One-pot Wittig olefination-Suzuki reaction - The compatibility of conjugated phosphoranes in Pd(0) catalysed C-C-bond forming reactions

Article abstract of DOI:10.1039/b516724h

Formylareneboronic acids and formylhetareneboronic acids can be subjected to a combined Suzuki coupling-Wittig olefination in their reaction with arene halides and conjugated phosphoranes. Also, the transformations can be carried out under ultrasonication

Full text of DOI:10.1039/b516724h

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www.rsc.org/njc | New Journal of Chemistry
One-pot Wittig olefination–Suzuki reaction—the compatibility of
conjugated phosphoranes in Pd(0) catalysed C–C-bond forming reactions
Thies Thiemann,*a Masataka Watanabe,b Yasuko Tanakaa and Shuntaro Matakaa
Received (in Montpellier, France) 24th November 2005, Accepted 13th December 2005
First published as an Advance Article on the web 13th January 2006
DOI: 10.1039/b516724h
Formylareneboronic acids and formylhetareneboronic acids can be subjected to a combined
Suzuki coupling–Wittig olefination in their reaction with arene halides and conjugated
phosphoranes. Also, the transformations can be carried out under ultrasonication in a biphasic
medium of aq. Na2CO3 and hexane–ether, where phosphonium salts are used as the starting
materials.
mylthienylboronic acids could be used in the reactions
Introduction
(Scheme 1). In all cases, the E-configurated acrylates are the
In the search for less time consuming processes and for
major isomer as can be expected for a Wittig olefination with a
stabilized phosphorane.1 Here, the E : Z-isomer ratios are
processes with less consumption of solvents both for the
reactions themselves and their work-up, multi-component
>90%, except for the products 4i, 4k and 4L, where the
one-pot transformations merit consideration. Within this field,
methoxy substituent, neighboring the formyl group, has a
stabilized phosphoranes offer interesting possibilities. p-Con-
directing effect and the E : Z ratio is smaller.
jugated phosphoranes such as 3 are stable towards oxygen and
The phosphorane component can be varied. Thus, not only
moisture. Their reactivity towards carbonyl groups varies with
the more reactive ester substituted methylidenephosphoranes
the character of the p-system in conjugation with the PQC
3a and 3e react well, but also the usually much less reactive
functionality.1 While aroylmethylidenephosphoranes such as
a-ketomethylidentriphenylphosphoranes, such as 3b–d and 3f.
In these cases, often longer reaction times are necessary.
3b react with carbaldehydes but not with ketones, 3a reacts
with both aldehydes and ketones in solution,1 but discrimi-
For the most part, here only the E-isomers can be isolated
nates between the two in favor of the aldehydes in solventless
reactions.2 The authors have shown the possibility of carrying
(Scheme 2).
Phenylmaleimide derived phosphorane 3g can be used in the
out C–C-bond forming reactions with haloaroylmethylidene-
reaction to form 4r. The reactivity of 3g is lower than that of
phosphoranes for the construction of libraries of aryl/heta-
rylaroylmethylidenephosphoranes.3 The stability of the p-con-
jugated phosphoranes, while still reactive towards carbonyl
the ester containing methylidenephosphoranes. Again, the
isomer formed is the E-product (Scheme 2).
Also, cyanomethylidenetriphenylphosphorane (3h) can be
groups, in a number of different reaction conditions provides
used as the phosphorane component in the transformations.
the opportunity to combine the Wittig olefination reaction
Thus, the reaction of 1b and 2a with 3h gave 4u in good yield.
with a second transformation in a one-pot procedure. Such
The E : Z ratio, however, was found to be almost 1 : 1. When
combinations have been forwarded previously, where in the
5b was reacted with 3h in benzene in the presence of benzoic
past the authors have described combinations of Wittig reac-
tions with [4 þ 2]-cycloaddition reactions.4 In the following,
acid, the E-isomer was formed (Scheme 3) almost exclusively.
The same phenomenon could be observed for the reaction of
the focus will be on methods of combining Suzuki-type C–C-
2-bromothiophene (1a) with 2a and 3h, where the one-pot
bond forming syntheses with Wittig reactions.
reaction in DME–aq. Na2CO3 gave 4s with an E : Z ratio of
63 : 37. A Wittig reaction with the preformed Suzuki coupling
product 5a in benzene in the presence of benzoic acid again
Results and discussion
gave predominantly the E-isomer of 4s. That this is not a
directing effect of the palladium itself could be shown by
When mixtures of aryl/hetaryl halides, formylaryl/hetaryl-
running the reaction of 5a and 3h in a solvent mixture of
boronic acids and ethoxycarbonylmethylidenephosphorane
DME and 2 M aq. Na2CO3, where again 4s was formed in an
(3a) were reacted under Pd(0) catalysis in a biphasic solution
E : Z ratio of 1 : 0.9. The influence of the solvent on the E : Z
of 1,2-dimethoxyethane and 2 M aq. Na2CO3, ethyl bisaryl/
ratio of the olefins formed in certain Wittig reactions has been
reported before.1 In the combined, one-pot reaction, DME
hetarylacrylates 4 were obtained in good yield. A variety of
commercially available formylarylboronic acids and for-
can in fact be exchanged for benzene, where the product forms
a Institute of Materials Chemistry and Engineering, Kyushu
University, 6-1, Kasuga-koh-en, Kasuga-shi, Fukuoka 816-8580,
Japan. E-mail: thies@cm.kyushu-u.ac.jp
in slightly lower yield, however, in an E : Z ratio of 10 : 1.
Under these conditions a higher catalyst loading is used. 4s can
be hydrolysed easily to the acrylamide 4t (Scheme 3).
b Interdisciplinary Graduate School of Engineering Sciences, Kyushu
University, 6-1, Kasuga-koh-en, Kasuga-shi, Fukuoka, 816-8580,
Japan
The dependence of the E : Z ratio on the solvent system in
these reactions is not limited to phosphorane 3h. The reaction
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Scheme 1 One-pot Wittig olefination–Suzuki coupling reaction—variation of the boronic acid and aldehyde components.
of 3-iodopyridine (1e) in DME–aq. Na2CO3 gives Z-4L as the
major product (E : Z, 12 : 88) (Scheme 4). Here again, a
change to benzene in presence of benzoic acid5 reverses the cis :
trans-specificity of this transformation, where the reaction of
5c and 3a gives predominantly E-4L (Scheme 4).
identify the regiochemistry of this reaction, coupling product
7a was subjected to hydrogenation over Pd/C to form 8 and to
subsequent hydrodesulfurization of 8 with Raney nickel to
give exclusively the fully reduced compound 9 (Scheme 6).
Wittig reactions of carbaldehydes with 10a and similar
phosphonium salts and phosphoranes in a two phase system
using ultrasonication had been carried out successfully by the
authors.7 A screening of the Suzuki coupling reactions with a
limited number of iodoarenes, such as with 1-iodonaphthalene
and phenylboronic acid to 1-phenylnaphthalene (hexane–ether
95 : 5 v/v; 2 M aq. Na2CO3, 98%) quickly showed that cross-
3-Bromobenzo[b]thiophene (6) also undergoes the above
transformation to give 3-substituted benzo[b]thiophenes 7 as
coupling products (Scheme 5). No coupling at the 2-position
or subsequent migration of the substituent to the 2-position, as
reported6 for Suzuki coupling reactions of 6 under other
reaction conditions, could be observed. To unambiguously
Scheme 2 One-pot Wittig olefination–Suzuki coupling reaction—variation of the phosphorane component.
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Scheme 3 Wittig reaction with cyanomethylidenetriphenylphosphorane—E : Z-isomeric dependence on reaction conditions.
coupling reactions also proceed successfully under conditions
where ultrasound is used.8–10 This led to the idea of combining
the two processes as described above, albeit under ultrasonica-
tion. The use of ultrasound allows for the reaction to be
carried out in a mixture of aq. 1 M Na2CO3, ether, and
hexane, where the organic solvents used have a relatively
low boiling point and can be quantitatively removed from
the aqueous phase during the work-up of the reaction. The
bulk reaction temperature is lower than in the previously
described experiments. Here, both the phosphorane and the
phosphonium salt can be employed with equal success as the
Wittig olefination component (Table 1). It must be noted that
the transformation of the phosphonium salt to the isolated
phosphorane involves the use of a chlorinated solvent, usually
dichloromethane, for extracting the phosphorane from the
basic aqueous phase. Using the phosphonium salt in the above
reaction avoids this process, which leads to a larger amount of
wash water contaminated with dichloromethane, as well as
drying and filtration procedures employed to obtain the pure
phosphorane. After the actual ultrasound assisted, combined
Suzuki coupling–Wittig olefination reaction, the product un-
fortunately still needs to be separated by column chromato-
graphy. This is in contrast to the ultrasound assisted Wittig
olefination of conjugated phosphoranes with aldehydes,7 run
in a biphasic system of aq. Na2CO3 and hexane–ether, where
the product can be siphoned off with the upper organic layer in
sufficient purity without any further purification.
Conclusions
With formylboronic acids as central building blocks, biaryl/
hetrarylacrylates, biaryl/hetarylenones, and acrylonitriles with
extended p-systems can be synthesized in one step by a
combined Suzuki cross-coupling–Wittig olefination reaction,
where stabilized phosphoranes are used. The reaction can also
be performed under ultrasound at ambient temperature in a
biphasic system with the organic phase consisting of hexane
and ether, which can be removed easily at the end of the
reaction.
Experimental
General remarks
Melting points were measured on a Yanaco microscopic hot
stage and are uncorrected. Infrared spectra were measured
Scheme 4 One-pot Suzuki–Wittig reaction with a halopyridine—E : Z-isomeric dependence on reaction conditions.
