Combined Suzuki coupling - Wittig olefination reaction in aqueous medium

Article abstract of DOI:10.1515/znb-2005-1215

Bromoarene carbaldehydes and bromoheteroarene carbaldehydes underwent a one-pot Suzuki cross coupling and Wittig olefination in aqueous medium to give compounds with extended π-systems.

Full text of DOI:10.1515/znb-2005-1215

Combined Suzuki Coupling – Wittig Olefination Reaction
in Aqueous Medium
Kyoko Yamamotoa, Masataka Watanabea, Kyoko Idetab, Shuntaro Matakab, and
Thies Thiemannb
a Interdisciplinary Graduate School of Engineering Sciences and
b Institute of Materials Chemistry and Engineering, Kyushu University, 6-1, Kasuga-koh-en,
Kasuga-shi, 816-8580, Japan
Reprint requests to Dr. T. Thiemann. E-mail: thies@cm.kyushu-u.ac.jp. Fax: (0081) +(0)92-583-7894
Z. Naturforsch. 60b, 1299 – 1307 (2005); received August 25, 2005
Bromoarene carbaldehydes and bromoheteroarene carbaldehydes underwent a one-pot Suzuki
cross coupling and Wittig olefination in aqueous medium to give compounds with extended
π-systems.
Key words: Suzuki Cross Coupling, Wittig Olefination, Aqueous Medium, One Pot Reaction
Introduction
of such transformations has been carried out in vari-
ous organic solvents [8], where usually the presence of
at least a small amount of water [8] is needed, or in a
biphasic medium. A number of different palladium cat-
alysts have been forwarded for the Suzuki cross cou-
pling reactions in water, where in certain cases also ad-
ditives have been used as mass transfer promoters [9].
While both Wittig olefination and Suzuki cross cou-
pling are known to proceed in water, the combination
of Wittig olefination and Suzuki cross coupling reac-
tion in an aqueous medium has not yet been studied.
Here, the authors report on the scope and limitations
of a one-pot protocol in water. A number of commer-
cially available palladium compounds were screened
as catalysts for this transformation.
One-pot, multicomponentreactions are of interest as
they often lead to reduction of solvent and necessitate
less time for work-up than the corresponding consec-
utive reaction sequence. Recently, we have shown ex-
amples of such multicomponent reactions in form of
one-pot Wittig olefinations combined with metal catal-
ysed cross-coupling reactions [1]. Thus far, these reac-
tions have been carried out in organic solvents such as
THF, dioxane or DME or in biphasic media [1]. In the
following, a protocol for a combined Suzuki-Miyaura
coupling – Wittig olefination procedure in purely aque-
ous medium is forwarded.
Stabilized and semi-stabilized Wittig reagents react
only very slowly with water, even at elevated tempera-
tures [2]. Therefore, it is possible to carry out Wittig
olefinations with these phosphoranes in aqueous [3]
or in biphasic medium [4]. In fact we and other au-
thors have shown that water is an effective medium for
the reaction of such phosphoranes, especially with car-
baldehydes. This may be due to the high relative con-
centrations of carbonyl component and phosphorane in
organic droplets formed by the two components within
the aqueous medium. Nevertheless, due to the gen-
erally low reactivity of carbonylmethylidenephospho-
ranes such as 3a and 3c, these more stabilized phos-
phoranes undergo Wittig olefination only with very re-
active ketones [5], even under these conditions.
Results
Initially, bromoarene (or heteroarene) carbalde-
hydes were reacted with a number of areneboron-
ic acids and stabilized and semi-stabilized phosphor-
anes/phosphonium salts, utilizing bis(triphenylphos-
phanyl)palladium(II) dichloride [10] as catalyst pre-
cursor in an aqueous Na2CO3 solution. Additional tri-
phenylphosphane (2 equiv. for every equiv. of cat-
alyst) was added. As phosphoranes, stabilized acyl-
substituted 3a and 3c were used as well as (alk-
oxycarbonyl)methylidene(triphenyl)phosphoranes 3b
and 3e. Semi-stabilized benzylidene(triphenyl)phos-
Suzuki cross coupling reactions have been reported phorane was used in form of its phosphonium bromide.
to occur in aqueous medium [6, 7], although the bulk The reactions with p-bromobenzaldehyde (2a) and 5-
c
0932–0776 / 05 / 1200–1299 $ 06.00 ꢀ 2005 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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K. Yamamoto et al. · Combined Suzuki Coupling – Wittig Olefination Reaction in Aqueous Medium
Table 1. Scope of the one pot Suzuki cross-coupling / Wittig olefination in aqueous medium.
aq. Na2CO3
Ph3P=CHR2
Ar1-B(OH)2
Br-Ar2-CHO
Ar1-Ar2HC=CHR1
+
+
2 mol% Pd(PPh3)2Cl2
4 mol% PPh3
65ºC, 9h
2
3
4
1
Br
H
Ph3P
R
CHO
O
O
B(OH)2
3a: R = CH3
3b: R = OCH3
3c: R = Ph
R
4a: R = CH3: 93%
4b: R = OCH3: 99%
4c: R = Ph: 78%
1a
2a
Cl
H
Br
Ph3P
R
Cl
CHO
B(OH)2
O
O
2a
3a / 3c
4d: for R = CH3: 85%
4e: for R = Ph: 64%
1b
R
H
Ph3P
R
CHO
O
O
Br
O
B(OH)2
R
O
1a
2b
3a - 3c
4f: for R = CH3: 87% (only E-isomer)
4g: for R = OCH3: 87% (E-); 11% (Z-)
4h: for R = Ph: 39% (only E-isomer)
H
O
Br
Ph3P
R
O
CHO
O
B(OH)2
O
1c
2a
3a - 3c
4i: for R = CH3: 69%
4j: for R = Ph: 49%
4k: for R = OCH3: 78%
R
H
Ph3P
CH3
CHO
O
O
Br
O
O
3a
O
O
B(OH)2
Ph3P+CH2COCH3 Cl-
2b
5a
1c
4m with phosphorane: 88%
4m with phosphonium salt: quant.
