Palladium-catalyzed allylic arylation of allylic ethers with arylboronic acids using hydrazone ligands

Article abstract of DOI:10.1002/ejoc.201201276

Unsymmetrical 1,3-diarylpropenes were synthesized in good to high yields by the palladium-catalyzed allylic arylation of allylic ethers, such as a cinnamyl phenyl ether, with a variety of arylboronic acids using a hydrazone 1a-Pd(OAc)₂ system in DMAc/H₂O. Using this catalyst, eugenol was also synthesized from allyl phenyl ether with (4-hydroxy-3- methoxyphenyl)boronic acid pinacol ester. A palladium-catalyzed allylic arylation of cinnamyl phenyl ether derivatives with a variety of arylboronic acids using 5 mol-% of a hydrazone 1a-Pd(OAc)₂ system in DMAc/H ₂O at 50 °C gave 1,3-diarylpropenes in good yields. We also succeeded with the synthesis of eugenol by a palladium-catalyzed allylic arylation. Copyright

Full text of DOI:10.1002/ejoc.201201276

FULL PAPER
DOI: 10.1002/ejoc.201201276
Palladium-Catalyzed Allylic Arylation of Allylic Ethers with Arylboronic Acids
Using Hydrazone Ligands
Takashi Mino,*[a] Taketo Kogure,[a] Taichi Abe,[a] Tomoko Koizumi,[a] Tsutomu Fujita,[a] and
Masami Sakamoto[a]
Keywords: Palladium / Hydrazones / Cross-coupling / N ligands / Homogeneous catalysis / Arylation
Unsymmetrical 1,3-diarylpropenes were synthesized in good
to high yields by the palladium-catalyzed allylic arylation of
allylic ethers, such as a cinnamyl phenyl ether, with a variety
of arylboronic acids using a hydrazone 1a–Pd(OAc)2 system
in DMAc/H2O. Using this catalyst, eugenol was also synthe-
sized from allyl phenyl ether with (4-hydroxy-3-meth-
oxyphenyl)boronic acid pinacol ester.
Introduction
The 1,3-diarylpropenes, which are known as intermedi-
ates in the synthesis of natural products and biologically
active compounds, have attracted considerable attention
from medicinal chemists.[1] Recently, 1,3-diarylpropenes
were synthesized by Tsukamoto et al.[2] by a palladium-cat-
alyzed allylic arylation of cinnamyl phenyl ether derivatives
using Pd(PPh3)4 in THF, and by Lipshutz et al.[3] using
PdCl2(DPEphos) in water with polyoxyethanyl-α-toco-
pheryl sebacate (MW Ͼ 1200) as an amphiphilic additive.
However, the phosphanes in palladium complexes are often
air-sensitive, toxic, or quite expensive. To the best of our
knowledge, examples of the palladium-catalyzed allylic
arylation of cinnamyl phenyl ether derivatives under phos-
phane-ligand-free conditions have not been explored. We
previously demonstrated that easily prepared and air-stable
hydrazones are effective ligands for palladium-catalyzed C–
C bond formation reactions[4] including the allylic arylation
of allylic esters with arylboronic acids.[5] The palladium-cat-
alyzed allylic arylation of allylic acetates or carbonates with
arylboronic acids or sodium tetraphenylborate have also
been reported by the Uozumi group,[6] the Zhang group,[7]
and the Sawamura group.[8] We now report the synthesis of
1,3-diarylpropenes by a palladium-catalyzed allylic aryl-
ation of cinnamyl phenyl ether derivatives with a variety of
arylboronic acids using air-stable phosphane-free hydraz-
ones 1 and 2 as ligands (Figure 1).
Figure 1. Hydrazones 1 and 2.