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Scheme 5 One-pot Wittig–Suzuki reaction with 3-bromobenzo[b]thiophene [3-bromothianaphthene (6)].
with a JASCO IR-700 instrument. 1H (at 270 MHz and 395.7
MHz) and 13C NMR (at 67.8 MHz and 99.45 MHz) were
recorded with a JEOL EX-270 and a JEOL Lambda 400 FT-
NMR spectrometer, respectively. The chemical shifts are
relative to TMS (solvent CDCl3, unless otherwise noted).
Mass spectra were measured with a JMS-01-SG-2-spectro-
meter (EI, 70 eV). Column chromatography was carried out
on Wakogel 300. For the ultrasonication, a 35 KHz Elma
Transsonic T-460 bath was used. The sonication experiments
were carried out at 35 1C. All experiments were purged with
argon at the start.
2b–2d were used as purchased from Aldrich. Raney nickel
(50%) was purchased from Kansai Shokubai Kagaku.
The products gained from the combined Suzuki coupling–
Wittig olefination procedure were for the most part obtained
as mixtures of E- and Z-isomers as marked in the text. When
crystalline, the pure E-isomers were obtained by crystallisation
from hexane–ether of the product mixture, which had already
been purified by column chromatography. When oils, the pure
E-isomers were obtained by careful chromatographic separa-
tion. Unless noted otherwise, the spectroscopic data given in
the experimental part pertain to the E-isomer only, while the
yield given is that of the E–Z isomeric mixture, with ratios as
shown in the schemes.
All chemical reagents were of reagent grade. Ethoxycarbo-
nylmethylidenetriphenylphosphorane (3a), while commer-
cially available, was prepared according to a procedure by
Considine.11 Benzoylmethylidenetriphenylphosphoranes (3b)
and acetylmethylidenetriphenylphosphorane (3c) were simi-
larly prepared according to Ramirez and Dershowitz12 from
a-chlorobenzophenone and chloroacetone, respectively. Phos-
phorane 3d3c was prepared by Suzuki cross-coupling from
p-bromobenzoylmethylidenetriphenylphosphorane. Phospho-
rane 3h was prepared according to Trippett and Walker13 and
phosphorane 3g by reaction of triphenylphosphine and N-
maleimide according to Hudson and Chopard.14 3-Bromoben-
zo[b]thiophene (6), also commercially available, was prepared
by monobromination of benzo[b]thiophene. 4-(Thien-20-yl)-
benzaldehyde (5a) and 4-(thien-30-yl)benzaldehyde (5b) were
prepared by Suzuki cross-coupling of 2a with 1a and 1b,
respectively.
Syntheses
Ethyl bisthienylacrylate (4a). A mixture of 1a (163 mg, 1.0
mmol), 2a (156 mg, 1.0 mmol), 3a (715 mg, 2.1 mmol) and
Pd(PPh3)4 (80 mg, 6.9 ꢁ 10ꢂ2 mmol) in a mixed solvent of
DME (3 mL) and aq. Na2CO3 (2 M, 1.3 mL) was heated at
65 1C for 9 h. Then, CHCl3 (10 mL) and water (10 mL) were
added and the mixture was extracted with chloroform. The
organic phase was dried over anhydrous MgSO4 and was
concentrated in vacuo. Column chromatography on silica gel
(hexane–ether–CHCl3, 10 : 1 : 1) gave 4a (230 mg, 87%).
E-4a: pale yellow crystals; mp 51 1C. IR (KBr) n 3070, 2978,
2934, 1704, 1622, 1451, 1368, 1328, 1300, 1272, 1224, 1203,
1163, 1040, 800, 697 cmꢂ1. 1H NMR (270 MHz, CDCl3) d 1.33
(t, 3H, 3J 7.0 Hz), 4.25 (q, 2H, 3J 7.0 Hz), 6.18 (d, 1H, 3J 15.7
Hz), 7.04 (dd, 1H, 3J 5.1 Hz, 3J 3.8 Hz), 7.10 (d, 1H 3J 3.8 Hz),
7.15 (d, 1H, 3J 3.8 Hz), 7.23 (dd, 1H, 3J 3.8 Hz, 4J 1.0 Hz), 7.26
2-Formylthien-5-ylboronic acid (2a), 3-formyl-4-methoxy-
boronic acid (2e), 2-, 3- and 4-formylphenylboronic acids
3
4
3
(dd, 1H, J 5.1 Hz, J 1.0 Hz), 7.72 (d, 1H, J 15.7 Hz). 13C
NMR (99.45 MHz, CDCl3) d 14.32, 60.49, 116.57, 124.29,
124.73, 125.57, 128.05, 132.07, 132.67, 136.67, 138.13, 140.24,
166.84 (CQO). MS (EI, 70 eV) m/z (%) = 264 (100, M1), 236
(13), 219 (58), 192 (66). HRMS (Found) 264.0281. Calc. for
C13H12O2S2: 264.0279. Anal. Calc. for C13H12O2S2 (264.3): C
59.07; H 4.58; found: C 59.34; H 4.66.
Ethyl 3-[50-(thien-300-yl)thien-20-yl]acrylate (4b). 1b (163 mg,
1.0 mmol), 2a (156 mg, 1.0 mmol), 3a (700 mg, 2.0 mmol) and
Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME (3 mL) and 2 M
aq. Na2CO3 (1.5 mL) were reacted at 85 1C for 8 h. The crude
Scheme 6 Reduction of benzo[b]thiophene 7a.
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Table 1 One-pot Suzuki cross-coupling–Wittig olefination protocol under sonoirradiation
Starting materials
Reaction conditions
Products
Pd(OAc)2, Pd(PPh3)4, hexane–ether
10 : 1, 1.5 M aq. Na2CO3, 5 h.
Pd(OAc)2, Pd(PPh3)4, hexane–ether
10 : 1, 1.5 M aq. Na2CO3, 5.5 h.
Pd(OAc)2, Pd(PPh3)4, hexane–ether
10 : 1, 1.5 M aq. Na2CO3, 5 h.
Pd(OAc)2, Pd(PPh3)4, hexane–ether
10 : 1, 1.5 M aq. Na2CO3, 8h.
Pd(OAc)2, Pd(PPh3)4, DME,
2 M aq. Na2CO3, 6 h.
Pd(OAc)2, Pd(PPh3)4, hexane–ether
10 : 1, 1.5 M aq. Na2CO3, 5 h.
Pd(OAc)2, Pd(PPh3)4, hexane–ether
10 : 1, 1.5 M aq. Na2CO3, 5 h.
product was purified by column chromatography on silica gel
(hexane–ether–CHCl3, 10 : 1 : 1) to give 4b (224 mg, 85%). E-
4b; slowly crystallizing yellow solid. IR (neat) n 3084, 2976,
mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME
(5 mL) and 2 M aq. Na2CO3 (2.5 mL) were reacted at 75 1C for
9 h. Column chromatography on silica gel (hexane–ether–
CHCl3, 10 : 1 : 1) gave 4c (268 mg, 93%). E-4c: pale yellow
needles; mp 97.5 1C. IR (KBr) n 2984, 2960, 2938, 1695, 1623,
1604, 1453, 1365, 1306, 1288, 1256, 1226, 1209, 1167, 1027,
1708, 1626, 1273, 1207, 1165, 966, 853, 807, 773 cmꢂ1 1H
.
NMR (270 MHz, CDCl3) d 1.33 (t, 3H, 3J 7.5 Hz), 4.25 (q, 2H,
3J 7.5 Hz), 6.24 (d, 1H, 3J 15.6 Hz), 7.12–7.39 (m, 5H), 7.73 (d,
1H, 3J 15.6 Hz). MS (EI, 70 eV) m/z (%) = 264 (100, M1), 236
(15), 219 (50), 192 (61), 147 (14). HRMS (Found) 264.0280.
Calc. for C13H12O2S2: 264.0279.
1
3
972, 803 cmꢂ1. H NMR (270 MHz, CDCl3) d 1.33 (t, 3H, J
3
7.0 Hz), 3.84 (s, 3H, OCH3), 4.25 (q, 2H, J 7.0 Hz), 6.18 (d,
3
1H, J 15.7 Hz), 6.93 (d, 2H, J 8.6 Hz), 7.14 (d, 1H, J 3.8
3
3
3
3
Hz), 7.18 (d, 1H, J 3.8 Hz), 7.53 (d, 2H, J 8.6 Hz), 7.72 (d,
1H, 3J 15.7 Hz). 13C NMR (99.45 MHz, CDCl3) d 14.33,
55.36, 60.48, 114.32 (2C), 117.71, 126.97, 128.09, 128.54 (2C),
Ethyl 3-[20-(400-methoxyphenyl)-thien-50-yl]acrylate (4c). 1c
(234 mg, 1.0 mmol), 2a (360 mg, 2.0 mmol), 3a (1.15 g, 3.0
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132.60, 132.78, 142.59, 144.19, 159.57, 167.11 (CQO). MS (EI,
70 eV) m/z (%) = 288 (21, M1), 264 (32), 194 (43), 149 (38).
HRMS (Found) 288.0820. Calc. for C16H16O3S: 288.0820.
Anal. calc. for C16H16O3S (288.4): C 66.64; H 5.59; found: C
66.63; H 5.62.
165 (28). HRMS (Found) 282.1254. Calc. for C18H18O3:
282.1256.
