A new synthetic method of (Z)-4-aryl-but-2-en-1-ols via Suzuki-Miyaura cross-coupling reaction of 4-substituted 1,2-oxaborol-2(5H)-ols with benzyl bromides

Article abstract of DOI:10.1002/cjoc.201201122

Z and E configuration 4-aryl-but-2-en-1-ols were isolated from several terrestrial plants, and (Z)-4-aryl-but-2en-1-ols were found to have choleretic activity. Strategies have been reported to synthesize (E)-4-aryl-but-2-en-1ols with high selectivity. However, there is no method to obtain (Z)-4-aryl-but-2-en-1-ols with high selectivity now. We developed a Suzuki-Miyaura cross-coupling reaction of 1,2-oxaborol-2(5H)-ols with benzyl bromides to synthesize (Z)-4-aryl-but-2-en-1-ols, the products were obtained in up to 94% isolated yield. Copyright

Full text of DOI:10.1002/cjoc.201201122

FULL PAPER
DOI: 10.1002/cjoc.201201122
A New Synthetic Method of (Z)-4-Aryl-but-2-en-1-ols via
Suzuki-Miyaura Cross-Coupling Reaction of 4-Substituted
1,2-Oxaborol-2(5H)-ols with Benzyl Bromides†
Yu, Taoa(于涛)
Wu, Xinyan*,a(伍新燕)
Yang, Jun*,b(杨军)
a Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and
Technology, 130 Meilong Road, Shanghai 200237, China
b Shanghai Institute of Organic Chemistry, Chinese Academy of Science, 345 Lingling Road, Shanghai 200032,
China
Z and E configuration 4-aryl-but-2-en-1-ols were isolated from several terrestrial plants, and (Z)-4-aryl-but-2-
en-1-ols were found to have choleretic activity. Strategies have been reported to synthesize (E)-4-aryl-but-2-en-1-
ols with high selectivity. However, there is no method to obtain (Z)-4-aryl-but-2-en-1-ols with high selectivity now.
We developed a Suzuki-Miyaura cross-coupling reaction of 1,2-oxaborol-2(5H)-ols with benzyl bromides to syn-
thesize (Z)-4-aryl-but-2-en-1-ols, the products were obtained in up to 94% isolated yield.
Keywords Suzuki-Miyaura cross-coupling reaction, palladium-catalyzed, (Z)-but-2-en-1-ols, benzyl bromides
Introduction
products. To our best knowledge, there is no report on
synthesizing (Z)-4-aryl-but-2-en-1-ols in high stereose-
lectivity.
Allylbenzenes are commonly found in a variety of
nature products,[1] and they have been exhibited as the
important fragment in pharmacological activity mole-
cules with the effect of anticancer.[2] As a special spe-
cies of allylbenzenes, Z and E 4-aryl-but-2-en-1-ols
were isolated from several terrestrial plants. For exam-
ple, phellodenol-C (1) was isolated from the leaves of
Phelloendron amurense,[3] fuscaxanthone D (2) was
isolated from Garcinia plants,[4] and ω-hydroxy moracin
(3) was isolated from the leaves of mulberry[5] (Figure
1). (Z)-4-Aryl-but-2-en-1-ols were found to have chol-
eretic activity by Okuno and Kitagawa.[6] To date, only
(E)-4-aryl-but-2-en-1-ols can be obtained easily with
high yield and selectivity. Marquez and Stratakis re-
ported a reduction of acrylic esters to prepare (E)-4-
aryl-but-2-en-1-ols,[7] Shindo reported a coupling reac-
tion of silylalkene with allyl bromides to form (E)-4-
aryl-but-2-en-1-ols.[8] There are several methods to
synthesize the (Z)-4-aryl-but-2-en-1-ols but in poor se-
lectivity. Kang reported the palladium-catalyzed cou-
pling reaction of vinyl epoxides with arylorganobismuth
compounds with the Z/E ratio 1∶3.4.[9] Lipshutz re-
ported a ring-open reaction of vinyl epoxides with aryl-
organocopper reagents with the Z/E ratio 1 ∶2.[10]
Tanaka reported the synthesis of 4-aryl-but-2-en-1-ols
by reduction of acrylate with the Z/E ratio 2∶3.[11] In
all these reactions, E configuration is the dominant
O
O
OH
HO
O
O
OCH3
OH
OH
OH
1
2
OH
HO
O
HO
OH
3
Figure 1 Structures of phellodenol-C (1), fuscaxanthone D (2),
ω-hydroxy moracin (3).