Results and Discussion
Initially, we sought the optimal reaction conditions for a
palladium-catalyzed allylic arylation using hydrazone–
Pd(OAc)2 systems. Cinnamyl phenyl ether and phenyl-
boronic acid were chosen as model substrates with 5 mol-
% Pd catalyst and a reaction time of 24 h under an argon
atmosphere at 50 °C (Table 1). Using 5 mol-% hydrazone 1a
as a ligand, we observed that the allylic arylation in the
presence of K2CO3 as a base in DMF/H2O as a solvent
proceeded to give the corresponding product (i.e., 3a) in
76% yield (Table 1, entry 1). We also tested other hydraz-
ones 1b–f and 2 (Table 1, entries 2–7), and found that
hydrazone 1a was a more effective ligand for this reaction
(Table 1, entry 1). Without any ligand, the reaction gave a
low yield of the desired product (Table 1, entry 8). Several
bases were tested (Table 1, entries 1 and 9–14). Ca(OH)2
was the most effective base in this reaction (Table 1, en-
try 12). Next, the effect of various solvents was investigated
(Table 1, entries 12 and 15–17). When we used DMAc/H2O
(DMAc = N,N-dimethylacetamide) instead of DMF/H2O,
[a] Department of Applied Chemistry and Biotechnology,
Graduate School of Engineering, Chiba University,
1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Fax: +81-43-290-3401
E-mail: tmino@faculty.chiba-u.jp
Homepage: http://chem.tf.chiba-u.jp/gacb06/index.html
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201201276.
Eur. J. Org. Chem. 2013, 1501–1505
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. Mino, T. Kogure, T. Abe, T. Koizumi, T. Fujita, M. Sakamoto
FULL PAPER
the yield increased to 94% (Table 1, entry 17). The effect of Table 2. Palladium-catalyzed allylic arylation of allylic ethers with
arylboronic acids.[a]
the ratio of DMAc and H2O was also investigated (Table 1,
entries 17–19). When the ratio of DMAc/H2O was 4:1 or
1:1 in the reaction, the yields decreased to 91 and 64%,
respectively. When the ratio of Pd(OAc)2/ligand 1a was 1:2
or 2:1 in the reaction, the yields also decreased to 90 and
61%, respectively (Table 1, entries 20 and 21). Without any
base in DMAc/H2O, the reaction gave a low yield of the
desired product (Table 1, entry 22). When we used Pd2-
(dba)3 (dba = dibenzylideneacetone) instead of Pd(OAc)2,
the yield slightly decreased to 87% (Table 1, entry 23).
When the reaction was carried out under an air atmosphere,
the yield also decreased to 79% (Table 1, entry 24). Finally,
when the reaction was carried out using 3 mol-% palladium
catalyst, the yield decreased to 68% (Table 1, entry 25).
Table 1. Optimization of the palladium-catalyzed allylic arylation
of cinnamyl phenyl ether with phenylboronic acid.[a]
Entry Ligand Base
Solvent (v/v)
Yield of 3a [%][b]
1
2
3
4
5
6
7
8
1a
1b
1c
1d
1e
1f
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
Na2CO3
K3PO4
Ca(OH)2 DMF/H2O (3:1)
CaCO3
KOH
Ca(OH)2 DMSO:H2O (3:1)
Ca(OH)2 MeCN:H2O (3:1)
Ca(OH)2 DMAc/H2O (3:1)
Ca(OH)2 DMAc/H2O (4:1)
Ca(OH)2 DMAc/H2O (1:1)
Ca(OH)2 DMAc/H2O (3:1)
Ca(OH)2 DMAc/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
DMF/H2O (3:1)
76
44
69
9
75
10
70
7
56
73
85
86
42
52
39
70
94
91
64
90
61
36
87
79
68
2
–
9
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a[c]
1a[d]
1a
1a
1a
1a
10
11
12
13
14
15
16
17
18
19
20
21
22
23[e]
24[f]
25[g]
DMF/H2O (3:1)
DMF/H2O (3:1)
–
DMAc/H2O (3:1)
Ca(OH)2 DMAc/H2O (3:1)
Ca(OH)2 DMAc/H2O (3:1)
Ca(OH)2 DMAc/H2O (3:1)
[a] Reaction conditions: cinnamyl phenyl ether (0.25 mmol), phen-
ylboronic acid (0.30 mmol), Pd(OAc)2 (5 mol-%), ligand (5 mol-%),
base (0.5 mmol), solvent (1.0 mL) at 50 °C for 24 h under Ar.
