mmol), Cu(OAc)2•H2O (0.4 mmol), and Cs2CO3 (0.06
o
mmol) in toluene (2 mL) at 125 C for 7 h under N2 gave the corresponding (E)-3-[2-(thiophen-3-
yl)phenyl]acrylates 6aa-6ae in 47-64% yields (entries 1-5). While N,N-dimethylacrylamide (5f) did not
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react at all (entry 6), diethyl vinylphosphonate (5g) coupled with 1a to give 6ag in a moderate yield
(entry 7). Not only these electron-deficient alkenes but also variously substituted styrenes 5h-n
underwent the dehydrogenative coupling to form 2’-styrylated products 6ah-6an (entries 8-14). In
addition to styrenes, 2-vinylnaphthalene (5o) could also be employed for this reaction (entry 15).
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5
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Table 2. Reaction of 3-Phenylthiophene (1a) with Alkenes 5a
[Cp*RhCl2]2
Cu(OAc)2•H2O
Cs2CO3
+
H
R
refluxing toluene
R
S
S
5
1a
6
product, % yield
entry
time (h)
5
CO2R
CO2R
S
5a: R = Bun
5b: R = Bui
5c: R = But
5d: R = Et
5e: R = Cyb
6aa: R = Bun, 60
6ab: R = Bui, 50
6ac: R = But, 52
6ad: R = Et, 47
6ae: R = Cy,b 64
1
2
3
4
5
7
7
7
7
7
R
R
S
6
7
7
10
5f: R = CONMe2
5g: R = P(O)(OEt)2
6af: R = CONMe2, 0
6ag: R = P(O)(OEt)2, 47
S
R
R
8
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10
10
10
10
10
5h: R = H
6ah: R = H, 58
6ai: R = Me, 53
6aj: R = But, 45
6ak: R = OMe, 53
6al: R = Ph, 65
6am: R = Cl, 63
6an: R = CF3, 63
5i: R = Me
5j: R = But
5k: R = OMe
5l: R = Ph
5m: R = Cl
5n: R = CF3
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14
S
15
10
5o
6ao, 50
a
Reaction conditions: 1a (0.4 mmol), 5 (0.2 mmol), [Cp*RhCl2]2 (0.01 mmol), Cu(OAc)2•H2O (0.4
mmol), Cs2CO3 (0.06 mmol) in toluene (2 mL) at 125 oC under N2. b Cy = cyclohexyl.
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The fact that the alkenylation took place selectively at the 2’-position on the phenyl ring of 1a rather
1
2
than on the thienyl moiety seems to support a reaction mechanism proposed in our preliminary
communication,6 involving thiophene π-unit directed C–H bond cleavage at the 2’-position, alkene
insertion, and β-hydrogen elimination to form 6 (Scheme 4).
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Scheme 4. Previously Proposed Mechanism for the Reaction of 1a with 5
R
6
1a
5
Cp*Rh
Cp*RhX2
Rh
X
–HX
–HX
R
H
Rh
*Cp
Cp*
S
S
X
However, we obtained a contradicting result in our subsequent study. Thus, in the treatment of C2-
deuterated 1a (1a-d1) with 5h under standard conditions for 2 h, the 2’-styrylation proceeded
accompanied by the loss of C2 deuterium to form 6ah-d0 (Scheme 5). In addition, no significant D/H
exchange was observed in the recovered 1a-d1. These results indicate that the coupling reaction involves
C–H(D) bond cleavages not only on the phenyl group but also on the thiophene ring.
Scheme 5. Reaction of 1a-d1 with 5h
[Cp*RhCl2]2 (0.01 mmol)
0% D
H
Ph
Cu(OAc)2•H2O (0.4 mmol)
Cs2CO3 (0.06 mmol)
S
6ah-d0, 12%a
+
Ph
83% D
D
toluene (2 mL)
125 oC, 2 h
S
5h
(0.2 mmol)
1a-d1
(83% D, 0.4 mmol)
80% D
D
S
1a-d1, 86%a
a Isolated yield based on the amount of 5h used.
Next, we investigated the source of the hydrogen introduced at the C2 position of coupling product
6ah in Scheme 5. Treatment of 1a-d0 with D2O or CD3CO2D in the presence and absence of 5h resulted
in no incorporation of deuterium in recovered 1a as well as produced 6ah (Schemes 6a-d). Finally, the
C2-deuterium incorporation in 6ah was observed, when deuterated styrene 5h-d8 was employed. Thus,
C2-deuterated 2’-styrylated product 6ah-d8 was obtained upon treatment of 1a with 5h-d8 (Scheme 6e).
In this case, deuterium was not incorporated in the recovered 1a at all.
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Scheme 6. Deuterium Incorporation
1
2
3
4
5
6
[Cp*RhCl2]2 (0.01 mmol)
Cu(OAc)2•H2O (0.4 mmol)
Cs2CO3 (0.06 mmol)
D2O (0.8 mmol)
(a)
toluene (2 mL)
125 oC, 2 h
7
8
9
0% D
H
H
S
S
1a-d0, 95%a
1a-d0
(0.4 mmol)
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60
[Cp*RhCl2]2 (0.01 mmol)
Cu(OAc)2•H2O (0.4 mmol)
Cs2CO3 (0.06 mmol)
CD3CO2D (0.8 mmol)
(b)
toluene (2 mL)
125 oC, 2 h
0% D
H
H
S
S
1a-d0, 96%a
1a-d0
(0.4 mmol)
[Cp*RhCl2]2 (0.01 mmol)
Cu(OAc)2•H2O (0.4 mmol)
Cs2CO3 (0.06 mmol)
D2O (0.8 mmol)
0% D
H
Ph
S
6ah-d0, 42%a
+
(c)
Ph
toluene (2 mL)
125 oC, 2 h
H
S
5h-d0
(0.2 mmol)
1a-d0
(0.4 mmol)
0% D
H
S
1a-d0, 58%a
[Cp*RhCl2]2 (0.01 mmol)
Cu(OAc)2•H2O (0.4 mmol)
Cs2CO3 (0.06 mmol)
0% D
Ph
H
S
CD3CO2D (0.8 mmol)
6ah-d0, 36%a
+
(d)
Ph
toluene (2 mL)
125 oC, 6 h
H
S
5h-d0
(0.2 mmol)
1a-d0
(0.4 mmol)
0% D
H
S
1a-d0, 64%a
91% D
D
C6D5
D
D
80% D
S
[Cp*RhCl2]2 (0.01 mmol)
Cu(OAc)2•H2O (0.4 mmol)
Cs2CO3 (0.06 mmol)
98% D
D
6ah-d8, 32%a
D
+
(e)
C6D5
toluene (2 mL)
125 oC, 2 h
H
S
D
5h-d8
(98% D, 0.2 mmol)
1a-d0
(0.4 mmol)
0% D
H
S
1a-d0, 68%a
a Isolated yield based on the amount of 5h used.
Based on these experimental results, a revised mechanism for the reaction of 1a with alkene 5 can be
proposed (Scheme 7). Coordination of the thienyl moiety of 1a to a Cp*RhIII center and subsequent
double C–H bond cleavages would occur to form a five-membered rhodacycle intermediate A, as in the
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reaction with alkynes (Scheme 1b). Then, alkene insertion into the resulting Rh–C bond to form B, β-
hydrogen elimination, and reductive elimination of 6 from C may take place to release a Cp*RhI
species, which is oxidized by CuII to regenerate the Cp*RhIII. As in the reaction with alkyne 2a (see
Table S1), the efficiency of the reaction of 1a with 5h was slightly enhanced by the addition of Cs2CO3.
Indeed, the yield of 6ah decreased to 40% in the absence of Cs2CO3. One of possible roles of Cs2CO3
seems to be the trap of HX formed during the coupling reaction.
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Scheme 7. Plausible Mechanism for the Reaction of 1a with 5
2 CuX2
2 CuX
R
H
Cp*Rh
S
6
Cp*RhX2
1a
S
2HX
H
R
Rh
S
Cp*
C
Rh
S
Cp*
A
Rh
S
R
R
Cp*
5
B
In addition, two parallel reactions of 1a-d0 and 1a-d1 with 5h were conducted separately under
standard conditions (Scheme 8). The observed KIE value 2.3:1 (kH/kD) in the early stage suggests that
the rate-determining step involves the C–H(D) bond cleavage at the C2-position of 1a.
Scheme 8. Parallel Reactions of 1a-d0 and 1a-d1a
[Cp*RhCl2]2 (0.01 mmol)
Cu(OAc)2•H2O (0.4 mmol)
Cs2CO3 (0.06 mmol)
+
Ph
toluene (2 mL)
125 oC, 0.75 h
Ph
6ah-d0, 14%b
D
H
S
S
5h
(0.2 mmol)
1a-d0
(0.4 mmol)
[Cp*RhCl2]2 (0.01 mmol)
Cu(OAc)2•H2O (0.4 mmol)
Cs2CO3 (0.06 mmol)
+
Ph
83% D
D
toluene (2 mL)
125 oC, 0.75 h
Ph
H
S
S
6ah-d0, 6%b
5h
(0.2 mmol)
1a-d1
(83% D, 0.4 mmol)
a
Reaction conditions: 1a (0.4 mmol), 5h (0.2 mmol), [Cp*RhCl2]2 (0.01 mmol), Cu(OAc)2•H2O (0.4
mmol), Cs2CO3 (0.06 mmol) in toluene (2 mL) at 125 C under N2 for 0.75 h. GC yield based on the
amount of 5h used.
o
b
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1
2
3
Conclusions
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6
7
8
We have demonstrated that the dehydrogenative annulation of phenylheteroarenes with alkynes can be
performed efficiently under rhodium catalysis. The procedure allows the ready construction of various
benzo-fused heterocyclic frameworks by a single treatment. The rhodium catalyst system is also
applicable to the dehydrogenative coupling with alkenes on the phenyl ring. Work is underway toward
further development of this procedure utilizing other π-electron systems.
