1-Bromo-2-(cyclopropylidenemethyl)benzene: A useful building block in the palladium-catalyzed reaction of 2-alkynylbenzenamine

Article abstract of DOI:10.1002/asia.201200122

A novel palladium-catalyzed domino reaction of 1-bromo-2- (cyclopropylidenemethyl)benzene and 2-alkynylbenzenamine is reported, which generates 2-(naphthalen-2-yl)benzenamines and 5H-indeno[1,2-c]quinolines via 6-endo and 5-exo cyclization, respectively. The regioselectivity for the final outcome can be affected by phosphine and N-heterocyclic carbene ligands. Copyright

Full text of DOI:10.1002/asia.201200122

DOI: 10.1002/asia.201200122
1-Bromo-2-(cyclopropylidenemethyl)benzene: A Useful Building Block in
the Palladium-Catalyzed Reaction of 2-Alkynylbenzenamine
Shaoyu Li,[a] Yong Luo,[a] Xiaocong Wang,[b] Minjie Guo,*[b] and Jie Wu*[a, c]
Abstract: A novel palladium-catalyzed domino reaction of 1-bromo-2-(cyclopropy-
lidenemethyl)benzene and 2-alkynylbenzenamine is reported, which generates 2-
(naphthalen-2-yl)benzenamines and 5H-indeno[1,2-c]quinolines via 6-endo and 5-
exo cyclization, respectively. The regioselectivity for the final outcome can be af-
Keywords: cyclization
reactions · homogeneous catalysis ·
palladium · synthetic methods
·
domino
G
fected by phosphine and N-heterocyclic carbene ligands.
Introduction
leading to an efficient preparation of 2-(naphthalen-2-yl)-
benzenamines and 5H-indeno[1,2-c]quinolines.
AHCTUNGTRENNUNG
Domino processes, in which one reagent or catalyst pro-
motes sequential reactions in a defined order, have been
widely used in organic synthesis.[1,2] Currently, this approach
is attractive for the generation of molecular diversity and
complexity in the field of chemical genetics.[3] As part of
a continuing effort in our laboratory for accessing privileged
scaffolds, we have been interested in the development of
cascade strategies for the construction of natural-product-
like compounds.[4,5] Recently, we disclosed a novel transfor-
mation for access to indene-incorporating molecules via
a palladium-catalyzed reaction of 2-alkynylhalobenzene with
related compounds.[5] The reaction process involved
a double insertion of triple bonds. This synthetic sequence is
highly selective and generates complex molecules with high
efficiency. Inspired by this study, we conceived that 1-
bromo-2-(cyclopropylidenemethyl)benzene would be an in-
teresting building block as well, due to its versatility in or-
ganic synthesis.[6] We now report an example by combina-
tion of 1-bromo-2-(cyclopropylidenemethyl)benzene and 2-
alkynylbenzenamine in the presence of a palladium catalyst,
Due to the structural similarity of 1-bromo-2-(cyclopropy-
lidenemethyl)benzene and 2-alkynylhalobenzene, we envi-
sioned that the transformation of 1-bromo-2-(cyclopropyli-
denemethyl)benzene and 2-alkynylbenzenamine was possi-
ble. As described in Scheme 1, an oxidative addition of pal-
ladium(0) to 1-bromo-2-(cyclopropylidenemethyl)benzene
1 would occur first to generate a palladium(II) species A.
Then 2-alkynylbenzenamine 2 would be involved via coordi-
nation of the triple bond with PdII. After insertion of PdII
into the triple bond, an intermediate B would be afforded.
The subsequent intramolecular insertion of PdII to the
double bond would result in two possible pathways (6-endo
and 5-exo). If the conversion proceeds along path I via 5-exo
cyclization, species C would be formed, which then proceeds
[7]
À
through C N coupling to furnish compound D. After in-
tramolecular rearrangement, product 4 would be obtained.
In the meantime, another pathway (path II) could not be ex-
cluded. After 6-endo cyclization, the intermediate F would
be generated. This species could easily undergo rearrange-
ment and b-H elimination to afford 2-(naphthalen-2-yl)ben-
zenamine 3. The hypothesis in Scheme 1 seems feasible.
Moreover, during the transformation, molecular complexity
and diversity could be ensured. Therefore, we started to ex-
plore the possibility of this conversion.
[a] S. Li, Y. Luo, Prof. J. Wu
Department of Chemistry, Fudan University
220 Handan Road, Shanghai 200433 (China)
Fax : (+86)216-564-1740
E-mail: jie_wu@fudan.edu.cn
Results and Discussion
[b] Dr. X. Wang, Prof. M. Guo
College of Science, Tianjin University of Science and Technology
Tianjin 300222 (China)
On the basis of the chemistry presented in Scheme 1, our
first attempt was performed for the reaction of 1-bromo-2-
(cyclopropylidenemethyl)benzene 1a with 2-alkynylbenzen-
amine 2a (Table 1). At the outset, the reaction was cata-
[c] Prof. J. Wu
Key Laboratory of Synthetic Organic Chemistry of Natural Substan-
ces
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
354 Fenglin Road, Shanghai 200032 (China)
lyzed by [Pd2ACHTUNRGTNEUNG(dba)3] in the presence of tBuONa in 1,4-diox-
ane under reflux conditions (Table 1, entry 1). However, the
reaction was not promising, and no reaction occurred. No
improvement was observed by addition of PCy3 as the
ligand (Table 1, entry 2). A trace amount of product was de-
tected when palladium chloride or palladium bromide was
Supporting information for this article, including experimental proce-
1
dure, characterization data, H and 13C NMR spectra of compounds 3
and 4, and X-ray crystal data of compound 3a and 4a, is available on
the WWW under http://dx.doi.org/10.1002/asia.201200122.
Chem. Asian J. 2012, 00, 0 – 0
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FULL PAPERS
conducted under the optimized
conditions (5 mol% [Pd-
AHCTUNGTRENN(GNU PPh3)2Cl2], 10 mol% phos-
phine L4 or NHC L7, tBuONa,
1,4-dioxane, 1058C). Table 2
summarizes results for the eval-
uation of the palladium-cata-
lyzed reactions. For the reac-
tions of 1-bromo-2-(cyclopropy-
lidenemethyl)benzene 1a, 2-al-
kynylbenzenamines with aryl or
heteroaryl groups attached on
the triple bond were all suitable
substrates under the standard
conditions. For instance, 1-
bromo-2-(cyclopropylideneme-
thyl)benzene 1a reacted with 2-
alkynylbenzenamine 2e (a 2-
thiophenyl group attached on
the triple bond) in the presence
of
a
phosphine ligand L4,
giving rise to compounds 3e
and 4e in 27% and 71% yield,
respectively (Table 2, entry 5).
