Mild and efficient barbier allylation reaction mediated by magnesium powder under solvent-free conditions

Article abstract of DOI:10.1016/j.tet.2010.12.035

A novel and highly efficient synthesis of homoallylic alcohols is achieved by the allylation of carbonyl compounds using magnesium powder as mediator under solvent-free conditions. A series of aldehydes and ketones are converted to the corresponding homoa

Full text of DOI:10.1016/j.tet.2010.12.035

Tetrahedron 67 (2011) 849e855
Contents lists available at ScienceDirect
Tetrahedron
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Mild and efficient barbier allylation reaction mediated by magnesium powder
under solvent-free conditions
,
b
,
a
a
Shunxi Li a, Jin-Xian Wang a , Xiaoliu Wen , Xiaofang Ma
*
a Institute of Chemistry, Department of Chemistry, Northwest Normal University, 967 Anning Road (E.), Lanzhou 730070, PR China
b State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730070, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 9 October 2010
Received in revised form 8 December 2010
Accepted 14 December 2010
Available online 17 December 2010
A novel and highly efficient synthesis of homoallylic alcohols is achieved by the allylation of carbonyl
compounds using magnesium powder as mediator under solvent-free conditions. A series of aldehydes
and ketones are converted to the corresponding homoallylic alcohols, the yields of the reaction is con-
siderably high (85e98%). The procedure is environment benign, operationally simple and easy to scale up
at room temperature.
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
potentially lead to some environmental pollution. So, the de-
velopment of more improved synthetic methods for the prepara-
Over recent years, the allylation of carbonyl compounds has
attracted tremendous interest in building blocks for the construc-
tion of various biologically active compounds and pharmaceutical
chemistry.1 Therefore, numerous reagents and methods have been
applied to accomplish synthetically useful homoallylic alcohols.2
Examples include various Lewis acids,3 metal salts,4 catalysts,5
tion of homoallylic alcohols remains an active research area.
Previously our program reported the allylation of carbonyl com-
pounds under solvent-free conditions.19a,26 In this paper, we focus on
the potential use of magnesium metal in solvent-free allylation re-
actions, we are interested in finding the allylation of carbonyl com-
pounds mediated by magnesium powder under solvent-free
conditions to synthesize the homopropargyl alcohols (Scheme 1)
possessed the following advantages: high yields, short reaction time,
low costs, reduced pollution, simplicity in process and handling.
b
-cyclodextrin,6 organometallic reagents in organic media, aque-
ous media,7,8 ionic liquids,9 and PEG.10 However, because of eco-
nomical and environmental concerns, organic chemists have been
confronted with a new challenge of finding novel methods in or-
ganic synthesis that can reduce and finally eliminate the impact of
volatile organic solvents and hazardous toxic chemicals on the
environment.11 This new challenge attracts considerable attention
because of increasing public interest in green chemistry.12
OH
R2= H
R1
O
Within the last several years, various metals have been exploi-
ted for mediating allylation of carbonyl compounds. Including In,13
Sb,14 Pb,15 Mn,16 Fe,17 Mg,7,18 Zn,8b,19 Sn,11,20,9b,8a Ga,21 Bi22 or or-
Mg
Br
R1
R2
solvent-free r.t
+
OH
R2
R2= Me, Et
ganometallic compounds, such as allylmercurybromide,23 tri-
R1
24b
allylaluminum,24a and allyltributylstannanes
mediated Barbier
R1 = Ph, Aryl, Heterocyclic, Aliphatic
reactions in aqueous medium are well known in the literature.
Though using of aqueous medium has a number of advantages,25 it
is notable that not all of the above aqueous Barbier reactions could
be conducted in fully aqueous media. Most of these reactions re-
quire long reaction time to improve the yields. In addition, many
allylmagnesium and allyllithium reagents are often very difficult to
handle, and the reactions have to be performed under strictly an-
hydrous, oxygen-free, low-temperature conditions for prolonged
lengths times and the use of a great deal of organic solvents can
Scheme 1. Magnesium powder mediated allylation of carbonyl compounds with
allylbromide under solvent-free conditions.
2. Results and discussion
In order to exploit the effect of different metals and solvents on
the yields of the reaction, a mixture of benzaldehyde, allylbromide,
solvent, and metal was stirred at room temperature. The results
were presented in Table 1.
* Corresponding author. E-mail address: wangjx@nwnu.edu.cn (J.-X. Wang).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.12.035

850
S. Li et al. / Tetrahedron 67 (2011) 849e855
Table 1
Table 2
.Allylation of aldehyde mediated by various metals under different conditionsa
Allylation of aldehydes mediated by magnesium powder under solvent-free
conditionsa
O
OH
OH
O
M
Br
H
Mg
solvent or solvent-free, r.t.
Br
solvent-free, r.t.
R
R
H
1a-s
3a-s
2
Entry
Mediator
Solvent
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
Ni
d
6
4
7
15
16
17
17
19
NRc
NRc
NRc
NRc
NRc
NRc
NRc
NRc
85
Entry
1
RCHO
Productb
Time/(min)
8(15d)
Yield/(%)c
85(81d)
Mn
Co
Fe
Al
W
Pb
Ti
Mg
Sn
d
d
CHO
3a
d
d
d
CHO
d
2
3
3b
3c
5(10d)
90(91d)
87
d
Cl
9
d
0.14
1
CHO
10
11
12
13
14
15
16
17
18
d
78
Zn
Mg
Mg
Mg
Mg
Mg
Mg
Mg
d
0.25
24
20
16
8
6
4
0.21
81
5
H2O
CH2Cl2
DMSO
EtOH
Et2O
DMF
THF
NRc
NRc
NRc
20
Cl
CHO
38
46
78
4
5
6
3d
3e
3f
6
6
5
91
86
94
Cl
a
Reaction conditions: benzaldehyde (2 mmol), allylbromide (3 mmol), metal
(3 mmol), solvent (2 mL), at room temperature.
CHO
Cl
b
Isolated yield.
c
Cl
NR: no reaction. Almost all of the benzaldehyde was recycled.
Cl
CHO
We first probed into different metals to mediate the reaction.
From Table 1, it was obvious that most metals, such as Ni, Mn, Co,
Fe, Al, W, Pb, and Ti did not give the desired product even after
prolonged stirring time (Table 1, entries 1e8) under solvent-free
conditions. When mediated by magnesium, the allylation went on
smoothly and the desired product was obtained under solvent-free
conditions (Table 1, entry 9). With tin powder as mediators in the
absence of solvent, the homoallylic alcohol was gained in 78% yield
after 1 h (Table 1, entry 10). For zinc powder, the allylation yield was
further enhanced to 81% at room temperature after 0.25 h (Table 1,
entry 11).