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Experimental Section
13
General. H and C NMR spectra were recorded at 400 and 100 MHz for CDCl3 solutions. HRMS
data were obtained by EI using a double focusing mass spectrometer, unless noted. GC analysis was
carried out using a silicon OV-17 column (i. d. 2.6 mm x 1.5 m). GC-MS analysis was carried out using
a CBP-1 capillary column (i. d. 0.25 mm x 25 m). The structures of all products listed below were
1 13
unambiguously determined by H and C NMR with the aid of NOE, COSY, HMQC, and HMBC
experiments.
Phenylheteroarenes 1b-j,9 1k-l,10 1m-n,11 1p-q,9 1r,12 1s,10 1t-w,9 1x-y,13 1z-aa,14 1cc,15 and 1ee,16 and
alkynes 2b-d,17 2e,18 2f,19 2g-h,17 2i,20 and 2o17 were prepared according to published procedures. A
Phenylheteroarene 1a-d1 was prepared as shown below. Other starting materials and reagents were
commercially available.
Preparation of 1a-d1. 2-Bromo-3-phenylthiophene was prepared according to published procedures.21
To a solution of 2-bromo-3-phenylthiophene (3.0 mmol, 720 mg) in Et2O (6 mL) was dropwise a
solution of nBuLi in hexane (1.63 M, 1.9 mL, 3.1 mmol) at –78 °C under N2. The reaction mixture was
stirred for 0.5 h and warmed to 0 °C, to which D2O (5 mL) was added slowly. The mixture was warmed
to room temperature and stirred overnight. Then, the reaction mixture was extracted with ethyl acetate
(100 mL). The organic layer was washed by water (100 mL, three times) and dried over Na2SO4. After
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evaporation of the solvents under vacuum, C2-deuterated 3-phenylthiophene (1a-d1) was isolated (338
mg, 70%).
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5
6
7
8
General Procedure for the Reaction of Phenylheteroarenes 1 with Alkynes 2. To a 20 mL two-
necked flask with a reflux condenser, a balloon, and a rubber cup were added phenylheteroarene 1 (0.4
mmol), alkyne 2 (0.2 mmol), [Cp*RhCl2]2 (0.01 mmol, 6 mg), Cu(OAc)2•H2O (0.4 mmol, 80 mg),
Cs2CO3 (0.06 mmol、20 mg), 1-methylnaphthalene (ca. 30 mg) as internal standard, and toluene (2
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mL). Then, the resulting mixture was stirred under nitrogen at 125 oC (bath temperature). After cooling,
the reaction mixture was extracted with ethyl acetate (100 mL) and ethylenediamine (2 mL). The
organic layer was washed by water (100 mL, three times), and dried over Na2SO4. After evaporation of
the solvents under vacuum, product 3 was isolated by column chromatography on silica gel using
hexane as eluant. Further purification by GPC (Gel Permeation Chromatography) was performed, if
needed.
Reaction of 1a-d1 with 5h-d0 (Scheme 5). To a 20 mL two-necked flask with a reflux condenser, a
balloon, and a rubber cup were added 3-phenylthiophene (1a-d1) (0.4 mmol, 64 mg; 83% D), styrene
(5h-d0) (0.2 mmol, 21 mg), [Cp*RhCl2]2 (0.01 mmol, 6 mg), Cu(OAc)2・H2O (0.4 mmol, 80 mg),
Cs2CO3 (0.06 mmol, 20 mg), 1-methylnaphthalene (ca. 30 mg) as internal standard, and toluene (2 mL).
o
Then, the resulting mixture was stirred under nitrogen at 125 C (bath temperature) for 2 h. After
cooling, the reaction mixture was extracted with ethyl acetate (100 mL) and ethylenediamine (2 mL).
The organic layer was washed by water (100 mL, three times), and dried over Na2SO4. After evaporation
of the solvents under vacuum, product 6ah-d0 (6 mg, 12%) and 1a-d1 (55 mg, 86%) were isolated by
column chromatography on silica gel using hexane as eluant.
Treatment of 1a-d0 with D2O (Scheme 6a). To a 20 mL two-necked flask with a reflux condenser, a
balloon, and a rubber cup were added 3-phenylthiophene (1a-d0) (0.4 mmol, 64 mg), [Cp*RhCl2]2 (0.01
mmol, 6 mg), Cu(OAc)2・H2O (0.4 mmol, 80 mg), Cs2CO3 (0.06 mmol, 20 mg), D2O (0.8 mmol, 16
o
mg) and toluene (2 mL). Then, the resulting mixture was stirred under nitrogen at 125 C (bath
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temperature) for 2 h. After cooling, the reaction mixture was extracted with ethyl acetate (100 mL) and
ethylenediamine (2 mL). The organic layer was washed by water (100 mL, three times), and dried over
Na2SO4. After evaporation of the solvents under vacuum, product 1a-d0 (61 mg, 95%) was isolated by
column chromatography on silica gel using hexane as eluant.
1
2
3
4
5
6
7
8
9
Treatment of 1a-d0 with CD3CO2D (Scheme 6b). To a 20 mL two-necked flask with a reflux
condenser, a balloon, and a rubber cup were added 3-phenylthiophene (1a-d0) (0.4 mmol, 64 mg),
[Cp*RhCl2]2 (0.01 mmol, 6 mg), Cu(OAc)2・H2O (0.4 mmol, 80 mg), Cs2CO3 (0.06 mmol, 20 mg),
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CD3CO2D (0.8 mmol, 51 mg) and toluene (2 mL). Then, the resulting mixture was stirred under
o
nitrogen at 125 C (bath temperature) for 2 h. After cooling, the reaction mixture was extracted with
ethyl acetate (100 mL) and ethylenediamine (2 mL). The organic layer was washed by water (100 mL,
three times), and dried over Na2SO4. After evaporation of the solvents under vacuum, product 1a-d0 (61
mg, 96%) was isolated by column chromatography on silica gel using hexane as eluant.
Reaction of 1a-d0 with 5h-d0 in the Presence of D2O (Scheme 6c). To a 20 mL two-necked flask
with a reflux condenser, a balloon, and a rubber cup were added 3-phenylthiophene (1a-d0) (0.4 mmol,
64 mg), styrene (5h-d0) (0.2 mmol, 21 mg), [Cp*RhCl2]2 (0.01 mmol, 6 mg), Cu(OAc)2・H2O (0.4
mmol, 80 mg), Cs2CO3 (0.06 mmol, 20 mg), D2O (0.8 mmol, 16 mg), 1-methylnaphthalene (ca. 30 mg)
as internal standard, and toluene (2 mL). Then, the resulting mixture was stirred under nitrogen at 125
oC (bath temperature) for 2 h. After cooling, the reaction mixture was extracted with ethyl acetate (100
mL) and ethylenediamine (2 mL). The organic layer was washed by water (100 mL, three times), and
dried over Na2SO4. After evaporation of the solvents under vacuum, product 6ah-d0 (22 mg, 42%) and
1a-d0 (37 mg, 58%) were isolated by column chromatography on silica gel using hexane as eluant.
Reaction of 1a-d0 with 5h-d0 in the Presence of CD3CO2D (Scheme 6d). To a 20 mL two-necked
flask with a reflux condenser, a balloon, and a rubber cup were added 3-phenylthiophene (1a-d0) (0.4
mmol, 64 mg), styrene (5h-d0) (0.2 mmol, 21 mg), [Cp*RhCl2]2 (0.01 mmol, 6 mg), Cu(OAc)2・H2O
(0.4 mmol, 80 mg), Cs2CO3 (0.06 mmol, 20 mg), CD3CO2D (0.8 mmol, 51 mg), 1-methylnaphthalene
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(ca. 30 mg) as internal standard, and toluene (2 mL). Then, the resulting mixture was stirred under
1
2
3
o
nitrogen at 125 C (bath temperature) for 6 h. After cooling, the reaction mixture was extracted with
4
5
6
7
8
ethyl acetate (100 mL) and ethylenediamine (2 mL). The organic layer was washed by water (100 mL,
three times), and dried over Na2SO4. After evaporation of the solvents under vacuum, product 6ah-d0 (19
mg, 36%) and 1a-d0 (41 mg, 64%) were isolated by column chromatography on silica gel using hexane
as eluant.