Palladium-catalyzed cross-coupling reactions are ex-
tremely powerful tools for the construction of multisub-
stituted alkenes with retention of double bond configu-
ration.[12] Suzuki cross-coupling reaction of alkenylbo-
ron with benzyl halides is a practical method for synthe-
sizing allylbenzenes because the organoboron reagents
are easily prepared, stable and low-toxic.[13] Fang re-
ported the preparation of 1,2-oxaborol-2(5H)-ols and
their palladium-catalyzed Suzuki-Miyaura cross-cou-
pling reaction with aryl halides.[14] Moreover, studies on
Suzuki-Miyaura cross-coupling reaction of benzyl hal-
ides with variety of organoboron compounds were re-
*
E-mail: xinyanwu@ecust.edu.cn, yangj@sioc.ac.cn
Received November 14, 2012; accepted December 11, 2012; published online December 17, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201201122 or from the author.
Dedicated to the 60th Anniversary of East China University of Science and Technology.
†
2798
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 2798—2804

A New Synthetic Method of (Z)-4-Aryl-but-2-en-1-ols via Suzuki-Miyaura Cross-Coupling Reaction
ported.[15]
indicated dppf was not a suitable ligand for the model
Herein, we report a new method for synthesizing
(Z)-4-aryl-but-2-en-1-ols via Suzuki-Miyaura cross-
coupling reaction between 1,2-oxaborol-2(5H)-ols and
benzyl bromides.
reaction (Entry 6). In addition, the cross-coupling reac-
tion using PdCl2(PPh3)2 without additional phosphine
ligand was tested, the corresponding product 6a was
1
obtained in 75% H NMR yield (Entry 7). It seems that
PdCl2(PPh3)2-PPh3 catalytic system is more efficient.
Next, different bases were surveyed. When K3PO4•
3H2O was replaced by KF, K2CO3 or NaOH, the
chemical yield was decreased to poor (Table 1, Entries 8
—10 vs. 3). When anhydrous K3PO4 was used as base,
Results and Discussion
Firstly, 4-phenyl-1,2-oxaborol-2(5H)-ol (4a) and
benzyl bromide (5a) were chosen as representative cou-
pling partners to optimize the reaction conditions of the
Suzuki-Miyaura cross-coupling reaction (Table 1).
When 3 mol% Pd(OAc)2 was used as pre-catalyst and
PPh3 as ligand, the desired coupling product 6a was
firstly isolated in 49% yield (Entry 1), and the configu-
ration of the double bond was determined to be Z form
by NOESY spectra. By replacing Pd(OAc)2 with PdCl2,
the yield increased from 49% to 69% (Entry 2), and the
yield increased to 83% using PdCl2(PPh3)2 (Entry 3).
Then different ligands were screened in the presence of
PdCl2(PPh3)2. PCy3 and PtBu3 were proved to promote
the Suzuki cross-coupling reaction of chloroalkanes,[16]
but in this coupling reaction the yields were much lower
than using PPh3 (Entries 4 and 5 vs. 3). The results also
1
the product obtained in 70% H NMR yield (Entry 11).
The results suggested the catalytic amount of water was
positive for the cross-coupling reaction.[17] The solvent
effect on cross-coupling reaction between 4a and 5a
was also investigated. In the nonpolar solvent such as
toluene and CH2Cl2, the yield decreased slightly (En-
tries 12 and 13). On the other hand, poor yield was ob-
tained when polar solvents such as DMF and MeOH
were chosen (Entries 14 and 15). Different temperature
and reaction time were also tested. The optimal reaction
condition was as follows: PdCl2(PPh3)2 as catalyst, PPh3
as ligand, K3PO4•3H2O as base, stirring in THF at 60
℃ for 2 h (Entry 18).