O
H
Ph3P
CH3
O
O
Br
O
CHO
2c
B(OH)2
1c
3a
4n: 49%
Br
Ph3P+CH2Ph Br-
B(OH)2
CHO
1d
2a
5b
4o: 83% (E/Z =56/44)
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K. Yamamoto et al. · Combined Suzuki Coupling – Wittig Olefination Reaction in Aqueous Medium
1301
Table 2. Limitation of the one pot Suzuki cross-coupling / Wittig olefination in aqueous medium.
CO2Me
CO2Me
Br
Br
2 mol% Pd(PPh3)2Cl2
H
CHO
4 mol% PPh3
Ph3P
+
+
OMe
aq. Na2CO3
65ºC, 9h
B(OH)2
O
6b
3a
6a
2d
1e
quant.
0%
CO2Me
CO2Me
Br
2 mol% Pd(PPh3)2Cl2
4 mol% PPh3
+
aq. Na2CO3
DME
65ºC, 9h
B(OH)2
85%
1e
6a
6b
OMe
Br
S
B(OH)2
Ph3P
+
S
S
CHO
O
not isolated
OMe
2 mol% Pd(PPh3)2Cl2
4 mol% PPh3
7a
1f
2a
H
aq. Na2CO3
65ºC, 9h
+
S
O
S
Br
3d
OMe
77%
O
7b
OMe
OMe
2 mol% Pd(PPh3)2Cl2
4 mol% PPh3
S
B(OH)2
Br
+
S
aq. Na2CO3
DME
65ºC, 18h
S
S
O
O
83%
7a
7b
1f
bromothien-2-yl carbaldehyde (2b) gave the desired than with p-substituted benzaldehydes, probably due
products, where alkoxycarbonyl substituted 3b and to the directing effect of the furan oxygen. The semi-
acetyl substituted 3a gave similarly good yields and the stabilized benzylidene(triphenyl)phosphorane, gained
yields with phenacyl substituted 3c were slightly lower from 5b, shows little stereoselectivity (E-4o:Z-4o =
(Table 1). In all cases, the keto-carbonyl substituted 56:44) as would be expected under the conditions used.
phosphoranes 3a and 3c gave only E-alkenes, while However, E- and Z-4o can be separated by simple col-
alkoxycarbonyl substituted 3b and 3d usually gave umn chromatography on silica gel (hexane).
E/Z-isomeric mixtures in varying proportions. When
bromofuran carbaldehyde (2b) was used as a build-
ing block, more Z-isomer (Z-4g, 11%) was formed
o-Formylarylhalides are known to give poorer
yields in reactions such as these. In the case of
2-bromobenzaldehyde (2c), the desired product 4n
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K. Yamamoto et al. · Combined Suzuki Coupling – Wittig Olefination Reaction in Aqueous Medium
Table 3. Screening of different Pd-catalysts for the one pot Suzuki cross-coupling / Wittig olefination procedure in aqueous
medium.
H
Br
aq. Na2CO3
cat.
Ph3P
+
+
CH3
CHO
O
B(OH)2
O
H3C
3a
4a
2a
1a
Pd(PPh3)2Cl2/PPh3: 93%
PdCl2:
Pd/C :
50%
31%
(10w% Batch B62685C)
Ph3P+CH2CO2Me Br-
Br
aq. Na2CO3
cat.
+
+
5c
B(OH)2
CHO
H
O
Ph3P
OR
4p-Me, 4p-Et
2a
1d
RO
3b / 3e
O
Pd(PPh3)2Cl2/PPh3: R = Me, with phosphonium salt 5c: 90%; E/Z 97/3
R = Me, with phosphorane 3b: 92%, E/Z 9/1
Pd(acac)2
with phosphorane 3b: 89%; E/Z 97/3
Pd(OAc)2
Pd/C
R = Me, with phosphorane 3b: 87%; E/Z 97/3
R = Me, with phosphorane 3b: 56%; E/Z 97/3
Pd(OH)2
R = Et, with phosphorane 3e: 63%; only E-isomer
detected
S
aq. Na2CO3
cat.
H
S
Br
Ph3P
+
+
CH3
CHO
O
B(OH)2
O
2a
3a
H3C
1g
Pd(PPh3)2Cl2/PPh3: 67%
4r
PdCl2:
Pd/C :
19%
53%
(10w% Batch B62685C)
S
H
aq. Na2CO3
cat.
Br
S
Ph3P
+
+
CH3
CHO
O
B(OH)2
1h
O
2a
3a
H3C
4s
Pd(PPh3)2Cl2/PPh3: 90%
PdCl2:
Pd/C :
34%
32%
(10w% Batch B62685C)
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K. Yamamoto et al. · Combined Suzuki Coupling – Wittig Olefination Reaction in Aqueous Medium
1303
formed only in 49% yield. Here, interestingly only ferent commercially available Pd/Cs may vary in their
E-4n was isolated, although it is known that 2c gives catalytic activity.
appreciable amounts of Z-product (in CHCl3: quant.