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Reaction of 1a-d0 with 5h-d8 (Scheme 6e). To a 20 mL two-necked flask with a reflux condenser, a
balloon, and a rubber cup were added 3-phenylthiophene (1a-d0) (0.4 mmol, 64 mg), styrene (5h-d8)
(0.2 mmol, 22 mg; 98% D), [Cp*RhCl2]2 (0.01 mmol, 6 mg), Cu(OAc)2・H2O (0.4 mmol, 80 mg),
Cs2CO3 (0.06 mmol, 20 mg), 1-methylnaphthalene (ca. 30 mg) as internal standard, and toluene (2 mL).
o
Then, the resulting mixture was stirred under nitrogen at 125 C (bath temperature) for 2 h. After
cooling, the reaction mixture was extracted with ethyl acetate (100 mL) and ethylenediamine (2 mL).
The organic layer was washed by water (100 mL, three times), and dried over Na2SO4. After evaporation
of the solvents under vacuum, product 6ah-d8 (17 mg, 32%) and 1a-d0 (44 mg, 68%) were isolated by
column chromatography on silica gel using hexane as eluant.
Parallel Reactions of 1a-d0 and 1a-d1 (Scheme 8). To a 20 mL two-necked flask were added 3-
phenylthiophene-d0 or –d1 (1a-d0 or 1a-d1) (0.4 mmol), styrene (5h) (0.2 mmol, 21 mg), [Cp*RhCl2]2
(0.01 mmol, 6 mg), Cu(OAc)2•H2O (0.4 mmol, 80 mg), Cs2CO3 (0.06 mmol, 20 mg), 1-
methylnaphthalene (ca. 30 mg) as internal standard, and toluene (2 mL). The resulting mixture was
o
stirred under N2 at 125 C for 0.75 h. GC and GC-MS analyses of the mixture confirmed formation of
6ah-d0 (14% from 1a-d0; 6% from 1a-d1): kH/kD = 2.3.
o
4,5-Diphenylnaphtho[2,1-b]thiophene (3aa):6 mp 189-190 C (pale yellow powder), 28 mg (84%);
1H NMR (400 MHz, CDCl3) δ 7.19-7.29 (m, 10H), 7.41-7.46 (m, 1H), 7.58 (d, J = 5.5 Hz, 1H), 7.59-
13
7.63 (m, 1H), 7.67 (d, J = 8.7 Hz, 1H), 8.09 (d, J = 5.5 Hz, 1H), 8.43 (d, J = 7.7 Hz, 1H); C NMR
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(100 MHz, CDCl3) δ 122.3, 123.6, 125.4, 126.1, 126.6, 126.7, 127.2, 127.7, 127.8, 128.0, 128.7, 130.0,
131.3, 131.5, 133.7, 134.8, 135.3, 138.8, 139.8, 139.9; HRMS m/z Calcd for C24H16S (M+) 336.0973,
found 336.0972.
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7
8
9
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4,5-Bis(4-methylphenyl)naphtho[2,1-b]thiophene (3ab):6 mp 193-194 C (brown powder), 63 mg
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(86%); 1H NMR (400 MHz, CDCl3) δ 2.31 (s, 3H), 2.33 (s, 3H), 7.05-7.08 (m, 6H), 7.17 (d, J = 8.0 Hz,
2H), 7.38-7.42 (m, 1H), 7.54 (d, J = 5.4 Hz, 1H), 7.56-7.60 (m, 1H), 7.67 (d, J = 8.0 Hz, 1H), 8.05 (d, J
13
= 5.5 Hz, 1H), 8.39 (d, J = 8.2 Hz, 1H); C NMR (100 MHz, CDCl3) δ 21.25, 21.30, 122.2, 123.5,
125.3, 126.0, 126.4, 127.9, 128.4 (overlapped), 128.7, 129.8, 131.3, 131.6, 133.7, 134.8, 135.2, 135.9,
136.1, 136.6, 137.1, 140.2; HRMS m/z Calcd for C26H20S (M+) 364.1286, found 364.1291.
4,5-Bis[4-(tert-butyl)phenyl]naphtho[2,1-b]thiophene (3ac):6 mp 233-234 oC (pale yellow powder),
1
59 mg (65%); H NMR (400 MHz, CDCl3) δ 1.26 (s, 9H), 1.28 (s, 9H), 7.08 (d, J = 8.4 Hz, 2H), 7.15
(d, J = 8.5 Hz, 2H), 7.20-7.25 (m, 4H), 7.41-7.45 (m, 1H), 7.55 (d, J = 5.4 Hz, 1H), 7.59-7.61 (m, 1H),
13
7.80 (d, J = 8.0 Hz, 1H), 8.07 (d, J = 5.6 Hz, 1H), 8.41 (d, J = 8.2 Hz, 1H); C NMR (100 MHz,
CDCl3) δ 31.25, 31.32, 34.42, 34.44, 122.2, 123.5, 124.3, 124.5, 125.3, 125.9, 126.3, 128.0, 128.7,
129.6, 131.2, 132.3, 133.9, 135.1, 135.2, 135.8, 136.9, 139.8, 149.3, 149.7; HRMS m/z Calcd for
C32H32S (M+) 448.2225, found 448.2227.
o
4,5-Bis(4-methoxyphenyl)naphtho[2,1-b]thiophene (3ad):6 mp 218-220 C (white powder), 60 mg
(76%); 1H NMR (400 MHz, CDCl3) δ 3.78 (s, 3H), 3.80 (s, 3H), 6.77-6.83 (m, 4H), 7.07-7.13 (m, 2H),
7.17-7.21 (m, 2H), 7.39-7.43 (m, 1H), 7.55 (d, J = 5.4 Hz, 1H), 7.56-7.60 (m, 1H), 7.69 (d, J = 7.3 Hz,
13
1H), 8.06 (d, J = 5.5 Hz, 1H), 8.39 (d, J = 8.5 Hz, 1H); C NMR (100 MHz, CDCl3) δ 55.09, 55.14,
113.2, 113.4, 122.3, 123.5, 125.3, 126.0, 126.4, 127.8, 128.7, 131.1, 131.2, 131.7, 132.45, 132.52,
133.6, 134.56, 135.1, 140.3, 158.2, 158.5; HRMS m/z Calcd for C26H20O2S (M+) 396.1184, found
396.1181.
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4,4'-(Naphtho[2,1-b]thiophene-4,5-diyl)bis(N,N-dimethylaniline) (3ae): mp 234-236 C (brown
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powder), 60 mg (71%); H NMR (400 MHz, CDCl3) δ 2.93 (s, 6H), 2.94 (s, 6H), 6.63 (d, J = 7.4 Hz,
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2H), 6.67 (d, J = 8.8 Hz, 2H), 7.07 (d, J = 8.8 Hz, 2H), 7.18 (d, J = 8.8 Hz, 2H), 7.36-7.41 (m, 1H), 7.51
(d, J = 5.2 Hz, 1H), 7.52-7.57 (m, 1H), 7.76 (d, J = 8.4 Hz, 1H), 8.04 (d, J = 5.6 Hz, 1H), 8.37 (d, J =
8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 40.5, 40.6, 111.9, 112.0, 122.2, 123.4, 125.0, 125.6, 126.1,
127.4, 128.1, 128.60, 128.64, 130.8, 132.2, 132.3, 134.0, 134.86, 134.89, 141.0, 149.0, 149.2; HRMS
m/z Calcd for C28H26N2S (M+) 422.1817, found 422.1819.
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4,5-Bis(4-bromophenyl)naphtho[2,1-b]thiophene (3af): mp 220-222 C (white powder), 54 mg
(54%); 1H NMR (400 MHz, CDCl3) δ 7.05 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.4 Hz, 2H), 7.40-7.46 (m,
5H), 7.58-7.64 (m, 3H), 8.07 (d, J = 5.5 Hz, 1H), 8.41 (d, J = 8.2 Hz, 1H); 13C NMR (100 MHz, CDCl3)
δ 121.2, 121.7, 122.4, 123.7, 125.7, 126.5, 126.9, 127.5, 128.8, 130.9, 131.1, 131.5, 131.6, 132.5, 133.0,
133.5, 135,7, 137.5, 138.4, 139.2; HRMS m/z Calcd for C24H14Br2S (M+) 491.9183, found 491.9185.
1,1'-(Naphtho[2,1-b]thiophene-4,5-diylbis(4,1-phenylene))diethanone (3ag): mp 251-252 oC
(white powder), 62 mg (62%); 1H NMR (400 MHz, CDCl3) δ 2.58 (s, 3H), 2.60 (s, 3H), 7.31 (d, J = 8.4
Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H), 7.44-7.48 (m, 1H), 7.58 (d, J = 8.2 Hz, 1H), 7.61-7.67 (m, 2H), 7.85-
13
7.89 (m, 4H), 8.10 (d, J = 5.6 Hz, 1H), 8.44 (d, J = 7.8 Hz, 1H); C NMR (100 MHz, CDCl3) δ 26.6
(overlapped), 122.4, 123.8, 125.9, 126.7, 127.2, 127.4, 127.9, 128.3, 128.9, 130.3, 130.6, 131.7, 132.6,
133.7, 135.7, 135.9, 136.0, 138.8, 143.8, 144.4, 197.7, 197.8; HRMS m/z Calcd for C28H20O2S (M+)
420.1184, found 420.1186.