Table 1 Optimization of a cross-coupling reaction for the synthesis of (Z)-4-aryl-but-2-en-1-olsa
Pd salt, ligand
base, solvent
+
OH
B
Br
O
OH
6a
4a
5a
Entry
1
Pd salt
Ligand
PPh3
PPh3
PPh3
PCy3
PtBu3
dppf
—
Base
Solvent
THF
Temp./℃
60
Time/h
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
8
Yieldb/%
49c
69
Pd(OAc)2
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
KF
2
PdCl2
THF
60
3
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2
THF
60
83
4
THF
60
22
5
THF
60
46
6
THF
60
37
7
THF
60
75
8
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
THF
60
30
9
K2CO3
THF
60
13
10
11
12
13
14
15
16
17
18
19
NaOH
THF
60
5
K3PO4
THF
60
70
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
K3PO4•3H2O
Toluene
CH2Cl2
DMF
MeOH
THF
80
78
60
45
60
24
60
3
r.t.
60
73
THF
87
90 (88c)
THF
60
2
THF
60
2
42
a
Conditions: 4-phenyl-1,2-oxaborol-2(5H)-ol (0.5 mmol), benzyl chloride (0.6 mmol), Pd (0.015 mmol, 3 mol%), ligand (0.03 mmol, 6
mol%), base (1.5 mmol, 3 equiv.), 4 mL solvent. b 1H NMR yield, 1-(4-nitrophenyl)ethanone as an internal standard. c Isolated yield.
Chin. J. Chem. 2012, 30, 2798—2804
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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2799

Yu, Wu & Yang
FULL PAPER
In some cases, a mixture of hydrophilic solvent with
water could improve the yield of cross-coupling reac-
tion.[17] So we studied the effect of water under the op-
timized reaction conditions (Table 2). Water was added
ranging from 0 to 100 equiv. according to the amount of
4-phenyl-1,2-oxaborol-2(5H)-ol. The yield was better
when 1—20 equiv. water was added. So water is proved
to promote the cross-coupling reaction, whether the liq-
uid water or water of crystallization.
With these optimized reaction conditions in hand,
the reactions of a variety of 1,2-oxaborol-2(5H)-ols and
benzyl bromides were conducted (Table 3). The results
indicated that benzyl bromides with substituents in the
ortho- and para-position were tolerated by the
cross-coupling reaction, whatever electron-withdrawing
groups (Entries 4, 8 and 10) or electron-donating groups
(Entries 2, 3 and 6). Both 4-aryl-1,2-oxaborol-2(5H)-ols
(Entries 1 — 11) and 4-alkyl-1,2-oxaborol-2(5H)-ols
(Entries 12—14) were cross-coupling with benzyl bro-
mides to obtain the corresponding products in good-to-
excellent yields (79%—94%), and the former was better
in this reaction.
Table 2 The effect of water on the cross-coupling reaction of
4-phenyl-1,2-oxaborol-2(5H)-ol with benzyl bromide
Entry
Equiv.a
Yieldb/%
1
2
3
4
5
6
7
0
1
70
88
88
90
86
74
70
Conclusions
In summary, we have developed an efficient method
to provide (Z)-4-aryl-but-2-en-1-ols via Suzuki-Miyaura
cross-coupling reaction between 1,2-oxaborol-2(5H)-ols
and benzyl bromides. The desired products were ob-
tained in good-to-excellent yields and excellent stereo-
selectivity. This coupling reaction provided a novel
strategy to synthesize a series of nature products con-
taining the but-2-en-1-ol fragment. The study on the
synthesis of natural products by this coupling reacion is
in progress.
5
9c
20
50
100
Base on the amount of 4-phenyl-1,2-oxaborol-2(5H)-ol. 1H
NMR yield, 1-(4-nitrophenyl)ethanone as an internal standard.
c Water of crystallization.
a
b
Table 3 Reaction conditions and yields of the synthesis of (Z)-4-aryl-but-2-en-1-ols 6a—6na
R2
R1
R1
PdCl2(PPh3)2 (3 mol%), PPh3
+
OH
B
O
.