[b] Isolated yields. [c] 10 mol-% 1a was used. [d] 2.5 mol-% 1a was
used. [e] 2.5 mol-% Pd2(dba)3 (i.e., 5 mol-% Pd) was used. [f] Reac-
tion temperature was 60 °C. [g] Arylboronic acid (0.35 mmol) was
used. [i] The reaction was carried out under air. [j] 3 mol-%
Pd(OAc)2 and 3 mol-% 1a were used.
[a] Reaction conditions: allyl ether (0.25 mmol), arylboronic acid
(0.30 mmol), Pd(OAc)2 (5 mol-%), ligand 1a (5 mol-%), Ca(OH)2
(0.5 mmol), DMAc (0.75 mL), and H2O (0.25 mL) at 50 °C for 24 h
under Ar. [b] Isolated yields. [c] Reaction time was 6 h; Ratio of 3f/
3s was 92:8 by 1H NMR spectroscopy. [d] Reaction temperature
was 80 °C. [e] 10 mol-% Pd(OAc)2 and ligand 1a were used. [f] Re-
action temperature was 60 °C. [g] Arylboronic acid (0.35 mmol)
was used. [h] Reaction time was 48 h at 60 °C. [i] Reaction time was
6 h; ratio of 3s/3f was 94:6 by 1H NMR spectroscopy. [j] Pinacol
ester was used.
Under the optimized reaction conditions (Table 1, en-
try 17), the scope and limitations of the reaction with re-
spect to both the cinnamyl phenyl ether derived and the
arylboronic acid components were explored (Table 2).
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Palladium-Catalyzed Allylic Arylation with Arylboronic Acids
MgSO4, and concentrated under reduced pressure. The residue was
purified by silica gel chromatography [hexane, hexane/ethyl acetate
(40–5:1), or hexane/diethyl ether (100:1)].
Using cinnamyl phenyl ether with 4-substituted arylboronic
acids such as 4-tolyl-, (4-methoxyphenyl)-, (4-chloro-
phenyl)-, and (4-hydroxyphenyl)boronic acid led to mod-
erate to good yields of the corresponding products (Table 2,
entries 1–4). When the reaction of (4-trifluoromethyl-
phenyl)boronic acid was carried out for 24 h, 3f (Ar1 = Ph,
Ar2 = 4-CF3C6H4) and 3s (Ar1 = 4-CF3C6H4, Ar2 = Ph)
were obtained in 80% yield (ratio of 3f/3s = 73:27). On the
other hand, the reaction for 6 h gave 3f with only a small
amount of 3s in 80% yield (Table 2, entry 5). The reaction
of 3- and 2-substituted arylboronic acids such as 3-tolyl-,
2-tolyl-, (2-fluorophenyl)-, and (2-hydroxyphenyl)boronic
acid also gave the corresponding products in moderate to
good yields (Table 2, entries 6–9). Moreover, (2,4,6-trimeth-
ylphenyl)-, [3,4-(methylenedioxy)phenyl]-, and 1-naphth-
ylboronic acid gave good yields (Table 2, entries 10–12). On
the other hand, the reaction of a heteroarylboronic acid, 3-
thiopheneboronic acid, did not gave the desired product,
unfortunately (Table 2, entry 13). We also tested the reac-
tion of various cinnamyl phenyl ether derivatives, which
were easily prepared by the hydrazone–palladium-catalyzed
Mizoroki–Heck reaction[4e] of allyl phenyl ether with the
corresponding aryl iodides, with phenylboronic acid
(Table 2, entries 14–19). The reaction of methyl-substituted
cinnamyl phenyl ethers and 4-methoxycinnamyl phenyl
ether gave the corresponding unsymmetrical 1,3-di-
phenylpropene derivatives in moderate to good yields
(Table 2, entries 14–18). When phenyl 4-(trifluoromethyl)-
cinnamyl ether was used, the reaction gave the correspond-
ing product (i.e., 3s) with small amount of 3f as a by-prod-
1
(3-Phenyl-1-propen-1-yl)benzene (3a):[5a] 94% as a colorless oil. H
NMR (300 MHz, CDCl3): δ = 7.17–7.37 (m, 10 H), 6.46 (d, J =
15.9 Hz, 1 H), 6.35 (dt, J = 15.9 and 6.3 Hz, 1 H), 3.55 (d, J =
6.3 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 140.1, 137.4,
131.0, 129.2, 128.6, 128.5 ϫ2, 127.1, 126.2, 126.1, 39.3 ppm. MS
(EI): m/z (%) = 194 (100) [M]+.