The selectivity was reversed
when NHC L7 was employed in
the reaction, which afforded the
desired products 3e and 4e in
74% and 23% yield, respec-
tively (Table 2, entry 5). How-
ever, the conditions were not
Scheme 1. A possible mechanism for the palladium-catalyzed reaction of 1-bromo-2-(cyclopropylidenemethyl)-
benzene and 2-alkynylbenzenamine.
used as catalyst in the reaction (Table 1, entries 3 and 4). To
our delight, the expected products were generated when pal-
ladium acetate was utilized (Table 1, entry 5). Interestingly,
the products via 6-endo and 5-exo cyclization were both ob-
served and isolated (3a, 25% yield; 4a, 20% yield). A simi-
lar outcome was obtained when PdACTHNUTRGNE(UNG CO2CF3)2 was employed
in the conversion (Table 1, entry 6). Further investigation re-
vealed that the selectivity could be improved by changing
suitable for 2-alkynylbenzenamines with an alkyl group at-
tached to the triple bond. Only a trace amount of product
was detected when R3 was changed to a cyclopropyl group.
A similar outcome was observed when R3 was n-butyl group
in the above reaction (data not shown in Table 2). For the
reactions of 1-bromo-2-(cyclopropylidenemethyl)benzene
1a, 2-alkynylbenzenamines 2 with different substitutions on
the aromatic ring were examined subsequently (Table 2, en-
tries 6–10). Methyl, isopropyl, chloro, and trifluoromethyl
groups were all tolerated under the standard conditions. 2-
Alkynylbenzenamines 2 with substitution on the amino
groups were tested in the meantime. It was found that N-
benzyl-2-alkynylbenzenamine 2k was effective in the con-
version (Table 2, entry 11). However, the reaction did not
proceed when R4 was changed to an acetyl group (Table 2,
entry 12). Subsequently, reactions of 2-alkynylbenzenamine
2a with substituted 1-bromo-2-(cyclopropylidenemethyl)-
benzenes were explored (Table 2, entries 13–16). As we can
see, all reactions proceeded well to afford the corresponding
products in good yields.
the catalyst to [PdACHTUNGTRENNUNG(PhCN)2Cl2] or [PdCAHTUNTGRNE(NUGN PPh3)2Cl2] (Table 1,
entries 7 and 8). However, the result was inferior when the
reaction temperature was reduced to 858C (Table 1,
entry 9). We next screened other bases and solvents; howev-
er, no better results were obtained (Table 1, entries 10–19).
Thus, we shifted our focus to the ligands. Different phos-
phine ligands such as PPh3, PACTHUNTRGNEUNG(C6F5)3, PtBu3, X-Phos, dppf,
and others developed by Buchwald[7f] were examined
(Table 1, entries 20–30). Gratifyingly, a good result was ob-
tained when L4 was utilized as a ligand in the reaction
(Table 1, entry 28: 3a, 31% yield; 4a, 64% yield). Further
screening of N-heterocyclic carbene ligands disclosed that
NHC L7 gave rise to an interesting outcome, which generat-
ed product 3a in 71% yield and compound 4a in 20%
yield, respectively (Table 1, entry 31). From these results, it
seems that the yield and selectivity are complementary by
using L4 or L7 as the ligand in the reaction.
Conclusions
Next, investigations with various 1-bromo-2-(cyclopropyli-
denemethyl)benzenes 1 and 2-alkynylbenzenamines 2 were
We have described a novel and efficient pathway for the
generation of 2-(naphthalen-2-yl)benzenamines and 5H-
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Palladium-Catalyzed Reaction of 2-Alkynylbenzenamine
Table 1. Initial studies for the palladium-catalyzed reaction of 1-bromo-2-(cyclopropylidenemethyl)benzene
1a with 2-alkynylbenzenamine 2a.
Experimental Section
General experimental procedure for the
palladium-catalyzed reaction of 1-
bromo-2-
(cyclopropylidenemethyl)benzene with
2-alkynylbenzenamine
A solution of 1-bromo-2-(cyclopropyli-
denemethyl)benzene 1 (0.6 mmol) in
1,4-dioxane (2.0 mL) was added to
a mixture of 2-alkynylbenzenamine 2
Entry
[Pd]
Ligand
Base
Solvent
T [8C]
Yield [%][a]
3a
4a
(0.3 mmol), [PdACHTUNGTRENUNG(PPh3)2Cl2] (10.5 mg,
1
2
3
4
5
6
7
8
N
(dba)3]
none
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PPh3
PACHTUNGTRENNU(G C6F5)3
PtBu3·HBF4
X-Phos
dppf
L1
L2
L3
L4
L5
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
K2CO3
K3PO4
Cs2CO3
KOH
tBuOLi
tBuOK
NaOMe
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
toluene
105
105
105
105
105
105
105
105
85
/
/
0.015 mmol), ligand (0.03 mmol), and
tBuONa (72.0 mg, 0.75 mmol). The re-
action was stirred under reflux. After
completion of reaction as indicated by
TLC, the mixture was cooled and di-
luted with CH2Cl2 (10 mL). The mix-
ture was filtered through a thin layer
of silica gel, and the solvent was
evaporated. The residue was purified
by column chromatography on silica
gel (eluted with petroleum ether/ethyl
acetate=30:1 to 8:1) to provide the
products 3 and 4.
trace
trace
25
30
40
44
15
/
/
/
30
/
24
/
trace
/
/
23
/
/
37
12
33
31
36
31
35
45
71
23
N
20
23
25
30
18
ACHTUNGTRENNUNG
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
23
20
N-Methyl-2-(1-phenyl-3-
vinylnaphthalen-2-yl)aniline (3a)
1H NMR (400 MHz, CDCl3): d=2.65
(s, 3H), 3.32 (s, 1H), 5.17 (dd, J=11.2,
1.2 Hz, 1H), 5.80 (dd, J=17.6, 1.2 Hz,
1H), 6.46–6.57 (m, 3H), 6.76 (dd, J=
7.2, 1.2 Hz, 1H), 7.07–7.09 (m, 2H),
7.14–7.26 (m, 4H), 7.32–7.34 (m, 1H),
7.45–7.51 (m, 2H), 7.91 (d, J=8.4 Hz,
1H), 8.16 ppm (s, 1H); 13C NMR
(100 MHz, CDCl3): d=30.9, 109.6,
115.5, 116.4, 124.2, 125.0, 126.1, 126.3,
126.9, 126.9, 127.4, 127.6, 128.2, 128.4,
129.2, 131.0, 131.1, 133.3, 134.8, 135.6,
135.8, 135.8, 138.8, 140.3, 146.9 ppm;
HRMS (ESI) calcd for C25H21N:
336.1752 (M+H+), found: 336.1755.
