Atom-efficient vinylic arylations with triarylbismuths as substoichiometric multicoupling reagents under palladium catalysis

Article abstract of DOI:10.1002/ejoc.200900487

The first atom-efficient arylation of vinylic iodides was achieved by using triarylbismuths as substoichiometric multicoupling reagents under palladium catalysis. Vinylic iodides were efficiently coupled with electronically divergent triarylbismuths to furnish the corresponding arylated products in short reaction times.

Full text of DOI:10.1002/ejoc.200900487

FULL PAPER
DOI: 10.1002/ejoc.200900487
Atom-Efficient Vinylic Arylations with Triarylbismuths as Substoichiometric
Multicoupling Reagents under Palladium Catalysis
[a]
[a]
[a]
Maddali L. N. Rao,* Deepak N. Jadhav, and Varadhachari Venkatesh
Keywords: Arylation / Bismuth / Palladium / Atom efficiency / Cross-coupling
The first atom-efficient arylation of vinylic iodides was
achieved by using triarylbismuths as substoichiometric
multicoupling reagents under palladium catalysis. Vinylic io-
dides were efficiently coupled with electronically divergent
triarylbismuths to furnish the corresponding arylated prod-
ucts in short reaction times.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
Introduction
to a metal center and their own stability in the presence of
[
11]
a metal catalyst. As a result, vinylic iodides are relatively
less studied, as they are more labile in comparison with
other vinylic substrates.
The coupling reaction of organic electrophiles with orga-
nometallic reagents is highly demanding methodology for
natural product synthesis and other applications in organic
Recently, vinylic phophonates were used as more-stable
[
1]
[2]
synthesis. Given their importance in industry, the search
[9e]
coupling partners for Suzuki cross-couplings. As is well
for new nucleophilic[ and electrophilic coupling partners
is inevitable to enrich this chemistry for further applications
in organic synthesis. With a view to develop a new class
of nucleophilic organometallic reagents that can serve in
substoichiometric amounts with respect to electrophilic
partners, we have unraveled novel and atom-efficient reac-
tivity of triarylbismuths[ for C–C bond formation reac-
3]
[4]
known, vinylic systems are an important class of com-
pounds in synthetic organic chemistry. Further, develop-
ment of new coupling reactions with vinylic substrates is
highly desirable due to their key role in the synthesis of
[1]
several natural products. In continuation of our interest
to develop more efficient cross-coupling reactions under rel-
atively mild catalytic conditions, we extended our efforts
towards coupling reactions of vinylic iodides with triaryl-
bismuths. During these efforts we have indeed found that
the cross-coupling of triarylbismuths with vinylic iodides is
efficient under palladium catalysis. We report here for the
first time the palladium-catalyzed arylation of vinylic io-
dides with functionalized triarylbismuths.
5]
[6,7]
tions under palladium catalysis.
Heck arylation is a novel strategy for the synthesis of
substituted alkenes.[8] However, arylation of vinylic sub-
strates through cross-coupling provides a facile approach
for the synthesis of highly substituted alkenes.[ Further,
chemoselective arylation is often a difficult task in the pres-
ence of functionalities that are more labile under metal con-
ditions. So, development of a task-specific, new catalytic
protocol is usually driven by the relative reactivity of the
nucleophilic and electrophilic coupling partners. In cross-
coupling reactions, this amenability thus depends on the
nucleophilic coupling partner and its reactivity under
metal-catalyzed conditions.
9]
Results and Discussion
In our initial optimization efforts, we investigated the
coupling of 4-iodo-1,2-dihydronaphthalene with tri-
phenylbismuth under palladium-catalyzed conditions
In general, vinylic substrates react efficiently under
(Table 1). The coupling reaction studied under different
metal-catalyzed conditions.[
9,10]
However, the reactivity pro-
conditions revealed that cesium carbonate in N,N-dimethyl-
acetamide (DMA) was the right combination to afford
good cross-coupling conversion to give 4-phenyl-1,2-dihy-
dronaphthalene in short reaction time (Table 1, Entry 9).
Other carbonates of sodium, potassium, and barium did
not produce respectable conversion in DMA solvent
files of these substrates vary depending on the nature of
the leaving groups, such as triflates, bromides, iodides, and
phosphonates. This variance in reactivity usually depends
on the relative ability of these substrates to oxidatively add
[
a] Department of Chemistry, Indian Institute of Technology Kan-
(Table 1, Entries 1–3). Whereas cesium carbonate as base in
pur,
Kanpur – 208 016, India
N-methyl-2-pyrrolidone (NMP) and N,N-dimethylform-
amide (DMF) solvents furnished reasonable conversion, the
reactivity was poor in THF and 1,4-dioxane solvents
(Table 1, Entries 4–7). The coupling reaction carried out at
Fax: +91-512-259-7532
E-mail: maddali@iitk.ac.in
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.200900487.
4300
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 4300–4306

Atom-Efficient Vinylic Arylations with Triarylbismuths under Pd Catalysis
8
0 °C did not improve the conversion (Table 1, Entry 8). 4-iodo-1,2-dihydronaphthalene under the established proto-
Further, loading of different amounts of base proved that col. The heteroarylation carried out with trithiophen-2-yl-
.2 equiv. is required to obtain better product conversion bismuth also furnished 2-(3,4-dihydronaphthalen-1-yl)thio-
Table 1, Entries 9–13). In the absence of cross-coupling phene (2m) as the product in high yield (Table 2, Entry 13).
1
(
with the vinyl iodide, we have invariably observed the for-
mation of biphenyl as a homocoupling side product from Table 2. Vinylic arylation with different triarylbismuths.[a,b]
triphenylbismuth in our coupling reactions. It is known that
triarylbismuths usually form homocoupling biaryls under
catalytic palladium conditions.[12a,12b] However, the amount
of biphenyl varied with respect to cross-coupling conver-
sion. Under the optimized protocol (Table 1, Entry 9), bi-
phenyl was formed in 12% isolated yield along with 72%
isolated yield of the cross-coupling product.
Table 1. Screening conditions.[a]
Entry
Base (equiv.)