Cl
CHO
7
8
3g
3h
6
5
90
92
Br
CHO
Br
Then we explored the allylation of benzaldehyde mediated by
magnesium under different solvents. We found that the desired
products were not observed after prolonged stirring time, when
distilled water, dimethyl sulfoxide or methylene dichloride was
used as solvent (Table 1, entries 12e14). And the solvent was eth-
anol, diethyl ether or N,N-dimethylformamide (Table 1, entries
15e17), the product was produced in low yields while the use of
magnesium powder in THF, the allylation yield was further en-
hanced to 78% at room temperature after 0.21 h (Table 1, entry 18).
It is obvious that product yield was higher (85%) under solvent-free
conditions in comparison to that (78%) in THF. Among the different
metals and solvents studied, magnesium powder was found to be
the most ideal metal for this allylation (Table 1, entry 9). So the
solvent-free conditions were necessary for the successful allylation
of benzaldehyde, which is a great improvement in reducing
chemical pollution.
In an effort to obtain improver yields, we conducted Table 1
mediated by magnesium powder at different temperatures under
solvent-free condition. As a result, we found that at 0 ꢀC no sig-
nificant formation of the desired product even after prolonged
stirring. When the reactions were performed under higher tem-
perature conditions, the products led to the generation of compli-
cated mixtures. Subsequently, it was found that allylation of
benzaldehyde proceeded smoothly at room temperature under
solvent-free condition. Then a variety of aldehydes were examined
using this allylation method (Scheme 1). The results are listed in
Table 2.
CHO
9
3i
3j
5(12d)
10
91(82d)
Br
CHO
10
94
OCH3
CHO
11
3k
10(15d)
95(86d)
H3CO
12
13
14
3l
12(20d)
12(15d)
6(15d)
93(84d)
91(82d)
86(77d)
CHO
CHO
S
3m
3n
O
CHO
CHO
15
16
3o
3p
6
5
88
89
H3CO
CHO
Br

S. Li et al. / Tetrahedron 67 (2011) 849e855
851
Table 2 (continued )
Table 3
Allylation of ketones mediated by magnesium powder under solvent-free
Entry
RCHO
Productb
Time/(min)
Yield/(%)c
conditionsa
OH
O
Mg
Br
CHO
CH3
CHO
R1
solvent-free r.t.
R1
4a-q
R2
17
18
3q
3r
6
7
90
91
R2
2
5a-q
Entry
Ketones
Productsb
Time/(min)
Yield/(%)c
O
1
5a
8(20d)
94(85d)
19
3s
10(20d)
82(80d)
CHO
O
a
Reaction conditions: aldehydes (2 mmol), allylbromide (3 mmol), magnesium
powder (3 mmol).
2
5b
5c
5d
5e
5f
9
92
b
All products were characterized by IR 1H NMR, 13C NMR, MS, and elemental
Cl
analyses for all new compound.
c
O
Isolated yield.
d
The yields in brackets are from the reaction mediated by zinc powder.19a
3
9(30d)
89(77d)
From the results shown in Table 2, it can be seen that most of the
reactions were complete in high yields within a short reaction time.
TLC analysis of the ether extract clearly showed a spot that corre-
sponds to the desired allylation product. In general, allylation of
various aldehydes (Table 2, entries 2, 4, 6e13, 17, 18) gave the cor-
responding products in good to excellent yields, but reaction times
were shorter than allylation of aldehydes by zinc powder19a under
solvent-free conditions. Moreover, the reaction conditions were
sufficiently mild not to affect the phenyl (Table 2, entry l), chloro
(Table 2, entries 2e6), bromide (Table 2, entries 7e9), and methoxy
(Table 2, entries 10 and 11) functionalities. As for thiophene-2-
carbaldehyde (Table 2, entry 12) and furan-2-carbaldehyde
(Table 2, entry 13) afforded moderate yields of the corresponding
homoallylic alcohols after long reaction times. It was noteworthy
O
4
7
95
O
5
8
94
O
6
7
92
O
7
5g
5h
5i
6
98
that a,b-unsaturated aldehydes were also allylated in good yields,
Cl
Cl
only the 1,2-addition products were obtained regioselectively
(Table 2, entries 14e17). Aliphatic aldehyde was also allylated
smoothly under same conditions in good yield (Table 2, entry 19). In
addition, substituent on the phenyl ring, whether electron-donat-
ing or electron-withdrawing, has no significant influence on the
reactions. Moreover, the position of the substituents on the phenyl
ring also has little effect on the product yields.
O
8
9(30d)
94(80d)
O
9
13
94
Thus far, the successful examples for allylation of ketones were
much less than those for aldehydes. It is possible that the lower
electrophilicity of the carbonyl carbon, are not so active in Barbier
type allylation as aldehydes.27,28
In our further investigations, it was found that not only alde-
hydes but also ketones can be applied under the same conditions,
furnishing various homoallylic alcohols in good to excellent yields.
The allylation results of a series of ketones were summarized in
Table 3.
FromTable 3, it is evident that the mostof ketones were complete
after 4e9 min at room temperature, and side reactions, such as
couplings has been not observed under solvent-free conditions.
Aromatic ketones reacted with allylbromide and generated the
corresponding homoallylic alcohols in good yields (Table 3, entries
1e3). The allylation of 1-(9H-fluoren-7-yl)ethanone (Table 3, entry
4), 1-(naphthalen-6-yl)ethanone (Table 3, entry 5), 1-(4-biphenyl)-
ethanone (Table 3, entry 6), bis(4-chlorophenyl)methanone (Table 3,
entry 7), and benzophenone (Table 3, entry 8) could be carried out
verywell. Then benzyl has been allylatedunder the same conditions,
the allylation proceeded smoothly and give the single addition
product (Table 3, entry 9). If the substrates were aliphatic ketones,
the corresponding homoallylic alcohols were obtained in good
O
O
10
11
12
13
14
5j
7(20d)
91(74d)
88(78d)
92
O
5k
5l
6(20d)
O
O
5
5
4
5m
92
S
91
5n
Br
S
O
(continued on next page)
yields (Table 3, entries 10 and 11). For a,b-unsaturated ketones, only

852
S. Li et al. / Tetrahedron 67 (2011) 849e855
characterized by IR, 1H NMR, 13C NMR, and MS, and elemental
Table 3 (continued )
analysis for all the new compounds.
