A novel palladium-catalyzed hydroalkoxylation of alkenes with a migration of double bond

Article abstract of DOI:10.1039/b800838h

A novel palladium-catalyzed addition of alcohols to olefins was developed, in which a migration of double bond was involved. By this new method, a variety of allylic ethers were prepared with moderate to high yields under mild conditions. The Royal Society of Chemistry.

Full text of DOI:10.1039/b800838h

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COMMUNICATION
www.rsc.org/obc | Organic & Biomolecular Chemistry
A novel palladium-catalyzed hydroalkoxylation of alkenes with a migration of
double bond†
Jiajing Tan, Zuhui Zhang and Zhiyong Wang*
Received 17th January 2008, Accepted 3rd March 2008
First published as an Advance Article on the web 17th March 2008
DOI: 10.1039/b800838h
A novel palladium-catalyzed addition of alcohols to olefins
was developed, in which a migration of double bond was
involved. By this new method, a variety of allylic ethers were
prepared with moderate to high yields under mild conditions.
Fig. 1 Palladium-catalyzed addition of alcohols to olefins.
Introduction
twice in our research. Also, this reaction broadens the scope of
Carbon–oxygen bond structures are widely present in natural
products and medicinally important compounds. The formation
of carbon–oxygen bonds, therefore, has stimulated considerable
interest in developing new methods and become one of the great
Li et al.’s work on the isomerization of double bonds that occurs
with ruthenium catalysts in water.12
In our initial studies, many catalysts as well as ligands were
investigated, as summarized in Table 1. The reaction conditions
aspects of organic synthesis. In the past few years, continuous
were optimized and the best conditions found were to use 10 mol%
efforts have been made in this field with various methods developed
of PdCl2 only, as shown in entry 1 of Table 1. By virtue of these
and strengthened. Ethers and esters with carbon–oxygen bonds
optimized conditions, the reaction afforded 2a with an isolated
are usually prepared under mild conditions via the addition
yield of 84%. The reactions under other palladium catalysts
of hydroxy groups of alcohols or carboxylic acids to olefins
such as Pd(OAc)2, PdCl2(CH3CN)2 and PdCl2(PhCN)2 could also
(hydroalkoxylation) catalyzed by Brønsted acids,1 main group
generate the desired products with fairly good yields (Table 1,
metals2 or transitional metals such as platinum,3 copper,4 silver,5
entries 2–4). Subsequently, we attempted to improve the reaction
gold,6 palladium7 and lanthanides.8 It is obvious that this method
by employing different ligands. Thus, aliphatic ligands, aryl amine
provides the potential of both regio- and enantiocontrol. In
ligands, pyridine-containing ligands and phosphorous ligands
particular, palladium catalysts, due to their extraordinary catalytic
were examined. However, all of them had negative influences on
activities and outstanding ability to tolerate a wide variety of
this reaction to different degrees (Table 1, entries 5–11). Having
functional groups, have received much attention.9 In most cases,
gained some crucial insights of the effect of different catalysts,
hydroalkoxylation of olefins catalyzed by palladium catalysts
further optimization was performed on exploring the effects of
involves a process in which the cationic palladium first activates
the solvent as well as the additives (Table 2). It was obvious that
the unsaturated carbon–carbon bonds by coordination and then
methanol is the best solvent while other additives all disfavor
the desired compounds are formed by the subsequent nucleophilic
this reaction to different degrees. Therefore, the best reaction
addition of the O–H groups and protonation of the Pd–carbon
conditions found are that the substrate 1a is treated with catalytic
bond.2
PdCl2 (10 mol%) in alcohols.
