InI3- or ZnI2-catalyzed reaction of hydroxylated 1,5-allenynes with thiols: A new access to 3,5-disubstituted toluene derivatives

Article abstract of DOI:10.1002/asia.201000267

Transition-metal-activated alkynes or allenes can accept nucleophilic attack and undergo direct addition of the nucleophiles to the unsaturated bonds or trigger subsequent rearrangement reactions. This chemistry has witnessed increasing development in recent years. In this report, we have focused on the metal-catalyzed reactions of a variety of substituted propargyl allenic alcohols and thiophenols using indiumACHTUNGTRENUNG(III) and zinc(II) catalysts, which can activate both the alcohol and alkyne. In this reaction, thio groups play the role of a nucleophile and trigger subsequent rearrangements to give benzene derivatives. The products can be further transformed into various 1,3,5-trisubstituted aromatic compounds by nickel-catalyzed coupling reactions through the cleavage of the C-S bonds.

Full text of DOI:10.1002/asia.201000267

FULL PAPERS
DOI: 10.1002/asia.201000267
InI3- or ZnI2-Catalyzed Reaction of Hydroxylated 1,5-Allenynes with Thiols:
A New Access to 3,5-Disubstituted Toluene Derivatives
Jie Ma,[a] Lingling Peng,[a] Xiu Zhang,[a] Zhe Zhang,[a] Melody Campbell,[a] and
Jianbo Wang*[a, b]
Abstract: Transition-metal-activated al-
kynes or allenes can accept nucleophil-
ic attack and undergo direct addition
of the nucleophiles to the unsaturated
bonds or trigger subsequent rearrange-
ment reactions. This chemistry has wit-
nessed increasing development in
recent years. In this report, we have fo-
cused on the metal-catalyzed reactions
of a variety of substituted propargyl al-
lenic alcohols and thiophenols using
indiumACTHNUGTRNEUNG(III) and zinc(II) catalysts,
which can activate both the alcohol
and alkyne. In this reaction, thio
groups play the role of a nucleophile
and trigger subsequent rearrangements
to give benzene derivatives. The prod-
ucts can be further transformed into
various 1,3,5-trisubstituted aromatic
compounds by nickel-catalyzed cou-
pling reactions through the cleavage of
Keywords: 1,5-allenyne
·
cross-
À
the C S bonds.
coupling · indium · nickel · thiols
Introduction
by those studies, we report herein the InI3- or ZnI2-catalyzed
reactions of thiols with hydroxylated 1,5-allenynes. These re-
actions lead to the formation of aromatic rings bearing thio-
aryl or thioalkyl groups. Furthermore, the sulfur group can
be replaced by an alkyl or an aromatic group through nick-
el(II)-catalyzed cross-coupling reactions, thus leading to the
formation of various 3,5-disubstituted toluene derivatives.
It has been well-known that transition metal catalysts can
activate alkynes, alkenes, and allenes, thus triggering attack
by nucleophiles. In particular, various cycloisomerization
processes have been observed in transition-metal-catalyzed
reactions of 1,n-enynes.[1] The transition-metal-catalyzed cy-
cloisomerization of 1,n-allenynes has also been well-stud-
ied.[2–7] Diverse reaction patterns have been observed in
these investigations. Malacria and co-workers have recently
reported the platinum- and gold-catalyzed cycloisomeriza-
tion of hydroxylated 1,5-allenynes, which led to the forma-
tion of a variety of cyclic compounds.[6] Liu and co-workers
have studied the PPh3AuCl/AgOTf-catalyzed hydrative car-
bocyclizations of 1,5- and 1,7-allenynes. In this reaction, hy-
dration occurs regioselectively at the triple bond, leading to
the chemoselective formation of cyclized ketones.[7] Inspired
Results and Discussion
This novel transformation was discovered serendipitously
during our recent study on the transition-metal-catalyzed re-
action of allenyl homopropargylic sulfides.[8] When allenic
homopropargylic sulfide 1 was exposed to a [{RuCl2ACHTUNGTRENNUNG(p-
cymene)}2] catalyst, the benzene derivative 2 was obtained
after treatment with trifluoroacetic acid [Eq. (1)]. Further-
more, we attempted to develop a general method for the
synthesis of allenyl homopropargylic sulfides, such as 1.
We expected that allenic sulfide 5 could be prepared by
the reaction of allenic alcohol 3a with thiophenol 4a at
room temperature in the presence of ZnI2 as a Lewis acid
[a] J. Ma, L. Peng, X. Zhang, Z. Zhang, M. Campbell, Prof. Dr. J. Wang
Beijing National Laboratory of Molecular Sciences (BNLMS)
Key Laboratory of Bioorganic Chemistry and Molecular Engineering
of Ministry of Education, College of Chemistry
Peking University, Beijing 100871 (China)
Fax : (+86)10-6275-7248
E-mail: wangjb@pku.edu.cn
[b] Prof. Dr. J. Wang
State Key Laboratory of Organometallic Chemistry
Chinese Academy of Sciences
Shanghai 200032 (China)
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Chem. Asian J. 2010, 5, 2214 – 2220

catalyst (Scheme 1).[9] Surprisingly, the expected allenic sul-
fide 5 was not isolated; instead, benzene derivative 6a was
obtained in 57% yield. To unambiguously establish the
Scheme 2. Mechanistic rationale.
In intermediate A, the enol thioester functions as a strong
nucleophile to attack the metal-activated triple bond to give
B. Protonation of B affords intermediate C, which proceeds
through rearrangement and deprotonation to afford the
final product.
Scheme 1. ZnI2-Catalyzed reaction of alcohol 3a with 4a. DCE=1,2-di-
chloroethane.
According to this mechanistic rationale, we expected that
the 1,5-allenyne system with other leaving groups instead of
a hydroxy group might also have similar reactivity. We
found that this was indeed the case; when methoxylated 1,5-
allenyne 8 was subjected to catalysis with ZnI2, the same
3,5-disubstituted toluene product was obtained in 73%
(Scheme 3).
structure of 6a, we oxidized it into its corresponding sulfone
7, whose structure was confirmed by single-crystal X-ray
analysis (Figure 1).[10]
Scheme 3. ZnI2-catalyzed reaction of methoxylated 1,5-allenyne 8 with
4a.