Ethyl 3-(p-methoxy-20,400-biphenyl)acrylate (4g). 1c (234 mg,
1.0 mmol), 2d (300 mg, 2.0 mmol), 3a (1.15 g, 3.3 mmol) and
Pd(PPh3)4 (60 mg, 5.2 ꢁ 10ꢂ2 mmol) in DME (5 mL) and 2 M
aq. Na2CO3 (2.5 mL) were reacted at 65 1C for 8 h. Column
chromatography on silica gel (hexane–ether–CHCl3, 10 : 1 :
1) yielded 4g (254 mg, 90%). E-4g: colorless oil. IR (neat): n
3058, 2980, 2934, 2902, 2836, 1713, 1633, 1478, 1443, 1305,
1267, 1246, 1179, 835, 764 cmꢂ1; 1H NMR (270 MHz, CDCl3)
d 1.33 (t, 3H, 3J 7.0 Hz, CH3), 3.87 (s, 3H, OCH3), 4.27 (q, 2H,
3J 7.0 Hz, OCH2), 6.62 (d, 1H, 3J 15.9 Hz), 6.94 (d, 2H, 3J 8.4
Ethyl 3-(p-methoxy-40,400-biphenyl)acrylate (4d). 1c (234 mg,
1.0 mmol), 2b (300 mg, 2.0 mmol), 3a (1.15 g, 3.3 mmol) and
Pd(PPh3)4 (60 mg, 5.2 ꢁ 10ꢂ2 mmol) in a solvent mixture of
DME (5 mL) and 2 M aq. Na2CO3 (2.5 mL) were reacted at
75 1C for 9 h. Column chromatography of the reaction
product on silica gel (hexane–ether–CHCl3, 10 : 1 : 1) gave
4d (262 mg, 93%). E-4d: colorless solid; mp 135 1C. IR (KBr) n
2980, 1707, 1630, 1600, 1497, 1308, 1256, 1194, 1173, 1034, 823
3
Hz), 7.17–7.43 (m, 6H), 8.00 (d, 1H, J 15.9 Hz). MS (70 eV)
m/z (%) 282 (91, M1), 209 (100). HRMS (Found) 282.1255.
1
3
cmꢂ1. H NMR (270 MHz, CDCl3) d 1.35 (t, 3H, J 7.0 Hz),
3
3
Calc. for C18H18O3: 282.1256.
3.87 (s, 3H, OCH3), 4.28 (q, 2H, J 7.0 Hz), 6.45 (d, 1H, J
16.2 Hz), 7.00 (d, 2H, 3J 8.6 Hz), 7.56 (d, 2H, 3J 8.6 Hz), 7.58
(bs, 4H), 7.72 (d, 1H, 3J 16.2 Hz). 13C NMR (99.45 MHz,
CDCl3) d 14.34, 55.35, 60.43, 114.29 (2C), 116.00, 121.54,
122.83, 126.41, 127.29, 127.44 (2C), 132.41, 137.21, 137.77,
147.40, 159.88, 167.00 (CQO). MS (EI, 70 eV) m/z (%) 282
(100, M1), 267 (3), 254 (8), 237 (20), 210 (14), 195 (10), 165
(14). HRMS (Found) 282.1258. Calc. for C18H18O3: 282.1256.
Anal. calc. for C18H18O3 (282.3): C 76.57; H 6.43; found: C
76.14; H 6.42.
Ethyl 3-[20-(thien-200-yl)phenyl]acrylate (4h). 1a (163 mg, 1.0
mmol), 2d (300 mg, 2.0 mmol), 3a (1.15 g, 3.3 mmol) and
Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME (5 mL) and 2 M
Na2CO3 (2.5 mL) were reacted at 65 1C for 9 h. Column
chromatography on silica gel (hexane–ether–CHCl3, 10 : 1 :
1) gave 4h (232 mg, 90%). E-4h: pale yellow oil. IR (neat)
n 3062, 2980, 2936, 1900, 1712, 1634, 1478, 1448, 1366, 1315,
1270, 1178, 1036, 986, 851, 763, 702 cmꢂ1
;
1H NMR (270
MHz, CDCl3) d 1.32 (t, 3H, 3J 7.0 Hz), 4.25 (q, 2H, 3J 7.0 Hz),
3
3
4
6.41 (d, 1H, J 16.1 Hz), 7.03 (dd, 1H, J 3.6 Hz, J 1.3 Hz),
7.13 (dd, 1H, 3J 4.9 Hz, 3J 3.6 Hz), 7.37–7.43 (m, 3H), 7.51 (m,
Ethyl 3-[40-(thien-200-yl)phenyl]acrylate (4e). 1a (163 mg, 1.0
mmol), 2b (300 mg, 2.0 mmol), 3a (1.15 g, 3.0 mmol) and
Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME (5 mL) and 2 M
aq. Na2CO3 (2.5 mL) were reacted at 75 1C for 8 h. Column
chromatography of the reaction mixture on silica gel (hexane–
ether–CHCl3, 10 : 1 : 1) gave 4e (238 mg, 92%). E-4e:
colorless solid; mp 102 1C. IR (KBr) n 2982, 1707, 1633,
1600, 1531, 1501, 1427, 1366, 1327, 1308, 1207, 1171, 1117,
1092, 1027, 983, 818, 710 cmꢂ1. 1H NMR (395.7 MHz, CDCl3)
d 1.34 (t, 3H, 3J 7.0 Hz), 4.27 (q, 2H, 3J 7.0 Hz), 6.44 (d, 1H, 3J
15.9 Hz), 7.09 (dd, 1H, 3J 5.1 Hz, 3J 3.6 Hz), 7.31 (dd, 1H, 3J
5.1 Hz, 4J 1.2 Hz), 7.37 (dd, 1H, 3J 3.6 Hz, 4J 1.2 Hz), 7.53 (d,
3
1H), 7.66 (m, 1H), 7.98 (d, 1H, J 16.1 Hz). 13C NMR (99.45
MHz, CDCl3) d 14.31, 60.45, 119.83, 126.44, 127.26, 127.62,
127.98, 128.86, 129.75, 130.84, 133.21, 135.04, 141.15, 143.62,
166.81; MS (70 eV): m/z (%) 258 (35), 213 (18), 185 (100), 184
(91), 152 (19). HRMS (Found) 258.0713. Calc. for C15H14O2S:
258.0715.
Ethyl 3-(60-methoxy-30-(400-methoxyphenyl)phenyl)acrylate
(4i). 1c (234 mg, 1.0 mmol), 2e (360 mg, 2.0 mmol), 3a (1.15
g, 3.0 mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in
DME (5 mL) and 2 M aq. Na2CO3 (3 mL) were reacted at
75 1C for 9 h. Column chromatography of the reaction
product on silica gel (hexane–ether–CHCl3, 10 : 1 : 1) yielded
4i (278 mg, 89%, E- : Z-4i: 86 : 14) as a pale yellow oil. E-4i:
IR (neat) n 2936, 2902, 2836, 1706, 1630, 1609, 1490, 1464,
3
3
3
2H, J 8.2 Hz), 7.62 (d, 2H, J 8.2 Hz), 7.66 (d, 1H, J 15.9
Hz). 13C NMR (99.45 MHz, CDCl3) d 14.33, 60.50, 117.97,
123.78, 125.64, 126.10 (2C), 128.23, 128.63 (2C), 133.44,
136.11, 143.43, 143.84, 166.98 (CQO); MS (EI, 70 eV) m/z
(%) 258 (100, M1), 230 (13), 213 (57), 186 (32), 184 (33).
HRMS (Found) 258.0712. Calc. for C15H14O2S: 258.0715.
Anal. calc. for C15H14O2S (258.3): C 69.74; H 5.46; found: C
69.94; H 5.46.
1
1274, 1244, 1179, 1124, 1055, 1025, 814 cmꢂ1; H NMR (270
MHz, CDCl3) d 1.34 (t, 3H, 3J 7.0 Hz, CH3), 3.86 (s, 3H,
OCH3), 3.92 (s, 3H, OCH3), 4.27 (q, 2H, J 7.0 Hz, OCH2),
3
6.59 (d, 1H, 3J 15.9 Hz), 6.93–6.99 (m, 3H), 7.46–7.51 (m, 3H),
4
3
7.68 (d, 1H, J 2.4 Hz), 8.02 (d, 1H, J 15.9 Hz). MS (EI, 70
eV) m/z (%) 312 (100, M1), 267 (11), 252 (26). HRMS
(Found) 312.1364. Calc. for C19H20O4: 312.1362.
Ethyl 3-(p-methoxy-30,400-biphenyl)acrylate (4f). 1c (234 mg,
1.0 mmol), 2c (300 mg, 2.0 mmol), 3a (1.15 g, 3.0 mmol) and
Pd(PPh3)4 (80 mg, 6.9 ꢁ 10ꢂ2 mmol) in DME (5 mL) and 2 M
aq. Na2CO3 (2.5 mL) were reacted for 9 h at 65 1C. Column
chromatography on silica gel (hexane–ether–CHCl3, 10 : 1 :
1) gave 4f (259 mg, 92%). E-4f: pale yellow oil. IR (neat):
n 2980, 2934, 2904, 2834, 1712, 1639, 1611, 1517, 1247, 1181,
Ethyl 3-[60-methoxy-30-(thien-200-yl)phenyl]acrylate (4j). 1a
(163 mg, 1.0 mmol), 2e (360 mg, 2.0 mmol), 3a (1.15 g, 3.3
mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME
(5 mL) and 2 M aq. Na2CO3 (2.5 mL) were reacted for 8 h at
65 1C. Column chromatography of the reaction product on
silica gel (hexane–CHCl3–ether, 10 : 1 : 1) yielded 4j (268 mg,
93%). E-4j: pale yellow crystals: mp 97 1C; IR (KBr) n 2986,
1032, 833, 794 cmꢂ1 1H NMR (270 MHz, CDCl3) d 1.35
.