DMF
DMSO
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
20
28
15
27
46
28
64
46
20
20
40
L6
L7
L8
[a] Yield of isolated product based on 2-alkynylbenzenamine 2a. dba=dibenzylideneacetone, Cy=cyclohexyl,
X-Pohs=2-dicyclohexylphosphino-2’,4’,6’-triisopropylbiphenyl, dppf=1,1’-bis(diphenylphosphino)ferrocene.
6-Ethyl-5-methyl-11-phenyl-5H-
indenoACHTNUTRGNEUNG[1,2-c]quinoline (4a)
1H NMR (400 MHz, CDCl3): d=1.49
(t, J=7.6 Hz, 3H), 3.39 (q, J=7.6 Hz,
2H), 3.71 (s, 3H), 7.02 (t, J=7.2 Hz,
1H), 7.27–7.30 (m, 2H), 7.33–7.42 (m,
3H), 7.50–7.58 (m, 5H), 7.96 (d, J=
8.0 Hz, 1H), 8.04 ppm (d, J=7.6 Hz,
1H); 13C NMR (100 MHz, CDCl3): d=
12.6, 24.1, 34.2, 114.8, 115.4, 118.9,
119.2, 120.8, 121.1, 122.9, 123.0, 124.1,
125.6, 125.8, 126.5, 126.7, 128.2, 128.9,
130.9, 136.4, 139.1, 142.5, 147.6 ppm;
HRMS (ESI) calcd for C25H21N:
336.1752 (M+H+), found: 336.1741.
indenoACHTUNGTRENNUNG[1,2-c]quinolines via a palladium-catalyzed domino
reaction of 1-bromo-2-(cyclopropylidenemethyl)benzene
and 2-alkynylbenzenamine. The regioselectivity of 6-endo
and 5-exo cyclization for the final outcome depends on the
ligand utilized in the reaction. Phosphine L4 and NHC L7
are found to be complementary for the regioselectivity in
the reaction. Exploration of 1-bromo-2-(cyclopropylidene-
methyl)benzenes for other transformations is under investi-
gation currently.
2-(1-(4-Methoxyphenyl)-3-vinylnaphthalen-2-yl)-N-methylaniline (3b)
1H NMR (400 MHz, CDCl3): d=2.65 (s, 3H), 3.32 (s, 1H), 3.73 (s, 3H),
5.16 (d, J=10.8 Hz, 1H), 5.78 (d, J=17.6 Hz, 1H), 6.48–6.57 (m, 3H),
6.71–6.77 (m, 3H), 7.00 (dd, J=8.0, 1.6 Hz, 1H), 7.05–7.10 (m, 2H),
7.31–7.35 (m, 1H), 7.44–7.48 (m, 1H), 7.54 (d, J=8.8 Hz, 1H), 7.90 (d,
J=8.0 Hz, 1H), 8.14 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d=30.9,
55.1, 109.6, 112.8, 113.1, 115.4, 116.5, 124.0, 125.2, 126.0, 126.2, 126.9,
128.1, 128.3, 130.3, 131.0, 132.1, 133.1, 133.3, 135.0, 135.6, 135.9, 140.0,
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Table 2. Palladium-catalyzed reaction of 1-bromo-2-(cyclopropylidene-
N-Methyl-2-(1-p-tolyl-3-vinylnaphthalen-2-yl)aniline (3c)
methyl)benzene 1 with 2-alkynylbenzenamine 2.
1H NMR (400 MHz, CDCl3): d=2.27 (s, 3H), 2.65 (s, 3H), 3.32 (s, 1H),
5.15 (dd, J1 =10.8, 1.2 Hz, 1H), 5.78 (dd, J=17.6, 1.2 Hz, 1H), 6.47–6.56
(m, 3H), 6.77 (dd, J=7.2, 1.2 Hz, 1H), 6.97–7.10 (m, 5H), 7.32 (dd, J=
6.8, 1.2 Hz, 1H), 7.43–7.47 (m, 1H), 7.52 (d, J=8.4 Hz, 1H), 7.89 (d, J=
8.0 Hz, 1H), 8.14 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d=21.3,
30.9, 109.6, 115.4, 116.5, 124.1, 125.3, 126.0, 126.2, 127.0, 128.1, 128.3,
128.4, 129.1, 130.9, 131.0, 133.0, 133.3, 134.8, 135.6, 135.7, 135.9, 136.2,
140.4, 147.0 ppm; HRMS (ESI) calcd for C26H23N: 350.1909 (M+H+),
found: 350.1909.
6-Ethyl-5-methyl-11-p-tolyl-5H-indenoACTHNUTRGENUG[N 1,2-c]quinoline (4c)
1H NMR (400 MHz, CDCl3): d=1.59 (t, J=7.2 Hz, 3H), 2.50 (s, 3H),
3.56 (q, J=7.2 Hz, 2H), 3.90 (s, 3H), 7.06–7.09 (m, 1H), 7.30–7.39 (m,
5H), 7.45–7.56 (m, 4H), 8.02 (d, J=8.0 Hz, 1H), 8.11 ppm (d, J=7.6 Hz,
1H); 13C NMR (100 MHz, CDCl3): d=12.6, 21.5, 24.1, 33.9, 114.9, 115.2,
118.9, 119.4, 120.8, 121.0, 122.8, 124.0, 125.8, 126.4, 128.2, 129.6, 130.6,
135.8, 136.0, 136.4, 142.7, 147.3 ppm; HRMS (ESI) calcd for C26H23N:
350.1909 (M+H+), found: 350.1904.