In conclusion, the authors have shown a novel one
yield, E : Z = 9 : 1), when subjected solely to the Wit- pot Wittig-olefination / Suzuki cross coupling protocol
tig reaction.
in aqueous medium. Phosphoranes suitable for the re-
action must either be stabilized or semi-stabilized. Best
results were found for haloarene carbaldehyde (halo-
hetarene carbaldehyde) that are either liquid or have
a low melting point. Melting point or hydrophobicity
of the boronic acid and/or phosphorane do not play a
large role for the outcome of the reaction. Important is
a relative good solubility of the initial Wittig product in
either organic or aqueous media, as due to the different
kinetics of Wittig reaction and Suzuki cross coupling
reaction for the most part the Wittig olefination pre-
ceeds the Suzuki cross-coupling. Pd(PPh3)2Cl2/PPh3
and Pd(acac)2 as catalysts give good results, but the
reaction also proceeds with a number of other Pd cata-
lysts.
In two instances the one-pot transformation failed
to proceed (Table 2). Thus, 1-bromo-2-formyl-3,4-
dihydronaphthalene (2d) undergoes no Suzuki cou-
pling under these conditions, and only the Wittig prod-
uct 6b can be isolated. In this case, some of the
naphthaleneboronic acid 1e is hydrolysed, but also
binaphthyl is formed as the homo-coupling product.
Compound 6b, however, undergoes Suzuki coupling
with naphthalene-2-boronic acid (1e) in a biphasic
system of DME and aq. Na2CO3. Also, the reaction
of p-bromobenzaldehyde (2a) with benzothiophene-
2-boronic acid 1f and phosphorane 3d [1a] did not
give the desired product. Here, again only the Wit-
tig product forms, which can be filtered off from the
ether extract of the reaction mixture. In all the cases
discussed, the Wittig olefination is the faster reac-
tion. That the Suzuki reaction proceeds generally with
benzothiophene-2-boronic acid (1f) can be seen in the
fact, that when 2a is used in a slight excess over
phosphorane 3d, the Suzuki coupling product of 2a
and 1f, 2-(4-formylphenyl)benzothiophene,can be iso-
lated. Wittig product 7b is very sparingly soluble in
Experimental Section
General: Boronic acids 1a – h and aldehydes 2a – c were
purchased from Aldrich. Phosphoranes 3b, 3e [12], 3a,
3c [13], 3d [1a], and the phosphonium salts 5a [13], 5b
[14] and 5c [12] were synthesized according to litera-
ture procedures. 1-Bromo-2-formyl-3,4-dihydronaphthalene
(2d) was synthesized from α-tetralone (Aldrich) by Arnold-
aqueous medium and most organic solvents, and it has Vilsmeier reaction [15]. The palladium catalysts were
obtained commercially: Pd/C (Kishida), PdCl2 (Wako),
Pd(PPh3)2Cl2 (Aldrich), Pd(OAc)2 (Kishida), Pd(OH)2
(Aldrich), Pd(acac)2 (Aldrich).
a high melting point, making it difficult for the Suzuki
cross-couplingto proceed. Again, a biphasic Suzuki re-
action of 7b in DME / aq. Na2CO3 gives 7a, albeit af-
◦
Melting points were measured on a Yanaco microscopic
hotstage and are uncorrected. IR spectra were measured
with JASCO IR-700 and Nippon Denshi JIR-AQ2OM ma-
chines. 1H and 13C NMR spectra were recorded with a
JEOL EX-270 (1H at 270 MHz and 13C at 67.8 MHz) and
JEOL Lambda 400 spectrometer (1H at 395 MHz and 13C
at 99.45 MHz). In some cases, the assignment of the carbon
signals was aided by DEPT (distortionless enhancement by
polarisation transfer) measurements, where (+) denotes ei-
ther primary or tertiary carbons, (−) secondary carbons and
(Cquat) quaternary carbons. The chemical shifts are relative to
TMS (solvent CDCl3, unless otherwise noted). Mass spectra
were measured with a JMS-01-SG-2 spectrometer [electron
impact mode (EI), 70 eV or fast atom bombardment (FAB)].
Column chromatography was carried out on Wakogel 300.
All reactions were run under an inert atmosphere.
ter a prolonged reaction time (18 h, 65 C). Also, 7a is
sparingly soluble in many organic solvents and can be
filtered off from the ether extract of the reaction mix-
ture.
A number of different palladium catalysts (2 mol%
Pd vs. the halide) were screened for this one-pot
Wittig olefination – Suzuki cross coupling protocol
in aqueous medium. Of these, the aforementioned
Pd(PPh3)2Cl2 and Pd(acac)2 gave the best results.
Slightly lower yields were found for Pd(OAc)2. The
exchange of phosphorane to phosphonium salt did not
change yield or E/Z selectivity of the reaction ap-
preciably, when Pd(PPh3)Cl2/PPh3 was used as cata-
lyst (Table 3). A fair yield (E-4p-Et, 63%) was found
with Pd(OH)2 (Pearlman’s catalyst), a catalytic system
not often used in metal catalysed cross-coupling reac-
tions. PdCl2 and Pd/C showed lower and more variable
yields. It must be noted that the Pd/C used was from
General procedure
4-[5’-(4”-Phenoxyphenyl)furan-2’-yl]but-3-en-2-one
a commercial source [11], where the reactivity of dif- (4m): A deaerated mixture of 5-bromofuran-2-yl carbalde-
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K. Yamamoto et al. · Combined Suzuki Coupling – Wittig Olefination Reaction in Aqueous Medium
hyde (2b) (350 mg, 2.0 mmol), acetylmethylidenetriphen- 688 cm−1. 1H NMR (270 MHz, CDCl3): δ = 7.42 – 8.07 (m,
ylphosphorane (3a) (1.2 g, 3.7 mmol), 4-phenoxybenzene 15H), 7.62 (d, 1H, 3J = 15.7 Hz), 7.77 (d, 2H, 3J = 8.6 Hz). –
boronic acid (1c) (760 mg, 3.5 mmol), Pd(PPh3)2Cl2 13C NMR (67.8 MHz, CDCl3): δ = 122.1, 125.4, 125.7,
(28 mg, 4 · 10−2 mmol), and triphenylphosphane (21 mg, 125.9, 126.3, 126.9, 128.1, 128.4 (2C), 128.5 (2C), 128.6
8 · 10−2 mmol) in aq. Na2CO3 (1.4 M, 15 ml) was held at (2C), 130.7 (2C), 131.3, 132.8, 133.8, 133.9, 138.3, 139.3,
◦
65 C for 9 h. Thereafter, the reaction mixture was cooled 143.2, 144.5, 190.5. – MS (EI, 70 eV): m/z (%) = 334 (100)
and extracted with chloroform (3 × 15 ml). The organic [M·], 207 (31). – HRMS (EI): found 334.1362; calcd. for
phase was dried over anhydrous MgSO4 and concentrated C25H18O: 334.1358.