(t, 3H, 3J 7.0 Hz), 3.86 (s, 3H, OCH3), 4.27 (q, 2H, 3J 7.0 Hz),
3
6.49 (d, 1H, 3J 15.9 Hz), 6.99 (d, 2H, J 8.4 Hz), 7.46–7.58
(m, 5H), 7.69 (s, 1H), 7.74 (d, 1H, 3J 15.9 Hz). MS (EI, 70 eV)
m/z (%) = 282 (100, M1), 267 (6), 254 (15), 237 (37), 195 (24),
1715, 1639, 1491, 1293, 1256, 1179, 1029, 987, 698 cmꢂ1; H
1
NMR (395.7 MHz, CDCl3) d 1.35 (t, 3H, 3J 7.0 Hz), 3.93
ꢀc
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364 | New J. Chem., 2006, 30, 359–369

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3
(s, 3H, OCH3), 4.28 (q, 2H, J 7.0 Hz), 6.58 (d, 1H, J 16.2
3
3
3H, OCH3), 4.27 (q, 2H, J 7.0 Hz), 6.60 (d, 1H, J 15.9 Hz),
3
3
3
3
Hz), 6.93 (d, 1H, J 8.5 Hz), 7.06 (dd, 1H, J 3.6 Hz, J 5.1
3
7.01 (d, 1H, J 8.5 Hz), 7.36 (m, 1H), 7.40–7.60 (m, 2H), 7.77
3
4
3
Hz), 7.22 (dd, 1H, J 3.6 Hz, J 1.0 Hz), 7.24 (dd, 1H, J 5.1
Hz, 4J 1.0 Hz), 7.58 (dd, 1H, 3J 8.5 Hz, 4J 2.4 Hz), 7.73 (d, 1H,
(m, 1H), 8.02 (d, 1H, 3J 15.9 Hz), 8.27 (m, 1H), 8.82 (d, 1H, 4J
1.6 Hz). MS (70 eV) m/z (%) 283 (17), 252 (3). HRMS (Found)
283.1213. Calc. for C17H17O3N: 283.1208.
3
4J 2.4 Hz), 7.99 (d, 1H, J 16.2 Hz). 13C NMR (99.45 MHz,
CDCl3) d 14.32, 55.36, 60.53, 114.30, 118.51, 126.20, 126.43,
128.15, 128.59, 129.26, 132.90, 134.89, 141.51, 144.61, 159.43,
166.98. MS (EI, 70 eV) m/z (%) 288 (100, M1), 243 (15), 229
(29), 200 (26). HRMS (Found) 288.0819. Calc. for C16H16O3S:
288.0820. Anal. calc. for C16H16O3S (288.4): C 66.64; H 5.59;
found: C 66.87; H 5.63.
(E)-1-(40-Thien-200-ylphenyl)-2-benzoylethene (4m). 1a (163
mg, 1.0 mmol), 2a (300 mg, 2.0 mmol), 3b (1.08 g, 2.8 mmol)
and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME (5 mL) and
2 M aq. Na2CO3 (2.5 mL) were reacted at 75 1C for 10 h.
Column chromatography of the reaction mixture on silica gel
(hexane–CHCl3–ether, 10 : 2 : 1) gave 4m (283 mg, 98%) as
pale yellow needles, mp 133 1C. IR (KBr) n 1659, 1633, 1599,
1336, 1219, 980, 820, 688 cmꢂ1. 1H NMR (270 MHz, CDCl3) d
7.11 (dd, 1H, 3J 5.1 Hz, 3J 3.8 Hz), 7.33 (dd, 1H, 3J 5.1 Hz, 4J
1.1 Hz), 7.40 (dd, 1H, 3J 3.8 Hz, 4J 1.1 Hz), 7.48–7.59 (m, 3H),
7.51 (d, 1H, 3J 15.7 Hz), 7.66 (vs, 4H), 7.82 (d, 1H, 3J 15.7 Hz),
8.03 (m, 2H). 13C NMR (99.45 MHz, CDCl3) d 121.72, 121.74,
125.80, 126.19 (2C), 128.28, 128.43 (2C), 128.63 (2C), 129.22
(2C), 132.79, 133.86, 136.45, 138.26, 143.43, 144.20, 190.46.
MS (EI, 70 eV) m/z (%) 290 (100, M1), 261 (6), 213 (18), 184
(22), 160 (19). HRMS (Found) 290.0765. Calc. for C19H14OS:
290.0765. Anal. calc. for C19H14OS (290.4): C 78.59; H 4.86;
found: C 78.77; H 4.90.
Ethyl
3-[60-methoxy-30-(400-ethoxycarbonylphenyl)phenyl]-
acrylate (4k). 1d (276 mg, 1.0 mmol), 2e (360 mg, 2.0 mmol),
3a (1.15 g, 3.0 mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol)
in DME (5 mL) and 2 M aq. Na2CO3 (2.5 mL) were reacted at
75 1C for 9 h. Column chromatography on silica gel (hexane–
CHCl3–ether, 10 : 1 : 1) yielded 4k (350 mg, 99%). E-4k:
colorless solid, mp 105 1C. IR (KBr) n 2976, 1706, 1603, 1488,
1
1392, 1366, 1273, 1195, 1111, 1051, 1022, 996, 770 cmꢂ1; H
3
NMR (395.7 MHz, CDCl3) d 1.35 (t, 3H, J 7.0 Hz), 1.41 (t,
3H, J 7.0 Hz), 3.95 (s, 3H, OCH3), 4.28 (q, 2H, J 7.0 Hz,
3
3
3
OCH2), 4.41 (q, 2H, 3J 7.0 Hz), 6.61 (d, 1H, J 16.1 Hz), 6.82
3
(d, 1H, J 8.4 Hz), 7.38 (m, 1H), 7.59–7.69 (m, 3H), 7.77 (d,
4
3
3
1H, J 2.2 Hz), 8.11 (d, 1H, J 8.5 Hz), 8.03 (d, 1H, J 16.1
Hz). 13C NMR (99.45 MHz, CDCl3) d 14.38 (2C), 55.72,
60.45, 60.98, 111.60, 119.49, 123.87, 126.44, 127.63 (2C),
128.97, 130.05 (2C), 132.54, 135.19, 139.67, 144.41, 158.37,
166.46, 167.32; MS (70 eV) m/z (%) 354 (100, M1), 309, 295,
262, 183. HRMS (Found) 354.1469. Calc. for C21H22O5:
354.1467.
(E)-1-(40-Thienyl-200-ylphenyl)-2-(2000,5000-dimethoxybenzoyl)
ethene (4n). 1a (35 mg, 0.21 mmol), 2a (32 mg, 0.21 mmol), 3c
(95 mg, 0.21 mmol) and Pd(PPh3)4 (12 mg, 1 ꢁ 10ꢂ5 mmol) in
DME (1 mL) and 2 M aq. Na2CO3 (0.5 mL) were reacted at 75
1C for 10 h. Column chromatography on silica gel (hexane–
CHCl3–ether, 5 : 1 : 1) gave 4n (68 mg, 91%) as a slowly
crystallizing pale yellow solid. IR (KBr) n 2934, 1650, 1586,
1
1493, 1412, 1329, 1222, 1165, 1037, 819, 726 cmꢂ1. H NMR
Ethyl 3-[60-methoxy-30-pyrid-300-ylphenyl]acrylate (4L).
Method A: 1e (205 mg, 1 mmol), 2e (360 mg, 2.0 mmol), 3a
(1.15 g, 3.0 mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol)
were reacted at 65 1C for 9 h. Column chromatography of the
reaction product on silica gel (hexane–ether–CHCl3, 3 : 3 : 1
to ether–hexane–CHCl3 3 : 1 : 1) yielded 4L (170 mg, 60%),
mixture of (E)- and (Z)-isomers >E-4L : Z-4L = 12 : 88] as
a light yellow oil. Z-4L: IR (neat) n 2978, 2836, 1715, 1630,
(395.75 MHz, CDCl3) d 3.81 (s, 3H, OCH3), 3.88 (s, 3H,
OCH3), 6.95 (d, 1H, 3J 8.9 Hz), 7.04 (dd, 1H, 3J 8.9 Hz, 4J 3.6
3
3
3
Hz), 7.10 (dd, 1H, J 5.1 Hz, J 3.6 Hz), 7.20 (dd, 1H, J 3.6
Hz, 4J 1.2 Hz), 7.32 (dd, 1H, 3J 5.1 Hz, 4J 1.2 Hz), 7.38 (d, 1H,
3
3
4J 3.6 Hz), 7.43 (d, 1H, J 15.9 Hz), 7.60 (d, 2H, J 8.5 Hz),
7.63 (d, 1H, J 15.9 Hz), 7.64 (d, 2H, J 8.5 Hz). 13C NMR
(99.45 MHz, CDCl3) d 55.91, 56.56, 113.39, 114.39, 119.18,
123.79, 125.65, 126.12 (2C), 126.60 (2C), 128.24, 129.03,
129.68, 134.17, 136.15, 142.56, 143.52, 152.57, 153.63,
192.39. MS (EI, 70 eV) m/z (%) 350 (54, M1), 243 (100),
165 (47). HRMS (Found) 350.0978. Calc. for C21H18O3S:
350.0977.