As this reaction provides a straightforward route to 1,3,5-
trisubstituted benzene derivatives, it may be useful in organ-
ic synthesis. Polysubstituted benzenes are highly useful com-
pounds and are widely used in industry as well as in the lab-
oratory. Efforts have been directed to the development of
efficient methods for the synthesis of this type of com-
pounds. The classic methods for preparing poly-substituted
benzenes is through electrophilic substitution of the benzene
ring,[11] although the transition-metal-catalyzed [2+2+2] cy-
clotrimerization of alkynes, and the [4+2] cyclotrimeriza-
tions are powerful alternative ways to access poly-substitut-
ed benzenes.[12]
Figure 1. X-ray crystallography of 7.
This unexpected reaction can be explained by a mechanis-
tic rationale depicted in Scheme 2. First, the metal acts as a
Lewis acid to activate the hydroxy group, and then thiophe-
nol attacks the central carbon of the allene. Elimination of
the hydroxy group leads to the formation of intermediate A.
With this background in mind, we proceeded to optimize
the reaction of hydroxylated 1,5-allenyne 3a with thiophenol
4a (Table 1). First, the solvent effect was studied and it was
found that the reaction occurred only in dichloromethane
and 1,2-dichloroethane (Table 1, entries 1 and 2). It was also
noted that raising the reaction temperature could shorten
the reaction time and slightly improve the yield (Table 1,
entry 2). Next, a series of metal catalysts were examined.
No reaction occurred in the presence of gold, ruthenium,
platinum, or magnesium catalysts in 1,2-dichloroethane at
Abstract in Chinese:
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FULL PAPERS
Table 1. Reaction of 3a and thiophenol 4 under various conditions.
Table 2. InI3-catalyzed reaction of 3a–j and thiophenol 4a.
Entry
Catalyst (mol%)
Solvent T [8C] t [h] Yield [%][a]
1
2
3
4
5
6
7
8
ZnI2 (40)
ZnI2 (40)
ZnI2 (40)
ZnI2 (40)
ZnI2 (40)
AuCl (5)
CH2Cl2
DCE
dioxane
toluene
THF
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
25
80
60
80
60
60
60
60
60
60
80
60
80
80
80
80
5
4
24
1
57
69
n.r.[b]
n.r.
n.r.
n.r.
n.r.
n.r.
n.r.
trace[c]
67
Entry
Substrate 3, R
t [h]
Product
Yield [%][a]
7
18
18
18
18
12
4
18
3
3
1
2
3
4
5
6
7
8
9
3a, Ph
1
1
3
5
1
1
1
3
1
1
6a
6b
6c
6d
6e
6 f
6g
6h
6i
73
66
57
64
56
82
69
–
45
64
ACHTUNGTRENNUNG[{RuCl2ACHTUNGTRENNUNG(p-cymene)}2] (5)
3b, p-ClC6H4
3c, m-BrC6H4
3d, m,p-Cl2C6H3
3e, o-CH3C6H4
3 f, p-FC6H4
3g, p-PhC6H4
3h, m-MeOC6H4
3i, PhCH2CH2
PtCl2 (5)
MgI2 (5)
ZnCl2 (40)
ZnBr2 (40)
9
10
11
12
13
14
15
16
ZnN
trace
trace
57
68
73
In(OTf)3 (10)
ACHTUNGTRENNUNG
[b]
InCl3 (20)
Inl3 (20)
Inl3 (20)
1
1
10
3j, CH
3A
6j
[a] Yield of isolated product after column chromatography on silica gel.
[b] Reaction gave a complex mixture.
[a] Yield of isolated product after column chromatography on silica gel.
[b] Starting material was recovered. [c] Reaction gave trace product.
THF=tetrahydrofuran, n.r.=no reaction.
formation of a complex mixture is likely due to unfavoura-
ble electronic effects. It is noted that the reaction with sub-
strates bearing alkyl substituents also worked well (Table 2,
entries 9 and 10).
Furthermore, the scope of this reaction was demonstrated
by the reaction of a series of thiols with 3 f (Table 3). With
aromatic thiols, 3,5-disubstituted toluenes were isolated in
high yields (Table 3, entries 1-8). The reaction with thiol 4e
took a little longer (5h; Table 3, entry 5), presumably owing
to steric effects of the thiol substrate. The reaction can also
be extended to alkyl thiols (Table 3, entries 9 and 10). In
these cases, reaction with ZnI2 catalyst gave better results.
608C (Table 1, entries 6–9). In addition to zinc halides, InBr3
and InI3 were also found to promote the reaction as cata-
lysts (Table 1, entries 14–16).[13,14] Finally, the optimized re-
action condition was identified as follows: with 10 mol% of
InI3, in 1,2-dichloroethane at 808C. Under such conditions,
the reaction afforded the product 6a in 73% yield.
Next, a series of hydroxylated 1,5-allenynes was prepared
in three steps according to the procedure shown in
Scheme 4. Homopropargylic alcohols 9a–j, which were
easily available from propargylic bromide and aldehyde,
were oxidized with PCC to afford allenyl ketones 10a–j.
Addition of propargylmagnesium bromide to allenyl ketone
gave the desired hydroxylated 1,5-allenynes 3a–j.
Table 3. InI3-catalyzed reaction of 3 f and thiol 4a–j.
Entry
Thiol 4, R
t [h]
Product
Yield [%]
1
2
3
4
5
6
7
8
4a, Ph
1
1
1
1
5
1
1
1
2
5
6 f
11a
11b
11c
11d
11e
11 f
11g
11h
11i
82
73
77
81
60
92
88
79
67
56
4b, 2-ClC6H4
4c, 2-BrC6H4
4d, 4-BrC6H4
4e, 2,6-Me2C6H3
4 f, 3-FC6H4
4g, 4-MeOC6H4
4h, naphthyl
4i, C6H5CH2
9[a]
10[a]
Scheme 4. Preparation of 3a–j.
4j, CH3ACHTNUGTRNEUNG(CH2)3
[a] The reaction was carried out with 40 mol% ZnI2 as the catalyst.