Entry R1
R2,R3,R4
L
Yield [%][a]
3
4
1
H (1a)
H, Ph, Me (2a)
L4 31 (3a) 64 (4a)
L7 71 (3a) 20 (4a)
L4 42 (3b) 51 (4b)
L7 82 (3b) 16 (4b)
2
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H (1a)
H, p-MeOC6H4, Me
(2b)
H, p-MeC6H4, Me (2c) L4 39 (3c) 31 (4c)
L7 75 (3c) 19 (4c)
2-(1-(4-Chlorophenyl)-3-vinylnaphthalen-2-yl)-N-methylaniline (3d)
3
1H NMR (400 MHz, CDCl3): d=2.66 (s, 3H), 3.21 (s, 1H), 5.17 (dd, J=
10.8, 1.2 Hz, 1H), 5.79 (dd, J=17.6, 1.2 Hz, 1H), 6.48–6.57 (m, 3H), 6.73
(dd, J=7.2, 1.2 Hz, 1H), 7.03 (dd, J=8.0, 2.0 Hz, 1H), 7.07–7.11 (m,
2H), 7.15 (dd, J=8.0, 2.0 Hz, 1H), 7.19–7.21 (m, 1H), 7.32–7.36 (m, 1H),
7.44–7.49 (m, 2H), 7.91 (d, J=8.4 Hz, 1H), 8.16 ppm (s, 1H); 13C NMR
(100 MHz, CDCl3): d=30.8, 109.7, 115.7, 116.6, 124.5, 124.7, 126.3, 126.4,
126.5, 127.7, 127.9, 128.3, 128.6, 130.6, 130.9, 132.3, 132.6, 132.8, 133.3,
134.9, 135.6, 137.3, 139.0, 146.8 ppm; HRMS (ESI) calcd for C25H20ClN:
370.1363 (M+H+), found: 370.1369.
4
H, p-ClC6H4, Me (2d)
L4 35 (3d) 50 (4d)
L7 75 (3d) 24 (4d)
L4 27 (3e) 71 (4e)
L7 74 (3e) 23 (4e)
5
H, 2-thiophenyl, Me
(2e)
H, cyclopropyl, Me (2 f) L4 trace
6
L7 trace
L4 29 (3 f) 59 (4 f)
7
Me, Ph, Me (2g)
iPr, Ph, Me (2h)
Cl, Ph, Me (2i)
CF3, Ph, Me (2j)
H, Ph, Bn (2k)
H, Ph, Ac (2l)
H, Ph, Me (2a)
H, Ph, Me (2a)
H, Ph, Me (2a)
L7 75 (3 f) 19 (4 f)
L4 27 (3g) 53 (4g)
L7 54 (3g) 7 (4g)
L4 43 (3h) 54 (4h)
L7 73 (3h) 20 (4h)
L4 35 (3i) 50 (4i)
L7 72 (3i) 9 (4i)
L4 25 (3j) 60 (4j)
L7 50 (3j) trace
L4 trace
8
11-(4-Chlorophenyl)-6-ethyl-5-methyl-5H-indenoACHTNUTRGNEUNG[1,2-c]quinoline (4d)
1H NMR (400 MHz, CDCl3): d=1.59 (t, J=7.6 Hz, 3H), 3.55 (q, J=
7.6 Hz, 2H), 3.90 (s, 3H), 7.09–7.13 (m, 1H), 7.33–7.35 (m, 1H), 7.37–
7.42 (m, 2H), 7.50–7.54 (m, 6H), 7.96 (dd, J1 =1.6 Hz, J2 =8.0 Hz, 1H),
8.12 ppm (d, J=8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=12.6, 24.2,
33.9, 114.9, 115.5, 117.7, 118.6, 121.0, 121.1, 123.0, 124.2, 125.7, 125.8,
126.7, 129.1, 132.2, 132.3, 136.3, 137.5, 142.2, 147.7 ppm; HRMS (ESI)
calcd for C25H20ClN: 370.1363 (M+H+), found: 370.1358.
9
10
11
12
13
14
15
L7 trace
N-Methyl-2-(1-(thiophen-3-yl)-3-vinylnaphthalen-2-yl)aniline (3e)
4,5-(OMe)2
(1b)
5-OMe (1c)
L4 15 (3k) 72 (4k)
L7 50 (3k) 29 (4k)
L4 10 (3l) 85 (4l)
L7 40 (3l) 20 (4l)
L4 30
(3m)
L7 64
(3m)
1H NMR (400 MHz, CDCl3): d=2.66 (s, 3H), 3.31 (s, 1H), 5.17 (dd, J=
12.4, 1.6 Hz, 1H), 5.78 (dd, J=17.6, 1.6 Hz, 1H), 6.49–6.60 (m, 3H), 6.77
(d, J=6.4 Hz, 1H), 6.87 (s, 1H), 6.98–6.99 (m, 1H), 7.09–7.14 (m, 2H),
7.34–7.39 (m, 1H), 7.45–7.49 (m, 1H), 7.68 (d, J=6.0 Hz, 1H), 7.90 (d,
J=8.4 Hz, 1H), 8.15 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d=30.9,
109.6, 115.5, 116.5, 124.1, 124.3, 126.2, 126.3, 126.7, 128.2, 128.5, 133.0,
133.3, 135.6, 135.7 ppm; HRMS (ESI) calcd for C23H19NS: 342.1316
(M+H+), found: 342.1318.
5-Me (1d)
58
(4m)
7 (4m)
16
5-F (1e)
H, Ph, Me (2a)
L4 39 (3n) 50 (4n)
L7 54 (3n) 41 (4n)
6-Ethyl-5-methyl-11-(thiophen-3-yl)-5H-indenoACTHNUTRGNE[NUG 1,2-c]quinoline (4e)
[a] Yield of isolated product based on 2-alkynylbenzenamine 2. Bn=
benzyl, Ac=acetyl.
1H NMR (400 MHz, CDCl3): d=1.50 (t, J=7.6 Hz, 3H), 3.59 (q, J=
7.6 Hz, 2H), 3.97 (s, 3H), 7.16–7.19 (m, 2H), 7.23–7.32 (m, 2H), 7.41 (d,
J=7.6 Hz, 1H), 7.45–7.49 (m, 1H), 7.53 (s, 1H), 7.77–7.78 (m, 1H), 7.82
(d, J=8.8 Hz, 1H), 7.95 (d, J=7.6 Hz, 1H), 8.12 ppm (d, J=7.6 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=12.9, 24.1, 35.1, 112.3, 113.9, 117.2,
118.6, 121.0, 121.4, 122.7, 123.4, 123.6, 124.0, 125.0, 126.1, 126.9, 127.3,
128.1, 130.3, 136.4, 138.6, 142.1, 149.3 ppm; HRMS (ESI) calcd for
C23H19NS: 342.1316 (M+H+), found: 342.1294.
146.9, 158.3 ppm; HRMS (ESI) calcd for C26H23NO: 366.1858 (M+H+),
found: 366.1849.