Subsequently, the optimized system was applied to the addition
of various alcohols to 1a and the results were listed in Table 3. It
Results and discussion
was found that the primary alcohols provided the desired products
In this communication, we disclose a novel approach toward
with moderate to good yields (Table 3, entries 1–3, 5 and 7) while
the palladium-catalyzed combination of alcohols and homoallylic
the secondary alcohol gave the product with slightly lower yield,
alcohols under mild conditions to afford a series of allylic ethers
perhaps due to the steric effect (Table 3, entry 4). Nevertheless,
efficiently (Fig. 1). It was noted that a process in which rearrange-
the influence of steric hindrance on the reaction was limited. Even
ment of the homoallylic alcohol occurs provides a delocalized allyl
for tert-butyl alcohol, which has great steric hindrance, the desired
products could be obtained with moderate yields (Table 3, entry
6). Moreover, we have expanded our investigation to acetic acid
as the nucleophile and the additional product 2i could also be
obtained (Table 3, entry 9).
cation structure10 and that subsequently a nucleophilic alcohol
attacks this cation, forming a carbon–oxygen bond. Compared
with the past research on palladium-catalyzed allylation with free
allylic alcohols,11 the p-allyl–palladium intermediate was formed
To further evaluate the scope of this reaction, a range of
homoallylic alcohol derivatives was subjected to the optimized
reaction conditions (Table 4). In general, substitution (MeO,
Br or Cl) at the ortho-position of the phenyl ring provided the
corresponding adducts with higher yields than substitution at the
para-position (Table 4, entries 1–3 and 5–7) regardless whether
the substituent was electron-withdrawing or electron-donating.
Hefei National Laboratory for Physical Science at Microscale, Joint
Laboratory of Green Synthetic Chemistry and Department of Chemistry,
University of Science and Technology of China, Hefei 230026, P. R. China.
E-mail: zwang3@ustc.edu.cn; Fax: (+86) 551-360-3185; Tel: (+86) 551-
360-3185
† Electronic supplementary information (ESI) available: Synthesis
of substances, characterization data for the products. See DOI:
10.1039/b800838h
1344 | Org. Biomol. Chem., 2008, 6, 1344–1348
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Table 1 Effect of different catalysts and ligands on the addition of methanol to olefinsa
Entry
Catalyst
Ligand
Isolated yield (%)
1
2
3
4
5
6
7
8
9
PdCl2
—
—
—
—
84
75
80
82
Trace
Trace
Trace
70
36
83
Pd(OAc)2
PdCl2(CH3CN)2
PdCl2(PhCN)2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
Pyridine
2,2ꢀ-Bipyridine
1,10-Phenanthroline
Benzene-1,2-diamine
N1,N1,N2,N2-Tetramethylethane-1,2-diamine
1,4-Diaza-bicyclo[2.2.2]octane
P(Ph)3
10
11
65
a Reaction conditions: 1 mmol of 1a in 5 mL of methanol with 10 mol% catalyst and 10 mol% ligand.
Table 2 Screening for different additives and solventsa
Table 4 Addition of methanol to various substratesa
Entry
Catalyst
Additive
Solvent
Isolated yield (%)
Entry
Substrate
Product
Isolated yield (%)
1
2
3
4
5
6
7
8
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
—
—
—
—
DMF
Toluene
Hexane
Acetone
Methanol
Methanol
Methanol
Methanol
30
72
70
25
62
66
63
50
1
2
3
4
5
6
7
8
9
R = 4-Cl
R = 4-Br
R = 4-MeO
R = 4-Me
R = 2-Cl
R = 2-Br
R = 4-MeO
R = 3-Cl
1b
1c
1d
1e
1f
2J
2l
60
78
70
74
64
86
80
57
81
2k
2m
2n
2o
2p
2q
2r
K2CO3
HCl
CH3COOH
Et3N
1g
1h
1i
a 1 mmol of 1a in 1 mL of methanol, in the presence of corresponding
additive (1 mmol) and solvent (5 mL) with 0.1 mmol PdCl2.
1j
Table 3 Addition of different alcohols to 1aa
10
1k
2s
74
a Reaction conditions: 0.2 M of 1b–1k in methanol with 10 mol% catalyst.