Solvent
Conversion [%][b]
1
2
3
4
5
6
7
8
9
K
Na
Ba
2
CO
CO
CO
3
(1.21)
(1.21)
(1.21)
(1.21)
(1.21)
(1.21)
(1.21)
(1.21)
(1.21)
(0.91)
(0.61)
(0.30)
DMA
DMA
DMA
DMF
NMP
Dioxane
THF
DMA
DMA
DMA
DMA
DMA
DMA
29
48
2
3
2
3
13
88 (63)[
c]
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
70
8
2
68[
90 (72)
70
d]
10
11
12
13
71
57
7
None
[
(
a] Reaction conditions: Vinyl iodide (1 equiv.), BiPh
3
0.303 equiv.), PdCl (PPh (0.0273 equiv.), base (1.21 equiv.), sol-
2
3 2
)
vent (3 mL), 60 °C. [b] Conversions are based on GC analysis.
[
c] Isolated yields are given in parenthesis.[ [d] At 80 °C.
13]
Thus, we have successfully driven the reaction towards
cross-coupling and obtained the arylation of vinyl iodides
with cesium carbonate in DMA at 60 °C for 1 h as opti-
mized conditions with the PdCl (PPh ) catalytic system
2
3 2
(Table 1, Entry 9). After obtaining the effective arylation of
vinylic iodides with triphenylbismuth, it was of interest to
further study the cross-coupling ability of diverse triarylbis-
muths with 4-iodo-1,2-dihydronaphthalene under the above
established protocol.
The arylations carried out with various functionalized
triarylbismuths were very successful and we obtained high
yields of the corresponding 4-aryl-1,2-dihydronaphthalenes
through facile arylation reaction of 4-iodo-1,2-dihydrona-
phthalene (Table 2). Thus, a diverse range of functionalized
triarylbismuths reacted smoothly under the present palla-
[
a] Reaction conditions: 4-Iodo-1,2-dihydronaphthalene (1 equiv.),
dium protocol. In elaboration, triarylbismuths with func- BiPh3 (0.303 equiv.), PdCl (PPh ) (0.0273 equiv.), Cs CO
tional groups such as halide and formyl groups reacted (1.21 equiv.), DMA (3 mL), 60 °C, 1 h. [b] Isolated yields.
2
3 2
2
3
[
13]
chemoselectively. Other triarylbismuths substituted with
methyl, methoxy, ethoxy, or acetyl groups also reacted ef-
The functionalized 4-aryl-1,2-dihydronaphthalene prod-
ficiently. This study clearly established the striking reactivity ucts that are obtained in this coupling reaction are useful
of electronically divergent triarylbismuths for arylations of precursors for the synthesis of substituted naphthalenes and
Eur. J. Org. Chem. 2009, 4300–4306
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4301

M. L. N. Rao, D. N. Jadhav, V. Venkatesh
FULL PAPER
also other derivatives.[14] Earlier, these compounds were Table 4. Coupling of α-iodostyrenes.[a,b]
synthesized either through Suzuki-type cross-coupling reac-
tions involving the corresponding vinylic triflate or the
Grignard addition reaction to α-tetralone followed by acid-
mediated elimination.[
14a,14b]
The present method of ob-
taining 4-aryl-1,2-dihydronaphthalenes through the cou-
pling reaction of triarylbismuths with 4-iodo-1,2-dihy-
dronaphthalene has a definitive advantage in terms of
atom-efficient coupling ability of triarylbismuths and also
short reaction times. It is to note that in these reactions
triarylbismuths were employed in substoichiometric
amounts with respect to the vinylic iodide.
The efficient reactivity that was observed with 4-iodo-
1,2-dihydronaphthalene led us to further explore the cou-
pling reactivity of triarylbismuths with 1-iodo-cyclohexenes
and 1-iodo-cyclooctene under the present protocol. As
summarized in Table 3, these reactions provided moderate
[
9g]
to good yields of the corresponding arylated products.
Table 3. Arylations of cycloalkenyl iodides.[a–c]
[
(
a] Reaction conditions: Vinylic iodide (1 equiv.), BiPh
3
0.303 equiv.), PdCl (PPh (0.0273 equiv.), Cs CO (1.21 equiv.),
2
3
)
2
2
3
[a] Reaction conditions: Vinylic iodide (1 equiv.), BiPh3
(0.303 equiv.), PdCl (PPh ) (0.0273 equiv.), Cs CO (1.21 equiv.),
DMA (3 mL), 60 °C, 1 h. [b] Isolated yields.
[13]
DMA (3 mL), 60 °C, 1 h. [b] Isolated yields. [c] Minor amounts
of alkenyl iodides remained unreacted after 1 h, as 0.1 equiv. in
excess was employed for the reactions.
2
3 2
2
3
[13]
Next, we have focused on arylation studies of α-iodostyr-
Thus, the arylation of α-iodostyrenes with triarylbis-
enes with triarylbismuths for the synthesis of 1,1-diarylethy- muths was obtained under relatively mild and faster reac-
lene derivatives. The coupling reactions of various function- tion conditions in comparison with the known reactivity of
alized α-iodostyrenes were studied with triarylbismuths as α-bromostyrenes with arylboronic acids. The cross-coupling
illustrated in Table 4. In general, these coupling reactions of α-bromostyrenes with arylboronic acids was carried out
afforded the corresponding 1,1-diaryl products in high at 130 °C for longer reaction times under palladium cataly-
[
10a]
yields. Further, the reaction of α-iodostyrene containing a sis.
p-bromo substituent reacted chemoselectively at the vinylic
The 1,1-diarylalkenes obtained in the above coupling are
terminus (Table 4, Entries 7–9). Coupling reactions carried useful precursors for the synthesis of biologically active
out with the corresponding naphthyl derivatives, that is, 2- compounds[15] and for other useful synthetic transforma-
(
1-iodovinyl)naphthalene, also showed good reactivity, fur- tions. The Wittig olefination of ketones or Grignard ad-
nishing the corresponding arylated products in high yields dition to carbonyl compounds and subsequent elimination
Table 4, Entries 10–12). procedures were reported for the synthesis of these com-
(
4302
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 4300–4306

Atom-Efficient Vinylic Arylations with Triarylbismuths under Pd Catalysis
pounds, in addition to cross-coupling methods. The present spectrophotometer. High-resolution mass spectra were recorded
using electrospray (ES) technique with a Waters HAB213 Q-Tof
method of obtaining these compounds through arylation of
α-iodostyrenes with triarylbismuths provides easy access to
the functionalized unsymmetrical 1,1-diarylalkenes in an
[5]
Premier Micromass spectrometer. Triarylbismuths and vinyl io-
dides[ were prepared according to literature procedures.
16]
atom-efficient manner.