in vacuo. The residue was subjected to column chromatog-
raphy on silica gel (hexane/ether/CHCl3 3:1:1) to give 4m
(535 mg, 88%) as a yellow solid; m. p. 95 C. – IR (KBr):
(E)-4-(Acetylethenyl)-3’-chlorobiphenyl (4d): Slowly so-
lidifying oil. – IR (KBr): ν = 1663, 1360, 1262, 1102,
◦
1
1010, 979, 867, 821, 787, 682, 590, 561 cm−1. – H NMR
ν = 1655, 1626, 1589, 1486, 1023, 965, 791, 754 cm−1. –
1H NMR (270 MHz, CDCl3): δ = 2.35 (s, 3H, CH3), 6.67
(d, 1H, 3J = 3.5 Hz), 6.68 (d, 1H, 3J = 15.6 Hz), 6.74
(d, 1H,3J = 3.5 Hz), 7.02 – 7.08 (m, 4H), 7.14 (m, 1H),
7.25 – 7.40 (m, 3H), 7.69 (d, 2H, 3J = 8.6 Hz). – 13C NMR
(67.8 MHz, CDCl3): δ = 27.5, 118.8, 121.3, 126.1, 126.6,
126.8, 127.6, 128.9, 129.6, 132.2, 133.2, 137.9, 141.3,
141.9, 142.9, 198.3. – MS (EI, 70 eV): m/z (%) = 304 (100)
[M+], 289 (79) [M+-CH3]. – HRMS: found: 304.1099;
calcd. for C20H16O3: 304.1099. – C20H16O3 (304.3): calcd.
C 78.93, H 5.30; found C 78.86, H 5.29.
(270 MHz, CDCl3): δ = 2.40 (s, 3H, CH3), 6.76 (d, 1H,
3J = 16.5 Hz), 7.32 – 7.65 (m, 8H), 7.51 (s, 1H). – 13C NMR
(67.8 MHz, CDCl3): δ = 27.69, 125.18, 127.17, 127.34,
127.61, 127.89, 128.84, 130.16, 134.01, 134.87, 141.74,
141.91, 142.63, 198.25. – MS (EI, 70 eV): m/z (%) = 258
(33) [{37Cl}M+], 256 (100) [{35Cl}M+], 241 (89), 178
(62), 145 (40). – HRMS (EI): found: 256.0656; calcd. for
C16H13O35Cl: 256.0655.
(E)-4-(Benzoylethenyl)-3’-chlorobiphenyl (4e): Slowly
solidifying oil. – IR (KBr): ν = 1653, 1604, 1579, 1219,
975, 832, 791, 770, 692 cm−1. – 1H NMR (270 MHz,
CDCl3): δ = 7.33 – 7.65 (m, 10H), 7.74 (d, 2H, 3J = 8.4 Hz),
7.85 (d, 1H, 3J = 15.7 Hz), 8.06 (m, 2H). – 13C NMR
(67.8 MHz, CDCl3): δ = 122.31, 125.20, 127.19, 127.60,
127.87, 128.52, 128.66, 129.04, 130.15, 132.84, 134.47,
134.86, 138.20, 141.79, 141.98, 144.07, 190.44. – MS
Physical and spectrocopic characterisation for the other
products obtained: E- and Z-4-phenylstilbenes, E-4o [16a]
and Z-4o [16b], as well as methyl E-phenylcinnamate (E-4p-
Me) [17] and ethyl E-phenylcinnamate (E-4p-Et) [1d] have
been described previously.
4-[4-(Naphthalen-1-yl)phenyl]but-3-en-2-one (4a): Col- (EI, 70 eV): m/z (%) = 320 (35) [{37Cl}M+], 318 (100)
orless solid, m. p. 85 ◦C. – IR (KBr): ν = 1658, 1618, 1255, [{35Cl}M+], 254 (11), 241 (15), 207 (53), 178 (54). – HRMS
1
1177, 994, 803, 778 cm−1. – H NMR (270 MHz, CDCl3) (EI): found 318.0812; calcd. for C21H15O35Cl: 318.0811.
δ = 2.43 (s, 3H, CH3), 6.81 (d, 1H, 3J = 16.2 Hz), 7.42 –
1-[5-(E)-(Acetylethenyl)furan-2-yl]naphthalene (4f): Yel-
7.94 (m, 10H), 7.67 (d, 2H, 3J = 8.1 Hz). – 13C NMR
low oil. – IR (neat): ν = 3052, 2924, 1663, 1612, 1555,
1504, 1392, 1360, 1281, 1254, 1181, 1024, 968, 793 cm−1. –
1H NMR (270 MHz, CDCl3): δ = 2.37 (s, 3H, CH3), 6.74 (d,
1H, 3J = 15.7 Hz), 6.85 (m, 2H), 7.37 (d, 1H, 3J = 15.7 Hz),
(67.8 MHz, CDCl3) δ = 27.6, 125.4, 125.7, 125.9, 126.3,
126.9, 127.2, 128.1, 128.2 (2C), 128.4, 130.7 (2C), 131.3,
133.4, 133.8, 139.2, 143.1, 143.2, 198.4. – MS (EI, 70 eV):
m/z (%) = 272 (100) [M+], 257 (28), 228 (32), 202 (26). –
HRMS (EI): found 272.1200; calcd. for C20H16O: 272.1201.