Entry
R-OH
Product
Isolated yield (%)
1
2
3
4
5
6
7
8
9
Methanol
Ethanol
2a
2b
2c
2d
2e
2f
2g
2h
2i
84
77
78
72
73
53
52
72
57
yield of 57% (entry 8). Even when the phenyl ring was replaced by a
naphthyl ring, the desired product 2r could also be obtained with
a good yield (Table 4, entry 9). More importantly, homoallylic
alcohol 1k with an aliphatic substituent was also reactive. The
reaction led to the desired product 2s with a yield of 74% (Table 4,
entry 10).
Afterwards, a tentative mechanism for this novel palladium-
catalyzed reaction was proposed on the basis of our experimental
results, as outlined in Fig. 2. Initially, the coordination of
palladium(II) to 1a activates the alkene toward the subsequent
migration of hydride from the C2 position to the C4 position at
the terminal of the chain. Then the structure of p-allyl–palladium10
is built up through the departure of the hydroxyl group and the
1-Propanol
2-Propanol
1-Butanol
tert-Butyl alcohol
Benzyl alcohol
Glycol
Acetic acid
a Reaction conditions: 0.2 M of 1a in alcohol or carboxylic acid with
10 mol% catalyst. Reaction temperature for entries 6 and 7 was 50 ◦C
while for others it was about 30 ◦C.
On the other hand, meta-substitution had little influence on the
reaction. For instance, 1i gave the corresponding adduct 2q with a
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alcohols and migration of the double bond. Further investigation
of the scope and mechanism of this reaction is ongoing in our
laboratory.
Experimental
IR (Perkin-Elmer, 2000FTIR), 1H NMR (CD3Cl, 400 or
300 MHz), 13C NMR (CDCl3, 100 or 75 MHz) and MS-GC
(HP 5890(II)/HP5972, EI. Analytical thin-layer chromatography
(TLC) plates were commercially available. Solvents were reagent
grade unless otherwise noted. All starting materials and reagents
are commercially available and were used as received.
Typical procedure of the addition of alcohols to olefins
Fig. 2 Proposed mechanism for the addition of methanol to 1a to form
(E)-(3-methoxybut-1-enyl)benzene.
To a solution of 1a (1 mmol) in 3 mL of MeOH, PdCl2 (0.1 mmol)
was added. Thereafter the mixture was heated at 30 ◦C under air
for 3 h, the methanol was evaporated under reduced pressure, and
the residual mixture was then purified by column chromatography
over silica gel to afford product 2a with high purity.
following methanol attack on this allyl–palladium complex forms
the carbon–oxygen bond, finally giving the stable product. To
support this mechanism, additional experiments were designed
and performed (Fig. 3). When methanol was replaced with d4-
methanol, only d3-2a was obtained, which indicated that C4
of d3-2a did not catch the proton from the hydroxy group in
methanol (Fig. 3, reaction 1). With this result in hand, 1l was also
synthesized (an intermediate mentioned in Li et al.’s mechanism12)
to be reacted with methanol under the above-mentioned reaction
conditions, and 2a could be obtained quantitatively as well (Fig. 3,
reaction 3). In addition, the result that (E)-buta-1,3-dienylbenzene
(1m) could not be converted to 2a under the same reaction con-
ditions also offered evidence to support the proposed mechanism
(Fig. 3, reaction 2). This palladium-catalyzed mechanism is similar
to the mechanism proposed by Li et al., where the reaction was
performed in water and catalyzed by a ruthenium complex.12
General procedure for allylation of carbonyl compounds in aqueous
medium13
To a mixture of the carbonyl compound (1 mmol) in 2 mL of
THF and 4 mL of saturated NH4Cl solution was added zinc
powder (0.130 g, 2 mmol) and allyl bromide (0.242 g, 2 mmol)
at room temperature. After the mixture was stirred for 0.5 h it was
extracted with ethyl acetate for three times. The combined organic
extracts were dried using anhydrous Na2SO4 and evaporated
under reduced pressure; the mixture was then purified by column
chromatography over silica gel to afford products 1a–1k with high
purity.