Representative Procedure: A hot, oven-dried Schlenk tube was
Similar to earlier couplings,[
1e,12a,12c]
the reaction mecha- charged with 4-iodo-1,2-dihydronaphthalene (211 mg, 0.825 mmol,
1
equiv.), Ph
(15.8 mg, 0.0225 mmol, 0.0273 equiv.), Cs
.21 equiv.), and dry DMA (3 mL) under a nitrogen atmosphere.
3
Bi (110 mg, 0.25 mmol, 0.303 equiv.), PdCl
2 3 2
(PPh )
nism may involve the initial oxidative addition of alkenyl
0
[11]
2
CO (326 mg, 1.0 mmol,
3
iodide to the Pd center
followed by a transmetalation
1
step involving triarylbismuths, which subsequently fur-
nishes the cross-coupling product through reductive elimi-
The contents were stirred at 60 °C in an oil bath for 1 h. After the
reaction was complete, the contents were cooled to room tempera-
ture, acidified with dilute HCl (10 mL), and then extracted with
ethyl acetate (15 mLϫ3). The combined organic extract was fur-
ther washed with water (2ϫ15 mL) and brine (15 mL) and dried
[
12a]
nation.
sideration the higher reactivity of alkenyl iodides towards
The proposed mechanism also takes into con-
0
[11]
the Pd center.
Additionally, the rationale is also based
on the known cross-coupling reactivity of organobismuth with anhydrous MgSO . The solvent was evaporated under reduced
4
[
12c]
compounds
mechanism involving other organometallic reagents. Af- raphy (petroleum ether) to obtain 4-phenyl-1,2-dihydronaphthalene
and the general cross-coupling reaction pressure. The crude product was purified by column chromatog-
[
1e]
(
2a) as a colorless liquid. Yield: 111 mg (72%). The yield was calcu-
lated with respect to the reactivity of 0.9 equiv. of Bi-Ph from tri-
phenylbismuth (0.3 equiv.) used.
ter initial involvement of triarylbismuth in transmetalation,
the subsequent transmetalations would involve reactions
with di- or monoarylbismuth reagents. This way, all the
three aryl groups would efficiently participate as multicou- For all the reactions, yields were calculated considering the three
aryl groups from triarylbismuth for cross-coupling. Thus, 0.3 equiv.
of BiAr is equal to 0.9 equiv. of Bi-Ar, and 0.9 equiv. of cross-
3
coupling product (0.75 mmol) corresponds to 100% yield.
pling reagents. Also, the formation of biaryl as a side prod-
uct indicates initial oxidative addition of triarylbismuth to
0
Pd . So, the coupling mechanism also goes through further
transmetalation with vinylic iodide and subsequent re- 4-Phenyl-1,2-dihydronaphthalene (2a):[ Colorless liquid (111 mg,
9b]
1
ductive elimination to the product. However, given the reac- 72%). H NMR (400 MHz, CDCl
3
): δ = 7.04–7.42 (m, 9 H, Ar-
0
H), 6.13 (t, J = 4.6 Hz, 1 H, 3-H), 2.90 (t, J = 7.9 Hz, 2 H, 1-H),
.43–2.48 (m, 2 H, 2-H) ppm. C NMR (100 MHz, CDCl ): δ =
3
40.7, 139.8, 136.7, 135.0, 128.7, 128.1, 127.6, 127.5, 127.0, 126.9,
26.1, 125.4, 28.2, 23.5 ppm. IR (film): ν˜ = 3055, 3023, 2931, 2882,
829, 1598, 1486, 1443, 1040, 1020, 786, 756, 737 cm . HRMS
ESI): calcd. for C16
tivity of vinylic iodides with the Pd center, it is most likely
1
3
2
1
1
2
initiated through its oxidative addition as given in the first
option. In any case, more specific studies are needed to
understand the mechanism clearly.
–
1
(
H
15 [M + H]+ 207.1174; found 207.1178.
4
-(4-Methylphenyl)-1,2-dihydronaphthalene (2b): Colorless liquid
Conclusions
1
(
3
127 mg, 77%). H NMR (400 MHz, CDCl ): δ = 7.01–7.26 (m, 8
We have demonstrated efficient vinylic arylations using H, Ar-H), 6.07 (t, J = 4.6 Hz, 1 H, 3-H), 2.85 (t, J = 7.9 Hz, 2 H,
1
3
triarylbismuths under palladium catalytic conditions. The 1-H), 2.36–2.44 (m, 5 H, 2-H and CH
3
) ppm. C NMR (100 MHz,
novel coupling reactivity of vinylic iodides with triarylbis- CDCl
3
): δ = 139.7, 137.8, 136.7, 136.6, 135.2, 128.8, 128.6, 127.4,
27.1, 126.8, 126.1, 125.4, 28.3, 23.5, 21.1 ppm. IR (film): ν˜ = 2951,
922, 2852, 2835, 1654, 1606, 1509, 1290, 1249, 1180, 1149, 1116,
030, 900, 834 cm . HRMS (ESI): calcd. for C17
21.1330; found 221.1331.
1
2
1
2
muths provided easy access to 4-aryl-1,2-dihydronaphtha-
lenes, 1-aryl-substituted cycloalkenes, and 1,1-diarylalkenes
in good to high yields. The substoichiometric loadings of
the triarylbismuth reagents with respect to the vinylic io-
dides under relatively mild conditions and short reaction
times successfully demonstrated the high and efficient reac-
tivity of triarylbismuths in carbon–carbon bond-forming
reactions under palladium catalysis. Further, this is the first
time that a cross-coupling study of triarylbismuths has been
combined with vinylic iodides under palladium catalysis.
–
1
+
H17 [M + H]
4
-(3,4-Dihydronaphthalen-1-yl)phenyl methyl ether (2c): Pale-yellow
1
liquid (114 mg, 64%). H NMR (400 MHz, CDCl
8.8 Hz, 2 H, Ar-H), 7.06–7.20 (m, 3 H, Ar-H), 7.00 (d, J =
.3 Hz, 1 H, Ar-H), 6.88 (d, J = 8.8 Hz, 2 H, Ar-H), 6.02 (t, J =
.6 Hz, 1 H, 3-H), 3.80 (s, 3 H, -OCH ), 2.81 (t, J = 7.9 Hz, 2 H,
-H), 2.33–2.38 (m, 2 H, 2-H) ppm. C NMR (100 MHz, CDCl ):
3
δ = 158.7, 139.2, 136.8, 135.2, 133.1, 129.7, 127.4, 126.8, 126.1,
3
): δ = 7.25 (d, J
=
7
4
1
3
1
3
1
1
25.3, 113.5, 55.2, 28.3, 23.4 ppm. IR (film): ν˜ = 3017, 2932, 2832,
–
1
606, 1509, 1487, 1288, 1245, 1176, 1034, 820, 767, 740 cm .