Entry
15
Ketones
Productsb
Time/(min)
Yield/(%)c
4.2.1. 1-Phenylbut-3-en-1-ol 3a. Oil,19a IR ( /cmꢂ1): 3372, 3073,
n
2907, 1641, 1493, 1445, 1043, 997, 917, 757, 701; 1H NMR (400 MHz,
O
5o
6
96
CDCl3):
d
¼7.39e7.23 (m, 5H), 5.84e5.74 (m, 1H), 5.18e5.12 (m, 2H),
4.72 (t, J¼8 Hz, 1H), 2.532.45 (m, 2H), 2.23 (s, 1H); 13C NMR
S
(100 MHz, CDCl3):
d¼143.8, 134.4, 128.3, 127.5, 125.8, 118.3, 73.2,
43.7; EI-MS (m/z, %) 148 (Mþ), 131, 107, 91, 79, 77, 51, 39.
16
5p
5q
6
8
88
O
O
4.2.2. 1-(2-Chloro-phenyl)but-3-en-1-ol 3b. Oil,5b IR ( /cmꢂ1): 3419,
n
3074, 2938, 1637, 1472, 1435, 1348, 1254, 1068, 914, 751; 1H NMR
(400 MHz, CDCl3):
¼7.58e7.18 (m, 4H), 5.92e5.82 (m, 1H),
5.22e5.14 (m, 3H), 2.67e2.34 (m, 2H), 2.15 (s, 1H); 13C NMR
(100 MHz, CDCl3):
¼141.1, 134.2, 131.6, 129.3, 128.4, 127.0, 118.7,
76.6, 69.5, 42.0; EI-MS (m/z, %) 182 (Mþ), 147, 141, 113, 105, 77.
d
17
91
d
O
O
a
Reaction conditions: ketones (2 mmol), allylbromide (3 mmol), magnesium
powder (3 mmol).
4.2.3. 1-(3-Chloro-phenyl)but-3-en-1-ol 3c. Oil,9b IR ( /cmꢂ1): 3377,
n
3075, 2927,1709,1641,1574,1429,1196, 994, 919; 1H NMR (400 MHz,
CDCl3):
¼7.36e7.17 (m, 4H), 5.84e5.73 (m, 1H), 5.19e5.10 (m, 2H),
4.72e4.68 (m, 1H), 2.55e2.43 (m, 2H), 2.14 (s, 1H); 13C NMR
(100 MHz, CDCl3):
¼145.8, 134.2, 133.8, 129.6, 127.5, 125.9, 123.9,
118.9, 72.5, 43.8; EI-MS (m/z, %) 182 (Mþ), 165, 141, 113, 77.
b
All products were characterized by IR 1H NMR, 13C NMR, MS.
c
d
Isolated yield.
d
The yields in brackets are from the reaction mediated by zinc powder.19a
d
the 1,2-addition products were obtained regioselectively in good
yields (Table 3, entries 12 and 13). Indeed, heterocyclic ketones react
almost as well as aromatic ketones (Table 3, entries 14e17).
4.2.4. 1-(4-Chloro-phenyl)but-3-en-1-ol 3d. Oil,5b IR ( /cmꢂ1) 3374,
n
3077, 2980, 2908, 1642, 1597, 1490, 1411, 1091, 919, 829; 1H NMR
(400 MHz, CDCl3):
¼7.33e7.24 (m, 4H), 5.83e5.72 (m, 1H),
5.19e5.14 (m, 2H), 4.73e4.69 (m, 1H), 2.54e2.41 (m, 2H), 2.10 (s,
d
3. Conclusion
1H); 13C NMR (100 MHz, CDCl3):
d
¼142.2, 133.9, 133.1, 128.5, 127.1,
In conclusion, magnesium powder was found to be an effective
metal for mediating allylation of carbonyl compounds under sol-
vent-free conditions at room temperature. This method reported
here compared with previously reported methods19a has the fol-
lowing advantages: (a) the high yields (the yields is rise height to
85e98% from 77 to 91%); (b) the reaction time is shortened to
4e13 min from 10 to 30 min; (c) easy to handle.
118.8, 72.5, 43.8; EI-MS (m/z, %) 182 (Mþ), 165, 141, 113, 77.
4.2.5. 1-(2,4-Dichlorphenyl)but-3-en-1-ol 3e. White solid,5b mp
60e61 ꢀC, IR ( /cmꢂ1) 3278, 3080, 2938, 1639, 1470,1071, 1045, 985,
n
926; 1H NMR (400 MHz, CDCl3):
(m, 1H), 5.20e5.09 (m, 3H), 2.63e2.57 (m, 1H), 2.37e2.29 (m, 1H),
d
¼7.52e7.26 (m, 3H), 5.87e5.81
2.17 (s, 1H); 13C NMR (100 MHz, CDCl3):
d
¼139.7, 133.7, 133.4, 132.2,
129.0, 128.0, 127.3, 119.1, 69.1, 41.9; EI-MS (m/z, %) 216 (Mþ), 199,
4. Experimental
175, 147, 111, 75, 51, 39.
4.1. General remarks
4.2.6. 1-(2,6-Dichloro-phenyl)but-3-en-ol 3f. Oil, IR (
3076, 2978, 2918,1641,1562,1435,1182,1083, 918, 869, 769; 1H NMR
(400MHz,CDCl3):
¼7.29e7.15(m, 3H), 5.89e5.78(m,1H), 5.52e5.46
(m, 1H), 5.17e5.08 (m, 2H), 2.95e2.84 (m, 2H), 2.64 (s, 1H); 13C NMR
n
/cmꢂ1): 3415,
1H NMR spectra were recorded on a Brucker AM-400 MHz and
Brucker AC-E 200 MHz spectrometers in CDCl3 with TMS as an
internal standard. 13C NMR spectra were obtained on a Brucker AM-
400 operating at 100 MHz or a Brucker AC-E 200 operating at
50 MHz. IR spectra were recorded on an Alpha Centauri FI-IR
spectrometer. Mass spectra were recorded on an HP 5988A and GC/
MS/DS instruments. Elemental analyses were carried out on Carlo
Erba-1106 instruments. Purification of products was performed via
flash chromatography with 200e400 mesh silica gel (15:1 petro-
leum/diethyl ether). All substrates and reagents were obtained
commercially, which were prepared by standard procedures.
d
(100 MHz, CDCl3):
d
¼137.1, 134.2, 133.8, 129.3, 128.9, 118.1, 71.4, 39.9;
EI-MS (m/z, %) 216 (Mþ), 216, 199, 175, 147, 111, 75, 39. Anal. Calcd for
C10H10OCl2: C, 55.33; H, 4.64. Found C, 55.46; H, 4.53.