(E)-(3-Methoxybut-1-enyl)benzene (2a)14. 1H NMR (CDCl3,
300 MHz, ppm): d = 7.41–7.22 (m, 5H), 6.54 (d, J = 15.9 Hz,
1H), 6.09 (dd, J = 15.9 Hz, 7.5 Hz, 1H), 3.92–3.87 (m, 1H), 3.32
(s, 3H), 1.33 (d, J = 6.3 Hz, 3H). 13C NMR (CDCl3, 75 MHz,
ppm): d = 136.8, 131.6, 131.5, 128.7, 127.8, 126.6, 78.3, 56.2, 21.6.
IR (liquid film, cm−1): m = 3027, 2975, 2927, 2820, 1686, 1494,
1450, 1369, 1199, 1139, 1111, 1084, 1042, 968, 748, 693. HRMS
calc. C11H14O: 162.1045. Found: 162.1040.
d3-(E)-(3-Methoxybut-1-enyl)benzene (d3-2a). 1H NMR
(CDCl3, 300 MHz, ppm): d = 7.41–7.21 (m, 5H), 6.53 (d, J =
15.9 Hz, 1H), 6.09 (dd, J = 15.9 Hz, 7.5 Hz, 1H), 4.05–3.96 (m,
1H), 1.33 (d, J = 6.3 Hz, 3H). 13C NMR (CDCl3, 75 MHz, ppm):
d = 136.8, 131.6, 131.4, 128.7, 127.7, 126.6, 78.1, 21.6. IR (liquid
film, cm−1): m = 3027, 2965, 2928, 2854, 2234, 2192, 2057, 1598,
1494, 1448, 1368, 1150, 1121, 1092, 1021, 968, 747, 693. HRMS
calc. C11H11D3O: 165.1233. Found: 165.1231.
Fig. 3 Supporting experiments to investigate the mechanism.
(E)-(3-Ethoxybut-1-enyl)benzene (2b). 1H NMR (CDCl3,
300 MHz, ppm): d = 7.38–7.21 (m, 5H), 6.51 (d, J = 15.9 Hz,
1H), 6.12 (dd, J = 15.9 Hz, 7.5 Hz, 1H), 4.05–3.96 (m, 1H), 3.62–
3.52 (m, 1H), 3.47–3.37 (m, 1H), 1.33 (d, J = 6.3 Hz, 3H), 1.21 (t,
J = 7.2 Hz, 3H). 13C NMR (CDCl3, 75 MHz, ppm): d = 136.9,
132.3, 130.9, 128.7, 127.7, 126.6, 76.4, 63.7, 21.9, 15.6. IR (liquid
film, cm−1): m = 3027, 2975, 2929, 2869, 1598, 1493, 1447, 1369,
1317, 1092, 967, 748, 693. HRMS calc. C12H16O: 176.1201. Found:
176.1223.
Conclusions
We have developed a novel palladium-catalyzed hydroalkoxylation
of homoallylic alcohols with a double bond migration. More
importantly, in this reaction a p-allyl–palladium complex was
involved and a process of isomerization of homoallyic alcohols
catalyzed by Pd(II) was determined. To the best of our knowledge,
it represents the first example of the palladium-catalyzed addition
of alcohols to olefins involving isomerization of homoallylic
1346 | Org. Biomol. Chem., 2008, 6, 1344–1348
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(E)-(3-Propoxybut-1-enyl)benzene (2c)15. 1H NMR (CDCl3,
300 MHz, ppm): d = 7.41–7.23 (m, 5H), 6.51 (d, J = 15.9 Hz,
1H), 6.12 (dd, J = 15.9 Hz, 7.2 Hz, 1H), 4.01–3.97 (m, 1H),
3.48–3.42 (m, 1H), 3.35–3.30 (m, 1H), 1.64–1.56 (m, 2H), 1.32 (d,
J = 6.0 Hz, 3H), 0.92 (t, J = 7.5 Hz, 3H). 13C NMR (CDCl3,
75 MHz, ppm): d = 137.0, 132.4, 130.8, 128.7, 127.7, 126.6, 76.5,
23.3, 21.8, 10.8. IR (liquid film, cm−1): m = 3060, 2969, 2931, 2874,
1598, 1494, 1451, 1369, 1318, 1090, 967, 748, 693. HRMS calc.