R2
K3PO4 3H2O, THF
Br
OH
6
5
4
Entry
1
1,2-Oxaborol-2(5H)-ols 4
Benzyl bromide 5
Product 6
Yieldb/%
88
Br
B
B
OH
OH
OH
O
O
O
6a
Br
2
3
88
92
OH
6b
Br
B OH
OH
6c
NO2
Br
4
91
B OH
O2N
OH
O
6d
2800
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 2798—2804

A New Synthetic Method of (Z)-4-Aryl-but-2-en-1-ols via Suzuki-Miyaura Cross-Coupling Reaction
Continued
Yieldb/%
Entry
5
1,2-Oxaborol-2(5H)-ols 4
Benzyl bromide 5
Product 6
Br
91
89
88
91
93
89
B
B
OH
OH
OH
O
O
6e
OCH3
Br
6
7
H3CO
OH
6f
Br
B OH
OH
O
6g
NO2
Br
8
B OH
O2N
OH
O
6h
H3CO
H3CO
Br
9
B OH
OH
O
O
6i
NO2
H3CO
H3CO
Br
10
O2N
B OH
OH
6j
Br
Br
Br
Br
11
12
13
14
94
83
79
85
OH
B
O
OH
6k
OH
B
O
OH
6l
B OH
O
OH
6m
OH
B
OH
O
6n
All reactions were performed with 4 (0.5 mmol), 5 (0.6 mmol), PdCl2(PPh3)2 (0.015mmol), PPh3 (0.03 mmol) and K3PO4•3H2O (1.5
mmol) in THF at 60 ℃. b Isolated yield.
a
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2801

Yu, Wu & Yang
FULL PAPER
Experimental
(23.65), 104 (17.76); HRMS (EI): calcd 238.1358,
found 238.1359 for C17H18O.
1H NMR spectra were recorded on Varian Mercury-
300 spectrometer, 13C NMR spectra were recorded on
Varian Mercury-400 spectrometer, chemical shifts (δ) of
1H NMR and 13C NMR spectra were recorded in CDCl3,
with tetramethylsilane as an internal standard. IR spec-
tra were recorded on Perkin-Elmer 983 spectrometer.
Low Resolution Mass spectra were recorded on HP
5973N spectrometer. High Resolution Mass spectra
were recorded on Premier CAB088 spectrometer.
Unless otherwise indicated, all reactions were car-
ried out under an argon atmosphere in dried Schlenk
tube with magnetic stirring. THF were freshly distilled
from sodium-benzophenone. 4-Substituted-1,2-oxaborol-
2(5H)-ols were synthesized by the method of refer-
ences.[14] Thin-layer chromatography was performed on
silica gel (GF 254). Column chromatograph was per-
formed on silica gel (300—400 mesh) eluting with pe-
troleum ether and ethyl acetate.
(Z)-2-Phenyl-4-p-tolylbut-2-en-1-ol (6c)
92%
yield, pale yellow solid; 1H NMR (CDCl3, 300 MHz) δ:
7.47 (d, J＝6.9 Hz, 2H), 7.37—7.29 (m, 3H), 7.13 (s,
4H), 6.07 (t, J＝7.5 Hz, 1H), 4.69 (s, 2H), 3.62 (d, J＝
7.8 Hz, 2H), 2.33 (s, 3H), 1.38 (s, 1H); 13C NMR
(CDCl3, 100 MHz) δ: 141.41, 140.06, 137.87, 136.47,
131.52, 130.03, 129.21, 128.98, 127.98, 127.10, 60.57,
34.77, 21.67; IR (KBr) ν: 3387 (s), 3323 (s), 3014 (m),
2911 (m), 1578 (s), 1513 (s), 1490 (s), 1439 (m), 1331
－
1
(m), 1006 (m), 808 (s), 769 (s), 694 (s), 504 (s) cm ;
MS (EI-LR) m/z: 238 (M＋, 1.27), 205 (100.00), 220
(95.13), 115 (39.64), 91 (32.24), 129 (29.09), 207
(28.29), 121 (25.27), 105 (23.51); HRMS (EI): calcd
238.1358, found 238.1361 for C17H18O.