3
7.50 – 7.59 (m, 3H), 7.79 (d, 1H, J = 7.3 Hz), 7.82 – 7.92
(m, 2H), 8.41 (d, 1H, 3J = 7.3 Hz). – 13C NMR (67.8 MHz,
Methyl (E)-p-(Naphthalen-1-yl)cinnamate (4b): Color- CDCl3): δ = 27.9, 112.2, 117.8, 124.0, 125.2, 125.3, 126.2,
less solid, m. p. 123 ◦C. – IR (KBr): ν = 3040, 2942, 1712, 126.7, 127.1, 127.5, 128.7, 129.3, 129.6, 130.2, 131.0, 150.7,
1631, 1503, 1435, 1323, 1196, 1172, 1013, 996, 839, 802, 156.2, 197.8. – MS (EI, 70 eV): m/z (%) = 262 (100) [M+],
1
781 cm−1. H NMR (270 MHz, CDCl3): δ = 3.84 (s, 3H, 247 (90), 219 (48), 191 (66), 189 (58). – HRMS (EI): found
COOCH3), 6.52 (d, 1H, 3J = 15.9 Hz), 7.35 – 7.86 (m, 7H), 262.0994; calcd. for C18H14O2: 262.0994.
3
3
7.53 (d, 2H, J = 8.4 Hz), 7.65 (d, 2H, J = 8.4 Hz), 7.79
(d, 1H, 3J = 15.9 Hz). – 13C NMR (67.8 MHz, CDCl3):
δ = 51.7, 117.9, 125.4, 125.7, 125.9, 126.2, 126.9, 128.0
(2C), 128.4, 130.6 (3C), 131.3, 133.4, 133.8, 139.3, 142.9,
144.5, 167.5. – MS (EI, 70 eV): m/z (%) = 288 (100)
[M+]. – HRMS (EI): found 288.1148; calcd. for C20H16O2:
288.1150. – C20H16O2 (288.3): calcd. C 83.31, H 5.59;
found C 83.13, H 5.59.
Methyl (Z)-3-[5’-(naphthalen-1”-yl)furan-2’-yl]acrylate
(Z-4g): Yellow oil. – IR (neat): ν = 3052, 2992, 2946,
1714, 1633, 1504, 1436, 1415, 1391, 1253, 1172, 1026, 919,
796 cm−1. – 1H NMR (270 MHz, CDCl3): δ = 3.79 (s,
3H, COOCH3), 5.81 (d, 1H, 3J = 12.9 Hz), 6.87 (d, 1H,
3J = 3.3 Hz), 6.93 (d, 1H, 3J = 12.9 Hz), 7.49 – 7.56 (m, 3H),
7.78 (dd, 1H, 3J = 7.4 Hz, 3J = 1.3 Hz), 7.80 – 7.91 (m, 3H),
8.42 (m, 1H). – 13C NMR (67.8 MHz, CDCl3): δ = 51.4,
1-(4-(E)-[Benzoylethenyl]phenyl)naphthalene (4c): Pale 112.4, 113.7, 119.2, 125.3, 125.4, 126.1, 126.6, 126.8, 127.8,
yellow solid, m. p. 123 ◦C. – IR (KBr): ν = 1661, 1600, 1554, 128.6, 129.2, 130.3, 130.5, 134.0, 150.7, 155.0, 166.6. –
1504, 1393, 1328, 1300, 1212, 1177, 1016, 1000, 799, 777, MS (EI, 70 eV): m/z (%) = 278 (100) [M+], 254 (60),
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K. Yamamoto et al. · Combined Suzuki Coupling – Wittig Olefination Reaction in Aqueous Medium
1305
253 (58). – HRMS: found 278.0943; calcd. for C18H14O3: 1592, 1492, 1438, 1337, 1311, 1276, 1190, 1169, 984, 821,
278.0943 and methyl (E)-3-[5’-(naphthalen-1”-yl)furan-2’- 760 cm−1. – 1H NMR (270 MHz, CDCl3): δ = 3.82 (s, 3H,
yl]-acrylate (E-4g): Yellow oil. – IR (neat): ν = 2946, 1700, COCH3), 6.46 (d, 1H,3J = 15.7 Hz), 7.05 – 7.58 (m, 13H),
1645, 1359, 1174, 1020, 974, 925, 804 cm−1. – 1H NMR 7.72 (d, 1H, 3J = 15.7 Hz). – 13C NMR (67.8 MHz, CDCl3):
(270 MHz, CDCl3): δ = 3.81 (s, 3H, COOCH3), 6.44 (d, δ = 52.6, 118.4, 119.9 (2C), 120.1 (2C), 124.4, 128.1 (2C),
3
1H, J = 15.7 Hz), 6.80 (d, 1H, 3J = 3.5 Hz), 6.82 (d, 1H, 129.2 (2C), 129.5 (2C), 130.7 (2C), 134.0, 135.9, 143.2,
3J = 3.5 Hz), 7.49 – 7.58 (m, 4H), 7.79 (dd, 1H, 3J = 7.3 Hz, 145.2, 157.8, 158.3, 168.3. – MS (EI, 70 eV): m/z (%) = 330
3J = 1.4 Hz), 7.89 (m, 2H), 8.42 (m, 1H). – 13C NMR (100) [M+], 299 (13), 206 (10), 178 (15). – HRMS (EI):
(67.8 MHz, CDCl3, DEPT 90, DEPT 135): δ = 51.7 (+, found 330.1254; calcd. for C22H18O3: 330.1256. C22H18O3 ·
OCH3), 111.9 (+, CH), 115.1 (+, CH), 116.9 (+, CH), 125.2 0.1H2O (331.9): calcd. C 79.54, H 5.52; found C 79.58,
(+, CH), 125.3 (+, CH), 126.1 (+, CH), 126.7 (+, CH), 127.0 H 5.51.