C13H18O: 190.1358. Found: 190.1339.
ppm): d = 170.4, 136.5, 131.6, 128.9, 128.7, 128.0, 126.7, 71.1,
21.5, 20.5. IR (liquid film, cm−1): m = 3028, 2981, 2932, 1736,
1494, 1448, 1371, 1241, 1149, 1042, 966, 749, 693. HRMS calc.
C12H14O2: 190.0994. Found: 190.1003.
(E)-1-Chloro-4-(3-methoxybut-1-enyl)benzene (2j). 1H NMR
(CDCl3, 400 MHz, ppm): d = 7.33–7.26 (m, 4H), 6.49 (d, J =
15.9 Hz, 1H), 6.07 (dd, J = 15.9 Hz, 7.5 Hz, 1H), 3.90–3.87 (m,
1H), 3.32 (s, 3H), 1.32 (d, J = 6.3 Hz, 3H). 13C NMR (CDCl3,
100 MHz, ppm): d = 135.3, 133.3, 132.3, 130.1, 128.8, 127.7, 78.0,
56.2, 21.4. IR (liquid film, cm−1): m = 3029, 2977, 2928, 1593,
1491, 1370, 1352, 1199, 1110, 1090, 969, 854, 809. HRMS calc.
C11H13ClO: 196.0655. Found: 196.0646.
(E)-(3-Isopropoxybut-1-enyl)benzene (2d)15. 1H NMR (CDCl3,
300 MHz, ppm): d = 7.40–7.20 (m, 5H), 6.50 (d, J = 16.2 Hz,
1H), 6.07 (dd, J = 15.9 Hz, 7.2 Hz, 1H), 4.16–4.10 (m, 1H), 3.75–
3.67 (m, 1H), 1.31 (d, J = 6.3 Hz, 3H), 1.16 (d, J = 6.3 Hz, 6H).
13C NMR (CDCl3, 75 MHz, ppm): d = 137.0, 133.0, 130.3, 128.7,
127.6, 126.6, 73.6, 68.6, 23.5, 22.3, 21.9. IR (liquid film, cm−1):
m = 3056, 2921, 1644, 1459, 1374, 1258, 1102, 800. HRMS calc.
C13H18O: 190.1358. Found: 190.1366.
(E)-1-Bromo-4-(3-methoxybut-1-enyl)benzene (2k). 1H NMR
(CDCl3, 300 MHz, ppm): d = 7.45–7.43 (m, 2H), 7.25 (d, J =
8.4 Hz, 2H), 6.47 (d, J = 15.9 Hz, 1H), 6.09 (dd, J = 15.9 Hz,
7.5 Hz, 1H), 3.91–3.86 (m, 1H), 3.32 (s, 3H), 1.32 (d, J = 6.3 Hz,
3H). 13C NMR (CDCl3, 75 MHz, ppm): d = 135.7, 132.5, 131.8,
130.1, 128.1 121.5, 78.0, 56.3, 21.4. IR (liquid film, cm−1): m =
2926, 1728, 1487, 1462, 1423, 1371, 1259, 1109, 1075, 1038, 1011,
970, 804. HRMS calc. C11H13BrO: 240.0150. Found: 240.0139.
(E)-(3-Butoxybut-1-enyl)benzene (2e). 1H NMR (CDCl3,
300 MHz, ppm): d = 7.40–7.23 (m, 5H), 6.51 (d, J = 15.9 Hz,
1H), 6.07 (dd, J = 15.9 Hz, 7.5 Hz, 1H), 4.00–3.96 (m, 1H), 3.54–
3.46 (m, 1H), 3.39–3.31 (m, 1H), 1.59–1.52 (m, 2H), 1.41–1.31
(m, 5H), 0.91 (t, J = 7.2 Hz, 3H). 13C NMR (CDCl3, 75 MHz,
ppm): d = 137.0, 132.5, 130.8, 128.7, 127.7, 126.6, 68.6, 32.2, 21.8,
19.6, 14.1. IR (liquid film, cm−1): m = 3026, 2957, 2871, 1459, 1369,
1243, 1090, 973, 747, 692. HRMS calc. C14H20O: 204.1514. Found:
204.1512.