6-Ethyl-11-(4-methoxyphenyl)-5-methyl-5H-indenoACHTNUTRGNEUNG[1,2-c]quinoline (4b)
N,4-Dimethyl-2-(1-phenyl-3-vinylnaphthalen-2-yl)aniline (3 f)
1H NMR (400 MHz, CDCl3): d=1.53 (t, J=7.2 Hz, 3H), 3.51 (q, J=
7.2 Hz, 2H), 3.84 (s, 3H), 3.91 (s, 3H), 7.04–7.08 (m, 3H), 7.28–7.36 (m,
3H), 7.46–7.52 (m, 4H), 7.99 (d, J=8.0 Hz, 1H), 8.09 ppm (d, J=7.6 Hz,
1H); 13C NMR (100 MHz, CDCl3): d=12.6, 24.1, 33.9, 55.4, 114.4, 114.8,
115.3, 118.9, 119.0, 120.8, 121.0, 122.8, 123.1, 124.0, 125.5, 125.7, 126.4,
128.2, 131.1, 131.8, 136.4, 142.8, 147.3, 158.4 ppm; HRMS (ESI) calcd for
C26H23NO: 366.1858 (M+H+), found: 366.1851.
1H NMR (400 MHz, CDCl3): d=2.09 (s, 3H), 2.63 (s, 3H), 3.17 (s, 1H),
5.17 (d, J=10.8 Hz, 1H), 5.81 (d, J=17.6 Hz, 1H), 6.39 (d, J=8.0 Hz,
1H), 6.51–6.58 (m, 2H), 6.87 (d, J=7.6 Hz, 1H), 7.06–7.23 (m, 5H), 7.32
(t, J=8.0 Hz, 1H), 7.45–7.50 (m, 2H), 7.91 (d, J=8.4 Hz, 1H), 8.16 ppm
(s, 1H); 13C NMR (100 MHz, CDCl3): d=20.4, 31.2, 109.8, 115.4, 124.0,
125.1, 125.4, 126.0, 126.1, 126.8, 126.9, 127.2, 127.6, 128.1, 128.7, 129.3,
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Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!

Palladium-Catalyzed Reaction of 2-Alkynylbenzenamine
131.0, 131.7, 132.7, 133.2, 135.0, 135.5, 135.8, 138.8, 140,2, 144.8 ppm;
6-Ethyl-5-methyl-11-phenyl-2-(trifluoromethyl)-5H-indenoACTHNGUTERNNU[G 1,2-c]quinoline
(4i)
HRMS (ESI) calcd for C26H23N: 350.1909 (M+H+), found: 350.1920.
6-Ethyl-2,5-dimethyl-11-phenyl-5H-indeno
[1,2-c]quinoline (4 f)
1H NMR (400 MHz, CDCl3): d=1.59 (t, J=7.2 Hz, 3H), 3.53 (q, J=
7.2 Hz, 2H), 3.89 (s, 3H), 7.36–7.45 (m, 2H), 7.53–7.55 (m, 8H), 8.11 (d,
J=7.6 Hz, 1H), 8.19 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d=12.6,
1H NMR (400 MHz, CDCl3): d=1.58 (t, J=7.6 Hz, 3H), 2.18 (s, 3H),
3.55 (q, J=7.6 Hz, 2H), 3.88 (s, 3H), 7.17 (d, J=8.4 Hz, 1H), 7.28–7.37
(m, 2H), 7.39–7.43 (m, 2H), 7.49–7.58 (m, 5H), 7.74 (s, 1H), 8.10 ppm
(d, J=7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=12.6, 21.0, 24.1,
33.9, 109.3, 112.4, 114.6, 115.2, 118.8, 120.6, 120.9, 122.9, 123.9, 125.9,
126.5, 127.6, 128.2, 128.7, 130.8, 132.3, 134.4, 139.0, 142.4, 147.3 ppm;
HRMS (ESI) calcd for C26H23N: 350.1909 (M+H+), found: 350.1905.
24.1, 34.5, 115.5, 115.8, 119.3, 121.2, 121.6, 122.6, 122.7, 122.9 (q, JCF
=
3.8 Hz), 124.2 (q, JCF =269.8 Hz), 124.7, 127.2, 128.3, 129.1, 130.2, 130.4,
137.8, 138.4, 142.6, 147.3 ppm; HRMS (ESI) calcd for C26H20F3N:
404.1626 (M+H+), found: 404.1621.
N-Benzyl-2-(1-phenyl-3-vinylnaphthalen-2-yl)aniline (3j)
1H NMR (400 MHz, CDCl3): d=3.78 (s, 1H), 4.20 (s, 2H), 5.21 (d, J=
10.8 Hz, 1H), 5.83 (d, J=17.2 Hz, 1H), 6.43 (d, J=8.4 Hz, 1H), 6.54–6.55
(m, 2H), 6.80 (d, J=7.2 Hz, 1H), 6.97–7.01 (m, 2H), 7.15–7.26 (m, 9H),
7.45–7.50 (m, 3H), 7.91 (d, J=7.6 Hz, 1H), 8.17 ppm (s, 1H); 13C NMR
(100 MHz, CDCl3): d=48.1, 67.1, 110.1, 115.5, 116.6, 124.2, 124.9, 126.1,
126.2, 126.9, 127.0, 127.2, 127.3, 127.6, 128.1, 128.2, 128.3, 128.5, 129.5,
131.1, 131.3, 132.7, 133.3, 134.7, 135.5, 135.9, 139.7, 140.4, 145.5 ppm;
HRMS (ESI) calcd for C31H25N: 412.2065 (M+H+), found: 412.2067.
4-Isopropyl-N-methyl-2-(1-phenyl-3-vinylnaphthalen-2-yl)aniline (3g)
1H NMR (400 MHz, CDCl3): d=1.02 (d, J=7.2 Hz, 6H), 2.60–2.65 (m,
4H), 3.22 (s, 1H), 5.18 (d, J=11.2 Hz, 1H), 5.82 (d, J=17.6 Hz, 1H),
6.42 (d, J=8.0 Hz, 1H), 6.56–6.63 (m, 2H), 6.90 (dd, J=8.4, 2.0Hz, 1H),
7.01–7.02 (m, 1H), 7.14–7.24 (m, 4H), 7.33 (t, J=8.0 Hz, 1H), 7.47 (t, J=
8.0 Hz, 1H), 7.52 (d, J=8.8 Hz, 1H), 7.92 (d, J=8.4 Hz, 1H), 8.17 ppm
(s, 1H); 13C NMR (100 MHz, CDCl3): d=23.8, 24.5, 31.2, 33.1, 109.5,
115.4, 123.9, 125.0, 125.9, 126.0, 126.1, 126.6, 126.7, 126.9, 127.1, 127.7,
128.1, 129.3, 129.4, 131.1, 133.2, 135.4, 135.4, 135.8, 136.8, 139.0,
145.1 ppm; HRMS (ESI) calcd for C28H27N: 378.2222 (M+H+), found:
378.2220.