1-Methyl-4-(3-phenyl-2-propen-1-yl)benzene (3b):[5a] 86% as a color-
1
less oil. H NMR (300 MHz, CDCl3): δ = 7.10–7.37 (m, 9 H), 6.45
(d, J = 15.9 Hz, 1 H), 6.34 (dt, J = 15.9 and 6.3 Hz, 1 H), 3.51 (d,
J = 6.3 Hz, 2 H), 2.32 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 137.5, 137.0, 135.7, 130.8, 129.5, 129.2, 128.53, 128.46, 127.0,
126.1, 38.9, 21.0 ppm. MS (EI): m/z (%) = 208 (100) [M]+.
1-Methoxy-4-(3-phenyl-2-propen-1-yl)benzene (3c):[5a] 92% as
a
white solid; m.p. 25–27 °C. 1H NMR (300 MHz, CDCl3): δ = 7.14–
7.37 (m, 7 H), 6.86 (dt, J = 8.7 and 2.8 Hz, 2 H), 6.43 (d, J =
15.9 Hz, 1 H), 6.33 (dt, J = 15.9 and 6.3 Hz, 1 H), 3.79 (s, 3 H),
3.49 (d, J = 6.2 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
158.0, 137.5, 132.2, 130.7, 129.7, 129.6, 128.5, 127.0, 126.1, 113.9,
55.3, 38.4 ppm. MS (EI): m/z (%) = 224 (100) [M]+.
1-Chloro-4-(3-phenyl-2-propen-1-yl)benzene (3d):[5b] 83% as a color-
1
less oil. H NMR (300 MHz, CDCl3): δ = 7.15–7.37 (m, 9 H), 6.44
(d, J = 15.6 Hz, 1 H), 6.30 (dt, J = 15.6 and 6.6 Hz, 1 H), 3.51 (d,
J = 6.6 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 138.6,
137.2, 131.9, 131.5, 130.0, 128.55, 128.52, 127.2, 126.1, 38.6 ppm.
MS (EI): m/z (%) = 228 (63) [M]+.
4-(3-Phenyl-2-propen-1-yl)phenol (3e):[9] 69% as a yellow solid; m.p.
60–62 °C. 1H NMR (300 MHz, CDCl3): δ = 7.12–7.40 (m, 5 H),
7.08 (d, J = 2.9 Hz, 2 H), 6.78 (dt, J = 8.5 and 2.9 Hz, 2 H), 6.43
uct (Table 2, entry 19). We also tested the synthesis of euge- (d, J = 15.8 Hz, 1 H), 6.32 (dt, J = 15.8 and 6.2 Hz, 1 H), 4.88 (s,
1 H), 3.47 (d, J = 6.2 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
nol using allyl phenyl ether with (4-hydroxy-3-meth-
oxyphenyl)boronic acid pinacol ester (Table 2, entry 20).
The reaction gave the corresponding product in moderate
δ = 153.9, 137.5, 132.3, 130.7, 129.8, 129.6, 128.5, 127.0, 126.1,
115.3, 38.4 ppm. MS (EI): m/z (%) = 210 (100) [M]+.
4-(3-Phenyl-2-propen-1-yl)-1-(trifluoromethyl)benzene (3f):[5a] 80%
as a colorless oil. 1H NMR (300 MHz, CDCl3): δ = 7.56 (d, J =
8.0 Hz, 2 H), 7.20–7.37 (m, 7 H), 6.48 (d, J = 15.7 Hz, 1 H), 6.32
(dt, J = 15.7 and 6.7 Hz, 1 H), 3.60 (d, J = 6.7 Hz, 2 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 144.3, 137.1, 131.9, 129.0, 128.58 (q,
J = 32.3 Hz), 128.56, 127.9, 127.4, 126.2, 125.4 (q, J = 3.7 Hz),
124.3 (q, J = 271.9 Hz), 39.1 ppm. MS (EI): m/z (%) = 262 (100)
[M]+.
yield.