(E)-1-Methoxy-4-(3-methoxybut-1-enyl)benzene
(2l)15. 1H
NMR (CDCl3, 300 MHz, ppm): d = 7.35–7.31 (m, 2H), 6.87–6.85
(m, 2H), 6.47 (d, J = 15.9 Hz, 1H), 5.95 (dd, J = 16.2 Hz,
7.8 Hz, 1H), 3.89–3.81 (m, 1H), 3.79 (s, 3H), 3.31 (s, 3H), 1.32 (d,
J = 6.3 Hz, 3H). 13C NMR (CDCl3, 75 MHz, ppm): d = 159.4,
131.0, 129.6, 129.4, 127.8, 114.1, 78.4, 56.1, 55.4, 21.7. IR (liquid
film, cm−1): m = 2960, 2928, 1608, 1512, 1462, 1300, 1248, 1176,
1108, 1082, 1036, 969, 819. HRMS calc. C12H16O2: 192.1150.
Found: 192.1159.
(E)-(3-tert-Butoxybut-1-enyl)benzene (2f)14. 1H NMR (CDCl3,
300 MHz, ppm): d = 7.37–7.20 (m, 5H), 6.48 (d, J = 15.9 Hz,
1H), 6.23 (dd, J = 15.9 Hz, 6.0 Hz, 1H), 4.31–4.27 (m, 1H), 1.27
(d, J = 6.3 Hz, 3H), 1.24 (s, 9H). 13C NMR (CDCl3, 75 MHz,
ppm): d = 137.5, 135.2, 128.6, 128.1, 127.3, 126.4, 74.1, 68.4, 28.7,
23.9. IR (liquid film, cm−1): m = 3027, 2975, 2929, 2868, 1688,
1598, 1494, 1449, 1369, 1316, 1153, 1092, 967, 748, 693. HRMS
calc. C14H20O: 204.1514. Found: 204.1516.
(E)-1-(3-Methoxybut-1-enyl)-4-methylbenzene (2m). 1H NMR
(CDCl3, 300 MHz, ppm): d = 7.29 (d, J = 7.8 Hz, 2H), 7.13 (d,
J = 7.8 Hz, 2H), 6.50 (d, J = 15.9 Hz, 1H), 6.02 (dd, J = 15.9 Hz,
7.5 Hz, 1H), 3.90–3.85 (m, 1H), 3.31 (s, 3H), 2.34 (s, 3H), 1.32 (d,
J = 6.3 Hz, 3H). 13C NMR (CDCl3, 75 MHz, ppm): d = 137.6,
134.0, 131.4, 130.6, 129.4, 126.5, 78.3, 56.1, 21.6, 21.3. IR (liquid
film, cm−1): m = 3023, 2975, 2926, 2855, 2819, 1513, 1459, 1370,
1198, 1139, 1110, 1082, 969, 800. HRMS calc. C12H16O: 176.1201.
Found: 176.1199.
(E)-[3-(Benzyloxy)but-1-enyl]benzene (2g)16. 1H NMR (CDCl3,
300 MHz, ppm): d = 7.41–7.22 (m, 10H), 6.54 (d, J = 15.9 Hz,
1H), 6.17 (dd, J = 15.9 Hz, 7.5 Hz, 1H), 4.62 (d, J = 12.0 Hz,
1H), 4.44 (d, J = 12.0 Hz, 1H), 4.15–4.06 (m, 1H), 1.38 (d, J =
6.6 Hz, 3H). 13C NMR (CDCl3, 75 MHz, ppm): d = 138.9, 136.8,
131.9, 131.5, 128.7, 128.5, 127.8, 127.6, 126.6, 76.0, 70.2, 21.9. IR
(liquid film, cm−1): m = 3029, 2972, 2925, 2855, 1599, 1494, 1452,
1369, 1145, 1072, 968, 746, 694. HRMS calc. C17H18O: 238.1358.