4.2.7. 1-(2-Bromo-phenyl)but-3-en-1-ol 3g. White solid,5a mp
33e34 ꢀC, IR ( /cmꢂ1):3297, 3070, 2933, 1640, 1498, 1465, 1433,
n
1065, 984, 913; 1H NMR (400 MHz, CDCl3):
d
¼7.58e7.51 (m, 1H),
7.33e7.18 (m, 3H), 5.90e5.82 (m, 1H), 5.22e5.14 (m, 3H), 2.66e2.60
(m, 1H), 2.42e2.34 (m, 1H), 2.16 (s, 1H); 13C NMR (100 MHz, CDCl3):
d
¼141.1, 134.2, 131.6, 129.3, 128.4, 127.0, 118.7, 69.5, 41.9; EI-MS
4.2. Typical experimental procedure for the synthesis of
homoallylic alcohols
(m/z, %) 226 (Mþ), 226, 209, 185, 157, 77, 51, 39.
4.2.8. 1-(3-Bromo-phenyl)but-3-en-1-ol 3h. Oil,5a IR
(n
/cmꢂ1):
Magnesium powder (3 mmol) was placed in a flame dried round
bottom flask (50 mL). Then carbonyl compounds (2 mmol) and
allybromide (3 mmol) were added. The resulting mixture was
stirred at room temperature and the reaction was monitored by
TLC. After complete conversion, saturated NH4Cl solution (15 mL)
was poured into the mixture. The mixture was extracted with Et2O
(3ꢁ10 mL) and the organic layer was separated, dried over anhy-
drous MgSO4, and evaporated. The pure products were obtained by
column chromatograph of the crude mixture on silica gel using
petroleum/ethyl acetate as an eluent. All the isolated products were
3373, 3076, 2978, 2906, 1643, 1433, 1166, 1035, 919, 701; 1H NMR
(400 MHz, CDCl3):
2H), 5.84e5.72 (m, 1H), 5.19e5.14 (m, 2H), 4.72e4.68 (m, 1H),
2.54e2.40 (m, 2H), 2.11 (s,1H); 13C NMR (100 MHz, CDCl3):
d
¼7.52 (s, 1H), 7.41e7.28 (m, 1H), 7.27e7.19 (m,
d
¼146.1,
133.8, 130.5, 129.9, 128.9, 124.4, 119.0, 109.7, 72.4, 43.8; EI-MS (m/z,
%) 226 (Mþ), 209, 185, 157, 105, 77, 51, 39.
4.2.9. 1-(4-Bromo-phenyl)but-3-en-1-ol 3i. Oil,5a IR (
3076, 2926, 2906, 1642, 1486, 1405, 1062, 1005, 919, 870; 1H NMR
(400 MHz, CDCl3):
¼7.48e7.43 (m, 2H), 7.26e7.18 (m, 2H),
n
/cmꢂ1): 3376,
d

S. Li et al. / Tetrahedron 67 (2011) 849e855
853
5.82e5.72 (m, 1H), 5.18e5.14 (m, 2H), 4.71e4.68 (m, 1H), 2.51e2.40
d
¼139.4, 137.4, 134.5, 128.9, 128.0, 126.4, 125.7, 118.0, 76.5, 40.0,
(m, 2H), 2.17 (s, 1H); 13C NMR (100 MHz, CDCl3):
d
¼142.7, 133.9,
13.6; EI-MS (m/z, %) 188 (Mþ), 171, 147, 129, 115, 91, 77, 51, 39.
131.4, 127.5, 121.2, 118.9, 72.5, 43.8; EI-MS (m/z, %) 226 (Mþ), 209,
185, 157, 105, 77, 51, 39.
4.2.18. 1-(Naphthalen-6-yl)but-3-en-1-ol 3r. Oil,6 IR ( /cmꢂ1): 3547,
n
3382, 3069, 2932, 1639, 1511, 1431, 1161, 1056, 917, 799, 778; 1H
NMR (400 MHz, CDCl3):
¼8.08e7.46 (m, 7H), 5.98e5.88 (m, 1H),
5.55e5.51 (m, 1H), 5.25e5.17 (m, 2H), 2.75e2.56 (m, 2H), 2.21 (s,
1H); 13C NMR (100 MHz, CDCl3):
4.2.10. 1-(2-Methoxy-phenyl)but-3-en-1-ol 3j. Oil,26b IR (
3412, 3072, 2938, 2837, 1640, 1596, 1462, 1240, 1045, 754; 1H NMR
(400 MHz, CDCl3):
n
/cmꢂ1):
d
d
¼7.34e7.23 (m, 2H), 6.99e6.85 (m, 2H),
d
¼139.4, 134.7, 133.7, 130.2, 128.9,
5.89e5.79 (m, 1H), 5.15e5.08 (m, 2H), 4.98e4.93 (m, 1H), 3.85 (s,
127.9, 126.0, 125.5, 125.4, 122.9, 122.8, 118.4, 69.9, 42.8; EI-MS
3H), 2.63e2.58 (m, 2H), 2.47 (s, 1H); 13C NMR (100 MHz, CDCl3):
(m/z, %) 198 (Mþ), 157, 127, 115, 91, 77, 51, 39.
d
¼156.3, 135.1, 131.6, 128.2, 126.7, 120.6, 117.5, 110.3, 69.6, 55.2, 41.8;
EI-MS (m/z, %) 178 (Mþ), 161, 147, 137, 121, 107, 94, 77.
4.2.19. Dec-1-en-4-ol 3s. Oil,4 IR (
1828, 1641, 1458, 1377, 995, 912; 1H NMR (400 MHz, CDCl3):
¼5.88e5.78 (m, 1H), 5.15e5.11 (m, 2H), 3.67e3.61 (m, 1H),
2.33e2.12 (m, 2H), 1.79 (s, 1H), 1.49e1.29 (m, 10H), 0.88 (t, J¼6.4 Hz,
n
/cmꢂ1): 3363, 3074, 2927, 2857,
4.2.11. 1-(4-Methoxy-phenyl)but-3-en-1-ol 3k. Oil,5b IR (
n
/cmꢂ1
)
d
3398, 3072, 2932, 1886, 1611, 1512, 1456, 1247, 1036, 917, 831; 1H
NMR (400 MHz, CDCl3):
d
¼7.28e7.25 (m, 2H), 6.89e6.86 (m, 2H),
3H); 13C NMR (100 MHz, CDCl3):
d
¼134.9,118.0, 70.6, 41.9, 36.8, 31.8,
5.83e5.76 (m, 1H), 5.16e5.11 (m, 2H), 4.70e4.66 (m, 1H), 3.81 (s,
29.3, 25.6, 22.6,14.0; EI-MS (m/z, %) 139 (MþꢂOH),115, 97, 69, 55, 41.