4,5-Bis[4-(trifluoromethyl)phenyl]naphtho[2,1-b]thiophene (3ah):6 mp 225-226 oC (white
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powder), 70 mg (74%); H NMR (400 MHz, CDCl3) δ 7.31 (d, J = 7.9 Hz, 2H), 7.37 (d, J = 7.9 Hz,
2H), 7.45-7.49 (m, 1H), 7.52-7.56 (m, 5H), 7.62 (d, J = 5.4 Hz, 1H), 7.64-7.68 (m, 1H), 8.10 (d, J = 5.5
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Hz, 1H), 8.44 (d, J = 8.12 Hz, 1H); C NMR (100 MHz, CDCl3) δ 122.4, 123.8, 124.0 (q, J = 270.5
Hz), 124.1 (q, J = 270.4 Hz), 124.9 (q, J = 3.7 Hz), 125.3 (q, J = 3.6 Hz), 126.0, 126.8, 127.2, 127.3,
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129.0, 129.3 (q, J = 32.2 Hz), 129.7 (q, J = 33.3 Hz), 130.3, 130.7, 131.8, 132.4, 133.5,136.1, 138.9,
142.3, 143.0; HRMS m/z Calcd for C26H14F6S (M+) 472.0720, found 472.0717.
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4,5-Di(naphthalen-2-yl)naphtho[2,1-b]thiophene (3ai): mp 215-217 C (white powder), 65 mg
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(75%); 1H NMR (400 MHz, CDCl3) δ 7.33-7.41 (m, 7H), 7.56-7.72 (m, 10H), 7.92 (s, 1H), 8.10 (d, J =
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5.6 Hz, 1H), 8.44 (d, J = 8.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 122.3, 123.6, 125.5, 125.8, 125.9
(overlapped), 126.0, 126.2, 126.8, 127.3, 127.61, 127.63, 127.7, 127.90, 127.92, 128.1 (overlapped),
128.9, 129.0, 129.6, 130.5, 131.6, 132.2, 132.4, 132.9, 133.0, 133.8, 134.8, 135.5, 136.4, 137.5, 140.1;
HRMS m/z Calcd for C32H20S (M+) 436.1286, found 436.1283.
4,5-Dipropylnaphtho[2,1-b]thiophene (3aj):6 mp 83-84 oC (white powder), 21 mg (79%); 1H NMR
(400 MHz, CDCl3) δ 1.09-1.14 (m, 6H), 1.68-1.85 (m, 4H), 3.00-3.04 (m, 2H), 3.09-3.13 (m, 2H), 7.49
(d, J = 5.4 Hz, 1H), 7.51-7.55 (m, 2H), 7.96 (d, J = 5.4 Hz, 1H), 8.07-8.11 (m, 1H), 8.30-8.34 (m, 1H);
13C NMR (100 MHz, CDCl3) δ 14.7 (overlapped), 23.2, 24.4, 30.7, 35.4, 122.6, 124.1, 124.2, 124.9,
125.1, 125.2, 128.7, 130.7, 132.0, 132.2, 134.4, 139.7; HRMS m/z Calcd for C18H20S (M+) 268.1286,
found 268.1288.
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4,5-Diheptylnaphtho[2,1-b]thiophene (3ak):6 mp 39-40 C (yellow powder), 65 mg (85%); H
NMR (400 MHz, CDCl3) δ 0.88-0.92 (m, 6H), 1.32-1.43 (m, 12H), 1.48-1.57 (m, 4H), 1.64-1.80 (m,
4H), 3.00-3.04 (m, 2H), 3.10-3.14 (m, 2H), 7.48 (d, J = 5.4 Hz, 1H), 7.51-7.54 (m, 2H), 7.95 (d, J = 5.4
Hz, 1H), 8.08-8.11 (m, 1H), 8.29-8.33 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 14.1 (overlapped), 22.7
(overlapped), 28.6, 29.1, 29.2, 29.8, 30.2, 30.3, 31.2, 31.8, 31.9, 33.3, 122.6, 124.1, 124.2, 124.9, 125.0,
125.2, 128.7, 130.7, 132.16, 132.23, 134.3, 139.7; HRMS m/z Calcd for C26H36S (M+) 380.2538, found
380.2534.
5-Methyl-4-phenylnaphtho[2,1-b]thiophene (3an):6 mp 69-71 oC (white powder), 27 mg (50%); 1H
NMR (400 MHz, CDCl3) δ 2.55 (s, 3H), 7.43-7.48 (m, 4H), 7.50-7.54 (m, 2H), 7.57-7.65 (m, 2H), 8.00
(d, J = 5.4 Hz, 1H), 8.14-8.17 (m, 1H), 8.37- 8.40 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 16.3, 122.2,
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124.0, 125.3, 125.5, 125.6, 125.9, 127.7, 127.8, 128.6, 128.8, 129.6, 131.3, 133.9, 134.1, 140.2, 140.6;
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HRMS m/z Calcd for C19H14S (M+) 274.0816, found 274.0815.
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4-Methyl-5-phenylnaphtho[2,1-b]thiophene (3an’):6 mp 114-116 C (white powder), 7 mg (12%);
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1H NMR (400 MHz, CDCl3) δ 2.42 (s, 3H), 7.30-7.33 (m, 2H), 7.35-7.39 (m, 1H), 7.46-7.48 (m, 2H),
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7.50-7.56 (m, 3H), 7.61 (d, J = 5.4 Hz, 1H), 8.07 (d, J = 5.4 Hz, 1H), 8.36 (d, J = 8.1 Hz, 1H); C
NMR (100 MHz, CDCl3) δ 19.1, 122.7, 123.4, 125.1, 125.29, 125.33, 127.2, 127.3, 127.7, 128.1, 128.4,
130.6, 131.6, 134.97, 134.98, 139.5, 139.6; HRMS m/z Calcd for C19H14S (M+) 274.0816, found
274.0814.
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5,6-Bis(3,4-dimethoxyphenyl)benzo[b]naphtho[1,2-d]thiophene (3ko): mp 231-233 C (pink
powder), 254 mg (50%); 1H NMR (400 MHz, CDCl3) δ 3.65 (s, 3H), 3.69 (s, 3H), 3.86 (s, 3H), 3.87 (s,
3H), 6.67-6.98 (m, 6H), 7.43-7.50 (m, 2H), 7.57 (t, J = 7.6 Hz, 1H), 7.71 (t, J = 8.0 Hz, 1H), 7.89 (s,
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1H), 7.90 (s, 1H), 8.88 (d, J = 8.4 Hz, 1H), 9.09 (d, J = 8.4 Hz, 1H); C NMR (125 MHz, DMSO-d6,
90 oC) δ 56.61, 56.66, 56.68, 56.7, 112.9, 113.0, 115.9, 117.1, 123.2, 123.8, 123.9, 124.5, 125.5, 125.9,
126.0, 126.2, 127.8, 128.6, 128.8, 130.3, 131.9, 132.6, 133.1, 134.5, 137.1, 137.9, 140.3, 141.6, 149.0,
149.36, 149.4, 149.5; HRMS (APCI) m/z Calcd for C32H27O4S ([M+H]+) 507.1625, found 507.1624.
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7-Methyl-4,5-diphenylnaphtho[2,1-b]thiophene (3ba):6 mp 162-163 C (white powder), 60 mg
(85%); 1H NMR (400 MHz, CDCl3) δ 2.42 (s, 3H), 7.18-7.29 (m, 10H), 7.43-7.46 (m, 2H), 7.55 (d, J =
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5.5 Hz, 1H), 8.05 (d, J = 5.4 Hz, 1H), 8.32 (d, J = 8.3 Hz, 1H); C NMR (100 MHz, CDCl3) δ 21.9,
122.2, 123.5, 126.5, 126.6, 126.9, 127.0, 127.1, 127.6, 127.9, 128.1, 130.0, 131.4, 131.6, 133.8, 134.4,
135.0, 135.3, 138.95, 139.03, 140.1; HRMS m/z Calcd for C25H18S (M+) 350.1129, found 350.1126.
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7-Methoxy-4,5-diphenylnaphtho[2,1-b]thiophene (3ca):6 mp 196-197 C (pale yellow powder), 49
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mg (66%); H NMR (400 MHz, CDCl3) δ 3.70 (s, 3H), 7.03 (d, J = 2.6 Hz, 1H), 7.18-7.28 (m, 11H),
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7.54 (d, J = 5.4 Hz, 1H), 7.99 (d, J = 5.5 Hz, 1H), 8.31 (d, J = 9.0 Hz, 1H); C NMR (100 MHz,
CDCl3) δ 55.1, 107.7, 117.2, 122.0, 123.9, 125.1, 126.69, 126.73, 127.1, 127.7, 127.9, 123.0, 131.4,
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132.6, 134.1, 134.2, 135.4, 137.9, 138.9, 140.0, 157.2; HRMS m/z Calcd for C25H18OS (M+) 366.1078,
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7-Chloro-4,5-diphenylnaphtho[2,1-b]thiophene (3da):6 mp 194-195 C (pale yellow powder), 74
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mg (98%); H NMR (400 MHz, CDCl3) δ 7.06-7.09 (m, 2H), 7.13-7.21 (m, 8H), 7.44 (q, J = 2.2, 8.7
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Hz, 1H), 7.49 (d, J = 5.5 Hz, 1H), 7.56 (d, J = 2.0 Hz, 1H), 7.92 (d, J = 5.5 Hz, 1H), 8.23 (d, J = 8.8
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 122.1, 125.2, 126.7 (overlapped), 126.99, 127.03, 127.3, 127.4,
127.9, 128.0, 129.8, 131.3, 131.4, 132.4, 134.0, 134.9, 135.1, 138.1, 139.5, 140.0; HRMS m/z Calcd for
C24H15ClS (M+) 370.0583, found 370.0586.