+
Experimental Section
17 17
HRMS (ESI): calcd. for C H O [M + H] 237.1279; found
237.1279.
General: All reactions were performed under a nitrogen atmosphere
by using Schlenk techniques. Standard procedures were followed to
purify solvents prior to use. Thin-layer chromatography and gas
chromatography (Clarus 500, Perkin–Elmer) was used to analyze
the crude reaction mixtures. Crude products were purified by col-
umn chromatography (230–400 mesh silica gel). Melting points re-
4-(3,4-Dihydronaphthalen-1-yl)phenyl ethyl ether (2d): Colorless li-
quid (163 mg, 87%). H NMR (400 MHz, CDCl ): δ = 7.28–7.31
3
1
(m, 2 H, Ar-H), 7.06–7.24 (m, 4 H, Ar-H), 6.93–6.95 (m, 2 H, Ar-
H), 6.08 (t, J = 4.6 Hz, 1 H, 3-H), 4.10 (q, J = 7.0 Hz, 2 H,
OCH
H), 1.48 (t, J = 7.0 Hz, 3 H, OCH
(100 MHz, CDCl ): δ = 158.1, 139.3, 136.8, 135.2, 133.0, 129.7,
2 3
CH ), 2.88 (t, J = 7.9 Hz, 2 H, 1-H), 2.40–2.45 (m, 2 H, 2-
1
13
13
ported are uncorrected. H and C NMR spectra were recorded
with a JEOL-Lambda 400 MHz spectrometer in CDCl as solvent
and the chemical shift (δ) values are expressed in parts per million
ppm). IR spectra were recorded with a Bruker vector 22-FTIR
2 3
CH ) ppm. C NMR
3
3
127.4, 126.8, 126.1, 125.3, 114.1, 63.4, 28.3, 23.4, 14.8 ppm. IR
(film): ν˜ = 3061, 2978, 2932, 1721, 1654, 1600, 1509, 1247, 1045,
(
Eur. J. Org. Chem. 2009, 4300–4306
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4303

M. L. N. Rao, D. N. Jadhav, V. Venkatesh
FULL PAPER
–
1
9
22, 824, 758, 697 cm . HRMS (ESI): calcd. for C18
H
19O [M + (m, 4 H, Ar-H), 7.45–7.50 (m, 3 H, Ar-H), 7.01–7.24 (m, 4 H, Ar-
+
H] 251.1436; found 251.1338.
H), 6.21 (t, J = 4.6 Hz, 1 H, 3-H), 2.89 (t, J = 7.9 Hz, 2 H, 1-H),
1
3
2
.43–2.48 (m, 2 H, 2-H) ppm. C NMR (100 MHz, CDCl
139.9, 138.3, 136.8, 135.1, 133.5, 132.6, 128.1, 127.9, 127.5, 127.3,
27.0, 126.2, 126.0, 125.6, 125.5, 28.3, 23.6 ppm. IR (KBr): ν˜ =
3052, 3015, 2932, 2879, 2827, 1593, 1481, 1446, 1426, 1270, 1188,
3
): δ =
4
-(4-Fluorophenyl)-1,2-dihydronaphthalene (2e): Colorless liquid
1
(146 mg, 87%). H NMR (400 MHz, CDCl
3
): δ = 6.89–7.31 (m, 8
1
H, Ar-H), 6.04 (t, J = 4.6 Hz, 1 H, 3-H), 2.83 (t, J = 7.9 Hz, 2 H,
13
1
-H), 2.36–2.41 (m, 2 H, 2-H) ppm. C NMR (100 MHz, CDCl
3
):
–
1
1
3
1155, 1125, 1041, 859, 823, 800, 769, 742, 659 cm . HRMS (ESI):
δ = 162.1 [d, JC,F = 243.5 Hz], 138.9, 136.7, 134.9, 130.2 (d, JC,F
calcd. for C H [M + H]+ 257.1330; found 257.1337.
2
=
7.4 Hz), 127.7, 127.5, 127.0, 126.2, 125.2, 115.0 (d,
J
C,F
=
20 17
2
1
1.4 Hz), 28.2, 23.4 ppm. IR (film): ν˜ = 3067, 2928, 1717, 1663,
3
,4-Dihydro-1,2Ј-binaphthalen-6Ј-yl methyl ether (2l): Pale-yellow
–1
598, 1505, 1227, 1158, 1054, 1014, 834, 783, 757 cm . HRMS
1
solid (168 mg, 78%). M.p. 114–116 °C. H NMR (400 MHz,
CDCl ): δ = 7.62–7.67 (m, 3 H, Ar-H), 7.35 (d, J = 8.5 Hz, 1 H,
Ar-H), 6.94–7.16 (m, 6 H, Ar-H), 6.10 (t, J = 4.6 Hz, 1 H, 3-H),
3.85 (s, 3 H, OCH ), 2.80 (t, J = 7.9 Hz, 2 H, 1-H), 2.33–2.38 (m,
+
(ESI): calcd. for C16
H
14F [M + H] 225.1080; found 225.1085.
3
4-(4-Chlorophenyl)-1,2-dihydronaphthalene (2f): Pale-yellow liquid
1
(126 mg, 70%). H NMR (400 MHz, CDCl
3
): δ = 7.04–7.30 (m, 7
3
3
1
H, Ar-H), 6.90 (d, J = 7.6 Hz, 1 H, Ar-H), 6.02 (t, J = 4.6 Hz, 1
H, 3-H), 2.79 (t, J = 7.9 Hz, 2 H, 1-H), 2.32–2.37 (m, 2 H, 2-H)
3
2 H, 2-H) ppm. C NMR (100 MHz, CDCl ): δ = 157.6, 139.8,
136.8, 136.1, 135.2, 133.7, 129.4, 129.0, 127.7, 127.5, 127.0, 126.9,
126.4, 126.2, 125.5, 118.8, 105.7, 55.3, 28.3, 23.6 ppm. IR (KBr): ν˜
= 3054, 3021, 2945, 2878, 2828, 1627, 1598, 1459, 1270, 1249, 1160,
1028, 988, 967, 945, 887, 854, 830, 813, 779, 767, 742, 675,
622 cm . HRMS (ESI): calcd. for C21
found 287.1438.
ppm. 13C NMR (100 MHz, CDCl
): δ = 139.2, 138.9, 136.7, 134.7,
32.9, 130.0, 128.4, 128.0, 127.6, 127.1, 126.2, 125.2, 28.1,
3.4 ppm. IR (film): ν˜ = 3062, 3025, 2934, 1717, 1662, 1587, 1487,
3
1
2
1
–1
–1
H
19O [M + H]+ 287.1436;
400, 1266, 1091, 1014, 822, 763, 738 cm . HRMS (ESI): calcd.