With hydroxylated 1,5-allenynes 3a–j in hand, we pro-
ceeded to study the InI3-catalyzed reaction with thiophenol
under the optimized reaction conditions (Table 2). The reac-
tion afforded the corresponding 3,5-disubstituted toluene
derivative 6a–j in moderate yields in most cases. The only
exception was the reaction with 3h, which contained a para-
methoxyphenyl aromatic substituent (Table 2, entry 8). The
Finally, as the thio group can be utilized in nickel-cata-
lyzed cross-coupling reactions,[15] we proceeded to replace
the thio group of the 3,5-disubstituted toluene products with
alkyl or aryl groups. As shown in Scheme 5, the nickel(II)-
catalyzed cross-coupling reaction of 6a, e, and g with
Grignard reagents 12a–c provided the corresponding cou-
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InI3- or ZnI2-Catalyzed Reaction of Hydroxylated 1,5-Allenynes with Thiols
ture. Finally, saturated NH4Cl (5 mL) was added. After removal of the
organic solvent in vacuum, the residue was extracted with ethyl ether.
The combined organic layers were dried over MgSO4 and evaporated,
and the residue was purified by column chromatography on silica gel
eluted with petroleum ether/EtOAc (20:1) to afford the corresponding
homopropargylic alcohol 1a–j.
A
solution of homopropargylic alcohol (5.0 mmol) and H5IO3
(5.25 mmol) in CH3CN (10 mL) was cooled to 08C. Then pyridinium
chlorochromate (0.1 mmol) was added by portion. The mixture was
stirred at room temperature for another 1–3 h. EtOAc (10 mL) and brine
(10 mL) were added after the reaction was completed. The mixture was
washed with Na2SO3 and the combined organic layers were dried over
MgSO4. After removal of organic solvent in vacuum the crude residue
was purified by column chromatography on silica gel eluted with petrole-
um ether/EtOAc (30:1) to afford the corresponding allenyl aldehyde 2a–
j.
Under a nitrogen atmosphere, magnesium metal (7.5 mmol) and mercury
chloride (0.075 mmol) were mixed in dry diethyl ether (5.0 mL) in a
50 mL round-bottomed flask. To the solution, propargyl bromide
(7.5 mmol) in anhydrous ethyl ether (5 mL) was then added dropwise at
608C over about 1 h. The reaction was kept at the same temperature
until the yellow solution turned cloudy. Then, a solution of homopropar-
gylic aldehyde 2a–j (5.0 mmol) in anhydrous ethyl ether (5 mL)was
added dropwise at À788C. The mixture was stirred for another 2–8 h at
the same temperature. Finally, saturated NH4Cl (5 mL) was added. After
removal of the organic solvent under vacuum, the residue was extracted
several times with diethyl ether. The combined organic layers were dried
over MgSO4 and evaporated, and the residue was purified by column
chromatography on silica gel eluted with petroleum ether/EtOAc (100:1,
60:1, 30:1, 20:1) to afford the corresponding allenyl homopropargylic al-
cohol 3a-j.
Scheme 5. Nickel(II)-catalyzed cross-coupling reaction.
pling products 13a–c in good yields. Thus, the InI3-catalyzed
reaction of hydroxylated 1,5-allenynes and thiols followed
by nickel(II)-catalyzed cross-coupling constitutes a novel
access to various 3,5-disubstituted toluene derivatives.
Conclusions
3a: Oil; IR (film) n˜ =3543, 3294, 3061, 1956, 1492, 1448, 1353, 1174, 108,
In conclusion, we have discovered an InI3- or ZnI2-catalyzed
cyclization reaction of hydroxylated 1,5-allenynes with
thiols, which affords various 3,5-disubstituted toluene deriv-
atives in good yields. This reaction provides a new entry to
1,3,5-trisubstituted benzene derivatives.
1042, 854, 764, 700 cmÀ1 1H NMR (CDCl3, 200 MHz): d=2.05 (t, J=
;
2.7 Hz, 1H), 2.72–2.92 (m, 3H), 4.99 (dd, J=6.8, 1.0 Hz, 2H), 5.59 (t, J=
6.8 Hz, 1H), 7.22–7.40 (m, 3H), 7.47–7.53 ppm (m, 2H); 13C NMR
(CDCl3, 50 MHz): d=33.47, 71.90, 73.68, 79.63, 79.91, 97.92, 125.28,
127.44, 128.16, 144.30, 206.30 ppm; EI-MS (m/z, relative intensity): 184
(M+, 1), 145 (94), 105 (100), 77 (63), 51 (22), 39 (27); HRMS calcd for
C13H12ONa [M+Na]+ 207.0780; found: 207.0773.
3b: Oil; IR (film): n˜ =3537, 3299, 1956, 1491, 1399, 1174, 1093, 1071,
1014, 909, 853, 828, 753, 723 cmÀ1 1H NMR (CDCl3, 200 MHz): d=2.07
;
Experimental Section
(t, J=2.7 Hz, 1H), 2.69–2.90 (m, 3H), 5.00 (dd, J=6.6, 0.6 Hz, 2H), 5.56
(t, J=6.6 Hz, 1H), 7.26–7.35 (m, 2H), 7.41–7.48 ppm (m, 2H); 13C NMR
(CDCl3, 50 MHz): d=33.47, 72.16, 73.49, 79.57, 79.87, 97.64, 126.92,
128.26, 133.30, 142.82, 206.36 ppm; EI-MS (m/z, relative intensity): 218
(M+, 1), 179 (91), 144 (22), 139 (100), 111 (39), 75 (22), 39 (35); HRMS
calcd for C13H11ClONa [M+Na]+ 241.0391; found: 241.0389.
General Procedure
All reactions were performed under a nitrogen atmosphere in a flame-
dried reaction flask, and the components were added via syringe. All sol-
vents were distilled prior to use. The boiling point of the petroleum ether
was 30–608C. Benzene and toluene were distilled from sodium prior to
use. CH2Cl2 was distilled from CaH2. For chromatography, 200–300 mesh
silica gel (Qingdao, China) was employed. For preparative TLC, 10–
40 mm silica gel GF254 (Qingdao, China) was used. Recrystallization was
from petroleum ether/ethyl acetate. 1H and 13C NMR spectra were re-
corded at 200 MHz and 50 MHz with Varian Mercury 200 spectrometer,
300 MHz and 75 MHz with Varian Mercury 300 spectrometer, or at
400 MHz and 100 MHz with Bruker ARX 400. Chemical shifts are re-
ported in ppm using tetramethylsilane as internal standard. IR spectra
were recorded with a Nicolet 5MX-S infrared spectrometer. Mass spectra
and HMRS were obtained on a VG ZAB-HS mass spectrometer. Ele-
mental analysis was conducted with Vario EL.