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7-Phenyl-4,5-dipropylnaphtho[2,1-b]thiophene (3ej): mp 116-117 C (white powder), 52 mg
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(76%); H NMR (400 MHz, CDCl3) δ 1.10-1.16 (m, 6H), 1.73-1.86 (m, 4H), 3.02-3.06 (m, 2H), 3.15-
3.19 (m, 2H), 7.39 (t, J = 7.6 Hz, 1H), 7.49-7.53 (m, 3H), 7.74 (d, J = 7.2 Hz, 2H), 7.78 (dd, J = 1.6, 8.4
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Hz, 1H), 7.97 (d, J = 5.6 Hz, 1H), 8.28 (d, J = 1.2 Hz, 1H), 8.37 (d, J = 8.4 Hz, 1H); C NMR (100
MHz, CDCl3) δ 14.7, 14.8, 23.2, 24.5, 30.7, 35.4, 122.6, 123.3, 124.4, 124.65, 124.67, 127.1, 127.5,
127.8, 128.9, 130.9, 132.3, 132.5, 134.2, 137.9, 139.8, 141.9; HRMS m/z Calcd for C24H24S (M+)
344.1599, found 344.1601.
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6-Fluoro-4,5-diphenylnaphtho[2,1-b]thiophene (3fa):6 mp 181-183 C (white powder), 62 mg
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(87%); H NMR (400 MHz, CDCl3) δ 7.09 (ddd, J = 1.1, 7.7, 13.2 Hz, 1H), 7.14-7.25 (m, 10H), 7.53
(td, J = 4.8, 7.9 Hz, 1H), 7.57 (d, J = 5.4 Hz, 1H), 8.03 (d, J = 5.5 Hz, 1H), 8.22 (d, J = 8.2 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 111.7 (d, J = 23.2 Hz), 119.8 (d, J = 4.2 Hz), 120.8 (d, J = 8.6 Hz),
122.5, 126.2, 126.6 (d, J = 9.3 Hz), 126.8, 127.2, 127.4, 127.8, 129.9, 130.2 (d, J = 4.1 Hz), 131.0 (d, J
= 3.3 Hz), 131.1 (d, J = 2.3 Hz), 135.0 (d, J = 2.9 Hz), 135.5, 139.3, 140.77, 140.81, 160.2 (d, J =
254.0 Hz); HRMS m/z Calcd for C24H15FS (M+) 354.0878, found 354.0876.
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1-Methyl-4,5-diphenylnaphtho[2,1-b]thiophene (3ga): mp 182-184 C (pale yellow powder), 69
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mg (98%); H NMR (400 MHz, CDCl3) δ 2.96 (d, J = 0.8 Hz, 3H), 7.17-7.27 (m, 11H), 7.42 (ddd, J =
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1.2 Hz, 6.8 Hz, 8.4 Hz, 1H), 7.60 (ddd, J =1.2, 6.8, 8.4 Hz, 1H), 7.70 (dd, J = 0.8, 8.4 Hz, 1H), 8.78 (d,
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J = 8.4 Hz, 1H); C NMR (100 MHz, CDCl3) δ 20.2, 123.3, 123.7, 124.8, 125.7, 126.6, 127.2, 127.6,
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127.9, 128.0, 130.1, 130.2, 131.4, 131.9, 133.1, 134.2, 134.8, 135.0, 139.0, 139.7, 141.7; HRMS m/z
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Calcd for C25H18S (M+) 350.1129, found 350.1127.
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71 mg (97%); 1H NMR (400 MHz, CDCl3) δ 2.51 (s, 3H), 2.81 (s, 3H), 7.17-7.27 (m, 10H), 7.39 (ddd, J
= 1.2, 7.2, 8.4 Hz, 1H), 7.57 (ddd, J = 1.2, 6.8, 8.4 Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 8.81 (d, J = 8.4
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Hz, 1H); C NMR (100 MHz, CDCl3) δ 14.1, 16.7, 123.2, 124.5, 125.4, 126.5, 127.1, 127.6, 127.8,
128.0, 129.8, 129.9, 130.0, 131.5, 132.0, 133.6, 133.8, 134.3, 134.7, 137.9, 139.2, 140.0; HRMS m/z
Calcd for C26H20S (M+) 364.1286, found 364.1287.
Methyl 4,5-diphenylnaphtho[2,1-b]thiophene-2-carboxylate (3ia): mp 221-222 oC (white powder),
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64 mg (81%); H NMR (400 MHz, CDCl3) δ 3.92 (s, 3H), 7.17-7.30 (m, 10H), 7.46 (ddd, J = 1.2, 7.2,
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8.4 Hz, 1H), 7.62-7.68 (m, 2H), 8.42 (d, J = 8.0 Hz, 1H), 8.78 (s, 1H); C NMR (100 MHz, CDCl3) δ
52.4, 123.4, 126.1, 126.90, 126.97, 127.5, 127.7, 128.10, 128.14, 128.6, 129.3, 129.9, 131.2, 131.5,
132.8, 133.6, 134.7, 137.8, 138.2, 139.0, 143.6, 163.3; HRMS m/z Calcd for C26H18O2S (M+) 394.1028,
found 394.1025.
4,5-Diphenylanthra[2,1-b]thiophene (3ja): mp 200-203 oC (white powder), 72 mg (93%); 1H NMR
(400 MHz, CDCl3) δ 7.20-7.33 (m, 10H), 7.42 (ddd, J = 1.2, 6.4, 8.0 Hz, 1H), 7.50 (ddd, J = 1.1, 6.4,
7.9 Hz, 1H), 7.57 (d, J = 5.2 Hz, 1H), 7.84 (d, J = 8.4 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 8.18 (s, 1H),
8.21 (d, J = 5.2 Hz, 1H), 8.89 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 121.6, 122.9, 125.1, 125.9, 126.2,
126.8, 127.1, 127.2, 127.5, 127.7, 127.8, 127.9, 128.6, 130.0, 130.6, 131.2, 131.5, 131.6, 133.4, 134.7,
135.0, 138.9, 139.6, 139.8; HRMS m/z Calcd for C28H18S (M+) 386.1129, found 386.1128.
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5,6-Diphenylbenzo[b]naphtho[1,2-d]thiophene (3ka):6 mp 205-206 C (white powder), 27 mg
(35%); 1H NMR (400 MHz, CDCl3) δ 7.21-7.30 (m, 10H), 7.48 (t, J = 8.5 Hz, 2H), 7.61 (t, J = 7.7 Hz,
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1H), 7.71-7.79 (m, 2H), 7.90 (d, J = 7.9 Hz, 1H), 8.91 (d, J = 8.4 Hz, 1H), 9.12 (d, J = 8.5 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 123.0, 123.1, 124.76, 124.82, 124.9, 125.2, 126.75, 126.83, 127.4, 127.7,
128.0, 128.57, 128.63, 130.1, 130.2, 131.3, 131.9, 134.1, 137.0, 137.4, 138.8, 139.7, 140.2, 141.1;
HRMS m/z Calcd for C28H18S (M+) 386.1129, found 386.1125.
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4,5-Dipropyl-7-(thiophen-3-yl)naphtho[2,1-b]thiophene (3mj): mp 165-166 oC (white powder), 40
1
mg (57%); H NMR (400 MHz, CDCl3) δ 1.10-1.17 (m, 6H), 1.72-1.86 (m, 4H), 3.01-3.05 (m, 2H),
3.14-3.18 (m, 2H), 7.44-7.46 (m, 1H), 7.50 (d, J = 5.2 Hz, 1H), 7.53-7.57 (m, 2H), 7.78 (dd, J = 1.6, 8.4
13
Hz, 1H), 7.95 (d, J = 5.6 Hz, 1H), 8.29 (d, J = 1.6 Hz, 1H), 8.33 (d, J = 8.8 Hz, 1H); C NMR (100
MHz, CDCl3) δ 14.7, 14.8, 23.2, 24.5, 30.7, 35.4, 120.3, 122.4, 122.6, 124.1, 124.5, 124.7, 126.4, 126.6,
127.8, 131.0, 132.2, 132.59, 132.61, 134.3, 139.7, 143.0; HRMS m/z Calcd for C22H22S2 (M+) 350.1163,
found 350.1160.