14Cl [M + H]+ 241.0784; found 241.0782.
-(3,4-Dihydronaphthalen-1-yl)phenyl methyl ether (2g): Pale-yellow
for C16
H
3
2-(3,4-Dihydronaphthalen-1-yl)thiophene (2m): Pale-yellow solid
1
1
liquid (151 mg, 85%). H NMR (400 MHz, CDCl
3
): δ = 6.85–7.29 (134 mg, 84%). M.p. 70–72 °C. H NMR (400 MHz, CDCl ): δ =
3
(
2
m, 8 H, Ar-H), 6.08 (t, J = 4.6 Hz, 1 H, 3-H), 3.79 (s, 3 H, OCH
3
), 7.39–7.41 (m, 1 H, Ar-H), 7.19–7.30 (m, 4 H, Ar-H), 7.06–7.11 (m,
.84 (t, J = 7.9 Hz, 2 H, 1-H), 2.36–2.41 (m, 2 H, 2-H) ppm. 13C
): δ = 159.4, 142.2, 139.7, 136.7, 134.9,
29.1, 127.6, 127.5, 126.9, 126.2, 125.4, 121.2, 114.1, 112.7, 55.2,
8.2, 23.4 ppm. IR (film): ν˜ = 3023, 2935, 2833, 1662, 1598, 1485,
2 H, Ar-H), 6.33 (t, J = 4.8 Hz, 1 H, 3-H), 2.87 (t, J = 7.9 Hz, 2
NMR (100 MHz, CDCl
3
H, 1-H), 2.41–2.46 (m, 2 H, 2-H) ppm. 13C NMR (100 MHz,
1
2
1
CDCl ): δ = 142.5, 136.6, 134.4, 132.8, 129.1, 127.5, 127.2, 127.0,
126.3, 125.5, 125.2, 124.0, 28.0, 23.4 ppm. IR (KBr): ν = 3098,
3
˜
–1
289, 1044, 782, 759, 740, 701 cm . HRMS (ESI): calcd. for 3060, 3027, 2926, 2880, 2825, 1477, 1428, 1272, 1095, 1021, 822,
C
17
H
17O [M + H]+ 237.1279; found 237.1276.
771, 740, 709, 618 cm . HRMS (ESI): calcd. for C H S [M +
H] 213.0738; found 213.0735.
–1
1
4
13
+
4-(3-Methylphenyl)-1,2-dihydronaphthalene (2h): Pale-yellow liquid
1
(
137 mg, 83%). H NMR (400 MHz, CDCl
H, Ar-H), 6.15 (t, J = 4.8 Hz, 1 H, 3-H), 2.93 (t, J = 7.8 Hz, 2 H,
-H), 2.45–2.50 (m, 5 H, 1-H and CH
) ppm. 13C NMR (100 MHz,
CDCl ): δ = 140.7, 139.9, 137.7, 136.7, 135.1, 129.4, 128.0, 127.7,
27.4, 127.3, 126.8, 126.1, 125.8, 125.4, 28.2, 23.4, 21.4 ppm. IR
film): ν˜ = 3023, 2927, 1662, 1602, 1485, 1451, 1273, 1042, 787,
3
): δ = 7.08–7.48 (m, 8
[9b]
Cyclohex-1-en-1-ylbenzene (3a):
Colorless liquid (68 mg, 57%).
1
H NMR (400 MHz, CDCl
.07 (m, 1 H, 2-H), 2.32–2.37 (m, 2 H, CH
CH ), 1.69–1.75 (m, 2 H, CH ), 1.57–1.64 (m, 2 H, CH
NMR (100 MHz, CDCl ): δ = 142.7, 136.6, 128.1, 126.4, 124.9,
24.7, 27.4, 25.8, 23.0, 22.1 ppm. IR (film): ν˜ = 3028, 2927, 2856,
3
): δ = 7.12–7.33 (m, 5 H, Ar-H), 6.04–
1
3
6
2
), 2.12–2.17 (m, 2 H,
3
13
2
2
2
) ppm.
C
1
(
3
1
1
–1
17 [M + H]+
7
2
59, 739, 705 cm . HRMS (ESI): calcd. for C17
21.1330; found 221.1330.
H
–1
642, 1598, 1493, 1444, 1075, 1033, 758, 741, 693 cm . HRMS
+
(
ESI): calcd. for C12
H
14 [M] 158.1096; found 158.1096.
1
-[4-(3,4-Dihydronaphthalen-1-yl)phenyl]ethanone (2i): Pale-yellow
17a]
(
4-tert-Butylcyclohex-1-en-1-yl)benzene (3b):[
Colorless liquid
1
3
solid (149 mg, 80%). M.p. 84–86 °C. H NMR (400 MHz, CDCl ):
δ = 8.00 (d, J = 7.8 Hz, 2 H, Ar-H), 7.48 (d, J = 8.0 Hz, 2 H, Ar-
H), 7.12–7.25 (m, 3 H, Ar-H), 6.98 (d, J = 7.6 Hz, 1 H, Ar-H),
1
(
97 mg, 60%). H NMR (400 MHz, CDCl
3
): δ = 7.14–7.33 (m, 5
H, Ar-H), 6.05–6.07 (m, 1 H, 2-H), 2.37–2.44 (m, 2 H, CH
.20 (m, 1 H, 4-H), 1.90–1.94 (m, 2 H, CH ), 1.22–1.30 (m, 2 H,
CH ): δ =
), 0.85 (s, 9 H, tBu) ppm. 13C NMR (100 MHz, CDCl
2
), 2.16–
2
2
6
3
.19 (t, J = 4.6 Hz, 1 H, 3-H), 2.89 (t, J = 7.9 Hz, 2 H, 1-H), 2.66 (s,
H, COCH
), 2.43–2.50 (m, 2 H, 2-H) ppm. 13C NMR (100 MHz,
): δ = 197.7, 145.8, 139.2, 136.7, 135.9, 134.4, 128.9, 128.8,
28.4, 128.3, 127.6, 127.3, 126.3, 125.2, 28.1, 26.5, 23.5 ppm. IR
KBr): ν˜ = 3021, 2943, 2885, 2831, 1675, 1601, 1355, 1308, 1267,
2
3
3
1
2
1
2
42.2 136.4, 128.1, 126.4, 124.9, 43.8, 32.2, 28.8, 27.4, 27.2,
4.4 ppm. IR (film): ν˜ = 3060, 2957, 2869, 1722, 1688, 1449, 1366,
018, 757, 699 cm . HRMS (ESI): calcd. for C16
14.1722; found 214.1725.