(Z)-4-(4-Nitrophenyl)-2-phenylbut-2-en-1-ol (6d)
1
91% yield, pale yellow solid; H NMR (CDCl3, 300
MHz) δ: 8.18 (d, J＝9.0 Hz, 2H), 7.44—7.37 (m, 7H),
6.00 (t, J＝7.8 Hz, 1H), 4.70 (s, 2H), 3.77 (d, J＝7.5 Hz,
2H), 1.48 (s, 1H); 13C NMR (CDCl3, 100 MHz) δ:
148.67, 147.42, 141.78, 140.95, 129.96, 129.38, 128.97,
128.44, 127.17, 124.60, 60.64, 35.09; IR (KBr) ν: 3355
(w), 1605 (s), 1594 (s), 1518 (s), 1491 (s), 1444 (m),
1345 (s), 1108 (s), 1007 (m), 856 (s), 751 (m), 696 (s)
General procedure for the synthesis of (Z)-4-aryl-
but-2-en-1-ols
An oven-dried Schlenk tube was charged with
1,2-oxaborol-2(5H)-ols (0.5 mmol), PdCl2(PPh3)2 (11
mg, 0.015 mmol), PPh3 (8 mg, 0.03 mmol), K3PO4•
3H2O (399 mg, 1.5 mmol). Benzyl bromides (0.6 mmol)
and THF (4 mL) were added under an argon atmosphere.
The reaction mixture was stirred at 60 ℃ followed by
TLC. After cooling to room temperature, the reaction
mixture was filrered through Celite. The solvent was
removed in vacuo, and the residue was purified by silica
gel column chromatography (5∶1, petroleum ether∶
ethyl aceate, V∶V) to obtain (Z)-4-aryl-but-2-en-1-ols
6a―6n.
－
＋
1
cm ; MS (EI-LR) m/z: 269 (M , 2.59), 91 (100.00),
120 (69.09), 251 (36.97), 204 (34.61), 115 (33.33), 192
(29.33), 77 (26.25), 191 (23.15); HRMS (EI): calcd
269.1052, found 269.1056 for C16H15NO3.
(Z)-4-(Naphthalen-2-yl)-2-phenylbut-2-en-1-ol (6e)
1
91% yield, pale yellow solid; H NMR (CDCl3, 300
MHz) δ: 7.87—7.82 (m, 3H), 7.71 (s, 1H), 7.54—7.32
(m, 8H), 6.19 (t, J＝7.5 Hz, 1H), 4.75 (s, 2H), 3.84 (d,
J＝7.5 Hz, 2H), 1.72 (s, 1H); 13C NMR (CDCl3, 100
MHz) δ: 141.27, 140.32, 138.39, 134.30, 133.99, 132.78,
130.95, 129.20, 128.91, 128.29, 128.14, 128.00, 127.80,
127.07, 126.74, 126.07, 60.45, 35.30; IR (KBr) ν: 3374
(w), 3305 (m), 1630 (m), 1601 (s), 1491 (m), 1438 (m),
1334 (m), 1006 (m), 824 (s), 748 (m), 695 (s), 469 (m)
(Z)-2,4-Diphenylbut-2-en-1-ol (6a) 88% yield,
1
yellow oil; H NMR (CDCl3, 300 MHz) δ: 7.47 (d, J＝
7.8 Hz, 2H), 7.37—7.24 (m, 8H), 6.08 (t, J＝7.8 Hz,
1H), 4.69 (s, 2H), 3.66 (d, J＝7.5 Hz, 2H), 1.56 (s, 1H);
13C NMR (CDCl3, 100 MHz) δ: 141.34, 140.92, 140.20,
131.18, 129.32, 129.19, 129.09, 127.99, 127.09, 126.91,
60.49, 35.16; IR (KBr) ν: 3345 (w), 3059 (m), 1601 (s),
1494 (s), 1453 (s), 1012 (m), 743 (s), 697 (s) cm ; MS
(EI-LR): 224 (M＋, 2.40), 91 (100.00), 206 (62.21), 115
(59.42), 105 (58.59), 120 (39.18), 77 (37.61), 205
(22.50), 107 (19.60); HRMS (EI): calcd 224.1201,
found 224.1198 for C16H16O.
－
＋
1
cm ; MS (EI-LR) m/z: 274 (M , 5.49), 115 (100.00),
141 (69.16), 91 (65.34), 165 (62.81), 256 (59.69), 77
(36.66), 144 (34.05), 142 (33.22); HRMS (EI): calcd
274.1358, found 274.1359 for C20H18O.