4,5,10,11-Tetrapropylanthra[2,1-b:6,5-b']dithiophene (4mj): mp 188-189 oC (pale yellow
powder), 13 mg (14%); 1H NMR (400 MHz, CDCl3) δ 1.15 (t, J = 7.6 Hz, 6H), 1.22 (t, J = 7.6 Hz, 6H),
1.81-1.91 (m, 8H), 3.05-3.09 (m, 4H), 3.28-3.32 (m, 4H), 7.56 (d, J = 5.4 Hz, 2H), 8.16 (d, J = 5.4 Hz,
2H), 9.04 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 14.8, 14.9, 23.3, 24.4, 30.9, 35.4, 119.4, 122.8, 124.0,
126.9, 128.8, 131.68, 131.71, 134.4, 139.4; HRMS m/z Calcd for C30H34S2 (M+) 458.2102, found
458.2098.
o
4,5-Dipropyl-8-(thiophen-3-yl)naphtho[2,1-b]thiophene (3nj): mp 91-92 C (brown powder), 20
1
mg (28%); H NMR (400 MHz, CDCl3) δ 1.10-1.16 (m, 6H), 1.69-1.86 (m, 4H), 3.00-3.06 (m, 2H),
3.10-3.14 (m, 2H), 7.45 (dd, J = 2.8, 5.2 Hz, 1H), 7.51 (d, J = 5.2 Hz, 1H), 7.57 (dd, J = 1.6, 5.2 Hz,
1H), 7.61 (dd, J = 1.2, 2.8 Hz, 1H), 7.78 (dd, J = 1.6, 8.4 Hz, 1H), 8.01 (d, J = 5.6 Hz, 1H), 8.11 (d, J =
13
8.8 Hz, 1H), 8.50 (d, J = 2.0 Hz, 1H); C NMR (100 MHz, CDCl3) δ 14.7 (overlapped), 23.2, 24.5,
30.7, 35.3, 120.5, 121.3, 122.5, 124.1, 124.4, 125.5, 126.3, 126.6, 128.9, 129.8, 132.05, 132.07, 132.4,
134.4, 140.2, 142.5; HRMS m/z Calcd for C22H22S2 (M+) 350.1163, found 350.1164.
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4,5,7,8-Tetrapropylanthra[2,1-b:7,8-b']dithiophene (4nj): mp 152-153 C (white powder), 32 mg
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(35%); H NMR (400 MHz, CDCl3) δ 1.15 (t, J = 7.2 Hz, 6H), 1.23 (t, J = 7.2 Hz, 6H), 1.81-1.90 (m,
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8H), 3.04-3.08 (m, 4H), 3.25-3.29 (m, 4H), 7.55 (d, J = 5.4 Hz, 2H), 8.19 (d, J = 5.4 Hz, 2H), 8.83 (s,
1H), 9.21 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 14.8, 15.0, 23.3, 24.5, 31.2, 35.5, 118.0, 120.9, 123.0,
123.9, 126.6, 128.8, 131.3, 132.0, 134.0, 139.7; HRMS m/z Calcd for C30H34S2 (M+) 458.2102, found
458.2103.
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4,5-Diphenylbenzo[1,2-b:4,3-b']dithiophene (3oa):22 mp 184-185 C (white powder), 12 mg (9%);
1H NMR (400 MHz, CDCl3) δ 7.23-7.34 (m, 10H), 7.54 (d, J = 5.4 Hz, 2H), 7.78 (d, J = 5.4 Hz, 2H);
13C NMR (100 MHz, CDCl3) δ 122.1, 127.2, 127.3, 128.1, 130.3, 131.4, 133.7, 139.36, 139.4; HRMS
m/z Calcd for C22H14S2 (M+) 342.0537, found 342.0538.
4,5-Diphenylbenzo[1,2-b:3,4-c']dithiophene (3oa’): oil, 18 mg (13%); 1H NMR (400 MHz, CDCl3)
δ 7.19-7.31 (m, 10H), 7.43 (d, J = 3.2 Hz, 1H), 7.46 (d, J = 5.3 Hz, 1H), 7.78 (d, J = 5.3 Hz, 1H), 7.91
13
(d, J = 3.3 Hz, 1H); C NMR (100 MHz, CDCl3) δ 114.0, 119.7, 123.1, 126.1, 126.8, 127.3, 127.9,
128.0, 130.0, 130.2, 130.8, 130.90, 130.94, 133.7, 138.7, 138.8, 139.1, 139.3; HRMS m/z Calcd for
C22H14S2 (M+) 342.0537, found 342.0539.
o
1,4,5-Triphenylnaphtho[2,1-b]thiophene (3pa): mp 188-190 C (brown powder), 62 mg (75%); H
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NMR (400 MHz, CDCl3) δ 7.19-7.33 (m, 13H), 7.49-7.58 (m, 5H), 7.65 (d, J = 8.4 Hz, 1H), 7.93 (d, J
= 8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 123.9, 125.0, 125.3, 125.6, 126.7, 127.3, 127.65, 127.72,
127.9, 128.0, 128.6, 129.3, 130.0, 130.1, 131.4, 132.0, 132.3, 133.9, 135.3, 138.9, 139.2, 139.6, 140.5,
141.3; HRMS m/z Calcd for C30H20S (M+) 412.1286, found 412.1283.
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5,6,8,9-Tetraphenyldinaphtho[2,1-b:1',2'-d]thiophene (4pa): mp 313-314 C (white powder), 16
mg (13%); 1H NMR (400 MHz, CDCl3) δ 7.17-7.30 (m, 20H), 7.48 (ddd, J = 1.2, 6.8, 8.0 Hz, 2H), 7.58
(ddd, J = 1.6, 6.8, 8.4 Hz, 2H), 7.77 (dd, J = 0.8, 8.4 Hz, 2H), 9.00 (d, J = 8.0 Hz, 2H); 13C NMR (100
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MHz, CDCl3) δ 124.4, 125.3, 126.0, 126.8, 127.2, 127.6, 127.8, 128.0, 129.3, 130.2, 131.1, 131.4,
132.1, 133.8, 137.0, 138.7, 139.3, 141.2; HRMS m/z Calcd for C44H28S (M+) 588.1912, found 588.1908.
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1-Phenyl-4,5-dipropylnaphtho[2,1-b]thiophene (3pj): oil, 336 mg (98%); H NMR (400 MHz,
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CDCl3) δ 1.13-1.17 (m, 6H), 1.70-1.89 (m, 4H), 3.04-3.08 (m, 2H), 3.11-3.15 (m, 2H), 7.16 (ddd, J =
1.2, 7.2, 8.4 Hz, 1H), 7.25 (s, 1H), 7.41-7.51 (m, 6H), 7.83 (d, J = 8.8 Hz, 1H), 8.08 (d, J = 8.8 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 14.78, 14.80, 23.2, 24.3, 30.9, 35.2, 123.2, 124.2, 124.5, 124.78, 124.83,
127.5, 128.5, 129.2, 129.5, 131.28, 131.34, 132.1, 132.6, 139.5, 140.8, 141.0; HRMS m/z Calcd for
C24H24S (M+) 344.1599, found 344.1597.
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5,6,12,13-Tetraheptylnaphtho[2,1-b]naphtho[1',2':4,5]thieno[2,3-d]thiophene (4qk): mp 215-216
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oC (pale yellow powder), 124 mg (85%); H NMR (400 MHz, CDCl3) δ 0.90-0.95 (m, 12H), 1.32-1.52
(m, 24H), 1.54-1.65 (m, 8H), 1.70-1.78 (m, 4H), 1.82-1.90 (m, 4H), 3.10-3.19 (m, 8H), 7.62 (ddd, J =
1.2, 6.8, 8.4 Hz, 2H), 7.71 (ddd, J = 0.8, 6.8, 8.0 Hz, 2H), 8.18 (d, J = 8.0 Hz, 2H), 8.59 (dd, J = 1.2,
13
8.4 Hz, 2H); C NMR (100 MHz, CDCl3) δ 14.1, 14.2, 22.7, 22.8, 28.9, 29.1, 29.2, 30.0, 30.3, 30.4,
31.3, 31.88, 31.93, 33.0, 124.9, 125.0, 125.3, 125.5, 127.3, 127.5, 131.0, 132.4, 133.0, 133.2, 142.5;
HRMS m/z Calcd for C50H68S2 (M+) 732.4762, found 732.4764.
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5,6-Diphenylnaphtho[2,1-b]benzofuran (3ra):5a mp 213- 215 C (white powder), 33 mg (90%); H
NMR (400 MHz, CDCl3) δ 7.23-7.33 (m, 10H), 7.43-7.49 (m, 3H), 7.62-7.65 (m, 1H), 7.72 (ddd, J =
13
1.2, 6.8, 8.4 Hz, 1H), 7.78 (d, J = 7.6 Hz, 1H), 8.44-8.49 (m, 1H), 8.72 (d, J = 8.0 Hz, 1H); C NMR
(100 MHz, CDCl3) δ 112.2, 116.8, 122.0, 123.2, 123.4, 124.5, 125.0, 125.9, 126.5, 126.87, 126.92,
127.1, 127.69, 127.73, 128.4, 128.7, 130.2, 131.0, 131.6, 135.5, 138.5, 138.8, 152.7, 156.0; HRMS m/z
Calcd for C28H18O (M+) 370.1358, found 370.1357.
4,5-Diphenylthieno[3,2-f]quinoline (3ua): mp 200-203 oC (yellow powder), 31 mg (47%); 1H NMR
(400 MHz, CDCl3) δ 7.20-7.31 (m, 10H), 7.51 (dd, J = 4.4, 8.4 Hz, 1H), 7.64 (d, J = 5.6 Hz, 1H), 8.06
(d, J = 5.6 Hz, 1H), 8.69 (dd, J = 1.6, 8.4 Hz, 1H), 8.94 (dd, J = 2.0, 4.4 Hz, 1H); 13C NMR (100 MHz,
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CDCl3) δ 120.8, 122.0, 123.8, 126.6, 127.3, 127.5, 127.7, 128.1, 129.8, 131.5, 131.9, 134.8, 135.8,
137.1, 138.1, 139.6, 140.1, 146.5, 149.2; HRMS m/z Calcd for C23H15NS (M+) 337.0925, found
337.0927.