(+, CH), 127.5 (Cquat), 128.7 (+, CH), 129.5 (+, CH), 130.2
(Cquat), 131.1 (+, CH), 134.0 (Cquat), 150.7 (Cquat), 155.9
(Cquat), 167.6 (Cquat, CO). – MS (EI, 70 eV): m/z (%) = 278
(100) [M+], 247 (24). – HRMS (EI): found 278.0940; calcd.
for C18H14O3: 278.0943.
4-[5’-(4”-Phenoxyphenyl)furan-2’-yl]but-3-en-2-one
(4m): Pale yellow solid, m. p. 95 ◦C. – IR (KBr) ν = 1655,
1626, 1589, 1486, 1023, 965, 791, 754 cm−1. – 1H NMR
(270 MHz, CDCl3): δ = 2.35 (s, 3H, CH3), 6.67 (d, 1H,
3J = 3.5 Hz), 6.68 (d, 1H, 3J = 15.6 Hz), 6.74 (d, 1H,
3J = 3.5 Hz), 7.02 – 7.08 (m, 4H), 7.14 (m, 1H), 7.25 – 7.40
(m, 3H), 7.69 (d, 2H, 3J = 8.6 Hz). – 13C NMR (67.8 MHz,
CDCl3): δ = 27.5, 118.8, 121.3, 126.1, 126.6, 126.8, 127.6,
128.9, 129.6, 132.2, 133.2, 137.9, 141.3, 141.9, 142.9,
198.3. – MS (EI, 70 eV): m/z (%) = 304 (100) [M+],
289 (79) [M+-CH3]. – HRMS: found 304.1099; calcd. for
C20H16O3: 304.1099. – C20H16O3 (304.1): calcd. C 78.93,
H 5.30; found C 78.86, H 5.29.
(E)-5-Benzoylethenyl-2-naphthalen-1’-ylfuran (4h): Dark
yellow oil. – IR (neat): ν = 3056, 2922, 1659, 1603, 1556,
1334, 1298, 1258, 1219, 1178, 1015, 701, 657 cm−1. –
1H NMR (270 MHz, CDCl3): δ = 6.79 (d, 1H, 3J = 3.5 Hz),
6.85 (d, 1H, 3J = 3.5 Hz), 7.62 (d, 1H, 3J = 15.1 Hz), 7.77
(d, 1H, 3J = 7.0 Hz), 7.18 – 7.98 (m, 12H). – 13C NMR
(67.8 MHz, CDCl3): δ = 111.3, 119.5, 120.0, 125.0, 125.5,
126.3, 127.6, 128.3, 128.5, 128.6, 129.2, 129.3, 129.5, 129.6,
130.3, 132.4, 134.0, 138.3, 151.5, 156.1, 189.9. – MS (EI,
70 eV): m/z (%) = 324 (18) [M+]. – HRMS (EI): found
324.1152; calcd. for C23H16O2: 324.1150.
2’-Acetylethenyl-4’-phenoxybiphenyl (4n): Colorless
oil. – IR (neat): ν = 3058, 2954, 2924, 2856, 1671, 1589,
1508, 1489, 1358, 1243, 1169, 1021, 1004, 980, 869, 842,
759 cm−1. – 1H NMR (270 MHz, CDCl3): δ = 2.26 (s,
3H, CH3), 6.65 (d, 1H,3J = 15.9 Hz), 6.99 – 7.48 (m, 12H),
7.58 (d, 1H, 3J = 15.9 Hz), 7.69 (m, 1H). – 13C NMR
(δ, CDCl3) 27.2, 118.2 (2C), 119.4 (2C), 123.7, 126.9,
127.7, 128.3, 129.0, 129.9 (2C), 130.1, 130.4, 132.2 (2C),
132.7, 134.6, 142.2, 156.7, 157.3, 198.5. – MS (EI, 70 eV):
m/z (%) = 314 (30) [M+], 271 (32), 178 (100). – HRMS:
found 314.1308; calcd. for C22H18O2: 314.1307; and
4-(2’-bromophenyl)-but-3-en-2-one as a colorless oil. – IR
(neat): ν = 3060, 3000, 2918, 1670, 1609, 1465, 1438, 1359,
(E)-4-Acetylethenyl-4’-phenoxy-biphenyl (4i): Pale yel-
◦
low flaky solid, m. p. 166 C. – IR (KBr) ν = 1663, 1592,
1492, 1361, 1274, 1258, 979, 812, 749, 690 cm−1. –
1H NMR (270 MHz, CDCl3): δ = 2.40 (s, 3H, CH3), 6.75
(d, 1H, 3J = 16.2 Hz), 7.05 – 7.62 (m, 13H), 7.59 (d, 1H,
3J = 16.2 Hz). – 13C NMR (67.8 MHz, CDCl3): δ = 27.5,
119.0, 119.2, 123.6, 126.9, 127.3, 128.3, 128.8, 129.8, 133.1,
134.9, 142.6, 142.9, 157.5, 159.7, 198.3. – MS (EI, 70 eV):
m/z (%) = 314 (100) [M+], 299 (33) 178 (34). – HRMS (EI):
found 314.1305; calcd. for C22H18O2: 314.1307.