Conclusions
In conclusion, we succeeded with the synthesis of unsym-
metrical 1,3-diarylpropenes in good to high yields by a pal-
ladium-catalyzed allylic arylation of cinnamyl phenyl ether
derivatives with a variety of arylboronic acids using 5 mol-
% of a hydrazone 1a–Pd(OAc)2 system in DMAc/H2O at
50 °C. We also obtained eugenol by the allylic arylation of
allyl phenyl ether with (4-hydroxy-3-methoxyphenyl)bor-
onic acid pinacol ester using a hydrazone 1a–Pd(OAc)2 sys-
tem.
1-Methyl-3-(3-phenyl-2-propen-1-yl)benzene (3g):[2] 89% as a color-
1
less oil. H NMR (300 MHz, CDCl3): δ = 7.03–7.37 (m, 9 H), 6.46
(d, J = 15.8 Hz, 1 H), 6.34 (dt, J = 15.8 and 6.6 Hz, 1 H), 3.51 (d,
J = 6.6 Hz, 2 H), 2.33 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 140.1, 138.1, 137.5, 130.9, 129.4, 129.3, 128.5, 128.4, 127.1,
126.9, 126.1, 125.7, 39.3, 21.4 ppm. MS (EI): m/z (%) = 208 (100)
[M]+.
1-Methyl-2-(3-phenyl-2-propen-1-yl)benzene (3h):[5a] 84% as a color-
less oil. 1H NMR (300 MHz, CDCl3): δ = 7.13–7.35 (m, 9 H), 6.28–
6.40 (m, 2 H), 3.53 (d, J = 4.9 Hz, 2 H), 2.33 (s, 3 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 138.2, 137.5, 136.4, 130.9, 130.2,
129.2, 128.51, 128.46, 127.0, 126.4, 126.1, 126.0, 36.8, 19.4 ppm.
MS (EI): m/z (%) = 208 (100) [M]+.
Experimental Section
General Procedure for the Palladium-Catalyzed Allylic Arylation of
Allylic Ethers with Arylboronic Acids: Arylboronic acid
(0.30 mmol) was added to a mixture of allylic ether (0.25 mmol),
Ca(OH)2 (0.5 mmol), Pd(OAc)2 (12.5 μmol), and ligand 1a
(12.5 μmol) in DMAc (0.75 mL) and H2O (0.25 mL) at room tem-
perature under an argon atmosphere. The mixture was stirred at
50 °C. After 24 h, the mixture was diluted with ethyl acetate and
water. The organic phase was washed with brine, dried with
1-Fluoro-2-(3-phenyl-2-propen-1-yl)benzene (3i): 85% as a colorless
oil. 1H NMR (300 MHz, CDCl3): δ = 7.17–7.37 (m, 7 H), 7.01–
7.11 (m, 2 H), 6.46 (d, J = 15.8 Hz, 1 H), 6.33 (dt, J = 15.8 and
6.6 Hz, 1 H), 3.57 (d, J = 6.6 Hz, 2 H) ppm. 13C NMR (75 MHz,
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. Mino, T. Kogure, T. Abe, T. Koizumi, T. Fujita, M. Sakamoto
FULL PAPER
CDCl3): δ = 161.0 (d, J = 244.2 Hz), 137.3, 131.4, 130.6 (d, J =
4.8 Hz), 128.5, 127.9 (d, J = 8.4 Hz), 127.6, 127.2, 127.1 (d, J =
16.7 Hz), 126.1, 32.2 (d, J = 3.3 Hz), 124.1 (d, J = 3.6 Hz), 115.3
(d, J = 21.5 Hz) ppm. MS (EI): m/z (%) = 212 (100) [M]+. HRMS
(APCI): calcd. for C15H14F [M + H]+ 213.1074; found 213.1084.