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5,6-Diphenylthieno[2,3-h]isoquinoline (3ua’): mp 201-202 C (white powder), 19 mg (27%); H
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NMR (400 MHz, CDCl3) δ 7.17-7.19 (m, 2H), 7.26-7.30 (m, 8H), 7.50 (d, J = 5.4 Hz, 1H), 7.72 (d, J =
13
5.5 Hz, 1H), 8.21 (d, J = 5.5 Hz, 1H), 8.54 (d, J = 5.8 Hz, 1H), 9.82 (s, 1H); C NMR (100 MHz,
CDCl3) δ 120.2, 121.3, 123.6, 127.2, 127.7, 127.9, 128.1, 128.7, 129.7, 131.4, 133.2, 134.67, 134.69,
137.2, 137.9, 139.0, 141.0, 143.7, 148.0; HRMS m/z Calcd for C23H15NS (M+) 337.0925, found
337.0926.
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4,5-Diphenylthieno[3,2-f]isoquinoline (3va): mp 222-223 C (light brown powder), 58 mg (86%);
1H NMR (400 MHz, CDCl3) δ 7.20-7.31 (m, 10H), 7.64 (d, J = 5.2 Hz, 1H), 8.06 (d, J = 5.6 Hz, 1H),
13
8.14 (dd, J = 0.8, 5.6 Hz, 1H), 8.68 (d, J = 5.6 Hz, 1H), 9.06 (s, 1H); C NMR (100 MHz, CDCl3) δ
116.4, 122.2, 126.3, 127.2, 127.60, 127.65, 127.8, 128.1, 129.8, 131.4, 131.8, 133.7, 134.3, 135.0,
136.8, 138.9, 143.6, 143.8, 152.0; HRMS m/z Calcd for C23H15NS (M+) 337.0925, found 337.0923.
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4,5-Diphenylthieno[2',3':5,6]benzo[1,2-g]quinoline (3wa): mp 272-273 C (pale yellow powder),
1
55 mg (70%); H NMR (400 MHz, CDCl3) δ 7.23-7.33 (m, 10H), 7.39 (dd, J = 4.0, 8.4 Hz, 1H), 7.62
(d, J = 5.2 Hz, 1H), 8.20 (d, J = 5.2 Hz, 1H), 8.37 (d, J = 8.4 Hz, 1H), 8.52 (s, 1H), 8.84 (s, 1H), 8.92
13
(dd, J = 1.6, 4.0 Hz, 1H); C NMR (100 MHz, CDCl3) δ 120.9, 121.8, 122.9, 126.3, 126.7, 127.0,
127.4, 127.7, 127.9, 128.0, 128.4, 129.9, 131.5, 133.3, 134.4, 134.7, 134.9, 135.9, 138.3, 139.5, 140.2,
144.7, 150.9; HRMS m/z Calcd for C27H17NS (M+) 387.1082, found 387.1078.
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2,4,5-Triphenylnaphtho[2,1-d]thiazole (3xa): mp 262-264 C (white powder), 62 mg (75%); H
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NMR (400 MHz, CDCl3) δ 7.21-7.31 (m, 10H), 7.45-7.51 (m, 4H), 7.66-7.70 (m, 2H), 8.15-8.18 (m,
13
2H), 9.02 (dd, J =1.2, 8.4 Hz, 1H); C NMR (100 MHz, CDCl3) δ 124.1, 126.3, 126.6, 126.9, 127.2,
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127.3, 127.4, 127.7, 128.1 (overlapped), 129.0, 129.7, 130.5, 131.5, 132.2, 132.4, 134.0, 134.5, 135.8,
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138.4, 140.5, 150.0, 167.3; HRMS m/z Calcd for C29H19NS (M+) 413.1238, found 413.1239.
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2-Methyl-4,5-diphenylnaphtho[1,2-d]thiazole (3ya): mp 258-260 oC (white powder), 55 mg (78%);
1H NMR (400 MHz, CDCl3) δ 2.90 (s, 3H), 7.18-7.30 (m, 10H), 7.46 (ddd, J = 1.6, 7.2, 8.4 Hz, 1H),
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7.63-7.69 (m, 2H), 8.86 (d, J = 8.3 Hz, 1H); C NMR (100 MHz, CDCl3) δ 20.1, 123.8, 126.1, 126.5,
126.8, 127.2, 127.3, 127.6, 127.7, 128.0, 129.6, 131.5, 132.0, 132.3, 134.7, 135.1, 138.5, 140.6, 148.6,
166.5; HRMS m/z Calcd for C24H17NS (M+) 351.1082, found 351.1079.
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2,4,5-Triphenylnaphtho[1,2-d]oxazole (3bba): mp 207-208 C (white powder), 61 mg (76%); H
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NMR (400 MHz, CDCl3) δ 7.23-7.34 (m, 10H), 7.42-7.50 (m, 4H), 7.66 (ddd, J = 1.2, 6.8, 8.0 Hz, 1H),
13
7.73 (d, J = 8.8 Hz, 1H), 8.25-8.27 (m, 2H), 8.68 (d, J = 8.0 Hz, 1H); C NMR (100 MHz, CDCl3) δ
122.2, 124.8, 125.6, 125.9, 126.6, 127.0, 127.2, 127.38, 127.41, 127.78, 127.81, 127.9, 128.8, 130.7,
131.0, 131.1, 131.7, 135.1, 136.2, 137.1, 138.3, 146.9, 162.5; HRMS m/z Calcd for C29H19NO (M+)
397.1467, found 397.1466.
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5,6-Diphenylnaphtho[2,1-b]benzofuran (3cca): mp 233-235 oC (yellow powder), 30 mg (44%); H
NMR (400 MHz, CDCl3) δ 2.72 (s, 3H), 7.20-7.33 (m, 10H), 7.42 (ddd, J =1.2, 6.8, 8.4 Hz, 1H), 7.64
(ddd, J = 1.2, 6.8, 8.0 Hz, 1H), 7.70 (d, J = 8.4 Hz, 1H), 8.54 (d, J = 8.4 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 14.8, 121.9, 124.7, 125.3, 125.6, 126.6, 127.0, 127.2, 127.74, 127.78, 127.82, 130.6, 130.8,
131.7, 135.1, 135.6, 136.0, 138.3, 147.0, 163.2; HRMS m/z Calcd for C24H17NO (M+) 335.1310, found
335.1313.
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(E)-Butyl 3-[2-(Thiophen-3-yl)phenyl]acrylate (6aa):6 oil, 34 mg (60%); H NMR (400 MHz,
CDCl3) δ 0.95 (t, J = 7.2 Hz, 3H), 1.36-1.46 (m, 2H), 1.62-1.69 (m, 2H), 4.17 (t, J = 6.6 Hz, 2H), 6.39
(d, J = 15.9 Hz, 1H), 7.14-7.16 (m, 1H), 7.23-7.24 (m, 1H), 7.33-7.44 (m, 4H), 7.66 (d, J = 7.1 Hz, 1H),
13
7.87 (d, J = 16.0 Hz, 1H); C NMR (100 MHz, CDCl3) δ 13.7, 19.2, 30.7, 64.3, 119.4, 124.2, 125.7,
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126.9, 127.6, 129.1, 129.8, 130.2, 132.9, 137.4, 140.4, 143.7, 167.0; HRMS m/z Calcd for C17H18O2S
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(M+) 286.1028, found 286.1027.
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(E)-isobutyl 3-(2-(Thiophen-3-yl)phenyl)acrylate (6ab): oil, 28 mg (50%); H NMR (400 MHz,
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CDCl3) δ 0.94 (s, 3H), 0.96 (s, 3H), 1.97 (m, 1H), 3.96 (d, J = 6.6 Hz, 2H), 6.41 (d, J = 16.0 Hz, 1H),
7.15 (dd, J = 1.2, 4.8 Hz, 1H), 7.23 (dd, J = 1.2, 2.8 Hz, 1H), 7.33-7.44 (m, 4H), 7.68 (d, J = 7.4 Hz,
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1H), 7.88 (d, J = 16.0 Hz, 1H); C NMR (100 MHz, CDCl3) δ 19.1, 27.8, 70.5, 119.4, 124.2, 125.7,
126.9, 127.6, 129.1, 129.8, 130.1, 132.9, 137.3, 140.3, 143.7, 166.9; HRMS m/z Calcd for C17H18O2S
(M+) 286.1028, found 286.1026.
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(E)-tert-Butyl 3-(2-(thiophen-3-yl)phenyl)acrylate (6ac): oil, 30 mg (52%); H NMR (400 MHz,
CDCl3) δ 1.50 (s, 9H), 6.34 (d, J = 16.0 Hz, 1H), 7.15 (dd, J = 1.2, 4.8 Hz, 1H), 7.23 (dd, J = 1.3, 3.0
13
Hz, 1H), 7.32-7.43 (m, 4H), 7.67 (d, J = 7.8 Hz, 1H), 7.79 (d, J = 16.0 Hz, 1H); C NMR (100 MHz,
CDCl3) δ 28.2, 80.4, 121.1, 124.1, 125.6, 126.7, 127.5, 129.1, 129.6, 130.1, 132.9, 137.3, 140.4, 142.5,
166.2; HRMS m/z Calcd for C17H18O2S (M+) 286.1028, found 286.1026.