3
3
1
1609, 1502, 1474, 1427, 1288, 1257, 1179, 1022, 802 cmꢂ1. H
3
NMR (395.7 MHz, CDCl3) d 1.18 (t, 3H, J 7.0 Hz), 3.89 (s,
3
3
3H, OCH3), 4.13 (q, 2H, J 7.0 Hz), 6.04 (d, 1H, J 12.3 Hz),
6.99 (d, 1H, 3J 8.4 Hz), 7.20 (d, 1H, 3J 12.3 Hz), 7.34 (m, 1H),
7.55 (m, 1H), 7.84 (bs, 2H), 8.55 (m, 1H), 8.83 (bs, 1H). 13C
NMR (99.45 MHz, CDCl3) d 14.09, 55.72, 60.20, 110.81,
120.69, 123.50, 124.63, 128.79, 129.40, 129.67, 133.93,
136.06, 138.55, 147.95, 148.00, 157.23, 166.13. MS (EI, 70
eV) m/z (%) 283 (100, M1), 252 (17), 238 (30), 224 (57), 195
(18), 167 (16). HRMS (Found) 283.1204. Calc. for
C17H17O3N: 283.1208.
(E)-1-(40-Thienyl-200-ylphenyl)-2-(4000-(p-trifluoromethylphenyl)
benzoyl)ethene (4o). 1a (64 mg, 0.43 mmol), 2a (70 mg, 0.43
mmol), 3d (220 mg, 0.42 mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ
10ꢂ2 mmol) in DME (2 mL) and 2 M aq. Na2CO3 (1 mL) were
reacted at 75 1C for 10 h. Column chromatography on silica
gel (hexane–CHCl3–ether, 1 : 1.5 : 1) gave 4o (88 mg, 48%) as
grayish plates, 261 1C. IR (KBr) n 1658, 1596, 1329, 1124,
1074, 815, 700 cmꢂ1. 1H NMR (270 MHz, CDCl3–DMSO-d6,
10 : 1 [v/v]) d 7.13 (dd, 1H, 3J 5.2 Hz, 3J 3.7 Hz), 7.32 (dd, 1H,
3J 3.7 Hz, 4J 1.2 Hz), 7.36–7.87 (m, 13H), 8.12 (d, 2H, 3J 10.2
Hz). MS (EI, 70 eV) m/z (%) 434 (32, M1), 153 (49), 77 (100).
HRMS (Found) 434.0953. Calc. for C26H17OF3S: 434.0952.
Anal. calc. for C26H17OF3S (434.4): C 71.88; H 3.94; found: C
72.00; H 4.12.
Method B: A solution of 1e (213 mg, 1.0 mmol), 2e (522 mg,
1.5 mmol) and benzoic acid (68 mg, 0.56 mmol) was heated at
75 1C for 9 h. The cooled solution was concentrated in vacuo
and the residue was purified by column chromatography on
silica gel (ether–CHCl3, 3 : 1) to give 4L (260 mg, 92%), (E)-
and (Z)-isomers [E-4L : Z-4L = 85 : 15], as a colorless oil. E-
4L: IR (KBr) n 3050, 2988, 2840, 1713, 1632, 1181, 721 cmꢂ1
.
1H NMR (270 MHz, CDCl3) d 1.35 (t, 3H, 3J 7.0 Hz), 3.87 (s,
ꢀc
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Ethyl (E)-3-[40-(thien-200-yl)phenyl]methacrylate (4p). 1a (163
mg, 1.0 mmol), 2a (300 mg, 2.0 mmol), 3e (1.17 g, 3.25 mmol)
and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ5 mol) in DME (5 mL) and
2.5 M aq. Na2CO3 (2.5 mL) were heated at 75 1C for 9 h.
Column chromatography of the reaction mixture on silica gel
gave 4p (257 mg, 94%) as an oil. IR (neat) n 2980, 1705, 1253,
1206, 1111, 1029 cmꢂ1. 1H NMR (270 MHz, CDCl3) d 1.35 (t,
3H, 3J 7.0 Hz, OCH2CH3), 2.16 (d, 3H, 4J 1.6 Hz, CH3), 4.29
(q, 2H, 3J 7.0 Hz, OCH2), 7.11 (dd, 1H, 3J 5.1 Hz, 3J 3.8 Hz),
7.30 (dd, 1H, 3J 5.1 Hz, 4J 1.3 Hz), 7.35 (dd, 1H, 3J 3.8 Hz, 4J
1.3 Hz), 7.42 (d, 2H, 3J 7.6 Hz), 7.66 (d, 2H, 3J 7.6 Hz), 7.69 (q,
and extracted with CHCl3 (2 ꢁ 15 mL). The combined organic
phase was dried over anhydrous MgSO4 and concentrated
in vacuo. The residue was subjected to column chromatogra-
phy on silica gel (ether–hexane–CHCl3, 3 : 3 : 1 to ether) to
give 5c (410 mg, 96%) as a colorless powder, mp 86 1C. IR
(KBr) n 3000, 2876, 1679, 1613, 1505, 1427, 1276, 1192, 1015,
800, 708 cmꢂ1 1H NMR (270 MHz, CDCl3) d 4.00 (s, 3H,
.
OCH3), 7.13 (d, 1H, 3J 8.6 Hz), 7.37 (m, 1H), 7.80 (dd, 1H, 3J
4
8.6 Hz, J 2.3 Hz), 7.88 (m, 1H), 8.07 (d, 1H, J 2.3 Hz), 8.59
4
3
4
4
4
(dd, 1H, J 4.9 Hz, J 1.7 Hz), 8.83 (dd, 1H, J 2.6 Hz, J 1.0
Hz), 10.53 (s, 1H, CHO). 13C NMR (99.45 MHz, CDCl3) d
55.92, 112.50, 123.58, 125.15, 126.94, 130.45, 133.91, 134.20,
135.07, 147.90, 148.54, 161.75, 189.43 (CHO). MS (70 eV) m/z
(%) 213 (100, M1), 196, 167, 153. HRMS (Found) 213.0791.
Calc. for C13H11O2N: 213.0790. Anal. calc. for C13H11O2N
(213.2): C 73.22; H 5.20; N 6.37; found: C 73.06; H 5.18; N
6.58.
4
1H, J 1.6 Hz). 13C NMR (67.8 MHz, CDCl3) d 15.17, 15.30,
61.86, 124.47, 126.26, 126.66 (2C), 129.11, 129.55, 131.29 (2C),
135.24, 136.00, 138.98, 144.69, 169.61. MS (EI, 70 eV) m/z (%)
272 (100, M1), 227 (37), 198 (94), 165 (49), 115 (34). HRMS
(Found) 272.0872. Calc. for C16H16O2S: 272.0871.
(E)-4-(40-[Thien-200-yl]phenyl)but-3-en-2-one (4q). 1a (163
mg, 1.0 mmol), 2a (300 mg, 2.0 mmol), 3f (1.05 g, 3.3 mmol)
and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME (5 mL) and
2 M aq. Na2CO3 (2.5 mL) were reacted at 75 1C for 10 h.
Column chromatography of the reaction mixture on silica gel
(hexane–CHCl3–ether, 10 : 2 : 1) gave 4q (221 mg, 97%) as a
colorless solid, mp 156 1C. IR (KBr) n 3074, 1657, 1601, 1424,
3-[40-(Thien-200-yl)phenyl]3-acrylonitrile (4s). Method A: 1a
(163 mg, 1.0 mmol), 2a (300 mg, 2.0 mmol), 3h (995 mg, 3.3
mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME (5
mL) and 2 M aq. Na2CO3 were reacted at 75 1C for 9 h. The
reaction products were separated by column chromatography
(hexane–CHCl3–ether, 10 : 2 : 1) to give 4s (206 mg, 98%) as
a 63 : 37 mixture of E- : Z-isomers.
1
1358, 1267, 1255, 978, 721, 701 cmꢂ1. H NMR (270 MHz,
CDCl3) d 2.39 (s, 3H, CH3), 6.72 (d, 1H, 3J 16.5 Hz), 7.09 (dd,
Method B: 5a (286 mg, 1.5 mmol) and 3h (895 mg, 3.0
mmol) in a mixture of DME (10 mL) and 2 M aq. Na2CO3 (5
mL) were reacted at 75 1C for 9 h. The reaction products were
separated by column chromatography on silica gel to give 4s
(284 mg, 89%) as a 91 : 9 mixture of E- : Z- isomers.
Method C: a solution of 5a (385 mg, 2.05 mmol), 3h (1.2 g,
4.1 mmol) and benzoic acid (170 mg, 1.39 mmol) in deaerated
benzene (15 mL) was kept at 75 1C for 9 h. Then, the cooled
solution was concentrated and the residue was separated by
column chromatography on silica gel (hexane–ether–CHCl3,
10 : 1 : 1) to give 4s as a mixture of isomers (E : Z, 97 : 3)
(410 mg, 95%). E-4s: IR (KBr) n 2212, 1602, 1424, 975, 806,
707 cmꢂ1. 1H NMR (270 MHz, CDCl3) d 5.91 (d, 1H, 3J 16.5
1H, 3J 5.1 Hz, 3J 3.8 Hz), 7.33 (dd, 1H, 3J 5.1 Hz, 4J 1.1 Hz),
3
4
3
7.38 (dd, 1H, J 3.8 Hz, J 1.1 Hz), 7.51 (d, 1H, J 16.5 Hz),
7.53 (d, 2H, 3J 8.4 Hz), 7.65 (d, 2H, 3J 8.4 Hz). 13C NMR
(99.45 MHz, CDCl3) d 27.56, 123.91, 125.79, 126.17, 126.81
(2C), 128.27 (2C), 128.88, 133.37, 136.42, 142.72, 143.34,
198.29. MS (EI, 70 eV) m/z (%) 228 (100, M1), 213 (92),
184 (38), 152 (14), 139 (11), 115 (13). HRMS (Found)
228.0610. Calc. for C14H12OS: 228.0609. Anal. calc. for
C14H12OS (228.3): C 73.65; H 5.30; found: C 73.45; H 5.32.