Found: 238.1349.
(E)-1-Chloro-2-(3-methoxybut-1-enyl)benzene (2n). 1H NMR
(CDCl3, 400 MHz, ppm): d = 7.55–7.53 (m, 1H), 7.36–7.34 (m,
1H), 7.23–7.17 (m, 2H), 6.92 (d, J = 15.9 Hz, 1H), 6.08 (dd, J =
15.9 Hz, 7.6 Hz, 1H), 3.96–3.92 (m, 1H), 3.34 (s, 3H), 1.34 (d, J =
6.4 Hz, 3H). 13C NMR (CDCl3, 100 MHz, ppm): d = 135.0, 134.4,
133.2, 129.8, 128.7, 127.7, 127.0, 126.9, 78.1, 56.2, 21.5. IR (liquid
film, cm−1): m = 3063, 2977, 2929, 2821, 1591, 1470, 1441, 1369,
1354, 1200, 1143, 1110, 1083, 1037, 969, 751, 693. HRMS calc.
C11H13ClO: 196.0655. Found: 196.0653.
(E)-2-(4-Phenylbut-3-en-2-yloxy)ethanol (2h). 1H NMR
(CDCl3, 300 MHz, ppm): d = 7.40–7.22 (m, 5H), 6.54 (d, J =
15.9 Hz, 1H), 6.11 (dd, J = 15.9 Hz, 7.5 Hz, 1H), 4.10–4.01 (m,
1H), 3.74 (t, J = 7.5 Hz, 2H), 3.67–3.61 (m, 1H), 3.52–3.45 (m,
1H), 2.05 (br, 1H), 1.36 (d, J = 6.3 Hz, 3H). 13C NMR (CDCl3,
75 MHz, ppm): d = 136.6, 131.5, 128.7, 127.8, 126.6, 77.2, 69.5,
62.1, 21.7. IR (liquid film, cm−1): m = 3433, 3027, 2974, 2929,
2866, 1494, 1450, 1371, 1147, 1106, 1061, 968, 750, 694. HRMS
calc. C13H18O2: 206.1307. Found: 206.1303.
(E)-1-Bromo-2-(3-methoxybut-1-enyl)benzene (2o). 1H NMR
(CDCl3, 300 MHz, ppm): d = 7.56–7.52 (m, 2H), 7.30–7.24 (m,
1H), 7.13–7.08 (m, 1H), 6.87 (d, J = 15.9 Hz, 1H), 6.02 (dd, J =
15.9 Hz, 7.5 Hz, 1H), 3.97–3.92 (m, 1H), 3.35 (s, 3H), 1.34 (d, J =
6.3 Hz, 3H). 13C NMR (CDCl3, 75 MHz, ppm): d = 136.8, 134.6,
133.1, 130.0, 129.0, 127.6, 127.3, 123.8, 78.0, 56.3, 21.5. IR (liquid
film, cm−1): m = 3060, 2975, 2928, 2820, 1588, 1466, 1438, 1369,
1353, 1200, 1142, 1109, 1042, 1024, 967, 751, 667. HRMS calc.
C11H13BrO: 240.0150. Found: 240.0153.