3H), 2.51e2.47 (m, 2H), 2.04 (s, 1H); 13C NMR (100 MHz, CDCl3):
d
¼158.9, 136.0, 134.6, 127.0, 118.2,113.7, 72.9, 55.2, 43.7; EI-MS (m/z,
4.2.20. 2-Phenylpent-4-en-2-ol 5a. Oil,9b IR (
2977, 1641, 1444, 1371, 1068, 916, 765, 699; 1H NMR (400 MHz,
CDCl3):
¼7.45e7.21 (m, 5H), 5.66e5.56 (m, 1H), 5.16e5.08 (m, 2H),
2.71e2.46 (m, 2H), 2.08 (s, 1H), 1.55 (s, 3H); 13C NMR (100 MHz,
n
/cmꢂ1): 3440, 3069,
%) 178 (Mþ), 161, 144, 137, 109, 94, 77, 51, 39.
d
4.2.12. 1-(Thiophen-2-yl)but-3-en-1-ol 3l. Oil,19a IR ( /cmꢂ1) 3362,
n
3026, 2906, 1641, 1438, 1030, 917, 749; 1H NMR (400 MHz, CDCl3):
CDCl3):
d
¼147.5, 133.6, 128.1, 126.5, 124.7, 119.4, 73.5, 48.4, 29.8; EI-
d
¼7.22e7.25 (m, 1H), 6.97e6.94 (m, 2H), 5.87e5.77 (m, 1H),
5.21e5.14 (m, 2H), 5.00e4.96 (m, 1H), 2.63e2.56 (m, 2H), 2.26 (s,
1H); 13C NMR (100 MHz, CDCl3):
¼147.7, 133.7, 126.5, 124.5, 123.6,
118.7, 69.3, 43.7; EI-MS (m/z, %) 154 (Mþ), 137, 113, 85, 58, 39.
MS (m/z, %) 162 (Mþ), 145, 121, 105, 77, 51, 43.
d
4.2.21. 2-(4-Chloro-phenyl)pent-4-en-2-ol 5b. Oil,9b IR /cmꢂ1
(n )
3431, 3076, 2977, 1641, 1490, 1094, 1007, 923, 828; 1H NMR
(400 MHz, CDCl3):
d
¼7.45e7.36 (m, 2H), 7.33e7.26 (m, 2H),
4.2.13. 1-(Furan-2-yl)but-3-en-1-ol 3m. Oil,5a IR ( /cmꢂ1) 3370,
n
5.64e5.53 (m, 1H), 5.15e5.12 (m, 2H), 2.67e2.45 (m, 2H), 2.07 (s,
3078, 2918, 1841, 1643, 1431, 1029, 920; 1H NMR (400 MHz, CDCl3):
¼7.38e7.26 (m, 1H), 6.34e6.25 (m, 2H), 5.86e5.77 (m, 1H),
5.20e5.13 (m, 2H), 4.75 (t, J¼6.8 Hz, 1H), 2.67e2.57 (m, 2H), 2.07 (s,
1H); 13C NMR (100 MHz, CDCl3):
¼155.9, 141.9, 133.6, 118.5, 110.0,
105.0, 66.8, 40.0; EI-MS (m/z, %) 138 (Mþ), 121, 97, 84, 69, 55, 39.
1H), 1.52 (s, 3H); 13C NMR (100 MHz, CDCl3):
d¼146.1, 133.1, 132.3,
d
128.2, 126.3, 119.8, 73.3, 48.3, 29.8; EI-MS (m/z, %) 196 (Mþ), 181,
155, 139, 111, 77, 43.
d
4.2.22. 3-Phenylhex-5-en-3-ol 5c. Oil,26b IR (
n
/cmꢂ1): 3475, 3067,
¼7.53e7.19
2934, 1684, 1445, 978, 761; 1H NMR (400 MHz, CDCl3):
d
4.2.14. (E)-1-Phenylhexa-1,5-dien-3-ol 3n. Oil,4 IR (
n
/cmꢂ1): 3371,
(m, 5H), 5.62e5.51 (m,1H), 5.14e5.07 (m, 2H), 2.73e2.46(m, 2H), 2.07
(s, 1H), 1.90e1.78 (m, 2H), 0.76 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz,
3078, 2915, 1641, 1431, 1009, 920, 738 cmꢂ1 1H NMR (400 MHz,
CDCl3):
;
d
¼7.41e7.21 (m, 5H), 6.60 (d, J¼16.0 Hz, 1H), 6.25 (d,
CDCl3):
d
¼145.6,133.5,127.9,126.3,125.3,119.4, 75.9, 46.8, 35.1, 7.7; EI-
J¼16.0 Hz, 1H), 5.91e5.80 (m, 1H), 5.22e5.13 (m, 2H), 4.36 (d,
MS (m/z, %) 159 (MþꢂOH), 147, 135, 117, 105, 91, 77, 57, 41, 39.
J¼5.6 Hz, 1H), 2.36e2.24 (m, 2H), 1.98 (s, 1H); 13C NMR (100 MHz,
CDCl3):
d
¼136.5, 133.9, 131.5, 130.2, 128.5, 127.6, 126.4, 118.4, 71.6,
4.2.23. 2-(9H-Fluoren-7-yl)pent-4-en-2-ol 5d. White solid,26a mp
41.9; EI-MS (m/z, %) 174 (Mþ), 157, 133, 115, 91, 77, 55, 39.
72e74 ꢀC, IR ( /cmꢂ1): 3475, 2976, 1670, 1456, 1269, 1101, 920, 771,
n
738; 1H NMR (400 MHz, CDCl3):
(m, 1H), 5.18e5.09 (m, 2H), 3.88 (m, 2H), 2.76e2.51 (m, 2H), 2.14 (s,
1H), 1.61 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
¼7.84e7.23 (m, 7H), 5.70e5.59
4.2.15. (E)-1-(4-Methoxypheny)hexa-1,5-dien-3-ol
/cmꢂ1): 3413, 3074, 2929, 1712, 1605, 1512, 1448, 1294, 1176, 1032,
971, 919; 1HNMR (400 MHz, CDCl3):
3o. Oil,
IR
(n
d
¼146.3, 143.3, 143.2,
d
¼7.33e7.26 (m, 2H), 6.89e6.83
141.4, 140.2, 133.7, 126.6, 126.5, 124.9, 123.4, 121.4, 119.7, 119.4, 73.8,
(m, 2H), 6.54 (d, J¼16.0 Hz,1H), 6.11 (d, J¼16.4 Hz 1H), 5.89e5.81 (m,
48.6, 36.9, 30.0, 26.7; EI-MS (m/z, %) 250 (Mþ), 209, 193, 165, 43, 39.