3c: Oil; IR (film): n˜ =3539, 3296, 1956, 1567, 1474, 1418, 1282, 1174,
1070, 1034, 996, 854, 787, 696 cmÀ1 1H NMR (CDCl3, 200 MHz): d=2.08
;
(t, J=2.7 Hz, 1H), 2.69–2.90 (m, 3H), 5.02 (dd, J=6.6, 0.8 Hz, 2H), 5.56
(t, J=6.6 Hz, 1H), 7.18–7.26 (m, 1H), 7.38–7.45 (m, 2H), 7.67–7.69 ppm
(m, 1H); 13C NMR (CDCl3, 50 MHz): d=33.45, 72.26, 73.39, 79.44, 80.01,
97.51, 122.41, 124.08, 128.67, 129.74, 130.56, 146.64, 206.37 ppm; EI-MS
(m/z, relative intensity): 262 (M+, 1), 225 (19), 223 (19), 183 (34), 144
(100), 115 (23), 76 (16), 39 (31); HRMS calcd for C13H11BrONa
[M+Na]+ 284.9886; found: 284.9877.
3d: Oil; IR (film): n˜ =3547, 3300, 1956, 1561, 1470, 1380, 1277, 1179,
1134, 1073, 1029, 854, 823, 710 cmÀ1 1H NMR (CDCl3, 200 MHz): d=
;
2.09 (t, J=2.7 Hz, 1H), 2.68–2.89 (m, 3H), 5.03 (dd, J=6.6, 1.0 Hz, 2H),
5.55 (t, J=6.6 Hz, 1H), 7.27–7.44 (m, 2H), 7.63 ppm (d, J=2.2 Hz, 1H);
13C NMR (CDCl3, 50 MHz): d=33.47, 71.90, 73.68, 79.63, 79.91, 97.92,
125.28, 127.44, 128.16, 144.30, 206.30 ppm; EI-MS (m/z, relative intensi-
ty): 252 (M+, 1), 215 (61), 213 (92), 173 (100), 145 (39), 115 (25), 75 (23),
39 (65), 28 (34) ; HRMS calcd for C13H11BrONa [M+H]+ 283.0182;
found: 253.0176.
Synthesis of Allenyl Homopropargylic Alcohols 3a–j
Under a nitrogen atmosphere, magnesium metal (7.5 mmol) and mercury
chloride (0.075 mmol) were mixed in anhydrous ethyl ether (5.0 mL) in a
50 mL round-bottomed flask. Propargyl bromide (7.5 mmol) in anhy-
drous ethyl ether (5 mL) was added dropwise to the solution heated at
608C over about 1 h. The reaction was then kept at the same temperature
until the yellow solution turned cloudy. Then a solution of aldehyde
(5.0 mmol) in anhydrous ethyl ether (5 mL) was added dropwise at
À238C. The mixture was stirred for another 1–4 h at the same tempera-
3e: Oil; IR (film): n˜ =3544, 3294, 3061, 1956, 1485, 1455, 1352, 1290,
1
1172, 1037, 910, 852, 761, 727, 683 cmÀ1; H NMR (CDCl3, 300 MHz): d=
2.07 (t, J=2.7 Hz, 1H), 2.50 (s, 3H), 2.76 (s, 1H), 2.94 (d, J=2.7 Hz,
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J. Wang et al.
FULL PAPERS
2H), 4.95 (d, J=6.9 Hz, 2H), 5.59 (t, J=6.9 Hz, 1H), 7.14–7.23 (m, 3H),
7.54–7.57 ppm (m, 1H); 13C NMR (CDCl3, 75 MHz): d=21.72, 31.90,
72.22, 74.49, 79.38, 80.03, 97.51, 125.44, 126.25, 127.65, 132.36, 136.08,
140.99, 206.49 ppm; EI-MS (m/z, relative intensity): 198 (M+, 1), 159
(100), 119 (81), 91 (57), 65 (18), 39 (35); HRMS calcd for C14H14ONa
[M+Na]+ 221.0937; found: 221.0932.
7.39 (m, 3H), 7.48–7.52 ppm (m, 2H); 13C NMR (CDCl3, 50 MHz): d=
30.30, 51.20, 71.00, 78.29, 79.64, 79.90, 93.66, 126.62, 127.45, 127.90,
142.15, 208.24 ppm. EI-MS (m/z, relative intensity): 165 (M+, 6), 159
(88), 144 (11), 127 (10), 115 (18), 86 (58), 84 (89), 47 (28), 35 (19), 28
(100); HRMS calcd for C14H15O [M+H]+ 199.1117; found: 199.1118.
Typical Procedure for the InI3-Catalyzed Reactions of 3a–j and Thiols
4a–j
3 f: Oil; IR (film): n˜ =3548, 3301, 1956, 1601, 1509, 1225, 1160, 1069, 910,
835, 815 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.07 (t, J=2.7 Hz, 1H),
;
2.72–2.88 (m, 3H), 5.00 (dd, J=6.6, 1.5 Hz, 2H), 5.58 (t, J=6.6 Hz, 1H),
6.99–7.07 (m, 2H), 7.45–7.51 ppm (m, 2H); 13C NMR (CDCl3, 75 MHz):
d=33.65, 72.08, 73.48, 79.71, 79.75, 97.76, 114.70, 114.98, 127.10, 127.20,
139.95, 139.99, 160.35, 163.61, 206.14 ppm; EI-MS (m/z, relative intensi-
ty): 202 (M+, 1), 163 (93), 123 (100), 95 (52), 75 (16), 39 (29); HRMS
calcd for C13H11FONa [M+Na]+ 225.0686; found: 225.0682.
Under a nitrogen atmosphere, allenyl homopropargylic alcohol 3a–j
(0.3 mmol), thiol (0.45 mmol), and InI3 (0.03 mmol) or ZnI2 (0.12 mmol)
were mixed in dry 1,2-dichloroethane (DCE, 5 mL). The reaction mixture
was stirred at 808C until the reaction was completed as judged by TLC.