－
1
(Z)-4-(4-Methoxyphenyl)-2-m-tolylbut-2-en-1-ol
1
(6f) 89% yield, white solid; H NMR (CDCl3, 300
MHz) δ: 7.29—7.08 (m, 6H), 6.86 (d, J＝8.4 Hz, 2H),
6.04 (t, J＝7.5 Hz, 1H), 4.67 (s, 2H), 3.79 (s, 3H), 3.59
(d, J＝7.8 Hz, 2H), 2.36 (s, 3H), 1.59 (s, 1H); 13C NMR
(CDCl3, 100 MHz) δ: 158.71, 139.93, 138.76, 132.98,
131.37, 130.00, 129.28, 129.08, 128.72, 127.81, 124.12,
114.69, 60.44, 55.93, 34.24, 22.15; IR (KBr) ν: 3335
(w), 2905 (m), 1608 (s), 1581 (s), 1509 (s), 1439 (m),
1299 (m), 1246 (s), 1172 (s), 1037 (s), 1010 (s), 818 (m),
(Z)-2-Phenyl-4-o-tolylbut-2-en-1-ol (6b)
88%
1
yield, white solid; H NMR (CDCl3, 300 MHz) δ: 7.48
(d, J＝7.5 Hz, 2H), 7.37—7.27 (m, 3H), 7.18 (s, 4H),
6.02 (t, J＝7.2 Hz, 1H), 4.70 (s, 2H), 3.63 (d, J＝7.5 Hz,
2H), 2.35 (s, 3H), 1.41 (s, 1H); 13C NMR (CDCl3, 100
MHz) δ: 141.36, 140.31, 139.26, 136.91, 131.02, 130.72,
129.31, 129.25, 128.02, 127.17, 127.11, 126.96, 60.61,
32.97, 20.27; IR (KBr) ν: 3346 (w), 3058 (s), 3021 (s),
2925 (m), 1600 (s), 1492 (m), 1461 (m), 1445 (m), 1380
－
1
783 (s), 698 (s), 538 (m) cm ; MS (EI-LR) m/z: 268
(M＋, 6.02), 250 (100.00), 145 (83.71), 121 (78.85), 137
(72.25), 91 (68.45), 115 (61.11), 219 (51.31), 129
(50.66); HRMS (EI): calcd 268.1463, found 268.1466
for C18H20O2.
－
1
(m), 1260 (m), 1012 (s), 745 (m), 697 (s) cm ; MS
(EI-LR) m/z: 238 (M＋, 2.37), 105 (100.00), 205 (43.90),
120 (41.03), 77 (36.36), 91 (35.55), 220 (33.81), 115
2802
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Chin. J. Chem. 2012, 30, 2798—2804

A New Synthetic Method of (Z)-4-Aryl-but-2-en-1-ols via Suzuki-Miyaura Cross-Coupling Reaction
1
(Z)-4-Phenyl-2-p-tolylbut-2-en-1-ol (6g)
88%
yield, white solid; H NMR (CDCl3, 300 MHz) δ: 7.32
—7.27 (m, 8H), 7.10 (s, 1H), 6.06 (t, J＝7.5 Hz, 1H),
4.67 (s, 2H), 3.65 (d, J＝7.5 Hz, 2H), 2.36 (s, 3H), 1.56
(s, 1H); 13C NMR (CDCl3, 100 MHz) δ: 141.29, 140.96,
140.20, 138.70, 130.88, 129.25, 129.05, 128.71, 127.80,
126.84, 124.13, 60.38, 35.10, 22.10; IR (KBr) ν: 3419
(w), 2918 (m), 1695 (m), 1602 (s), 1455 (m), 1260 (s),
1
yield, pale yellow solid; H NMR(CDCl3, 300 MHz) δ:
7.38—7.14 (m, 9H), 6.05 (t, J＝7.5 Hz, 1H), 4.68 (s,
2H), 3.66 (d, J＝7.8 Hz, 2H), 2.35 (s, 3H), 1.38 (s, 1H);
13C NMR (CDCl3, 100 MHz) δ: 140.57, 139.59, 137.87,
137.30, 129.84, 129.45, 128.82, 128.61, 126.49, 126.40,
60.04, 34.67, 21.24; IR (KBr) ν: 3385 (w), 3020 (m),
2907 (m), 1601 (s), 1512 (s), 1492 (s), 1442 (m), 1327
(m), 1005 (m), 923 (m), 818 (m), 749 (s), 699 (s), 640
－
1
1165 (m), 1028 (s), 783 (s), 744 (s), 697 (s) cm ; MS
(EI-LR) m/z: 238 (M＋, 4.02), 91 (100.00), 119 (57.98),
220 (56.82), 105 (46.45), 115 (38.35), 205 (32.48), 77
(29.68), 65 (26.47); HRMS (EI): calcd 238.1358, found
238.1357 for C17H18O.