1H), 5.22e5.17 (m, 2H), 4.34e4.29 (m, 1H), 3.82 (s, 3H), 2.46e2.33
(m, 2H), 1.84 (s, 1H); 13C NMR (100 MHz, CDCl3):
d¼159.2, 134.1,
4.2.24. 2-(Naphthalen-6-yl)pent-4-en-2-ol 5e. Oil,26a IR (
3432, 3058, 2976, 1637, 1438, 1127, 918, 820, 749; 1H NMR
(400 MHz, CDCl3):
¼7.91e7.43 (m, 7H), 5.66e5.55 (m, 1H),
5.17e5.09 (m, 2H), 2.82e2.55 (m, 2H), 2.21 (s, 1H), 1.63 (s, 3H); 13C
NMR (100 MHz, CDCl3):
n
/cmꢂ1):
129.9, 129.3, 129.3, 127.6, 118.3,113.9, 71.8, 55.2, 42.0; EI-MS (m/z, %)
204 (Mþ), 187, 173, 163, 145, 121, 107, 91, 77, 55, 39; Anal. Calcd. For
C13H16O2: C, 74.13; H, 7.92. Found C, 74.04; H, 7.86.
d
d¼144.9, 133.5, 133.1, 132.2, 128.1, 127.8,
4.2.16. (Z)-2-Bromo-1-phenylhexa-1,5-dien-3-ol
/cmꢂ1): 3541, 3376, 3074, 2915, 1640, 1441, 1038, 920, 864; 1H
NMR (400 MHz, CDCl3):
3p. Oil,26b
IR
127.4, 126.0, 125.6, 123.5, 123.1, 119.6, 73.7, 48.2, 29.9; EI-MS (m/z, %)
(n
212 (Mþ), 197, 171, 127, 43, 39.
d
¼7.62e7.59 (m, 2H), 7.38e7.23 (m, 3H),
7.08 (s, 1H), 5.86e5.76 (m, 1H), 5.23e5.15 (m, 2H), 4.35e4.30 (m,
4.2.25. 2-(4-Biphenyl)pent-4-en-2-ol 5f. Oil,26a IR (
3070, 2976, 1639, 1486, 1075, 919, 840, 696; 1H NMR (400 MHz,
CDCl3):
¼7.60e7.25 (m, 9H), 5.70e5.64 (m, 1H), 5.19e5.14 (m, 2H),
2.75e2.51 (m, 2H), 2.08 (s, 1H), 1.58 (s, 3H); 13C NMR (100 MHz,
CDCl3):
¼146.6, 140.7, 133.6, 128.7, 127.1, 127.0, 126.8, 125.2, 119.6,
73.5, 48.3, 29.9; EI-MS (m/z, %) 238 (Mþ), 221,197,165,152, 77, 43, 39.
n
/cmꢂ1): 3433,
1H), 2.64e2.49 (m, 2H), 2.24 (s, 1H); 13C NMR (100 MHz, CDCl3):
d
¼134.9, 133.6, 133.2, 129.0, 128.9, 128.2, 128.1, 118.7, 76.4, 40.3; EI-
d
MS (m/z, %) 252 (Mþ), 252, 211, 193, 131, 103, 77, 51, 39.
d
4.2.17. (E)-2-Methyl-1-phenylhexa-1,5-dien-3-ol
3q. Oil,26b
/cmꢂ1): 3400, 3052, 2923, 1664, 1441, 1031, 917, 733, 704; 1H NMR
(400 MHz, CDCl3):
IR
(n
d
¼7.35e7.20 (m, 5H), 6.53 (s, 1H), 5.85e5.80 (m,
4.2.26. 1,1-Bis(4-chloro-phenyl)but-3-en-1-ol
5g. Oil,26a
/cmꢂ1): 3548, 3077, 2926, 1639, 1489, 1094, 1006, 824; 1H NMR
(400 MHz, CDCl3):
¼7.37e7.24 (m, 8H), 5.64e5.57 (m, 1H),
IR
1H), 5.21e5.14 (m, 2H), 4.23 (dd, J¼7.2, 5.6 Hz, 1H), 2.48e2.39 (m,
(n
2H), 1.93(s, 1H), 1.86e1.61 (m, 3H); 13C NMR (100 MHz, CDCl3):
d

854
S. Li et al. / Tetrahedron 67 (2011) 849e855
5.27e5.19 (m, 2H), 3.00 (d, J¼6.8 Hz, 2H), 2.55 (s, 1H); 13C NMR
73.6, 47.6, 30.8, 29.2, 14.9; EI-MS (m/z, %) 196 (Mþ), 181, 155, 139,
113, 59, 43, 41, 39.
(100 MHz, CDCl3):
d
¼144.5, 132.9, 132.5, 128.4, 127.3, 121.3, 76.1,
46.4; EI-MS (m/z, %) 251 (Mþ), 139, 135, 111, 75, 55, 41, 39.
4.2.35. 2-(5-Methylfuran-2-yl)pent-4-en-2-ol
/cmꢂ1): 3411, 3077, 2981, 1684, 1373, 1097, 921, 786; 1H NMR
(400 MHz, CDCl3):
¼6.05 (s, 1H), 5.87 (s, 1H), 5.72e5.67 (m, 1H),
5.15e5.11 (m, 2H), 2.68e2.51 (m, 2H), 2.27 (s, 3H), 2.13 (s, 1H), 1.51
5p. Oil,26a
IR
4.2.27. 1,1-Diphenylbut-3-en-1-ol 5h. Oil,19a IR /cmꢂ1): 3551,
(
n
(n
3061, 1812, 1651, 1444, 1167, 995, 919, 700; 1H NMR (400 MHz,
CDCl3):
¼7.49e7.18 (m, 10H), 5.71e5.60 (m, 1H), 5.26e5.15 (m,
2H), 3.08e3.06 (m, 2H), 2.56 (s, 1H); 13C NMR (100 MHz, CDCl3):
d
d
(s, 3H); 13C NMR (100 MHz, CDCl3):
d
¼157.3, 151.2, 133.4, 118.9,
d
¼146.4, 133.3, 128.1, 126.8, 125.9, 120.5, 76.8, 46.6; EI-MS (m/z, %)
105.8, 105.3, 70.5, 46.0, 26.3, 13.5; EI-MS (m/z, %) 166 (Mþ), 149, 135,
224 (Mþ), 207, 183, 165, 105, 91, 77, 51, 39.