1-Methoxy-4-(3-phenyl-1-propen-1-yl)benzene (3r):[5a] 60% as a col-
orless oil. 1H NMR (300 MHz, CDCl3): δ = 7.19–7.33 (m, 7 H),
6.81–6.86 (m, 2 H), 6.40 (d, J = 15.8 Hz, 1 H), 6.21 (dt, J = 15.8
and 6.8 Hz, 1 H), 3.79 (s, 3 H), 3.53 (d, J = 6.8 Hz, 2 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 158.8, 140.4, 130.4, 130.3, 128.6,
128.4, 127.2, 127.0, 126.1, 113.9, 55.3, 39.3 ppm. MS (EI): m/z (%)
= 224 (100) [M]+.
2-(3-Phenyl-2-propen-1-yl)phenol (3j):[9] 60% as a yellow solid; m.p.
47–49 °C. 1H NMR (300 MHz, CDCl3): δ = 7.12–7.37 (m, 7 H),
6.91 (td, J = 7.4 and 1.1 Hz, 1 H), 6.82 (d, J = 8.0 Hz, 1 H), 6.51
(d, J = 15.9 Hz, 1 H), 6.39 (dt, J = 15.9 and 6.2 Hz, 1 H), 4.93 (s,
1 H), 3.57 (d, J = 6.2 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 154.0, 137.0, 128.5, 131.5, 130.4, 127.9, 127.3, 126.2, 125.6,
125.3, 121.0, 115.7, 34.1 ppm. MS (EI): m/z (%) = 210 (100) [M]+.
4-(3-Phenyl-1-propen-1-yl)-1-(trifluoromethyl)benzene (3s): 63% as
a colorless oil. 1H NMR (300 MHz, CDCl3): δ = 7.53 (d, J =
8.3 Hz, 2 H), 7.43 (d, J = 8.2 Hz, 2 H), 7.23–7.32 (m, 5 H), 6.45–
6.48 (m, 2 H), 3.57 (d, J = 3.9 Hz, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 140.9, 139.5, 132.1, 129.8, 128.7, 128.6, 129.0 (q, J =
32.3 Hz), 126.4, 126.2, 125.4 (q, J = 3.8 Hz), 124.2 (q, J =
271.6 Hz), 39.3 ppm. MS (EI): m/z (%) = 262 (100) [M]+. HRMS
(ESI): calcd. for C16H12F3 [M + H]+ 261.0897; found 261.0896.
Eugenol (3t):[11] 40% as a colorless oil. 1H NMR (300 MHz,
CDCl3): δ = 6.83–6.86 (m, 1 H), 6.67–6.70 (m, 2 H), 5.95 (ddt, J
= 6.6, 10.1, and 16.9 Hz, 1 H), 5.50 (s, 1 H), 5.04–5.11 (m, 2 H),
3.87 (s, 3 H), 3.32 (d, J = 6.6 Hz, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 146.4, 143.9, 137.8, 131.9, 121.1, 115.5, 114.2, 111.1,
55.8, 39.9 ppm. MS (EI): m/z (%) = 164 (100) [M]+.
2,4,6-Trimethyl-1-(3-phenyl-2-propen-1-yl)benzene (3k): 83% as a
colorless oil. 1H NMR (300 MHz, CDCl3): δ = 7.14–7.30 (m, 5 H),
6.87 (s, 2 H), 6.19–6.32 (m, 2 H), 3.51 (d, J = 4.0 Hz, 2 H), 2.30
(s, 6 H), 2.27 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 137.6,
136.6, 135.5, 133.1, 129.8, 128.9, 128.4, 127.7, 126.9, 126.0, 32.6,
20.9, 19.9 ppm. MS (EI): m/z (%) = 236 (100) [M]+. HRMS
(APCI): calcd. for C18H20 [M]+ 236.1560; found 236.1556.
3,4-Methylenedioxy-1-(3-phenyl-2-propen-1-yl)benzene (3l):[9] 73%
1
as a white solid; m.p. 38–40 °C. H NMR (300 MHz, CDCl3): δ =
Supporting Information (see footnote on the first page of this arti-
7.17–7.36 (m, 5 H), 6.68–6.77 (m, 3 H), 6.43 (d, J = 15.8 Hz, 1 H),
6.31 (dt, J = 15.8 and 6.5 Hz, 1 H), 5.92 (s, 2 H), 3.46 (d, J =
6.5 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 147.7, 145.9,
137.4, 133.9, 130.9, 129.3, 128.5, 127.1, 126.1, 121.4, 109.2, 108.2,
100.8, 39.0 ppm. MS (EI): m/z (%) = 238 (100) [M]+.