－
＋
1
(m), 518 (m) cm ; MS (EI-LR) m/z: 238 (M , 14.39),
115 (100.00), 220 (89.58), 91 (84.37), 105 (80.77), 129
(67.75), 132 (63.93), 205 (56.46), 128 (44.07); HRMS
(EI): calcd 238.1358, found 238.1355 for C17H18O.
(Z)-4-(4-Nitrophenyl)-2-p-tolylbut-2-en-1-ol (6h)
(Z)-2-(2-Phenylethylidene)hexan-1-ol (6l)
83%
yield, colorless oil; 1H NMR (CDCl3, 300 MHz) δ: 7.31
—7.16 (m, 5H), 5.51 (t, J＝7.5 Hz, 1H), 4.23 (s, 2H),
3.45 (d, J＝7.8 Hz, 2H), 2.16 (t, J＝7.5 Hz, 2H), 1.46—
1.28 (m, 5H), 0.90 (t, J＝7.2 Hz, 3H); 13C NMR (CDCl3,
100 MHz) δ: 141.75, 140.37, 129.17, 128.96, 127.34,
126.64, 61.02, 35.59, 34.41, 31.19, 23.20, 14.64; IR
(KBr) ν: 3332 (w), 3062 (m), 2928 (m), 1603 (s), 1494
1
91% yield, pale yellow solid; H NMR (CDCl3, 300
MHz) δ: 8.17 (d, J＝9.0 Hz, 2H), 7.41 (d, J＝8.7 Hz,
2H), 7.35 (d, J＝7.8 Hz, 2H), 7.17 (d, J＝8.1 Hz, 2H),
5.96 (t, J＝7.5 Hz, 1H), 4.68 (d, J＝6.0 Hz, 2H), 3.76 (d,
J＝7.8 Hz, 2H), 2.35 (s, 3H), 1.45 (t, J＝5.7 Hz, 1H);
13C NMR (CDCl3, 100 MHz) δ: 148.81, 147.38, 141.60,
138.31, 137.93, 130.09, 129.95, 128.10, 127.04, 124.58,
60.59, 35.07, 21.75; IR (KBr) ν: 3346 (w), 2915 (m),
1605 (s), 1595 (s), 1518 (s), 1436 (m), 1345 (s), 1109
(s), 1005 (m), 855 (s), 819 (s), 750 (s), 699 (s), 500 (s)
－
1
(s), 1453 (m), 1378 (s), 1013 (w), 740 (s), 698 (s) cm ;
MS (ESI-LR) m/z: 227.2 (M＋Na＋); HRMS (ESI):
calcd 227.1406, found 227.1414 for C14H20NaO.
(Z)-2-(2-Phenylethylidene)pentan-1-ol (6m) 79%
yield, colorless oil; 1H NMR (CDCl3, 300 MHz) δ: 7.32
—7.17 (m, 5H), 5.53 (t, J＝7.5 Hz, 1H), 4.25 (s, 2H),
3.46 (d, J＝7.5 Hz, 2H), 2.15 (t, J＝7.8 Hz, 2H), 1.47—
1.29 (m, J＝7.5 Hz, 2H), 1.24 (s, 1H), 0.92 (t, J＝7.2
Hz, 3H); 13C NMR (CDCl3, 100 MHz) δ: 141.74,
140.14, 129.19, 128.96, 127.61, 126.66, 61.05, 38.02,
34.43, 22.08, 14.55; IR (KBr) ν: 3340 (w), 3027 (m),
2958 (m), 1603 (s), 1494 (s), 1453 (m), 1013 (w), 740
－
＋
1
cm ; MS (EI-LR) m/z: 283 (M , 9.62), 105 (100.00),
134 (31.11), 91 (26.37), 115 (25.49), 106 (19.28), 265
(19.20), 117 (18.68), 119 (17.67); HRMS (EI): calcd
283.1208, found 283.1212 for C17H17NO3.