125, 109, 95, 43, 39.
4.2.28. 2-Hydroxy-1,2-diphenylpent-4-en-1-one 5i. White solid,26a
4.2.36. 2-(Furan-2-yl)pent-4-en-2-ol 5q. Oil,26a IR (
3077, 2981, 1672, 1367, 1159, 921, 737; 1H NMR (400 MHz, CDCl3):
¼7.26 (s, 1H), 6.31e6.18 (m, 2H), 5.71e5.62 (m, 1H), 5.15e5.10 (m,
2H), 2.70e2.51 (m, 2H), 2.22 (s,1H),1.53 (s, 3H); 13C NMR (100 MHz,
n
/cmꢂ1): 3415,
mp 91e92 ꢀC, IR ( /cmꢂ1): 3462, 3062, 1672, 1443, 1359, 1219,
n
995, 932, 699, 513; 1H NMR (400 MHz, CDCl3):
10H), 5.78e5.68 (m, 1H), 5.13e4.98 (m, 2H), 4.19 (s, 1H), 3.16e2.94
(m, 2H); 13C NMR (100 MHz, CDCl3):
d¼7.74e7.24 (m,
d
d
¼200.7, 141.7, 134.4, 132.7,
CDCl3):
d
¼159.1, 141.5, 133.2, 119.2, 109.9, 104.6, 70.7, 46.1, 26.4; EI-
132.2, 130.1, 128.8, 128.0, 128.0, 125.5, 120.3, 81.3, 43.8; EI-MS
MS (m/z, %) 151 (MþꢂH), 135, 120, 111, 95, 79, 43, 39.
(m/z, %) 252 (Mþ), 235, 211, 181, 163, 105, 77, 51, 39.
Acknowledgements
4.2.29. 4-Methylnon-1-en-4-ol 5j. Oil,19a IR (
2935, 1642, 1454, 1149, 1002, 917; 1H NMR (400 MHz, CDCl3):
¼5.91e5.81 (m, 1H), 5.15e5.08 (m, 2H), 2.23e2.19 (m, 2H), 1.65
(s,1H), 1.48e1.25 (m, 8H), 1.16 (s, 3H), 0.91 (s, 3H); 13C NMR
n
/cmꢂ1): 3392, 3073,
The work was supported by the Natural Science Foundation of
China (Grant 20272047, 20572086), the Gansu Natural Science
Foundation of China (0308RJZA-100) and Key Laboratory of Eco-
Environment-Related Polymer Material (NorthwestNormal Uni-
versity), Ministry of the Education of China.
d
(100 MHz, CDCl3):
d
¼134.1, 118.5, 72.1, 46.2, 41.8, 32.3, 26.6,
23.5, 22.6, 14.0; EI-MS (m/z, %) 139 (MþꢂOH), 115, 99, 83, 71,
55, 43.
4.2.30. 1-Allylcyxlohex-2-enol 5k. Oil,19a IR (
n
/cmꢂ1): 3406, 3073,
References and notes
2934, 1668, 1434, 1172, 984, 732; 1H NMR (400 MHz, CDCl3):
1. (a) Vasylyev, M.; Alper, H. J. Org. Chem. 2010, 75, 2710e2713; (b) Nicolaou, K. C.;
Khim, D. W.; Baati, R. Angew. Chem., Int. Ed. 2002, 41, 3701e3704; (c) Hoen-
berer, K. R.; Hamblet, C. L.; Leighton, J. L. J. Am. Chem. Soc. 2000, 122,
12894e12895.
2. (a) Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207e2293; (b) Tietze, L.;
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5. (a) Lakshmi Kantam, M.; Venkanna, G. T.; Shiva Kumar, K. B.; Balasu-
brahmanyam, V.; Venkateswarlu, G.; Sreedhara, B. Adv. Synth. Catal. 2008, 350,
1497e1502; (b) Chaudhuri, M. K.; Dehury, S. K.; Hussain, S. Tetrahedron Lett.
2005, 46, 6247e6251.
d
¼5.93e5.80 (m, 2H), 5.63e5.61 (m, 1H), 5.15e5.10 (m, 2H), 2.31 (d,
J¼7.2 Hz, 2H), 2.07e2.00 (m, 1H), 1.74e1.60 (m, 6H); 13C NMR
(100 MHz, CDCl3):
d
¼133.6, 132.1, 130.0, 118.4, 69.0, 46.6, 35.4, 25.1,
18.8; EI-MS (m/z, %) 120 (MþꢂH2O), 97, 79, 67, 55, 41.
4.2.31. (E)-3-Methyl-1-phenylhexa-1,5-dien-3-ol
/cmꢂ1): 3398, 3072, 2974, 1641, 1445, 1104, 970, 749; 1H NMR
(400 MHz, CDCl3):
5l. Oil,26a
IR
(n
d
¼7.39e7.20 (m, 5H), 6.61 (d, J¼16.4 Hz, 1H),
6.32 (d, J¼16 Hz, 1H), 5.87e5.78 (m, 1H), 5.18e5.14 (m, 2H),
2.47e2.33 (m, 2H), 1.82 (s, 1H), 1.69 (s, 1H), 1.39 (s, 3H); 13C
6. Krishnaveni, N. S.; Surendra, K.; Kumar, V. P.; Srinivas, B.; Suresh Reddy, C.;
Rama Rao, K. Tetrahedron Lett. 2005, 46, 4299e4301.
7. (a) Li, C. J.; Zhang, W. C. J. Am. Chem. Soc. 1998, 120, 9102e9103; (b) Fleury, L. M.;
Ashfeld, B. L. Tetrahedron Lett. 2010, 51, 2427e2430.
NMR (100 MHz, CDCl3):
d
¼136.8, 136.1, 133.5, 128.5, 127.3, 126.3,
119.3, 72.3, 47.2, 27.8; EI-MS (m/z, %) 188 (Mþ), 171, 147, 129, 115,
77, 43, 39.
8. (a) Chan, T. H.; Yang, Y.; Li, C. J. J. Org. Chem. 1999, 64, 4452e4455; (b) Lu, W. S.;
Chan, T. H. J. Org. Chem. 2000, 65, 8589e8594.
9. (a) Lu, J.; Ji, S. J.; Qian, R.; Chen, J. P.; Liu, Y.; Loh, T. P. Synlett 2004, 534e536; (b)
Tang, L.; Ding, L.; Chang, W. X.; Li, J. Tetrahedron Lett. 2006, 47, 303e306.