THF (2 mL) and 10% KOH (3 mL) were then added. The mixture was
extracted with CH2Cl2 and the combined organic layers were dried over
Na2SO4. After removal of organic solvent under vacuum, the residue was
purified by column chromatography on silica gel eluted with petroleum
ether to afford the pure product 6a–j or 11a–i.
3g: White solid; IR (film): n˜ =3546, 3292, 3030, 1956, 1600, 1486, 1401,
1176, 1072, 1007, 910, 840, 766, 734, 697 cmÀ1
;
1H NMR (CDCl3,
300 MHz): d=2.06 (t, J=2.7 Hz, 1H), 2.77–2.92 (m, 3H), 5.00 (dd, J=
6.6, 2.1 Hz, 2H), 5.61 (t, J=6.6 Hz, 1H), 7.29–7.34 (m, 1H), 7.38–7.44
(m, 2H), 7.55–7.59 ppm (m, 6H); 13C NMR (CDCl3, 75 MHz): d=33.46,
72.01, 73.59, 79.72, 79.90, 97.86, 125.70, 126.78, 126.96, 127.22, 128.66,
140.13, 140.50, 143.25, 206.09 ppm; EI-MS (m/z, relative intensity): 260
(M+, 3), 221 (100), 181 (52), 152 (31), 76 (9), 39 (22); HRMS calcd for
C19H16ONa [M+Na]+ 283.1093; found: 283.1090.
6a: Oil; IR (film): n˜ =3058, 1581, 1570, 1477, 1439, 1076, 1024, 896, 853,
760, 740, 690 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.33 (s, 3H), 7.16–
;
7.53 ppm (m, 13H); 13C NMR (CDCl3, 75 MHz): d=21.34, 126.89,
126.94, 127.00, 127.04, 127.48, 128.69, 129.13, 130.53, 130.77, 135.79,
135.88, 139.34, 140.40, 142.12 ppm; EI-MS (m/z, relative intensity): 290
(M+, 100), 181 (16), 179 (9), 166 (39), 165 (41), 115 (5); HRMS calcd for
C20H18S [M+] 290.1129; found: 290.1132.
3h: Oil; IR (film): n˜ =3464, 3289, 2940, 2835, 1956, 1601, 1487, 1431,
1317, 1289, 1253, 1151, 1041, 855, 784, 701 cmÀ1
;
1H NMR (CDCl3,
6b: Oil; IR (film): n˜ =2988, 1578, 1494, 1477, 1439, 1386, 1093, 1013, 862,
300 MHz): d=2.06 (t, J=2.7 Hz, 1H), 2.74–2.89 (m, 3H), 3.80 (s, 3H),
5.00 (dd, J=6.6, 2.1 Hz, 2H), 5.58 (t, J=6.6 Hz, 1H), 6.80–6.84 (m, 1H),
7.04–7.11 (m, 2H), 7.24–7.30 ppm (m, 1H); 13C NMR (CDCl3, 75 MHz):
d=33.48, 55.14, 71.91, 73.61, 79.65, 79.88, 97.83, 111.25, 112.62, 117.58,
129.11, 146.00, 159.38, 206.13 ppm; EI-MS (m/z, relative intensity): 214
(M+, 4), 175 (100), 135 (58), 107 (25), 92 (28), 77 (26), 39 (40); HRMS
calcd for C14H14O2Na [M+Na]+ 237.0886; found: 237.0881.
824, 739, 690 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.33 (s, 3H), 7.14–
;
7.43 ppm (m, 12H); 13C NMR (CDCl3, 75 MHz): d=21.33, 126.57,
126.63, 127.06, 128.27, 128.84, 129.18, 130.63, 130.97, 133.54, 135.57,
136.21, 138.83, 139.50, 140.83 ppm; EI-MS (m/z, relative intensity): 310
(M+, 100), 274 (10), 260 (21), 165 (21). 129 (5); HRMS calcd for
C19H15ClS [M+] 310.0583; found: 310.0579.
6c: Oil; IR (film): n˜ =2956, 1590, 1576, 1558, 1477, 1439, 1387, 1070,
3i: Oil; IR (film): n˜ =3298, 3025, 2944, 1956, 1603, 1497, 1454, 1354,
1024, 908, 850, 782, 738, 688 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.34
;
1278, 1178, 1049, 946, 850, 742, 693 cmÀ1
;
1H NMR (CDCl3, 300 MHz):
(s, 3H), 7.16–7.45 (m, 11H), 7.66–7.67 ppm (m, 1H); 13C NMR (CDCl3,
75 MHz): d=21.33, 122.82, 125.67, 126.81, 127.05, 129.19, 130.08, 130.20,
130.37, 130.91, 131.00, 135.59, 136.19, 139.55, 140.59, 142.54 ppm; EI-MS
(m/z, relative intensity): 354 (M+, 100), 274 (13), 260 (27), 166 (39), 165
(80); HRMS calcd for C19H115BrS [M+] 354.0078; found: 354.0075.
d=1.90–2.07 (m, 2H), 2.09 (t, J=2.7 Hz, 1H), 2.32 (s, 1H), 2.54 (dd, J=
2.7, 1.5 Hz, 2H), 2.69–2.76 (m, 2H), 5.00 (dd, J=6.6, 2.1 Hz, 2H), 5.39 (t,
J=6.6 Hz, 1H), 7.15–7.31 ppm (m, 5H); 13C NMR (CDCl3, 75 MHz): d=
30.14, 31.83, 41.85, 71.53, 72.03, 79.32, 80.04, 96.84, 125.77, 128.29, 128.34,
141.93, 205.98 ppm; EI-MS (m/z, relative intensity): 194 (M+, 22), 173
(18), 145 (9), 131 (9), 107 (9), 105 (30), 91 (100), 77 (15), 67 (19), 51 (14),
39 (40); HRMS calcd for C15H16ONa [M+Na]+ 235.1093; found:
235.1099.
6d: Oil; IR (film): n˜ =2977, 1575, 1550, 1477, 1439, 1367, 1301, 1136,
1
1083, 1026, 901, 864, 817, 747, 691 cmÀ1; H NMR (CDCl3, 300 MHz): d=
2.34 (s, 3H), 7.16–7.45 (m, 10H), 7.59 ppm (d, J=2.1 Hz, 1H); 13C NMR
(CDCl3, 75 MHz): d=21.33, 126.27, 126.41, 126.54, 127.03, 127.21, 128.84,
129.17, 129.24, 130.41, 130.60, 131.03, 131.10, 131.60, 132.78, 135.34,
136.59, 139.62, 139.69, 140.44 ppm; EI-MS (m/z, relative intensity): 344
(M+, 100), 294 (19), 165 (16), 123 (15), 84 (33), 66 (38); HRMS calcd for
C19H14Cl2S [M+] 344.0193; found: 344.0194.