(Z)-2-(4-Methoxyphenyl)-4-phenylbut-2-en-1-ol
(6i) 93% yield, dust color solid; 1H NMR (CDCl3, 300
MHz) δ: 7.41 (d, J＝8.7 Hz, 2H), 7.34—7.19 (m, 5H),
6.88 (d, J＝8.7 Hz, 2H), 6.00 (t, J＝7.5 Hz, 1H), 4.67 (s,
2H), 3.81 (s, 3H), 3.64 (d, J＝7.5 Hz, 2H), 1.36 (s, 1H);
13C NMR (CDCl3, 100 MHz) δ: 159.26, 139.14, 133.24,
129.13, 128.83, 128.60, 127.73, 126.40, 114.17, 60.05,
55.51, 34.66; IR (KBr) ν: 3398 (w), 2952 (m), 2834 (s),
1605 (s), 1512 (s), 1454 (m), 1286 (m), 1183 (s), 1030
－
＋
1
(s), 698 (s) cm ; MS (ESI-LR) m/z: 213.1 (M＋Na );
HRMS (ESI): calcd 213.1250, found 213.1257 for
C13H18NaO.
(Z)-2-Phenethyl-4-phenylbut-2-en-1-ol (6n) 85%
yield, colorless oil; 1H NMR (CDCl3, 300 MHz) δ: 7.39
—7.19 (m, 10H), 5.51 (s, 1H), 4.25 (s, 2H), 3.43 (d,
J＝7.2 Hz, 2H), 2.79 (s, 2H), 2.49 (s, 2H), 1.28 (s, 1H);
13C NMR (CDCl3, 100 MHz) δ: 142.54, 141.42, 139.37,
129.12, 128.98, 128.90, 128.13, 126.61, 126.46, 60.93,
37.49, 35.41, 34.30; IR (KBr) ν: 3355 (w), 3026 (m),
2924 (s), 1602 (s), 1495 (s), 1453 (s), 1029 (m), 743 (s),
－
1
(m), 834 (s), 743 (s), 699 (s), 531 (m) cm ; MS (EI-LR)
m/z: 254 (M＋, 3.46), 135 (100.00), 91 (34.83), 121
(19.06), 77 (18.07), 240 (15.94), 92 (12.90), 136 (9.31),
107 (8.61); HRMS (EI): calcd 254.1307, found
254.1308 for C17H18O2.
(Z)-2-(4-Methoxyphenyl)-4-(4-nitrophenyl)but-2-
en-1-ol (6j) 89% yield, pale yellow solid; H NMR
－
＋
1
1
698 (s) cm ; MS (ESI-LR) m/z: 275.2 (M＋Na );
HRMS (ESI): calcd 275.1406, found 275.1408 for
C18H20NaO.
(CDCl3, 300 MHz) δ: 8.17 (d, J＝8.7 Hz, 2H), 7.42—
7.38 (m, 4H), 6.90 (d, J＝8.4 Hz, 2H), 5.92 (t, J＝7.8
Hz, 1H), 4.67 (d, J＝5.1 Hz, 2H), 3.82 (s, 3H), 3.75 (d,
J＝7.8 Hz, 2H), 1.46 (t, J＝5.4 Hz, 1H); 13C NMR
(CDCl3, 100 MHz) δ: 160.07, 148.90, 141.14, 133.24,
129.95, 128.31, 127.72, 127.38, 124.59, 114.81, 60.57,
56.03, 35.06; IR (KBr) ν: 3368 (w), 2932 (m), 1605 (s),
1595 (s), 1516 (s), 1458 (m), 1346 (s), 1249 (s), 1184
(s), 1110 (s), 1017 (m), 826 (m), 751 (s) cm ; MS
(EI-LR) m/z: 299 (M＋, 24.37), 91 (100.00), 121 (90.69),
115 (77.97), 206 (72.89), 77 (46.51), 105 (34.42), 178
(34.12), 89 (33.38); HRMS (EI): calcd 299.1158, found
299.1157 for C17H17NO4.
Acknowledgement
We are grateful for the financial support from Na-
tional Natural Science Foundation of China (Nos.
20802088, 91017006, 90917017) and the Fundamental
Research Funds for the Central Universities.
－
1
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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2804
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Chin. J. Chem. 2012, 30, 2798—2804