CDCl
1
(
3
–
1
+
H22 [M]
–1
1
185, 1111, 1037, 953, 787, 770, 748, 692, 644 cm . HRMS (ESI):
+
[17b]
calcd. for C18
H
17O [M + H] 249.1279; found 249.1275.
1-(4-tert-Butylcyclohex-1-en-1-yl)-4-methylbenzene (3c):
solid (105 mg, 61%). M.p. 67–69 °C. H NMR (400 MHz, CDCl
White
1
3
):
4
-(3,4-Dihydronaphthalen-1-yl)benzaldehyde (2j): White solid
1
δ = 7.28 (d, J = 8.1 Hz, 2 H, Ar-H), 7.11 (d, J = 8.1 Hz, 2 H, Ar-
H), 6.09 (t, J = 2.7 Hz, 1 H, 2-H), 2.22–2.54 (m, 6 H, CH ,CH
and 4-H), 1.93–2.00 (m, 2 H, CH ), 1.28–1.40 (m, 2 H, CH ), 0.91
s, 9 H, tBu) ppm. 13C NMR (100 MHz, CDCl
): δ = 139.4, 136.1,
136.0, 128.8, 124.8, 124.0, 43.8, 32.2, 28.8, 27.4, 27.2, 24.4,
(135 mg, 77%). M.p. 53–55 °C. H NMR (400 MHz, CDCl
3
): δ =
3
2
,
1
8
1
0.02 (s, 1 H, CHO), 7.88 (d, J = 8.3 Hz, 2 H, Ar-H), 7.51 (d, J =
.0 Hz, 2 H, Ar-H), 7.08–7.21 (m, 3 H, Ar-H), 6.93 (d, J = 7.3 Hz,
H, Ar-H), 6.17 (t, J = 4.6 Hz, 1 H, 3-H), 2.84 (t, J = 7.9 Hz, 2
2
2
(
3
13
H, 1-H), 2.39–2-45 (m, 2 H, 2-H) ppm. C NMR (100 MHz,
CDCl ): δ = 191.8, 147.3, 139.2, 136.7, 135.3 134.2, 129.7, 129.3,
27.7, 127.4, 126.3, 125.2, 28.1, 23.5 ppm. IR (KBr): ν˜ = 3023,
927, 2851, 2829, 1699, 1602, 1209, 1167, 1092, 1019, 827, 811,
2
1
C
1.0 ppm. IR (KBr): ν˜ = 3031, 2959, 2870, 1644, 1511, 1467, 1284,
256, 1180, 1038, 829, 802, 775 cm . HRMS (ESI): calcd. for
3
–
1
1
2
7
+
17
H
24 [M] 228.1878; found 228.1876.
–
1
67, 740, 701, 669 cm . HRMS (ESI): calcd. for C17
H15O [M +
(3d):[17b]
1
-(4-tert-Butylcyclohex-1-en-1-yl)-4-methoxybenzene
+
H] 235.1123; found 235.1126.
1
White solid (119 mg, 65%). M.p. 78–80 °C. H NMR (400 MHz,
CDCl ): δ = 7.32 (d, J = 8.6 Hz, 2 H, Ar-H), 6.85 (d, J = 8.8 Hz,
): δ = 7.83–7.86 2 H, Ar-H), 6.04 (t, J = 2.8 Hz, 1 H, 2-H), 3.80 (s, 3 H, OCH ),
3,4-Dihydro-1,2Ј-binaphthalene (2k): Pale-yellow solid (163 mg,
3
1
85%). M.p. 52–53 °C. H NMR (400 MHz, CDCl
3
3
4304
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 4300–4306

Atom-Efficient Vinylic Arylations with Triarylbismuths under Pd Catalysis
2
1
.21–2.51 (m, 3 H, CH
.38 (m, 2 H, CH
), 0.91 (s, 9 H, tBu) ppm. 13C NMR (100 MHz,
): δ = 158.4, 135.7, 134.9, 125.8, 123.2, 113.5, 55.2, 43.8,
2.2, 28.9, 27.4, 27.2, 27.2, 24.4 ppm. IR (KBr): ν˜ = 3023, 2949,
2
and 4-H), 1.92–1.99 (m, 2 H, CH
2
), 1.24–
7.21–7.28 (m, 4 H, Ar-H), 7.12 (d, J = 7.8 Hz, 2 H, Ar-H), 6.83
(d, J = 8.3 Hz, 2 H, Ar-H), 5.33 (s, 1 H, =CH ), 5.30 (s, 1 H,
=CH ), 4.03 (q, J = 7.1 Hz, 2 H, OCH CH ), 2.35 (s, 3 H, CH ),
1.41 (t, J = 7.0 Hz, 3 H, OCH CH ) ppm. C NMR (100 MHz,
867, 1644, 1512, 1390, 1362, 1258, 1208, 848, 817, 799, 773 cm . CDCl ): δ = 158.6, 149.3, 138.9, 137.3, 133.9, 129.3, 128.7, 128.1,
25O [M + H] 245.1905; found 114.0, 112.1, 63.4, 21.1, 14.8 ppm. IR (KBr): ν˜ = 3025, 2978, 2923,
2
2
CDCl
3
2
3
2
2
3
1
3
3
2
3
–
1
3
+
HRMS (ESI): calcd. for C17
2
H
–
1
45.1906.
2853, 1651, 1605, 1510, 1245, 1176, 1090, 1019, 923, 890, 760 cm .
+
-Phenylcyclooctene (3e):[17a] Colorless liquid (102 mg, 73%). 1
HRMS (ESI): calcd. for C H O [M + H] 239.1436; found
1
H
17 19
239.1436.