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(E)-Ethyl 3-(2-(thiophen-3-yl)phenyl)acrylate (6ad): oil, 24 mg (47%); H NMR (400 MHz,
CDCl3) δ 1.31 (t, J = 7.1 Hz, 3H), 4.23 (q, J = 7.1 Hz, 2H), 6.39 (d, J = 15.9 Hz, 1H), 7.15 (dd, J = 1.6,
5.2 Hz, 1H), 7.23 (dd, J = 1.6, 3.2 Hz, 1H), 7.33-7.44 (m, 4H), 7.66 (d, J = 8.0 Hz, 1H), 7.87 (d, J =
16.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.3, 60.4, 119.4, 124.2, 125.7, 126.9, 127.6, 129.1, 129.8,
130.2, 132.9, 137.4, 140.3, 143.8, 166.9; HRMS m/z Calcd for C15H14O2S (M+) 258.0715, found
258.0714.
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(E)-Cyclohexyl 3-(2-(thiophen-3-yl)phenyl)acrylate (6ae): oil, 40 mg (64%); H NMR (400 MHz,
CDCl3) δ 1.26-1.57 (m, 6H), 1.71-1.75 (m, 2H), 1.85-1.89 (m, 2H), 4.84-4.90 (m, 1H), 6.39 (d, J = 15.6
Hz, 1H), 7.15 (dd, J = 1.6, 5.2 Hz, 1H), 7.24 (dd, J = 1.2, 2.8 Hz, 1H), 7.33-7.44 (m, 4H), 7.67 (d, J =
13
7.8 Hz, 1H), 7.87 (d, J = 15.6 Hz, 1H); C NMR (100 MHz, CDCl3) δ 23.6, 25.4, 31.6, 72.5, 120.0,
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124.2, 125.7, 126.9, 127.6, 129.2, 129.7, 130.1, 133.0, 137.4, 140.4, 143.5, 166.3; HRMS m/z Calcd for
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C19H20O2S (M+) 312.1184, found 312.1182.
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(E)-Diethyl 2-(thiophen-3-yl)styrylphosphonate (6ag): oil, 30 mg (47%); H NMR (400 MHz,
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CDCl3) δ 1.32 (dd, J = 0.4, 6.8 Hz, 6H), 4.10 (qd, J = 7.2, 14.4 Hz, 4H), 6.23 (dd, J = 17.6, 18.8 Hz,
1H), 7.13 (dd, J = 1.6, 5.2 Hz, 1H), 7.22 (dd, J = 1.2, 2.8 Hz, 1H), 7.34-7.41 (m, 4H), 7.55-7.65 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 16.4 (d, J = 6.5 Hz), 61.7 (d, J = 5.6 Hz), 115.5 (d, J = 190.0 Hz),
124.1, 125.7, 126.7 (d, J = 1.24 Hz), 127.6, 129.0, 129.8, 130.2 (d, J = 1.3 Hz), 133.4 (d, J = 22.7 Hz),
137.0, 140.3, 147.2 (d, J = 7.0 Hz); HRMS m/z Calcd for C16H19O3PS (M+) 322.0793, found 322.0795.
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(E)-3-(2-Styrylphenyl)thiophene (6ah):6 oil, 30 mg (58%); 1H NMR (400 MHz, CDCl3) δ 7.03 (d, J
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= 16.4 Hz, 1H), 7.21-7.43 (m, 12H), 7.71 (d, J = 7.6 Hz, 1H); C NMR (100 MHz, CDCl3) δ 123.6,
125.2, 126.1, 126.5, 127.5 (overlapped), 127.6, 127.9, 128.7, 129.4, 129.7, 129.9, 135.75, 135.77, 137.5,
141.3; HRMS m/z Calcd for C18H14S (M+) 262.0816, found 262.0813.
(E)-3-(2-(4-Methylstyryl)phenyl)thiophene (6ai): oil, 30 mg (53%); 1H NMR (400 MHz, CDCl3) δ
2.96 (s, 3H), 7.00 (d, J = 16.4 Hz, 1H), 7.13-7.40 (m, 11H), 7.70 (d, J = 7.6 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 21.2, 123.5, 125.1, 126.0, 126.4, 126.9, 127.3, 127.5, 129.3, 129.4, 129.7, 129.9, 134.8,
135.6, 135.9, 137.4, 141.4; HRMS m/z Calcd for C19H16S (M+) 276.0973, found 276.0975.
(E)-3-(2-(4-(tert-Butyl)styryl)phenyl)thiophene (6aj): oil, 29 mg (45%); 1H NMR (400 MHz,
CDCl3) δ 1.32 (s, 9H), 7.01 (d, J = 16.4 Hz, 1H), 7.19-7.23 (m, 2H), 7.27-7.40 (m, 9H), 7.71 (d, J = 7.6
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 31.3, 34.6, 123.6, 125.1, 125.6, 126.1, 126.3, 127.2, 127.4,
127.5, 129.4, 129.5, 129.9, 134.8, 135.6, 136.0, 141.4, 150.7; HRMS m/z Calcd for C22H22S (M+)
318.1442, found 318.1441.
(E)-3-(2-(4-Methoxystyryl)phenyl)thiophene (6ak): oil, 31 mg (53%); 1H NMR (400 MHz, CDCl3)
δ 3.81 (s, 3H), 6.87 (d, J = 8.8 Hz, 2H), 6.98 (d, J = 16.0 Hz, 1H), 7.10 (d, J = 16.4 Hz, 1H), 7.21 (dd, J
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The Journal of Organic Chemistry
= 1.6, 5.2 Hz, 1H), 7.27-7.39 (m, 7H), 7.69 (d, J = 7.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 55.3,
114.1, 123.5, 125.1, 125.8, 125.9, 127.2, 127.5, 127.7, 129.2, 129.4, 129.9, 130.4, 135.5, 136.1, 141.5,
159.2; HRMS m/z Calcd for C19H16OS (M+) 292.0922, found 292.0921.
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(E)-3-(2-(2-([1,1'-Biphenyl]-4-yl)vinyl)phenyl)thiophene (6al): oil, 44 mg (65%); 1H NMR (400
MHz, CDCl3) δ 7.07 (d, J = 16.0 Hz, 1H), 7.22-7.61 (m, 12H), 7.56-7.61 (m, 4H), 7.74 (d, J = 7.4 Hz,
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1H); 13C NMR (100 MHz, CDCl3) δ 123.6, 125.2, 126.1, 126.9, 127.0, 127.30, 127.34, 127.57, 127.58,
128.0, 128.8, 129.2, 129.4, 130.0, 135.8 (overlapped), 136.6, 140.3, 140.6, 141.4; HRMS m/z Calcd for
C24H18S (M+) 338.1124, found 338.1131.
(E)-3-(2-(4-Chlorostyryl)phenyl)thiophene (6am): oil, 38 mg (63%); 1H NMR (400 MHz, CDCl3)
δ 6.97 (d, J = 16.0 Hz, 1H), 7.18-7.41 (m, 11H), 7.69 (d, J = 7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3)
δ 123.6, 125.3, 126.1, 127.6, 127.7, 127.8, 128.4, 128.5, 128.8, 129.4, 130.0, 133.1, 135.4, 135.8, 136.0,
141.3; HRMS m/z Calcd for C18H13ClS (M+) 296.0426, found 296.0426.
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(E)-3-(2-(4-(trifluoromethyl)styryl)phenyl)thiophene (6an): oil, 41 mg (63%); H NMR (400
MHz, CDCl3) δ 7.04 (d, J = 16.0 Hz, 1H), 7.19 (dd, J = 1.6, 5.2 Hz, 1H), 7.27 (dd, J = 1.2, 3.2 Hz, 1H),
7.30-7.43 (m, 5H), 7.49 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 9.2 Hz, 2H), 7.71-7.73 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 123.7, 124.2 (q, J = 270.0 Hz), 125.4, 125.6 (q, J = 3.8 Hz), 126.2, 126.6, 127.7, 128.1
(overlapped), 129.2 (q, J = 32.6 Hz), 129.3, 130.1, 130.4, 135.1, 136.1, 140.9, 141.1; HRMS m/z Calcd
for C19H13F3S (M+) 330.0690, found 330.0692.
(E)-3-(2-(2-(Naphthalen-2-yl)vinyl)phenyl)thiophene (6ao): oil, 31 mg (50%); 1H NMR (400 MHz,
CDCl3) δ 7.20 (d, J = 16.4 Hz, 1H), 7.24 (dd, J = 1.2, 4.8 Hz, 1H), 7.31-7.48 (m, 8H), 7.60 (dd, J = 1.6,
8.4 Hz, 1H), 7.76-7.82 (m, 5H);13C NMR (100 MHz, CDCl3) δ 123.5, 123.6, 125.3, 125.9, 126.1, 126.3,
126.6, 127.59, 127.60, 127.7, 128.0, 128.2, 128.3, 129.4, 129.8, 130.0, 132.9, 133.6, 135.1, 135.8
(overlapped), 141.4; HRMS m/z Calcd for C22H16S (M+) 312.0973, found 312.0971.
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