1
cle): Copies of H and 13C NMR spectra of the products.
Acknowledgments
1-(3-Phenyl-2-propen-1-yl)naphthalene (3m):[5a] 92% as a white so-
The Authors gratefully acknowledge the financial support by Chiba
lid; m.p. 73–74 °C. 1H NMR (300 MHz, CDCl3): δ = 8.07–8.11 (m, University (Iodine Research Project and COE Start-up Program).
1 H), 7.84–7.88 (m, 1 H), 7.74–7.77 (m, 1 H), 7.15–7.54 (m, 9 H),
6.43–6.56 (m, 2 H), 4.00 (d, J = 4.8 Hz, 2 H) ppm. 13C NMR
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36.4 ppm. MS (EI): m/z (%) = 244 (73) [M]+.
1-Methyl-4-(3-phenyl-1-propen-1-yl)benzene (3n):[5a] 94% as a color-
1
less oil. H NMR (300 MHz, CDCl3): δ = 7.19–7.33 (m, 7 H), 7.10
(d, J = 8.0 Hz, 2 H), 6.43 (d, J = 15.8 Hz, 1 H), 6.30 (dt, J = 15.8
and 6.6 Hz, 1 H), 3.54 (d, J = 6.6 Hz, 2 H), 2.32 (s, 3 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 140.3, 136.8, 134.7, 130.9, 21.1, 129.2,
128.6, 128.4, 128.1, 126.1, 126.0, 39.3 ppm. MS (EI): m/z (%) = 208
(100) [M]+.
1-Methyl-3-(3-phenyl-1-propen-1-yl)benzene (3o):[5b] 94% as a col-
orless oil. 1H NMR (300 MHz, CDCl3): δ = 7.15–7.33 (m, 8 H),
7.02 (d, J = 6.4 Hz, 1 H), 6.29–6.46 (m, 2 H), 3.54 (d, J = 6.1 Hz,
2 H), 2.32 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 140.2,
138.0, 137.4, 131.1, 129.0, 128.6, 128.5, 128.4, 127.9, 126.8, 126.1,
123.3, 39.3, 21.4 ppm. MS (EI): m/z (%) = 208 (100) [M]+.
1-Methyl-2-(3-phenyl-1-propen-1-yl)benzene (3p):[10] 93% as a color-
less oil. 1H NMR (300 MHz, CDCl3): δ = 7.40–7.44 (m, 1 H), 7.12–
7.34 (m, 8 H), 6.66 (d, J = 15.6 Hz, 1 H), 6.23 (dt, J = 15.6 and
6.9 Hz, 1 H), 3.57 (d, J = 6.9 Hz, 2 H), 2.34 (s, 3 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 140.3, 136.6, 135.1, 130.5, 130.2,
129.0, 128.6, 128.5, 127.0, 126.1, 126.0, 125.6, 39.6, 19.8 ppm. MS
(EI): m/z (%) = 208 (100) [M]+.
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1,3-Dimethyl-5-(3-phenyl-1-propen-1-yl)benzene (3q): 94% as a col-
orless oil. 1H NMR (300 MHz, CDCl3): δ = 7.18–7.33 (m, 5 H),
6.98 (s, 2 H), 6.85 (s, 1 H), 6.27–6.43 (m, 2 H), 3.53 (d, J = 5.8 Hz,
2 H), 2.28 (s, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 140.3,
137.9, 137.4, 131.1, 128.8 ϫ2, 128.7, 128.4, 126.1, 124.0, 39.4,
21.2 ppm. MS (EI): m/z (%) = 222 (100) [M]+. HRMS (ESI): calcd.
for C17H19 [M + H]+ 223.1481; found 223.1484.
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Received: September 25, 2012
Published Online: January 29, 2013
Eur. J. Org. Chem. 2013, 1501–1505
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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