3
NMR (400 MHz, CDCl ): δ = 7.09–7.39 (m, 5 H, Ar-H), 5.89–5.98
(
1
m, 1 H, 2-H), 2.52–2.62 (m, 2 H, CH
2
), 2.17–2.25 (m, 2 H, CH
2
),
):
1
-[1-(4-Bromophenyl)vinyl]-3-methoxybenzene (4g): Pale-yellow li-
.47–1.58 (m, 8 H, 4ϫCH
2
) ppm. 13C NMR (100 MHz, CDCl
3
1
quid (178 mg, 82%). H NMR (400 MHz, CDCl
3
): δ = 7.45–7.48
δ = 143.2, 140.2, 128.1, 127.9, 126.3, 125.7, 29.9, 29.4, 28.4, 27.4,
(
m, 2 H, Ar-H), 7.21–7.29 (m, 3 H, Ar-H), 6.85–6.91 (m, 3 H, Ar-
2
1
1
6.9, 26.1 ppm. IR (film): ν˜ = 3023, 2921, 2850, 1597, 1491, 1468,
H), 5.48 (d, J = 1.0 Hz, 1 H, =CH
2
), 5.46 (s, 1 H, =CH
): δ = 159.5, 148.9,
42.4, 140.2, 131.2, 129.8, 129.2, 121.7, 120.7, 114.8, 113.9, 113.3,
2
), 3.80 (s,
–1
H
18 [M]+
446, 1020, 757, 695 cm . HRMS (ESI): calcd. for C14
86.1409; found 186.1402.
) ppm. 13C NMR (100 MHz, CDCl
3
1
H, OCH
3
3
-Methoxy-3-(1-phenylvinyl)benzene (4a):[17c] Pale-yellow liquid 55.2 ppm. IR (film): ν˜ = 3002, 2933, 2834, 1660, 1585, 1486, 1462,
1
1
–1
(115 mg, 73%). H NMR (400 MHz, CDCl
3
): δ = 7.22–7.32 (m, 6
), 3.78 (s,
) ppm. 13C NMR (100 MHz, CDCl
H, OCH ): δ = 159.4, 149.9,
3 3
1322, 1285, 1236, 1177, 1072, 1046, 834, 785, 752 cm . HRMS
(ESI): calcd. for C15
and 291.0208; found 289.0229 and 291.0060.
+
H, Ar-H), 6.85–6.92 (m, 3 H, Ar-H), 5.45 (s, 2 H, =CH
2
H
14BrO [M + H]+ and [M + H + 2] 289.0228
3
1
5
1
42.9, 141.3, 129.0, 128.2, 128.1, 127.7, 120.8, 114.3, 113.9, 113.1,
1-Bromo-4-[1-(4-methoxyphenyl)vinyl]benzene (4h): White solid
5.2 ppm. IR (film): ν˜ = 3055, 2933, 2833, 1576, 1487, 1327, 1284,
1
(
7
2
169 mg, 78%). M.p. 82–84 °C. H NMR (400 MHz, CDCl
3
): δ =
.45–7.47 (m, 2 H, Ar-H), 7.20–7.26 (m, 4 H, Ar-H), 6.86–6.88 (m,
H, Ar-H), 5.41 (s, 1 H, =CH ), 5.35 (s, 1 H, =CH ), 3.83 (s, 3 H,
–1
239, 1182, 1046, 897, 777, 698 cm . HRMS (ESI): calcd. for
15O [M + H]+ 211.1123; found 211.1128.
15
C H
2
2
1
-Methoxy-4-(1-phenylvinyl)benzene (4b):[10a] Pale-yellow solid
3 3
OCH ) ppm. C NMR (100 MHz, CDCl ): δ = 159.5, 148.5, 140.7,
13
1
(101 mg, 64%). M.p. 61–63 °C. H NMR (400 MHz, CDCl
3
): δ =
133.4, 131.2, 129.9, 129.3, 121.6, 113.6, 113.3, 55.3 ppm. IR (KBr):
ν = 3006, 2953, 2929, 2834, 1604, 1482, 1292, 1250, 1178, 900, 840,
7
1
.26–7.33 (m, 7 H, Ar-H), 6.86 (d, J = 8.6 Hz, 2 H, Ar-H), 5.39 (s,
˜
1
3
–1
+
H, =CH
2
), 5.35 (s, 1 H, =CH
): δ = 159.2, 149.4, 141.7, 133.9, 129.3,
28.2, 128.0, 127.6, 113.4, 112.9, 55.2 ppm. IR (KBr): ν˜ = 3030,
2
), 3.82 (s, 3 H, OCH
3
) ppm.
C
15 14
787, 758 cm . HRMS (ESI): calcd. for C H BrO [M + H] and
[M + H + 2]
291.0168.
NMR (100 MHz, CDCl
3
+
289.0228 and 291.0208; found 289.0226 and
1
2
7
2
951, 2834, 1658, 1508, 1289, 1249, 1178, 1150, 1028, 901, 841,
–1
15O [M + H]+
H
1-Bromo-4-[1-(4-ethoxyphenyl)vinyl]benzene (4i): White solid
84, 746, 707 cm . HRMS (ESI): calcd. for C15
11.1123; found 211.1126.
1
(
182 mg, 82%). M.p. 76–78 °C. H NMR (400 MHz, CDCl
3
): δ =
.22–7.34 (m, 6 H, Ar-H), 6.81–6.86 (m, 2 H, Ar-H), 5.31–5.40 (m,
H, =CH ), 4.03 (q, J = 7.0 Hz, 2 H, OCH CH ), 1.41 (t, J =
.0 Hz, 3 H, OCH ) ppm. C NMR (100 MHz, CDCl ): δ =
7
2
7
1
6
1
1
7
-Ethoxy-4-(1-phenylvinyl)benzene (4c): Pale-yellow solid (118 mg,
2
2
3
1
0%). M.p. 72–73 °C. H NMR (400 MHz, CDCl
3
): δ = 7.24–7.33
13
2
CH
3
3
(
m, 7 H, Ar-H), 6.82–6.85 (m, 2 H, Ar-H), 5.38 (d, J = 1.2 Hz, 1
H, =CH ), 5.33 (d, J = 1.2 Hz, 1 H, =CH ), 4.04 (q, J = 7.1 Hz, 2
H, OCH CH ), 1.41 (t, J = 7.0 Hz, 3 H, OCH
NMR (100 MHz, CDCl ): δ = 158.7, 149.6, 141.8, 133.8, 129.3,
28.3, 128.0, 127.5, 114.1, 112.7, 63.4, 14.8 ppm. IR (KBr): ν˜ =
58.8, 148.5, 140.8, 133.2, 131.2, 129.9, 129.2, 121.6, 114.1, 113.2,
2
2
3.4, 14.8 ppm. IR (KBr): ν˜ = 2980, 2925, 1641, 1604, 1507, 1480,
1
3
2
3
2
CH
3
) ppm.