1
1283, 1257, 1203, 1177, 1026, 974, 563 cm−1. – H NMR
4-(E)-Benzoylethenyl-4’-phenoxy-biphenyl (4j): Pale yel-
low solid, m. p. 177 ◦C. – IR (KBr): ν = 3058, 1659 cm−1
;
(270 MHz, CDCl3) δ = 2.43 (s, 3H, CH3), 6.62 (d, 1H,
3J = 16.2 Hz), 7.01 – 7.37 (m, 2H), 7.59 – 7.64 (m, 2H), 7.89
(d, 1H, 3J = 16.2 Hz). – 13C NMR (67.8 MHz, CDCl3) 28.1,
126.5, 128.7, 128.7, 130.8, 132.3, 134.4, 142.8, 199.2. –
MS (FAB, 3-nitrobenzyl alcohol): m/z (%) = 227 (39)
[{81Br}MH+], 225 (41) [{79Br}MH+]. – MS (EI, 70 eV):
m/z (%) = 226 (5) [{81Br}M+], 224 (5) [{79Br}M+], 211
(11) [{81Br}M+-CH3], 209 (11) [{79Br}M+-CH3], 183 (8),
181 (9), 145 (100). – HRMS: found 223.9837; calcd. for
C10H9O79Br: 223.9837.
1H NMR (270 MHz, CDCl3): δ = 7.05 – 8.03 (m, 15H), 7.62
(d, 2H, 3J = 8.4 Hz), 7.67 (d, 2H, 3J = 8.4 Hz), 7.85 (d, 1H,
3J = 15.7 Hz). – 13C NMR (67.8 MHz, CDCl3, DEPT 90,
DEPT 135): δ = 119.0 (+, CH), 119.2 (+, CH), 121.8 (+,
CH), 123.6 (+, CH), 127.3 (+, CH), 128.4 (+, CH), 128.5
(+, CH), 128.6 (+, CH), 129.0 (+, CH), 129.8 (+, CH), 132.7
(+, CH), 133.6 (Cquat), 135.0 (Cquat), 138.3 (Cquat), 142.6
(Cquat), 144.4 (+, CH), 156.9 (Cquat), 157.5 (Cquat), 190.5
(Cquat, CO). – MS (EI, 70 eV) m/z (%) = 376 (89) [M+], 314
(100), 299 (41), 178 (63). – HRMS (EI): found 376.1461;
calcd. for C27H20O2: 376.1463. C27H20O2 ·0.1H2O (377.9):
calcd. C 85.73, H 5.38; found C 85.63, H 5.28.
4-[4’-(Benzo[b]thien-3”-yl)phenylbut-3-en-2-one (4r):
◦
Yellow crystals, m. p. 104 C. – IR (KBr): ν = 1683, 1597,
1320, 1172, 989, 821, 796, 764, 736 cm−1. – 1H NMR
Methyl 4-(E)-(4’-phenoxyphenyl)cinnamate (4k): Color- (600 MHz, CDCl3): δ = 2.40 (s, 3H, CH3), 6.77 (d,
less solid, m. p. 193 ◦C. – IR (KBr): ν = 2944, 1718, 1638, 1H,3J = 16.2 Hz), 7.39 (m, 2H), 7.44 (s, 1H), 7.57 (d,
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1306
K. Yamamoto et al. · Combined Suzuki Coupling – Wittig Olefination Reaction in Aqueous Medium
1H, 3J = 16.2 Hz), 7.62 (d, 2H, 3J = 8.3 Hz), 7.65 (d, 761 cm−1. – 1H NMR (270 MHz, CDCl3) δ = 2.58 (dd,
2H, 3J = 8.3 Hz), 7.91 (m, 2H). – 13C NMR (67.8 MHz, 2H,3J = 8.4 Hz,3J = 7.3 Hz), 2.88 (dd, 2H, 3J = 8.4 Hz,
CDCl3): δ = 27.6, 122.7, 123.0, 124.2, 124.6, 124.7, 3J = 7.3 Hz), 3.81 (s, 3H, COOCH3), 6.13 (d, 1H, 3J =
127.2, 128.7 (2C), 129.2 (2C), 133.6, 137.2, 137.5, 138.2, 15.9 Hz), 7.15 (m, 1H), 7.24 – 7.28 (m, 2H), 7.78 (m, 1H),
140.8, 142.9, 198.3. – MS (EI, 70 eV): m/z (%) = 278 (93) 8.11 (d, 1H, 3J = 15.9 Hz). – 13C NMR (67.8 MHz, CDCl3):
[M+]. – HRMS (EI): found 278.0764; calcd. for C18H14OS: δ = 25.9, 27.5, 52.8, 120.0, 127.0, 127.0, 128.7, 129.3,
278.0765. – C18H14OS (278.4): calcd. C 77.66, H 5.12; 129.5, 133.3, 133.9, 137.2, 144.3, 167.4. – MS (EI, 70 eV):
found C 77.57, H 5.12.
m/z (%) = 294 (11) [{81Br}M+], 292 (11) [{79Br}M+], 213
(100). – HRMS: found 292.0100; calcd. for C14H13O279Br:
292.0099.