5-Benzyl-6-ethyl-11-phenyl-5H-indenoACTHNUTRGENUG[N 1,2-c]quinoline (4j)
1H NMR (400 MHz, CDCl3): d=1.59 (t, J=7.2 Hz, 3H), 3.44 (q, J=
7.2 Hz, 2H), 5.60 (s, 2H), 7.01 (t, J=7.2 Hz, 1H), 7.16–7.24 (m, 3H),
7.30–7.45 (m, 7H), 7.52–7.60 (m, 5H), 7.97 (d, J=8.0 Hz, 1H), 8.11 ppm
(d, J=7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=13.1, 24.2, 50.1,
115.1, 116.4, 119.0, 119.9, 121.1, 121.2, 123.0, 123.1, 124.4, 125.5, 125.6,
125.9, 126.6, 126.7, 127.7, 128.2, 128.9, 129.2, 130.8, 135.8, 136.8, 138.9,
142.9, 147.6 ppm; HRMS (ESI) calcd for C31H25N: 412.2065 (M+H+),
found: 412.2048.
6-Ethyl-2-isopropyl-5-methyl-11-phenyl-5H-indenoACHTNUTRGNEUNG[1,2-c]quinoline (4g)
1H NMR (400 MHz, CDCl3): d=1.03 (d, J=6.8 Hz, 6H), 1.53 (t, J=
7.6 Hz, 3H), 2.69–2.76 (m, 1H), 3.49 (q, J=7.6 Hz, 2H), 3.81 (s, 3H),
7.19–7.21 (m, 1H), 7.29 (t, J=7.6 Hz, 1H), 7.34–7.42 (m, 3H), 7.50–7.59
(m, 5H), 7.84 (d, J=2.0 Hz, 1H), 8.08 ppm (d, J=7.6 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=12.6, 23.8, 24.0, 33.4, 34.2, 114.5, 115.2, 118.8,
118.9, 120.6, 121.0, 122.9, 123.0, 123.9, 125.6, 126.0, 126.5, 128.3, 128.8,
131.0, 134.5, 139.3, 142.4, 143.3, 147.4 ppm; HRMS (ESI) calcd for
C28H27N: 378.2222 (M+H+), found: 378.2218.
2-(6,7-Dimethoxy-1-phenyl-3-vinylnaphthalen-2-yl)-N-methylaniline (3k)
1H NMR (400 MHz, CDCl3): d=2.66 (s, 3H), 3.36 (s, 1H), 3.70 (s, 3H),
3.83 (s, 3H), 5.11 (d, J=10.8 Hz, 1H), 5.74 (d, J=17.2 Hz, 1H), 6.46–6.54
(m, 3H), 6.75–6.79 (m, 2H), 7.04–7.08 (m, 2H), 7.17–7.25 (m, 5H),
8.04 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d=30.9, 55.7, 56.0, 105.6,
106.4, 109.4, 114.3, 116.3, 122.5, 125.3, 126.8, 127.4, 127.6, 128.2, 128.5,
129.1, 129.2, 130.8, 131.2, 133.1, 133.8, 134.7, 135.8, 138.8, 147.0, 149.5,
149.8 ppm; HRMS (ESI) calcd for C27H25NO2: 396.1964 (M+H+), found:
396.1961.
4-Chloro-N-methyl-2-(1-phenyl-3-vinylnaphthalen-2-yl)aniline (3h)
1H NMR (400 MHz, CDCl3): d=2.61 (s, 3H), 3.32 (s, 1H), 5.19 (d, J=
11.2 Hz, 1H), 5.80 (d, J=17.2 Hz, 1H), 6.36 (d, J=8.8 Hz, 1H), 6.47–6.54
(m, 1H), 6.76 (d, J=2.0 Hz, 1H), 7.00 (dd, J1 =2.0 Hz, J2 =8.4 Hz, 1H),
7.05–7.06 (m, 1H), 7.14–7.20 (m, 3H), 7.25–7.35 (m, 2H), 7.45–7.50 (m,
2H), 7.90 (d, J=8.0 Hz, 1H), 8.15 ppm (s, 1H); 13C NMR (100 MHz,
CDCl3): d=30.9, 110.6, 116.0, 121.0, 124.4, 126.3, 126.5, 126.5, 126.9,
127.1, 127.6, 127.7, 128.1, 128.2, 129.0, 130.6, 131.0, 132.7, 133.3, 133.4,
135.2, 135.4, 138.4, 140.5, 145.6 ppm; HRMS (ESI) calcd for C25H20ClN:
370.1363 (M+H+), found: 370.1360.
6-Ethyl-8,9-dimethoxy-5-methyl-11-phenyl-5H-indenoACTHNUTRGNE[NUG 1,2-c]quinoline
(4k)
1H NMR (400 MHz, CDCl3): d=1.57 (t, J=7.2 Hz, 3H), 3.43 (q, J=
7.2 Hz, 2H), 3.84 (s, 3H), 3.88 (s, 3H), 4.00 (s, 3H), 6.99 (s, 1H), 7.00–
7.02 (m, 1H), 7.29–7.33 (m, 1H), 7.42–7.47 (m, 2H), 7.52–7.60 (m, 5H),
7.90 ppm (d, J=8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=12.5, 23.9,
34.2, 56.0, 57.1, 101.1, 105.7, 115.3, 118.9, 120.8, 121.8, 122.7, 122.9, 125.2,
125.9, 126.6, 129.0, 130.7, 132.2, 135.9, 137.1, 139.1, 145.3, 146.2,
148.3 ppm; HRMS (ESI) calcd for C27H25NO2: 396.1964 (M+H+), found:
396.1953.