(E)-3-(40 -Thien-200 -ylphenyl)methylidenyl-N-phenyl-4(H)-
maleimide (4r). A mixture of 1a (163 mg, 1.0 mmol), 2a (300
mg, 2.0 mmol), 3g (1.3 g, 3.0 mmol) and Pd(PPh3)4 (50 mg,
4.3 ꢁ 10ꢂ2 mmol) in DME (5 mL) and 2 M aq. Na2CO3 (2.5
mL) was heated to 75 1C for 9 h. The reaction products were
separated by column chromatography on silica gel (ether–
chloroform–hexane, 2 : 1 : 1) to give 4r (110 mg, 32%) as a
colorless solid, mp 286 1C. IR (KBr) n 1770, 1706 (s), 1658,
3
3
3
Hz), 7.10 (dd, 1H, J 5.1 Hz, J 4.0 Hz), 7.34 (dd, 1H, J 5.1
Hz, 3J 1.2 Hz), 7.38 (dd, 1H, 3J 4.0 Hz, 4J 1.2 Hz), 7.39 (d, 1H,
3J 16.5 Hz), 7.45 (d, 2H, 3J 8.6 Hz), 7.65 (d, 2H, 3J 8.6 Hz). 13
C
NMR (67.8 MHz, CDCl3) d 95.88, 118.25, 124.34, 126.14,
126.26 (2C), 128.01 (2C), 128.37, 132.44, 137.13, 143.02,
149.79. MS (70 eV) m/z 211 (100, M1), 166 (9), 139 (7).
HRMS (Found) 211.0456. Calc. for C13H9NS: 211.0456. Anal.
calc. for C13H9NS (211.3): C 73.90; H 4.29; N 6.66; found: C
73.89; H 4.35; N 6.62.
1
1598, 1497, 1389, 1196, 1175, 718, 701 cmꢂ1. H NMR (270
MHz, DMSO-d6) d 3.87 (bs, 2H), 7.18 (m, 1H), 7.35 (d, 2H, 3J
7.3 Hz), 7.40–7.56 (m, 3H), 7.57 (bs, 1H), 7.62 (bd, 1H, 3J 5.1
Hz), 7.65 (bd, 1H, 3J 3.8 Hz), 7.73 (d, 2H, 3J 8.4 Hz), 7.78 (d,
2H, 3J 8.4 Hz). 13C NMR (99.45 MHz, CDCl3) d 32.22, 124.80
(2C), 124.89, 125.11, 125.74, 126.85 (2C), 127.15, 128.27 (2C),
128.84 (2C), 131.20, 132.04, 132.63, 133.21, 134.97, 142.41,
169.97, 173.46. MS (EI, 70 eV) m/z (%) 345 (9) [M1], 198 (10),
153 (44), 136 (39), 77 (100). HRMS (Found) 345.0824. Calc.
for C21H15O2NS: 345.0824.
Method D: a solution of 1a (163 mg, 1.0 mmol), 2a (300 mg,
2.0 mmol), 3a (995 mg, 3.3 mmol) and Pd(PPh3)4 (90 mg, 7.7 ꢁ
10ꢂ2 mmol) in benzene (10 mL) and 2 M aq. Na2CO3 was
reacted at 75 1C for 9 h and separated as above to give 4s (167
mg, 79%) as a 91 : 9 mixture of E : Z-isomers.
(E)-3-[40-(Thien-200-yl)phenyl]-acrylamide (4t). H2O2 (aq., 30
wt%, 10 mL) was given dropwise to a mixture of 4s (418 mg,
2.0 mmol), tetrabutylammonium hydrogensulfate (410 mg, 1.2
mmol) in CH2Cl2 (50 mL).17 Thereafter, aq. NaOH (20 wt%,
8 mL) was added at 0 1C. The resulting mixture was stirred at
rt for 4 h. Thereafter water (15 mL) was added and the mixture
2-Methoxy-5-(pyrid-30-yl)-benzaldehyde (5c)15,16. A mixture
of 1e (410 mg, 2.0 mmol), 2a (720 mg, 4.0 mmol), and
Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in DME (10 mL) and
2 M Na2CO3 (5 mL) was reacted at 75 1C for 9 h. Thereafter,
the cooled reaction mixture was diluted with water (10 mL)
ꢀc
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366 | New J. Chem., 2006, 30, 359–369

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was extracted with CH2Cl2 (3 ꢁ 15 mL). The organic phase
was dried over MgSO4 and concentrated in vacuo. The residue
was separated on silica gel (ether to ether–ethyl acetate) to give
4t (256 mg, 56%) as a colorless solid, mp 243 1C. IR (KBr) n
for C19H16O2S (308.4): C 74.00; H 5.23; found: C 74.22; H
5.29.
3-[50-(200-Ethoxycarbonylethenyl)-20-methoxyphenyl]benzo[b]
thiophene (7b). A mixture of 6 (426 mg, 2.0 mmol), 2e (720 mg,
2.0 mmol), 3a (2.2 g, 6.3 mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ
10ꢂ2 mmol) in DME (10 mL) and 2 M aq. Na2CO3 (5 mL)
were reacted at 65 1C for 9 h. Chromatography of the reaction
product on silica gel (hexane–ether–CHCl3, 5 : 1 : 1) pro-
vided 7b (670 mg, 99%; E-7b : Z-7b, 92 : 8) as an oil. E-7b: IR
3400, 3165, 1675, 1620, 1415, 1405, 1243, 979, 825, 707 cmꢂ1
.
3
1H NMR (270 MHz, DMSO-d6) d 6.62 (d, 1H, J 15.9 Hz),
7.08 (bs, 1H), 7.16 (m, 1H), 7.42 (d, 1H, 3J 15.9 Hz), 7.52 (bs,
3
3
1H), 7.55 (m, 2H), 7.57 (d, 2H, J 8.1 Hz), 7.69 (d, 2H, J 8.1
Hz). 13C NMR (67.8 MHz, DMSO-d6) d 122.19, 124.25,
125.68 (2C), 126.24, 128.28 (2C), 128.62, 133.34, 134.55,
138.40, 142.65, 166.58. MS (FAB, 3-nitrobenzyl alcohol) m/z
(%) 230 (MH1, 16). HRMS (Found) 230.0635. Calc. for
C13H12ONS: 230.0640 (FAB, MH1). Anal. calc. for
C13H11ONS (229.3): C, 68.09; H, 4.84; N, 6.11; found: C,
68.33; H, 4.84; N, 6.12.
1
(neat) n 2960, 1714, 1634, 1488, 1030, 989, 818, 736 cmꢂ1. H
NMR (270 MHz, CDCl3) d 1.36 (t, 3H 3J 7.3 Hz), 3.94 (s, 3H,
OCH3), 4.27 (q, 2H, 3J 7.3 Hz), 6.58 (d, 1H, 3J 16.2 Hz), 7.04
3
(d, 1H, J 8.3 Hz), 7.36 (s, 1H), 7.35–7.43 (m, 2H), 7.56 (dd,
3
4
4
1H, J 8.3 Hz, J 2.2 Hz), 7.73 (d, 1H, J 2.2 Hz), 7.84–7.93
(m, 2H), 8.04 (d, 1H, 3J 16.2 Hz). MS (EI, 70 eV) m/z (%) 338
(100, M1), 310 (3), 293 (8), 279 (17), 268 (15), 250 (23), 221
(19), 211 (11), 195 (6), 149 (14). HRMS (Found) 338.0977.
Calc. for C20H18O3S: 338.0977.
3-[40-(Thien-300-yl)phenyl]-acrylonitrile (4u). Method A: a
mixture of 1b (163 mg, 1.0 mmol), 2a (300 mg, 2.0 mmol),
3h (995 mg, 3.3 mmol), Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in
DME (5 mL) and 2 M aq. Na2CO3 (2.5 mL) was reacted at 65
1C for 9 h. Column chromatography of the reaction product
on silica gel (hexane–ether–CHCl3, 5 : 2 : 1) provided 4u (205
mg, 97%) as a mixture of E- and Z-isomers (E : Z, 1 : 0.9),
which was not separated further, colorless solid, mp 105 1C.
IR (KBr) [E/Z-(4u)] n 3102, 2212, 1602, 1530, 1427, 1206,
(E)-3-(40-[200-Benzoylethenyl]phenyl)benzo[b]thiophene (7c).
A mixture of 6 (213 mg, 1.0 mmol), 2a (300 mg, 2.0 mmol),
3b (1.08 g, 3.0 mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol)
in DME (5 mL) and 2 M aq. Na2CO3 (2.5 mL) were held at
75 1C for 9 h. The reaction mixture was separated by column
chromatography on silica gel (hexane–chloroform–ether, 3 :
2 : 1) to give 7c (313 mg, 92%) as a yellow solid. IR (KBr) n
1187, 975, 870, 851, 815, 785 cmꢂ1 1H NMR (395.7 MHz,
.
CDCl3) d Z-(4u): 5.44 (d, 1H, 3J 12.1 Hz), 7.12 (d, 1H, 3J 12.1
3059, 1659, 1599, 1433, 1331, 1214, 1016, 750, 691 cmꢂ1. H
1
3
Hz), 7.47 (m, 2H), 7.55 (m, 1H), 7.67 (d, 2H, J 8.2 Hz), 7.86
NMR (270 MHz, CDCl3) d 7.37–7.71 (m, 6H), 7.60 (d, 1H, 3J
(d, 2H, 3J 8.2 Hz). E-(4u): 5.88 (d, 1H 3J 16.7 Hz), 7.41 (d, 1H,
3J 16.7 Hz), 7.47 (m, 2H), 7.51 (d, 2H, 3J 8.4 Hz), 7.55 (m, 1H),
7.63 (d, 2H, 3J 8.4 Hz). 13C NMR (67.8 MHz, CDCl3) d 95.84,
118.33, 121.65, 126.05, 126.83, 126.97 (2C), 128.01 (2C),
132.34, 138.07, 141.02, 150.03. MS (EI, 70 eV) m/z (%) 211
(38, M1). HRMS (Found) 211.0459. Calc. for C13H9NS:
211.0459. Anal. calc. for C13H9NS (211.3): C 73.90; H 4.29;
N 6.66; found: C 73.96; H 4.38; N 6.71.