(E)-4-Phenylbut-3-en-2-yl acetate (2i)17. 1H NMR (CDCl3,
300 MHz, ppm): d = 7.37–7.22 (m, 5H), 6.60 (d, J = 15.9 Hz,
1H), 6.19 (dd, J = 15.9 Hz, 7.5 Hz, 1H), 5.58–5.48 (m, 1H), 2.07
(s, 1H), 1.41 (d, J = 6.6 Hz, 3H). 13C NMR (CDCl3, 75 MHz,
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(E)-1-Methoxy-2-(3-methoxybut-1-enyl)benzene
(2p). 1H
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NMR (CDCl3, 300 MHz, ppm): d = 7.48–7.45 (m, 1H), 7.22
(d, J = 7.5 Hz, 1H), 6.95–6.83 (m, 3H), 6.10 (dd, J = 15.9 Hz,
7.8 Hz, 1H), 3.90–3.83 (m, 4H), 3.32 (s, 3H), 1.33 (d, J = 6.6 Hz,
3H). 13C NMR (CDCl3, 75 MHz, ppm): d = 156.9, 132.1, 128.8,
127.0, 126.4, 125.8, 120.8, 111.1, 78.7, 56.1, 55.6, 21.7. IR (liquid
film, cm−1): m = 2974, 2931, 1597, 1490, 1463, 1291, 1244, 1107,
1082, 1029, 975, 751. HRMS calc. C12H16O2: 192.1150. Found:
192.1143.
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(E)-1-Chloro-3-(3-methoxybut-1-enyl)benzene (2q). 1H NMR
(CDCl3, 400 MHz, ppm): d = 7.38–7.37 (m, 1H), 7.26–7.22 (m,
3H), 6.48 (d, J = 15.9 Hz, 1H), 6.11 (dd, J = 15.9 Hz, 7.4 Hz, 1H),
3.91–3.87 (m, 1H), 3.32 (s, 3H), 1.32 (d, J = 6.4 Hz, 3H). 13C NMR
(CDCl3, 100 MHz, ppm): d = 138.7, 134.6, 133.2, 129.90, 129.86,
127.6, 126.4, 124.7, 77.9, 56.2, 21.4. IR (liquid film, cm−1): m =
3062, 2978, 2923, 2821, 1594, 1566, 1475, 1370, 1352, 1111, 968,
779, 685. HRMS calc. C11H13ClO: 196.0655. Found: 196.0659.
(E)-1-(3-Methoxybut-1-enyl)naphthalene (2r). 1H NMR
(CDCl3, 400 MHz, ppm): d = 8.13–8.11 (m, 1H), 7.86–7.84 (m,
1H), 7.78 (d, J = 8.4 Hz, 1H), 7.61 (d, J = 6.8 Hz, 1H), 7.52–7.43
(m, 3H), 7.29 (d, J = 15.7 Hz, 1H), 6.13 (dd, J = 15.7 Hz, 7.6 Hz,
1H), 4.04–4.01 (m, 1H), 3.41 (s, 3H), 1.41 (d, J = 6.0 Hz, 3H). 13
C
NMR (CDCl3, 100 MHz, ppm): d = 134.9, 134.6, 133.8, 131.3,
128.71, 128.65, 128.1, 126.2, 125.9, 125.8, 124.1, 123.8, 78.4, 56.3,
21.7. IR (liquid film, cm−1): m = 3058, 2976, 2928, 2819, 1590,
1447, 1395, 1369, 1198, 1141, 1111, 1087, 969, 794, 775. HRMS
calc. C15H16O: 212.1201. Found: 212.1209.
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(E)-(4-Methoxypent-2-enyl)benzene (2s)18. 1H NMR (CDCl3,
300 MHz, ppm): d = 7.32–7.17 (m, 5H), 5.80–5.72 (m, 1H), 5.42
(dd, J = 15.3 Hz, 7.5 Hz, 1H), 3.73–3.67 (m, 1H), 3.39 (d, J =
6.6 Hz, 2H), 3.26 (s, 3H), 1.41 (d, J = 6.0 Hz, 3H). 13C NMR
(CDCl3, 75 MHz, ppm): d = 140.4, 133.4, 131.6, 128.7, 128.6,
128.4, 78.0, 56.0, 38.8, 21.5. IR (liquid film, cm−1): m = 3028, 2977,
2929, 2819, 1494, 1452, 1370, 1200, 1114, 1090, 1044, 972, 844,
745, 699. HRMS calc. C12H16O: 176.1201. Found: 176.1200.
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (20472078 and 30572234) and support from
the Chinese Academy of Sciences.
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1348 | Org. Biomol. Chem., 2008, 6, 1344–1348
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The Royal Society of Chemistry 2008
©