2-Chloro-6-ethyl-5-methyl-11-phenyl-5H-indenoACTHNUTRGNE[NUG 1,2-c]quinoline (4h)
1H NMR (400 MHz, CDCl3): d=1.52 (t, J=8.0 Hz, 3H), 3.42 (q, J=
8.0 Hz, 2H), 3.75 (s, 3H), 7.20–7.23 (m, 1H), 7.30–7.33 (m, 2H), 7.36 (d,
J=7.2 Hz, 1H), 7.44–7.45 (m, 1H), 7.53–7.54 (m, 5H), 7.87 (d, J=2.0 Hz,
1H), 8.05 ppm (d, J=8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=12.5,
24.0, 34.4, 116.7, 119.2, 120.3, 121.1, 121.3, 124.2, 124.2, 124.3, 124.9,
126.3, 127.0, 128.2, 128.3, 129.1, 130.5, 134.9, 138.1, 142.3, 147.4 ppm;
HRMS (ESI) calcd for C25H20ClN: 370.1363 (M+H+), found: 370.1361.
2-(6-Methoxy-1-phenyl-3-vinylnaphthalen-2-yl)-N-methylaniline (3l)
1H NMR (400 MHz, CDCl3): d=2.66 (s, 3H), 3.35 (s, 1H), 3.94 (s, 3H),
5.16 (d, J=11.2 Hz, 1H), 5.79 (d, J=17.6 Hz, 1H), 6.46–6.55 (m, 3H),
6.76 (dd, J=7.2 Hz, 1H), 7.00 (dd, J=9.2, 2.0 Hz, 1H), 7.04–7.08 (m,
2H), 7.13–7.19 (m, 3H), 7.20–7.24 (m, 2H), 7.41 (d, J=9.2 Hz, 1H),
8.07 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d=30.9, 55.4, 105.8,
109.5, 115.4, 116.3, 118.8, 123.0, 125.1, 126.8, 127.3, 127.5, 128.2, 128.5,
129.1, 130.9, 131.2, 132.5, 135.9, 136.0, 138.9, 147.1, 157.9 ppm; HRMS
(ESI) calcd for C26H23NO: 366.1858 (M+H+), found: 366.1860.
N-Methyl-2-(1-phenyl-3-vinylnaphthalen-2-yl)-4-(trifluoromethyl)aniline
(3i)
1H NMR (400 MHz, CDCl3): d=2.68 (d, J=5.2, 3H), 3.66 (q, J=5.2,
1H), 5.19 (d, J=11.2 Hz, 1H), 5.82 (d, J=17.2 Hz, 1H), 6.43–6.53 (m,
2H), 7.00–7.02 (m, 2H), 7.13–7.20 (m, 3H), 7.22–7.29 (m, 2H), 7.32–7.36
(m, 1H), 7.47–7.51 (m, 2H), 7.92 (d, J=8.4 Hz, 1H), 8.17 ppm (s, 1H);
13C NMR (100 MHz, CDCl3): d=30.4, 108.5, 116.1, 123.7, 124.4, 124.5,
124.6, 125.1 (q, JCF =269.2 Hz), 125.7 (q, JCF =4.8 Hz), 126.3, 126.6, 127.0,
127.1, 127.6, 127.6, 128.2, 128.4 (q, JCF =3.8 Hz), 128.8, 130.9, 132.7, 133.2,
133.5, 135.1, 135.2, 138.4, 140.8, 149.3 ppm; HRMS (ESI) calcd for
C26H20F3N: 404.1626 (M+H+), found: 404.1615.
6-Ethyl-8-methoxy-5-methyl-11-phenyl-5H-indenoACHTNUTRGNEUNG[1,2-c]quinoline (4l)
1H NMR (400 MHz, CDCl3): d=1.54 (t, J=8.0 Hz, 3H), 3.41 (q, J=
8.0 Hz, 2H), 3.79 (s, 3H), 3.91 (s, 3H), 6.99–7.03 (m, 2H), 7.28–7.31 (m,
1H), 7.40–7.42 (m, 3H), 7.49–7.57 (m, 4H), 7.66 (s, 1H), 7.90 ppm (d, J=
7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=12.4, 24.0, 34.2, 56.2, 106.8,
111.5, 114.7, 115.3, 119.3, 122.8, 123.3, 124.4, 125.4, 126.2, 126.6, 128.8,
Chem. Asian J. 2012, 00, 0 – 0
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
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Minjie Guo, Jie Wu et al.
FULL PAPERS
129.2, 130.8, 136.4, 137.2, 139.0, 147.6, 155.3 ppm; HRMS (ESI) calcd for
Ed. 2006, 45, 7134–7186; i) D. Enders, C. Grondal, M. R. M. Hꢁttl,
Angew. Chem. 2007, 119, 1590–1601; Angew. Chem. Int. Ed. 2007, 46,
1570–1581; j) L. F. Tietze, G. Brasche, K. Gericke, Domino Reactions
in Organic Synthesis; Wiley-VCH, Weinheim, Germany, 2006; k) L. F.
Tietze, A. Dꢁfert, F. Lotz, L. Sçlter, K. Oum, T. Lenzer, T. Beck, R.
Herbst-Irmer, J. Am. Chem. Soc. 2009, 131, 17879–17884; l) L. F.
Tietze, M. A. Dꢁfert, T. Hungerland, K. Oum, T. Lenzer, Chem. Eur.
J. 2011, 17, 8452–8461.
C26H23NO: 366.1858 (M+H+), found: 366.1855.
N-Methyl-2-(6-methyl-1-phenyl-3-vinylnaphthalen-2-yl)anilineACTHNUTRGNE(UNG 3m)
1H NMR (400 MHz, CDCl3): d=2.36 (s, 3H), 2.65 (s, 3H), 3.32 (s, 1H),
5.13 (d, J=11.2 Hz, 1H), 5.77 (d, J=17.2 Hz, 1H), 6.45–6.55 (m, 3H),
6.75 (d, J=7.2 Hz, 1H), 7.04–7.08 (m, 2H), 7.13–7.24 (m, 5H), 7.31 (d,
J=8.0 Hz, 1H), 7.82 (d, J=8.4 Hz, 1H), 8.12 ppm (s, 1H); 13C NMR
(100 MHz, CDCl3): d=22.1, 30.9, 109.5, 115.0, 116.4, 123.9, 125.2, 125.7,
126.7, 127.3, 127.6, 128.1, 128.3, 128.5, 129.2, 131.0, 131.1, 131.5, 132.9,
134.6, 134.9, 135.8, 135.9, 139.0, 139.6, 146.9 ppm; HRMS (ESI) calcd for
C26H23N: 350.1909 (M+H+), found: 350.1913.
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Chem. Commun. 2011, 47, 11137–11139.