15.7 Hz), 7.66 (d, 2H, 3J 8.2 Hz), 7.78 (d, 2H, 3J 8.2 Hz), 7.88
3
(d, 1H, J 15.7 Hz), 7.94 (m, 2H), 8.06 (m, 2H). MS (70 eV)
m/z 340 (24, M1), 284 (37), 266 (22), 253 (26), 238 (100), 207
(67). HRMS (Found) 340.0923. Calc. for C23H16OS: 340.0922.
3-[40-(200-Ethoxycarbonylethyl)phenyl]benzo[b]thiophene (8).
7a (600 mg, 1.95 mmol) and 10 wt% Pd/C (245 mg, 0.23
mmol Pd) in a solvent mixture of EtOH (75 mL) and benzene
(75 mL) were stirred under hydrogen atmosphere for 2 d. The
progress of the reaction was monitored by periodic sampling
Method B: a solution of 5b (282 mg, 1.5 mmol), 3h (850 mg,
2.8 mmol) and benzoic acid (75 mg, 0.61 mmol) in deaerated
benzene (15 mL) was kept at 75 1C for 9 h. Then, the cooled
solution was concentrated and the residue was separated by
column chromatography on silica gel (hexane–ether–CHCl3,
10 : 1 : 1) to give 4u as a mixture of isomers (E : Z, 95 : 5)
(310 mg, 98%).
1
and H NMR determination of the crude mixture. After the
reaction was finished, Pd/C was filtered off and the filtrate was
concentrated in vacuo. Column chromatography of the residue
on silica gel (hexane–ether, 3 : 1) gave 8 (408 mg, 67%) as a
colorless oil. IR (neat): n 2980, 1730, 1495, 1427, 1182, 762,
736 cmꢂ1. 1H NMR (395.7 MHz, CDCl3): d 1.26 (t, 3H, 3J 7.2
Hz), 2.69 (t, 2H, 3J 7.5 Hz), 3.03 (t, 2H, 3J 7.5 Hz), 4.16 (q, 2H,
3J 7.2 Hz), 7.32 (d, 2H, 3J 8.0 Hz), 7.38 (s, 1H), 7.39 (m, 2H),
7.52 (d, 2H, 3J 8.0 Hz), 7.91 (m, 2H). 13C NMR (99.45 MHz,
CDCl3) d 14.23, 30.71, 35.85, 60.46, 122.90, 123.15, 124.27,
124.36, 127.19 (2C), 128.67 (2C), 128.71, 128.77, 133.97,
137.83, 139.96, 140.66, 172.88 (CQO); MS (EI, 70 eV) m/z
(%) 310 (40, M1), 254 (77), 223 (27), 180 (100), 167 (78).
HRMS (Found) 310.1029. Calc. for C19H18O2S: 310.1028.
3-[40 -(200 -Ethoxycarbonylethenyl)phenyl]benzo[b]thiophene
(7a). 6 (639 mg, 3.0 mmol), 2a (500 mg, 3.33 mmol), 3a (1.22 g,
3.5 mmol) and Pd(PPh3)4 (50 mg, 4.3 ꢁ 10ꢂ2 mmol) in a
solvent mixture of DME (20 mL) and 2 M aq. Na2CO3 (14
mL) were reacted at 75 1C for 9 h. Column chromatography of
the reaction product on silica gel (hexane–ether–chloroform,
5 : 1 : 1) provided 7a (650 mg, 70%). E-7a: colorless solid; mp
98 1C. IR (KBr) n 3110, 3066, 2978, 2924, 1707, 1632, 1607,
1321, 1309, 1175, 1032, 991, 824, 808, 764, 734 cmꢂ1. 1H NMR
(270 MHz, CDCl3) d 1.36 (t, 3H, 3J 7.0 Hz), 4.29 (q, 2H, 3J 7.0
Hz), 6.48 (d, 1H, 3J 15.9 Hz), 7.31–7.43 (m, 3H), 7.62 (bs, 4H),
Methyl 3-(40[-100-phenylethyl]phenyl)propionate (9). To a sus-
pension of freshly prepared18 Raney nickel (750 mg, 50 wt%)
in ethanol (10 mL) was added 8 (400 mg, 1.29 mmol). The
mixture was stirred at rt under a hydrogen atmosphere (1 bar)
for 15 h. Then, the metal was filtered off, the reaction mixture
concentrated in vacuo to dryness and the residue was subjected
3
7.75 (d, 1H, J 15.9 Hz), 7.88–7.94 (m, 2H). MS (EI, 70 eV)
m/z (%) 308 (100, M1), 280 (10), 263 (21), 234 (24). HRMS
(Found) 308.0872. Calc. for C19H16O2S: 308.0871. Anal. calc.
ꢀc
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to column chromatography on silica gel (hexane–ether, 10 : 1)
to give 9 (310 mg, 85%) as a colorless oil. IR (neat): n 3024,
2970, 2928, 1737, 1511, 1493, 1451, 1372, 1290, 1181, 700
1271, 1173, 1105, 1034, 982 cmꢂ1
.
1H NMR (270 MHz,
CDCl3) d 1.35 (t, 3H, 3J 7.0 Hz, CH3), 1.42 (t, 3H, 3J 7.0
Hz, CH3), 4.28 (q, 2H, J 7.3 Hz, OCH2), 4.44 (q, 2H, J 7.0
3
3
1
3
3
cmꢂ1. H NMR (270 MHz, CDCl3) d 1.23 (t, 3H, J 7.5 Hz),
Hz, OCH2), 6.52 (d, 1H, J 15.9 Hz), 7.44–7.78 (m, 6H), 7.76
3
3
1.61 (d, 3H, J 7.3 Hz), 2.61 (t, 2H, 3J 7.5 Hz), 2.89 (t, 2H, J
(d, 1H, 3J 15.9 Hz), 8.13 (d, 2H, 3J 8.4 Hz). MS (FAB, 3-
nitrobenzyl alcohol) m/z (%) 325 (MH1, 35). HRMS (Found):
325.1441. Calc. for C20H21O4: 325.1440 (MH1, FAB).
3
3
7.5 Hz), 4.11 (sept., 1H, J 7.3 Hz), 4.13 (q, 2H, J 7.5 Hz),
7.08–7.32 (m, 9H). MS (70 eV) m/z (%) 282 (79, M1), 267
(100), 193 (60). HRMS (Found): 282.1617. Calc. for
C19H22O2: 282.1620.
Ethyl 3-[30-(thien-200-yl)phenyl]acrylate (11d). A mixture of
1a (360 mg, 2.2 mmol), 2b (660 mg, 4.4 mmol), 10a (2.36 g, 5.5
mmol), Pd(OAc2) (30 mg, 0.13 mmol) and Pd(PPh3)4 (12 mg,
1 ꢁ 10ꢂ2 mmol) in hexane–ether (5 mL, 10 : 1 v/v) and 1.5 M
aq. Na2CO3 (10 mL) was sonoirradiated for 5 h to give 11d
(567 mg, quant). E-11d: pale yellow oil. IR (neat) n 3062, 2980,
(E)-Ethyl 3-(50-[400-ethoxycarbonylphenyl]phenyl)methacry-
late (11c). General procedure for one-pot Suzuki coupling–
Wittig olefination under ultrasonication. A solution of 1d (276
mg, 1.0 mmol), 2e (360 mg, 2.0 mmol), 10b (1.10 g, 2.5 mmol),
Pd(PPh3)4 (15 mg, 1.3 ꢁ 10ꢂ2 mmol) and Pd(OAc)2 (20 mg,
8.9 ꢁ 10ꢂ2 mmol) in a biphasic mixture of 2 M Na2CO3 (10
mL), hexane (10 mL) and ether (2 mL) was placed in a straight
bottomed flask tightly covered with Saran wraps [polyvinyli-
dene chloride] and was sonicated in a 35 KHz Elma Transso-
nic T-460 bath for 8 h. Thereafter, the mixture was diluted
with water (15 mL) and extracted with hexane–ether (5 : 1, 20
mL). The organic phase was dried over anhydrous MgSO4 and
concentrated in vacuo. The residue was subjected to column
chromatography on silica gel (hexane–ether–CHCl3, 4 : 1 : 1)
to give 11c (320 mg, 87%) as a colorless oil. IR (neat): n 2980,
2870, 1719, 1606, 1490, 1462, 1367, 1270, 1179, 1108, 1023, 772
cmꢂ1. 1H NMR (270 MHz, CDCl3) d 1.34 (t, 3H, CH3, 3J 7.0
Hz), 1.39 (t, 3H, CH3, 3J 7.0 Hz), 2.10 (d, 3H, CH3, 4J 1.6 Hz),
3.89 (s, 3H, OCH3), 4.29 (q, 2H, 3J 7.0 Hz), 4.40 (q, 2H, 3J 7.0
Hz), 7.01 (d, 1H, 3J 8.6 Hz), 7.53–7.57 (m, 2H), 7.61 (d, 2H, 3J
1
2936, 1900, 1712, 1634 cmꢂ1. H NMR (270 MHz, CDCl3) d
3
1.35 (t, 3H, J 7.3 Hz, CH3), 4.28 (q, 2H, J 7.3 Hz, OCH2),
3
3
3
6.49 (d, 1H, J 15.9 Hz), 7.09 (dd, 1H, J 5.1 Hz, J 3.5 Hz),
7.32 (dd, 1H, 3J 5.1 Hz, 4J 1.2 Hz), 7.34 (dd, 1H, 3J 3.5 Hz, 4J
3
1.2 Hz), 7.37–7.62 (m, 3H), 7.71 (d, 1H, J 15.9 Hz), 7.74 (s,
1H). MS (FAB, 3-nitrobenzyl alcohol) m/z 259 (MH1, 63).