3j: Oil; IR (film): n˜ =3312, 2930, 2858, 1958, 1466, 1376, 1278, 1126,
1
1058, 951, 846, 743, 721, 702, 697, 685 cmÀ1; H NMR (CDCl3, 400 MHz):
d=0.87–0.90 (m, 4H), 1.29–1.39 (m, 10H), 1.65–1.70 (m, 3H), 2.08 (t, J=
2.7 Hz, 1H), 2.16 (s, 1H), 2.49 (t, J=2.7 Hz, 2H), 4.95 (d, J=6.6 Hz,
2H), 5.32 ppm (t, J=6.6 Hz, 1H); 13C NMR (CDCl3, 100 MHz): d=
14.03, 22.56, 23.69, 29.51, 31.61, 31.74, 40.19, 71.28, 72.21, 79.05, 80.35,
97.09, 205.97 ppm; EI-MS (m/z, relative intensity): 192 (M+, 2), 153 (99),
135 (16), 113 (100), 107 (96), 95 (16), 85 (74), 79 (32), 67 (88), 57 (28), 43
(85); HRMS calcd for C13H20O [M+] 192.1514; found: 192.1516.
6e: Oil; IR (film): n˜ =2963, 1573, 1477, 1439, 1261, 1084, 1025, 854, 798,
758, 742, 691 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.21 (s, 3H), 2.34 (s,
;
3H), 7.01 (s, 1H), 7.10 (s, 1H), 7.16–7.32 (m, 8H), 7.37–7.40 ppm (m,
2H); 13C NMR (CDCl3, 75 MHz): d=20.41, 21.30, 125.71, 127.00, 127.35,
128.69, 128.81, 129.14, 129.57, 129.76, 130.28, 131.08, 135.21, 135.24,
135.73, 138.71, 141.14, 142.80 ppm; EI-MS (m/z, relative intensity): 290
(M+, 100), 275 (5), 181 (16), 165 (42), 115 (6); HRMS calcd for C20H18S
[M+] 290.1129; found: 290.1132.
Preparation of Methoxylated 1,5-Allenyne 8
Under
a nitrogen atmosphere, allenyl homopropargylic alcohol 3a
(0.5 mmol) and NaH (0.6 mmol) were mixed in dry THF (5 mL) in a
25 mL round-bottomed flask. The reaction mixture was stirred at room
temperature for about 20 min. Then, methyl iodide (10 mmol) was added
to the mixture. The mixture was stirred for another 2 h at 608C. Upon
completion of the reaction, saturated NH4Cl (5 mL) was added. After re-
moval of the organic solvent under vacuum, the crude residue was ex-
tracted with diethyl ether. The combined organic layers were dried over
MgSO4 and evaporated, and the crude residue was purified by column
chromatography on silica gel eluted with petroleum ether/EtOAc (100:1)
to afford the pure product.
6 f: Oil; IR (film): n˜ =1606, 1573, 1510, 1477, 1439, 1232, 1159, 1024, 829,
780, 741, 690 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.32 (s, 3H), 7.02–
;
7.46 ppm (m, 12H); 13C NMR (CDCl3, 75 MHz): d=21.30, 115.40,
115.68, 126.71, 126.98, 128.53, 128.64, 129.15, 130.39, 130.87, 135.70,
136.02, 136.46, 136.50, 139.42, 141.08, 160.83, 164.10 ppm; EI-MS (m/z,
relative intensity): 294 (M+, 100), 279 (13), 259 (5), 184 (5), 170 (6);
HRMS calcd for C19H15FS [M+] 294.0879; found: 294.0880.
6g: White solid; IR (film): n˜ =2921, 1573, 1477, 1439, 1083, 1024, 854,
826, 758, 736, 702 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.34 (s, 3H),
;
7.16–7.45 (m, 11H), 7.56–7.63 ppm (m, 6H); 13C NMR (CDCl3, 75 MHz):
d=21.37, 126.78, 126.84, 126.96, 127.34, 127.41, 128.76, 129.16, 130.58,
130.83, 135.84, 135.91, 139.25, 139.42, 140.27, 140.49, 141.58 ppm; EI-MS
8: Oil; IR (film): n˜ =3296, 2939, 2827, 1954, 1492, 1447, 1326, 1263, 1199,
1090, 1006, 848, 766, 700 cmÀ1 1H NMR (CDCl3, 200 MHz): d=1.94 (t,
;
J=2.7 Hz, 1H), 2.75 (dd, J=16.8, 2.7 Hz, 1H), 2.88 (dd, J=16.8, 2.7 Hz,
1H), 3.30 (s, 3H), 4.98 (d, J=7.2 Hz, 2H), 5.48 (t, J=6.6 Hz, 1H), 7.26–
2218
www.chemasianj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 2214 – 2220

InI3- or ZnI2-Catalyzed Reaction of Hydroxylated 1,5-Allenynes with Thiols
(m/z, relative intensity): 352 (M+, 100), 336 (5), 260 (2), 239 (3), 226 (3),
165 (3); HRMS calcd for C25H20S [M+] 352.1286; found: 352.1288.
4H), 7.41–7.46 ppm (m, 4H); 13C NMR (CDCl3, 75 MHz): d=21.36,
55.28, 114.96, 115.36, 115.65, 123.93, 124.15, 125.58, 127.61, 128.55, 128.65,
135.25, 136.77, 138.95, 139.16, 140.87, 159.77, 160.80, 164.07 ppm; EI-MS
(m/z, relative intensity): 324 (M+, 100), 309 (17), 294 (3), 265 (3), 183 (4),
170 (3); HRMS calcd for C20H17OFS [M+] 324.0984; found: 324.0987.