6-Ethyl-5,8-dimethyl-11-phenyl-5H-indenoACTHNUGRTNEUNG[1,2-c]quinoline (4m)
1H NMR (400 MHz, CDCl3): d=1.58 (t, J=7.6 Hz, 3H), 2.47 (s, 3H),
3.54 (q, J=7.6 Hz, 2H), 3.89 (s, 3H), 7.01–7.05 (m, 1H), 7.14 (d, J=
7.6 Hz, 1H); 7.29 (s, 1H), 7.33–7.37 (m, 1H), 7.41–7.44 (m, 1H), 7.49–
7.57 (m, 5H), 7.92 (d, J=8.0 Hz, 1H), 7.99 ppm (d, J=8.0 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=12.6, 21.9, 24.1, 34.3, 115.2, 118.9, 120.8,
122.3, 122.7, 122.9, 125.8, 126.0, 126.4, 126.5, 128.8, 130.8, 133.9, 136.4,
139.1, 143.0, 146.6 ppm; HRMS (ESI) calcd for C26H23N: 350.1909
(M+H+), found: 350.1904.
2-(6-Fluoro-1-phenyl-3-vinylnaphthalen-2-yl)-N-methylaniline (3n)
1H NMR (400 MHz, CDCl3): d=2.66 (s, 3H), 3.30 (s, 1H), 5.18 (d, J=
11.2 Hz, 1H), 5.79 (d, J=17.6 Hz, 1H), 6.46–6.55 (m, 3H), 6.74 (d, J=
7.2 Hz, 1H), 7.05–7.23 (m, 7H), 7.47–7.53 (m, 2H), 8.08 ppm (s, 1H);
13C NMR (100 MHz, CDCl3): d=30.8, 109.6, 110.9 (d, 2JCF =20.0 Hz),
2
4
116.2 (d, JCF =23.9 Hz), 116.4, 123.4 (d, JCF =4.8 Hz), 124.7, 127.0, 127.4,
127.7, 128.4, 129.1, 129.6 (d, 3JCF =9.6 Hz), 129.8, 130.9, 131.0, 134.1(d,
3JCF=9.5 Hz), 134.1, 135.5, 136.7, 138.6, 140.6, 146,9, 160.9 ppm (d, JCF
=
1
246.0 Hz); HRMS (ESI) calcd for C25H20FN: 354.1658 (M+H+), found:
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Y. Wei, K. Mizuno, H. Maeda, Chem. Rev. 2010, 110, 5883–5913;
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3179; j) A. Brandi, S. Cicchi, F. M. Cordero, A. Goti, Chem. Rev.
2003, 103, 1213–1270; k) J. Terao, M. Tomita, S. P. Singh, N. Kambe,
Angew. Chem. 2010, 122, 148–151; Angew. Chem. Int. Ed. 2010, 49,
144–147; l) S. Saito, K. Maeda, R. Yamasaki, T. Kitamura, M. Naka-
gawa, K. Kato, I. Azumaya, H. Masu, Angew. Chem. 2010, 122,
1874–1877; Angew. Chem. Int. Ed. 2010, 49, 1830–1833; m) E. Naka-
mura, S. Yamago, Acc. Chem. Res. 2002, 35, 867–877; n) C. Su, J.
Cao, X. Huang, L. Wu, X. Huang, Chem. Eur. J. 2011, 17, 1579–1585;
o) B.-L. Lu, Y. Wei, M. Shi, Chem. Eur. J. 2010, 16, 10975–10979;
p) B. Hu, J. Zhu, S. Xing, J. Fang, D. Du, Z. Wang, Chem. Eur. J.
2009, 15, 324–327; q) S. Ma, L. Lu, J. Zhang, J. Am. Chem. Soc. 2004,
126, 9645–9660; r) S. Brꢂse, J. Rꢁmper, K. Voigt, S. Albecq, G.
Thurau, R. Villard, B. Waegell, A. de Meijere, Eur. J. Org. Chem.
354.1668.
6-Ethyl-8-fluoro-5-methyl-11-phenyl-5H-indenoACTHNUTRGNE[NUG 1,2-c]quinoline (4n)
1H NMR (400 MHz, CDCl3): d=1.54 (t, J=7.6 Hz, 3H), 3.41 (q, J=
7.6 Hz, 2H), 3.83 (s, 3H), 7.02–7.09 (m, 2H), 7.31–7.35 (m, 1H), 7.39–
7.47 (m, 3H), 7.49–7.55 (m, 4H), 7.72 (dd, J1 =1.6 Hz, J2 =11.2 Hz, 1H),
7.92 ppm (d, J=7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=12.4, 24.0,
2
2
34.3, 107.1 (d, JCF =24.8 Hz), 111.8 (d, JCF =23.9 Hz), 115.4, 118.7, 119.4
(d, 3JCF =9.6 Hz), 123.2 (d, 4JCF =5.8 Hz), 125.5, 126.5, 126.7, 128.5 (d,
3JCF =8.6 Hz), 128.9, 130.8, 136.3, 138.7, 138.7, 148.3, 159.2 ppm (d, JCF
=
1
231.7 Hz); HRMS (ESI) calcd for C25H20FN: 353.1580 (M+), found:
353.1586.
CCDC 857229 and CCDC 857230 contain the supplementary crystallo-
graphic data for for the structures 3a and 4a. These data can be obtained
free of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
Financial support from the National Natural Science Foundation of
China (Nos. 20972030, 21032007) is gratefully acknowledged.
´
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Received: February 8, 2012
Published online: && &&, 0000
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www.chemasianj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!

FULL PAPERS
Domino Reactions
Shaoyu Li, Yong Luo, Xiaocong Wang,
Minjie Guo,* Jie Wu*
&&&& — &&&&
1-Bromo-2-(cyclopropylidenemethyl)-
benzene: A Useful Building Block in
the Palladium-Catalyzed Reaction of
2-Alkynylbenzenamine
This way or that: A novel palladium-
catalyzed domino reaction of 1-bromo-
2-(cyclopropylidenemethyl)benzene
and 2-alkynylbenzenamine is reported,
which generates 2-(naphthalen-2-
c]quinolines via 6-endo and 5-exo cycli-
zation, respectively. The regioselectiv-
ity for the final outcome can be
affected by phosphine and N-heterocy-
clic carbene ligands.
yl)benzenamines and 5H-indenoACTHNUTRGENUG[N 1,2-
Chem. Asian J. 2012, 00, 0 – 0
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
7
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These are not the final page numbers! ÞÞ