C
–1
391, 1287, 1248, 1180, 1147, 844, 729, 716 cm . HRMS (ESI):
3
16BrO [M + H]+ and [M + H + 2]+ 303.0385 and
H
calcd. for C16
05.0364; found 303.0383 and 305.0210.
1
3
8
2
3
033, 2981, 2929, 1656, 1507, 1445, 1392, 1244, 1180, 1045, 899,
2-(1-Phenylvinyl)naphthalene (4j):[
9e]
Pale-yellow liquid (131 mg,
): δ = 7.75–7.84 (m, 5 H, Ar-
), 5.55
) ppm. C NMR (100 MHz, CDCl ): δ
150.0, 141.5, 138.9, 133.3, 132.9, 128.3, 128.2, 127.7, 127.6, 127.5,
–1
17O [M + H]+
H
43, 783, 707 cm . HRMS (ESI): calcd. for C16
25.1279; found 225.1279.
1
76%). H NMR (400 MHz, CDCl
3
H), 7.34–7.49 (m, 7 H, Ar-H), 5.59 (d, J = 1.0 Hz, 1 H, =CH
2
1
-Methoxy-3-[1-(4-methylphenyl)vinyl]benzene (4d): Pale-yellow li-
1
3
(d, J = 1.2 Hz, 1 H, =CH
2
3
1
quid (126 mg, 75%). H NMR (400 MHz, CDCl
m, 5 H, Ar-H), 6.83–6.92 (m, 3 H, Ar-H), 5.42 (d, J = 1.0 Hz, 1
H, =CH ), 5.39 (s, 1 H, =CH ), 3.77 (s, 3 H, OCH ), 2.35 (s, 3 H,
CH ): δ = 159.4, 149.8, 143.2,
) ppm. 13C NMR (100 MHz, CDCl
3
): δ = 7.11–7.24
=
(
1
1
7
2
27.2, 126.3, 126.1, 126.0, 114.7 ppm. IR (film): ν˜ = 3054, 2922,
610, 1492, 1444, 1382, 1270, 1143, 1119, 1018, 895, 858, 820, 777,
49, 711, 696 cm . HRMS (ESI): calcd. for C18
31.1174; found 231.1176.
2
2
3
3
3
–
1
+
H15 [M + H]
1
2
1
38.4, 137.4, 129.0, 128.8, 128.1, 120.9, 113.9, 113.6, 113.1, 55.2,
1.1 ppm. IR (film): ν˜ = 3001, 2924, 1656, 1511, 1485, 1455, 1284,
–1
241, 1180, 1043, 966, 874, 835, 782, 750, 702 cm . HRMS (ESI):
2-[1-(4-Methylphenyl)vinyl]naphthalene (4k): Pale-yellow liquid
(137 mg, 75%). H NMR (400 MHz, CDCl ): δ = 7.75–7.80 (m, 4
+
1
calcd. for C16
H
17O [M + H] 225.1279; found 225.1279.
3
H, Ar-H), 7.40–7.46 (m, 3 H, Ar-H), 7.25 (d, J = 8.3 Hz, 2 H, Ar-
1
-Methoxy-4-[1-(4-methylphenyl)vinyl]benzene (4e): Pale-yellow so-
[17d]
1
2
H), 7.13 (d, J = 7.8 Hz, 2 H, Ar-H), 5.49–5.50 (m, 2 H, =CH ),
lid (110 mg, 65%). M.p. 73–74 °C.
CDCl ): δ = 7.22–7.28 (m, 4 H, Ar-H), 7.13 (d, J = 8.3 Hz, 2 H,
Ar-H), 6.83–6.86 (m, 2 H, Ar-H), 5.31–5.33 (m, 2 H, =CH ), 3.81
) ppm. 1 C NMR (100 MHz,
): δ = 159.2, 149.3, 138.9, 137.4, 134.2, 129.3, 128.8, 128.1,
H NMR (400 MHz,
1
3
2.35 (s, 3 H, CH
3 3
) ppm. C NMR (100 MHz, CDCl ): δ = 149.9,
3
139.1, 138.6, 137.5, 133.3, 132.9, 128.9, 128.2, 128.1, 127.6, 127.2,
2
3
126.4, 126.0, 125.9, 114.1, 21.1 ppm. IR (film): ν˜ = 3055, 3023,
(
3 3
s, 3 H, OCH ), 2.35 (s, 3 H, CH
–
1
2
923, 1653, 1607, 1538, 1276, 1236, 1018, 951, 859, 771, 752 cm .
CDCl
3
HRMS (ESI): calcd. for C19
245.1338.
H
17 [M + H]+ 245.1330; found
1
1
13.4, 112.2, 55.3, 21.1 ppm. IR (KBr): ν˜ = 3009, 2952, 2834, 1654,
509, 1290, 1248, 1180, 1029, 900, 834, 759, 730 cm . HRMS
–1
+
(ESI): calcd. for C16
H
17O [M + H] 225.1279; found 225.1275.
2
-[1-(4-Methoxyphenyl)vinyl]naphthalene (4l): White solid (139 mg,
1
1-Ethoxy-4-[1-(4-methylphenyl)vinyl]benzene (4f): White solid
71%). M.p. 92–94 °C. H NMR (400 MHz, CDCl
3
): δ = 7.77–7.83
1
3
(130 mg, 73%). M.p. 49–51 °C. H NMR (400 MHz, CDCl ): δ =
(m, 4 H, Ar-H), 7.44–7.47 (m, 3 H, Ar-H), 7.29–7.31 (m, 2 H, Ar-
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M. L. N. Rao, D. N. Jadhav, V. Venkatesh
FULL PAPER
H), 6.86–6.88 (m, 2 H, Ar-H), 5.47 (s, 2 H, =CH
3 3
OCH ): δ = 159.4, 149.5, 139.2,
2
), 3.82 (s, 3 H,
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1
1
1
34.0, 133.3, 132.9, 129.4, 128.1, 127.5, 127.2, 126.5, 126.1, 125.9,
13.6, 113.4, 55.3 ppm. IR (KBr): ν˜ = 3058, 2954, 2853, 1680, 1626,
–1
508, 1464, 1361, 1280, 1018, 941, 859, 821, 746 cm . HRMS
+
(ESI): calcd. for C19H17O [M + H] 261.1279; found 261.1279.
4
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Received: May 5, 2009
Published Online: July 17, 2009
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Eur. J. Org. Chem. 2009, 4300–4306