6i: Oil; IR (film): n˜ =2920, 1597, 1577, 1559, 1477, 1453, 1439, 1260,
1
1083, 1024, 849, 802, 738, 703, 697 cmÀ1; H NMR (CDCl3, 400 MHz): d=
2.30 (s, 3H), 2.85–2.93 (m, 4H), 6.93 (s, 1H), 7.05 (d, J=5.9 Hz, 2H),
7.17–7.33 ppm (m, 10H); 13C NMR (CDCl3, 100 MHz): d=21.21, 29.69,
37.59, 37.70, 125.94, 126.62, 128.32, 128.40, 128.53, 128.67, 129.05, 129.75,
130.36, 134.71, 136.38, 138.96, 141.49, 142.77 ppm; EI-MS (m/z, relative
intensity): 304 (M+, 100), 213 (72), 198 (24), 197 (9), 180 (8), 165 (8), 137
(10), 91 (19); HRMS calcd for C21H21S [M+H]+ 305.1359; found:
305.1358.
11g: Oil; IR (film): n˜ =1606, 1572, 1510, 1454, 1231, 1159, 1132, 1014,
943, 849, 823, 813, 744 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.33 (s,
;
3H), 7.02–7.09 (m, 2H), 7.17 (s, 1H), 7.22 (s, 1H), 7.38–7.47 (m, 7H),
7.71–7.80 (m, 3H), 7.88 ppm (s, 1H); 13C NMR (CDCl3, 75 MHz): d=
21.34, 115.42, 115.71, 126.18, 126.58, 126.77, 127.39, 127.71, 128.57, 128.65,
128.69, 128.85, 129.77, 130.29, 132.25, 132.92, 133.75, 136.16, 136.47,
136.51, 139.50, 141.16, 160.86, 164.14 ppm; EI-MS (m/z, relative intensi-
ty): 344 (M+, 100), 329 (18), 296 (5), 235 (5), 183 (8), 170 (7) , 154 (7);
HRMS calcd for C21H17FS [M+] 344.1035; found: 344.1038.
6j: Oil; IR (film): n˜ =2926, 2857, 1577, 1558, 1478, 1439, 1377, 1081,
1024, 998, 848, 792, 738, 726, 719, 716, 711, 707, 696 cmÀ1 1H NMR
;
(CDCl3, 400 MHz): d=0.87 (t, J=6.6 Hz, 3H), 1.26–1.31 (m, 6H), 1.54–
1.57 (m, 2H), 2.27 (s, 3H), 2.51 (t, J=7.6 Hz, 2H) , 6.89 (s, 1H), 7.01 (s,
2H), 7.18–7.31 (m, 5H), 7.48–7.50 ppm (m, 1H); 13C NMR (CDCl3,
100 MHz): d=14.05, 21.21, 22.56, 28.90, 31.27, 31.65, 35.65, 126.52,
127.12, 127.50, 128.49, 128.70, 129.00, 129.03, 129.45, 130.26, 134.46,
136.57, 138.83, 143.98 ppm; EI-MS (m/z, relative intensity): 284 (M+,
100), 214 (47), 213 (12), 198 (15), 197 (11), 165 (9), 136 (10), 105 (61);
HRMS calcd for C19H24S [M+] 284.1599; found: 284.1601.
11h: Oil; IR (film): n˜ =2923, 1606, 1575, 1511, 1454, 1377, 1227, 1160,
1130, 1098, 1077, 1049, 993, 959, 833, 778, 765, 697 cmÀ1 1H NMR
;
(CDCl3, 400 MHz): d=2.35 (s, 3H), 4.15 (s, 2H), 7.07–7.16 (m, 4H),
7.25–7.33 (m, 7H), 7.42–7.47 ppm (m, 2H); 13C NMR (CDCl3, 100 MHz):
d=18.04, 21.36, 21.39, 38.99, 63.63, 102.72, 115.40, 115.57, 115.69, 115.85,
120.15, 123.37, 125.45, 126.03, 127.19, 128.47, 129.10, 130.47, 135.86,
136.71, 139.01, 139.53, 140.84, 143.09 ppm; EI-MS (m/z, relative intensi-
ty): 308 (M+, 28), 217 (3), 202 (6), 183 (5), 91 (100), 65 (10); HRMS
calcd for C20H18FS [M+H]+ 309.1108; found: 309.1115.
11a: Oil; IR (film): n˜ =1605, 1573, 1511, 1451, 1431, 1230, 1160, 1033,
830, 748, 696 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.38 (s, 3H), 7.02–
;
11i: Oil; IR (film): n˜ =2957, 1606, 1575, 1510, 1463, 1225, 1159, 1097,
7.13 (m, 5H) , 7.23 (s, 1H) , 7.32 (s, 1H) , 7.36–7.51 ppm (m, 4H);
13C NMR (CDCl3, 75 MHz): d=21.33, 115.49, 115.77, 127.20, 127.89,
128.57, 128.68, 128.76, 129.69, 130.02, 132.48, 132.94, 133.09, 136.24,
136.27, 136.44, 139.88, 141.48, 160.92, 164.18 ppm; EI-MS (m/z, relative
intensity): 328 (M+, 95), 293 (96), 278 (100), 183 (21), 170 (12); HRMS
calcd for C19H14FClS [M+] 328.0489; found: 328.0486.
1014, 828, 781, 694 cmÀ1 1H NMR (CDCl3, 400 MHz): d=0.93 (t, J=
;
7.4 Hz, 3H), 1.42–1.51 (m, 2H), 1.62–1.70 (m, 2H), 2.38 (s, 1H), 2.96 (t,
J=7.2 Hz, 2H), 7.08–7.13 (m, 4H), 7.25 (s, 1H), 7.28 (d, J=1.6 Hz, 1H),
7.48–7.53 ppm (m, 2H); 13C NMR (CDCl3, 100 MHz): d=13.63, 21.41,
21.96, 31.22, 33.22, 115.45, 115.67, 124.46, 125.43, 128.12, 128.64, 128.72,
136.95, 136.98, 137.52, 138.98, 140.83, 161.28, 163.73 ppm; EI-MS (m/z,
relative intensity): 274 (M+, 83), 309 (17), 218 (100), 203 (16), 198 (25),
183 (30), 170 (14), 57 (10), 49 (10), 41 (21), 29 (37); HRMS calcd for
C17H20FS {[M+H]}+ 275.1264; found: 275.1263.