10. Choudary, B. M.; Jyothi, K.; Sateesh, M.; Kantam, M. L. Synlett 2004, 231e234.
11. Wang, Z. Y.; Zha, Z. G.; Zhou, C. L. Org. Lett. 2002, 4, 1683e1685.
12. 12(a) Anastas, P. T.; Wraner, J. C. Green Chemistry: Theory and Practice; Oxford
University: New York, NY, 1997; (b) Li, C. J.; Chan, T. H. Organic Reactions in
Aqueous Media; John Wiley: New York, NY, 1997.
4.2.32. (E)-3-methyl-1-(thiophen-2-yl)hexa-1,5-dien-3-ol
5m. Oil,26a IR ( /cmꢂ1): 3405, 3074, 2974,1641,1370,1108, 960, 920,
n
697; 1H NMR (400 MHz, CDCl3):
J¼16 Hz, 1H), 6.15 (d, J¼16 Hz, 1H), 5.87e5.77 (m, 1H), 5.18e5.13 (m,
d
¼7.14e6.92 (m, 3H), 6.74 (d,
2H), 2.44e2.30 (m, 2H),1.84 (s, 1H),1.36 (s, 3H); 13C NMR (100 MHz,
13. (a) Loh, T. P.; Zhou, J. R.; Yin, Z. Org. Lett. 1999, 1, 1855e1857; (b) Hilt, G.;
Ismolko, K.; Waloch, C. Tetrahedron Lett. 2002, 43, 1437e1439; (c) Tan, K. T.;
Chng, S. S.; Cheng, H. S.; Loh, T. P. J. Am. Chem. Soc. 2003, 125, 2958e2963.
14. (a) Wang, W.; Shi, L.; Huang, Y. Tetrahedron 1990, 46, 3315e3320; (b) Li, L. H.;
Chan, T. H. Tetrahedron Lett. 2000, 41, 5009e5012.
CDCl3):
d
¼142.0, 135.8, 133.3, 127.3, 125.5, 123.9, 120.8, 119.4, 72.1,
47.1, 27.8; EI-MS (m/z, %) 194 (Mþ), 192, 177, 161, 153, 135, 122, 109,
97, 43, 39.
15. Zhou, J. Y.; Jia, Y.; Sun, G. F.; Wu, S. H. Synth. Commun. 1997, 27, 1899e1906.
16. (a) Li, C. J.; Meng, Y.; Yi, X. H.; Ma, J.; Chan, T. H. J. Org. Chem. 1998, 63,
7498e7504; (b) Li, C. J.; Meng, Y.; Yi, X. H.; Ma, J.; Chan, T. H. J. Org. Chem. 1997,
62, 8632e8633.
17. Chan, T. C.; Lau, C. P.; Chan, T. H. Tetrahedron Lett. 2004, 45, 4189e4191.
18. (a) Wada, M.; Fukuma, T.; Morioka, M.; Takahashi, T.; Miyoshi, N. Tetrahedron
Lett. 1997, 38, 8045e8048; (b) Zhang, W. C.; Li, C. J. J. Org. Chem. 1999, 64,
3230e3236.
19. (a) Wang, J.-X.; Jia, X. F.; Meng, T. J.; Xin, L. Synthesis 2005, 17, 2838e2844; (b)
Ishino, Y.; Mihara, M.; Kageyama, M. Tetrahedron Lett. 2002, 43, 6601e6604; (c)
Yi, X.; Haberman, J. X.; Li, C. J. Synth. Commun. 1998, 28, 2999e3009; (d)
Marton, D.; Stivanello, D.; Tagliavini, G. J. Org. Chem. 1996, 61, 2731e2737; (e)
Chung, W.; Higashiya, S.; Oba, Y.; Welch, J. T. Tetrahedron 2003, 59,
10031e10036.
4.2.33. 2-(5-Bromothiophen-2-yl)pent-4-en-2-ol
/cmꢂ1): 3406, 3077, 2977, 1644, 1439, 1372, 1114, 923, 796; 1H
NMR (400 MHz, CDCl3):
¼6.87 (d, J¼3.6 Hz, 1H), 6.63 (d, J¼3.6 Hz,
1H), 5.77e5.67 (m, 1H), 5.19e5.12 (m, 2H), 2.66e2.48 (m, 2H), 2.33
5n. Oil,26a
IR
(
n
d
(s, 1H), 1.57 (s 3H); 13C NMR (100 MHz, CDCl3):
d
¼154.5, 132.7,
129.5, 122.4, 120.1, 110.4, 72.9, 48.7, 30.1; EI-MS (m/z, %) 246 (Mþ),
231, 229, 207, 43, 39.
4.2.34. 2-(2,5-Dimethylthiophen-3-yl)pent-4-en-2-ol 5o. Oil,26a IR
(n
/cmꢂ1): 3439, 3072, 2922, 1662, 1445, 1369, 1142, 917, 829; 1H
20. (a) Mukaiyama, T.; Harada, T. Chem. Lett. 1981, 1527e1528; (b) Tan, X. H.; Hou,
Y. Q.; Huang, C.; Liu, L.; Guo, Q. X. Tetrahedron 2004, 60, 6129e6136; (c)
Andrews, P. C.; Peatt, A. C.; Raston, C. L. Tetrahedron Lett. 2002, 43,
7541e7543.
NMR (400 MHz, CDCl3):
5.16e5.12 (m, 2H), 2.50e2.14 (m, 8H), 2.03 (s, 1H), 1.51 (s, 3H); 13C
NMR (100 MHz, CDCl3):
¼142.1, 134.2, 133.9, 131.2, 125.6, 119.1,
d
¼6.54 (s, 1H), 5.77e5.67 (m, 1H),
d

S. Li et al. / Tetrahedron 67 (2011) 849e855
855
21. (a) Wang, Z.; Yuan, S.; Li, C. J. Tetrahedron Lett. 2002, 43, 5097e5099; (b)
Andrews, P. C.; Peatt, A. C.; Raston, C. L. Tetrahedron Lett. 2004, 45,
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22. Minato, M.; Tsuji, J. Chem. Lett. 1988, 2049e2052.
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24. (a) Shen, K. H.; Yao, C. F. J. Org. Chem. 2006, 71, 3980e3983; (b) Loh, T. P.; Xu, J.
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Tetrahedron 1996, 52, 5643e5665.
26. (a) Zhou, W. J.; Yan, W. J.; Wang, J.-X.; Wang, K. H. Synlett 2008, 137e141; (b)
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