HRMS (Found) 259.0790. Calc. for C15H15O2S: 259.0793
(MH1, FAB).
Ethyl 3-(p-trifluoro-40,400-biphenyl)acrylate (11e). A mixture
of 1f (600 mg, 2.2 mmol), 2b (660 mg, 4.4 mmol), 10a (2.36 g,
5.5 mmol), Pd(OAc2) (30 mg, 0.13 mmol) and Pd(PPh3)4 (12
mg, 1 ꢁ 10ꢂ2 mol) in hexane–ether (5 mL, 10 : 1 v/v) and 1.5 M
aq. Na2CO3 (10 mL) was sonoirradiated for 5 h to give 11e
(420 mg, 60%). E-11e: IR (KBr): n 2986, 1706, 1635, 1614,
1326, 1175, 1118, 1069, 997, 822 cmꢂ1. H NMR (270 MHz,
1
CDCl3) d 1.31 (t, 3H, 3J 7.3 Hz), 4.29 (q, 2H, 3J 7.3 Hz), 6.48
4
3
8.4 Hz), 7.84 (q, 1H, J 1.6 Hz), 8.11 (d, 2H, J 8.4 Hz). 13C
NMR (99.45 MHz, CDCl3) d 14.34 (2C), 22.64, 55.69, 60.83,
60.94, 110.95, 125.47, 126.48, 128.44 (2C), 128.84, 129.01,
129.42, 130.13 (2C), 132.01, 134.31, 144.80, 157.69, 166.50,
168.47. MS (70 eV) m/z (%) 368 (M1, 100), 337 (M1–CH3O,
33), 309 (M1–C2H4–CH3O, 64). HRMS (Found): 368.1622.
Calc. for C22H24O5: 368.1624.
3
3
(d, 1H, J 15.9 Hz), 7.62 (s, 4H), 7.71 (s, 4H), 7.73 (d, 1H, J
15.9 Hz). 13C NMR (99.45 MHz, CDCl3) d 14.32, 60.60,
118.83, 125.85 (2C), 125.90 (2JC–F 12 Hz) 127.32 (2C),
127.71 (2C), 128.65 (2C), 129.85 (1JC–F 135 Hz), 129.99,
134.37, 141.35, 143.69, 166.87. MS (70 eV) m/z (%) 320
(M1, 96), 275 (100), 248 (34), 178 (36). HRMS (Found):
320.1206. Calc. for C18H15O2F3: 320.1024.
(E)-Ethyl
3-(100 -ethoxycarbonyl-40,400 -biphenyl)acrylate
(11a). A mixture of 1d (610 mg, 2.2 mmol), 2b (660 mg, 4.4
mmol), 10a (2.36 g, 5.5 mmol), Pd(OAc2) (30 mg, 0.13 mmol)
and Pd(PPh3)4 (12 mg, 1 ꢁ 10ꢂ2 mmol) in hexane–ether (5 mL,
10 : 1 v/v) and 1.5 M aq. Na2CO3 (10 mL) was sonoirradiated
for 5 h to give 11a (606 mg, 85%). E-11a: colorless oil. IR
(KBr) n 2974, 1706, 1634, 1371, 1309, 1275, 1216, 1179, 1105,
993, 831, 773 cmꢂ1. 1H NMR (270 MHz, CDCl3) d 1.35 (t, 3H,
References
1 O. I. Kolodiazhnyi, Phosphorus Ylides – Chemistry and Application
in Organic Synthesis, Wiley-VCH, Weinheim, 1999.
2 T. Thiemann, M. Watanabe, Y. Tanaka and S. Mataka, New J.
Chem., 2004, 28, 578.
3 (a) T. Thiemann, K. Umeno, D. Ohira, E. Inohae, T. Sawada and
S. Mataka, New J. Chem., 1999, 23, 1067; (b) T. Thiemann, K.
Umeno, E. Inohae and S. Mataka, Rep. Inst. Adv. Mater. Study,
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Tanaka, H. Gorohmaru and S. Mataka, J. Chem. Soc., Perkin
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4 For a one-pot Wittig olefination, Diels–Alder reaction, see: T.
Thiemann, D. Ohira, Y. Q. Li, T. Sawada, S. Mataka, K. Rauch,
M. Noltemeyer and A. de Meijere, J. Chem. Soc., Perkin Trans. 1,
2000, 2968.
5 For the use of benzoic acid in Wittig olefination reactions with
stabilized phosphoranes, see: (a) C. Ruechardt, S. Eichler and P.
Panse, Angew. Chem., 1963, 75, 858 (Angew. Chem., Int. Ed. Engl.,
1963, 2, 619); (b) H. J. Bestmann and J. Lienert, Chem.-Ztg., 1970,
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6 S. Kim, J. Yang and F. DiNinno, Tetrahedron Lett., 1999, 40, 2909.
7 (a) M. Watanabe, G. Ribeiro Morais, S. Mataka, K. Ideta and T.
Thiemann, Z. Naturforsch., B: Chem. Sci., 2005, 60, 909, for
3J 7.3 Hz, CH3), 1.42 (t, 3H, J 7.3 Hz, CH3), 4.28 (q, 2H, J
7.3 Hz, OCH2), 4.41 (q, 2H, 3J 7.3 Hz, OCH2), 6.49 (d, 1H, 3J
15.9 Hz), 7.60–7.72 (m, 6H), 7.73 (d, 1H, 3J 15.9 Hz), 8.12 (d,
2H, 3J 8.4 Hz). MS (FAB, 3-nitrobenzyl alcohol) m/z (%) 325
(MH1, 48). HRMS (Found): 325.1438. Calc. for C20H21O4:
325.1440 (MH1, FAB).
3
3
Ethyl 3-(100-ethoxycarbonyl-30,400-biphenyl)acrylate (11b). A
mixture of 1d (610 mg, 2.2 mmol), 2c (660 mg, 4.4 mmol), 10a
(2.36 g, 5.5 mmol), Pd(OAc2) (30 mg, 0.13 mmol) and
Pd(PPh3)4 (12 mg, 1 ꢁ 10ꢂ2 mmol) in hexane–ether (5 mL,
10 : 1 v/v) and 1.5 M aq. Na2CO3 (10 mL) was sonoirradiated
for 5.5 h to give 11b (712 mg, quant). E-11b: pale yellow oil. IR
(neat) n 2980, 2902, 1706, 1639, 1609, 1476, 1445, 1398, 1367,
ꢀc
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368 | New J. Chem., 2006, 30, 359–369

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Wittig–Horner olefination reactions see also: ; (b) A. Fuentes,
J. M. Marinas and J. V. Sinisterra, Tetrahedron Lett., 1987, 28,
2951; (c) J. V. Sinisterra, A. Fuentes and J. M. Marinas, J. Org.
Chem., 1987, 52, 3875.
8 For Suzuki cross-coupling and homocoupling reactions under
ultrasound, see: G. Cravotto, G. Palmisano, S. Tollari, G. M.
Nano and A. Penoni, 9th Meeting of the European Society of
Sonochemistry, Badajoz 2004, OC-34, p. 107 (homocoupling);
T. Thiemann, 9th Meeting of the European Society of Sonochem-
istry, Badajoz 2004, IL-8, Abstract Book, p. 31 (cross-coupling);
V. Polackova, M. Hut’ka and S. Toma, 9th Meeting of the
European Society of Sonochemistry, Badajoz, 2004, P-38, Abstract
Book, p. 197 (cross-coupling) and ref. 9.
10 Suzuki coupling under ultrasound in ionic liquids has also been
reported: R. Rajagopal, D. V. Jarikote and K. V. Srinivasan,
Chem. Commun., 2002, 616.
11 Wm. J. Considine, J. Org. Chem., 1962, 27, 647.
12 F. Ramirez and S. Dershowitz, J. Org. Chem., 1957, 22, 41.
13 S. Trippett and D. M. Walker, J. Chem. Soc., 1959, 3874.
14 R. F. Hudson and D. A. Chopard, Helv. Chim. Acta, 1963, 46,
2178.
15 (a) H. R. Howard and B. T. O’Neill, PCT Int. Appl. WO 9413663,
Pfizer Inc., USA, 1994; (b) S. J. Warrelow, E. C. Boyd and R. K.
Alexander, PCT Int. Appl. WO 9535283, Celltech Therapeutics
Ltd., UK, 1995.
16 For Suzuki cross-coupling reactions with halopyridines, see: H.
Chaumeil, C. Le Drian and A. Defoin, Synthesis, 2002, 757.
17 S. Cacchi, D. Misiti and F. L. Torre, Synthesis, 1980, 243.
18 Autorenkollektiv, Organikum, VEB Deutsche Verlag der Wis-
senschaften, 1988, p. 655.
9 (a) G. Cravotto, M. Beggiato, A. Penoni, G. Palmisano, S. Tollari,
J. M. Leveque and W. Bonrath, Tetrahedron Lett., 2005, 46, 2267;
(b) V. Polackova, M. Hut’ka and S. Toma, Ultrason. Sonochem.,
2005, 12, 99.
ꢀc
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