11b: Oil; IR (film): n˜ =1606, 1572, 1511, 1446, 1427, 1233, 1159, 1098,
1020, 830, 747, 711 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.36 (s, 3H),
;
6.95–7.14 (m, 5H) , 7.22 (s, 1H) , 7.31 (s, 1H) , 7.41–7.54 ppm (m, 4H);
13C NMR (CDCl3, 75 MHz): d=21.33, 115.49, 115.77, 122.92, 127.18,
127.79, 128.00, 128.56, 128.66, 128.99, 129.67, 132.71, 132.95, 133.11,
136.19, 136.24, 138.70, 139.93, 141.51, 160.90, 164.16 ppm; EI-MS (m/z,
relative intensity): 374 (M+, 34), 372 (34), 293 (44), 278 (100), 183 (10),
170 (8); HRMS calcd for C19H14FBrS [M+] 371.9984; found: 371.9980.
Typical Procedure for the Nickel(II)-Catalyzed Reactions of 6a, e, g and
Grignard Reagents 12a–c
Under a nitrogen atmosphere, the Grignard reagent (1.5 mmol) and
[NiCl2ACTHNUGTRNE(UNG PPh3)2] (0.015 mmol) were mixed in dry toluene (5 mL) in a
11c: Oil; IR (film): n˜ =1597, 1575, 1511, 1472, 1427, 1263, 1221, 1159,
25 mL round-bottomed flask. The reaction mixture was stirred at room
temperature for about 15 min. Then, sulfane (0.3 mmol) was added to the
mixture. The mixture was stirred for another 3 to 7 h at 1008C. Upon the
completion of the reaction, saturated NH4Cl (5 mL) was added. After re-
moval of the organic solvent under vacuum, the residue was extracted
with diethyl ether. The combined organic layers were dried over MgSO4
and evaporated, and the residue was purified by column chromatography
on silica gel eluted with petroleum ether to afford the pure product.
1063, 879, 830, 777, 679 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.38 (s,
;
3H), 6.86–6.92 (m, 1H) , 6.96–7.00 (m, 1H) , 7.07–7.13 (m, 3H) , 7.20–
7.30 (m, 3H) , 7.41 (s, 1H) , 7.46–7.51 ppm (m, 2H); 13C NMR (CDCl3,
75 MHz): d=21.33, 113.31, 113.59, 115.51, 115.75, 115.80, 116.14, 116.45,
125.03, 125.07, 127.70, 128.20, 128.61, 128.72, 130.23, 130.34, 131.87,
134.02, 136.36, 139.18, 139.28, 139.80, 141.45, 160.96, 161.33, 164.23,
164.62 ppm; EI-MS (m/z, relative intensity): 372 (M+, 100), 293 (15), 278
(36), 252 (10), 201 (12), 183 (21), 170 (13), 122 (12), 108 (12); HRMS
calcd for C19H14FBrS [M+] 371.9984; found: 371.9987.
11d: Oil; IR (film): n˜ =2922, 1600, 1573, 1509, 1460, 1378, 1296, 1219,
1161, 1116, 1034, 898, 829, 773, 692 cmÀ1 1H NMR (CDCl3, 300 MHz):
;
d=2.28 (s, 3H), 2.45 (s, 6H), 6.71 (s, 1H), 6.91 (s, 1H), 7.03–7.09 (m,
3H), 7.18–7.23 (m, 3H), 7.38–7.42 ppm (m, 2H); 13C NMR (CDCl3,
75 MHz): d=21.46, 21.90, 115.36, 115.65, 121.21, 124.53, 124.89, 128.46,
128.53, 128.63, 129.33, 130.18, 136.87, 136.92, 138.51, 139.12, 140.83,
143.86, 160.80, 164.06 ppm; EI-MS (m/z, relative intensity): 322 (M+,
100), 186 (11), 136 (52), 135 (18); HRMS calcd for C21H19FS [M+]
322.1192; found: 322.1194.
Acknowledgements
The project was generously supported by the NSFC (Grant No.
20832002, 20772003, 20821062), the Ministry of Education of China, and
the National Basic Research Program of China (973 Program, No.
2009CB825300).
11e: Oil; IR (film): n˜ =1604, 1573, 1510, 1470, 1385, 1230, 1159, 1087,
1069, 1008, 829, 779, 695 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.36 (s,
;
[1] For selected reviews, see: a) C. Aubert, O. Buisine, M. Malacria,
Chem. Rev. 2002, 102, 813; b) S. A. Hashmi, Chem. Rev. 2007, 107,
3180; c) A. Fꢁrstner, P. W. Davies, Angew. Chem. 2007, 119, 3478;
Angew. Chem. Int. Ed. 2007, 46, 3410; d) C. H. M. Amijs, C. Ferrer,
A. M. Echavarren, Chem. Commun. 2007, 698; e) E. Jimꢂnez-
NfflÇez, A. M. Echavarren, Chem. Commun. 2007, 333; f) A. R.
Chianese, S. J. Lee, M. R. Gagnꢂ, Angew. Chem. 2007, 119, 4118;
Angew. Chem. Int. Ed. 2007, 46, 4042; g) L. Zhang, J. Sun, S. A.
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3H), 7.06–7.14 (m, 3H) , 7.18–7.25 (m, 3H) , 7.35 (s, 1H) , 7.38–7.50 ppm
(m, 4H); 13C NMR (CDCl3, 75 MHz): d=21.34, 115.50, 115.79, 120.82,
127.19, 127.23, 128.59, 128.69, 130.86, 131.95, 132.21, 135.08, 135.42,
136.33, 136.38, 139.68, 141.33 ppm; EI-MS (m/z, relative intensity): 312
(M+, 100), 296 (10), 276 (7), 254 (7), 183 (13), 170 (8), 127 (7); HRMS
calcd for C19H14F2 S [M+] 312.0784; found: 312.0782.
11 f: Oil; IR (film): n˜ =1593, 1573, 1510, 1493, 1460, 1288, 1246, 1173,
1160, 1099, 1031, 828, 779, 693 cmÀ1 1H NMR (CDCl3, 300 MHz): d=
;
2.31 (s, 3H), 3.80 (s, 3H), 6.88–6.91 (m, 2H), 6.97 (s, 1H), 7.04–7.11 (m,
Chem. Asian J. 2010, 5, 2214 – 2220
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
2219

J. Wang et al.
FULL PAPERS
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Received: April 13, 2010
Published online: July 30, 2010
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