(E)-4-[4’-(Thien-3”-yl)phenylbut-3-en-2-one (4s): Pale
brown crystals. – IR (KBr): ν = 1658, 1360, 1263, 979,
782 cm−1. – 1H NMR (270 MHz, CDCl3): δ = 2.38 (s,
3H, CH3), 6.72 (d, 1H, 3J = 16.4 Hz), 7.40 (dd, 1H, J =
1.7 Hz, J = 1.3 Hz), 7.42 (dd, 1H, J = 3.1 Hz, J = 1.3 Hz),
7.51 (d, 1H, 3J = 16.4 Hz), 7.51 (dd, 1H, 3J = 2.1 Hz,
J = 1.7 Hz), 7.56 (d, 2H, J = 8.3 Hz), 7.62 (d, 2H, J =
8.3 Hz). – 13C NMR (67.8 MHz, CDCl3): δ = 27.5, 121.3,
126.1, 126.6, 126.8 (2C), 126.9 (2C), 128.9, 133.2, 137.9,
141.3, 142.9, 198.3. – MS (EI, 70 eV): m/z (%) = 228 (100)
[M+]. – HRMS (EI): found 228.0607; calcd for C14H12OS:
228.0609. – C14H12OS · 0.1H2O (230.1): calcd. C 73.07,
H 5.34; found C 73.10, H 5.28.
(E)-5-(4-Anisyl)-thien-2-yl-4-(benzothien-◦2-yl)phenylvin-
ylketone (7a): Greenish powder, m. p. 178 C (dec.). – IR
(KBr): ν = 1649, 1540, 1522, 1434, 1255, 1176, 1030, 829,
798, 576 cm−1. – 1H NMR (270 MHz, CDCl3): δ = 3.86
(s, 3H, OCH3), 6.94 (d, 2H, 3J = 8.9 Hz), 6.98 – 7.84
(m, 14H), 7.43 (s, 1H). – 13C NMR (67.8 MHz, CDCl3):
δ = 55.43, 114.58 (2C), 120.40, 121.56, 122.02, 122.31,
123.02, 123.80, 124.73, 124.77, 126.82 (2C), 127.69 (2C),
129.07 (2C), 129.78, 132.21, 133.02, 133.12, 134.71,
136.29, 142.06, 142.63, 153.33, 160.55, 187.46.
(E)-5-(4-Anisyl)-thien-2-yl-4-bromophenylvinylketone
(7b): Pale yellow solid, m. p. 229 ◦C. – IR (KBr): ν = 1653,
1598, 1450, 1250, 1110, 1068, 1030, 830, 795, 764 cm−1. –
1H NMR (270 MHz, CDCl3): δ = 3.86 (s, 3H, OCH3),
6.96 (d, 2H, 3J = 8.6 Hz), 7.28 (d, 1H, 3J = 4.0 Hz),
7.40 (d, 1H, 3J = 15.7 Hz), 7.51 (d, 2H, 3J = 8.6 Hz),
7.55 (d, 2H, 3J = 8.6 Hz), 7.63 (d, 2H, 3J = 8.6 Hz),
7.77 (d, 1H, 3J = 15.7 Hz), 7.80 (d, 1H, 3J = 4.0 Hz);
13C NMR (67.8 MHz, CDCl3): δ = 55.36, 114.59 (2C),
122.05, 123.05, 124.71, 126.17, 127.71 (2C), 129.79 (2C),
132.22 (2C), 133.13, 133.83, 142.08, 143.16, 153.49,
160.59, 181.34. – MS (FAB, 3-nitrobenzyl alcohol): m/z
(%) = 401 (2.5) [{81Br}MH+], 399 (2.4) [{79Br}MH+]. –
HRMS (FAB): found 399.0058; calcd. for C20H16O279BrS:
399.0054.
3
3
Methyl [-1,2-dihydro-4-(naphthalen-2-yl)naphthalen-3
-yl]acrylate (6a): Colorless solid, m. p. 128 ◦C. – IR (KBr):
ν = 3052, 2932, 1717, 1612, 1431, 1306, 1169, 847, 821,
744 cm−1. – 1H NMR (270 MHz, CDCl3): δ = 2.68 (dd,
3
3
2H, J = 8.4 Hz, 3J = 7.0 Hz), 2.96 (dd, 2H, J = 8.4 Hz,
3J = 7.0 Hz), 3.63 (s, 3H, COOCH3), 6.06 (d, 1H, 3J =
15.9 Hz), 6.68 (d, 1H, 3J = 8.1 Hz), 7.03 (m, 1H), 7.17 – 7.54
(m, 5H), 7.45 (d, 1H, 3J = 15.9 Hz), 7.67 (s, 1H), 7.81 – 7.93
(m, 3H). – 13C NMR (67.8 MHz, CDCl3): δ = 24.3, 28.0,
51.4, 117.2, 126.3, 126.3, 126.5, 127.3, 127.8, 127.9, 128.0,
128.1, 128.3, 128.4, 129.6, 131.8, 132.8, 133.2, 135.2, 136.1,
136.9, 144.1, 144.5, 167.8. – MS (EI, 70 eV): m/z (%) =
340 (57) [M+], 281 (100), 265 (44), 252 (14). – HRMS
(EI): found 340.1460; calcd. for C24H20O2: 340.1463. –
C24H20O2 (220.3): calcd. C 84.68, H 5.92; found: C 84.67, Acknowledgements
H 5.95.
The authors thank Ms. Yasuko Tanaka for obtaining the
mass spectra of the compounds. Elemental analysis was
performed at the Centre of Elemental Analysis, Kyushu
University, Hakozaki Campus.
Methyl 3-(1’-bromo-3’,4’-dihydronaphthalen-2’-yl)acryl-
ate (6b): Colorless oil. – IR (neat): ν = 3062, 3018, 2948,
1717, 1614, 1307, 1277, 1233, 1171, 1038, 977, 946, 857,
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Unauthenticated
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K. Yamamoto et al. · Combined Suzuki Coupling – Wittig Olefination Reaction in Aqueous Medium
1307
[6] For a review, see: W. A. Herrmann, C.-P. Reisinger,
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Unauthenticated
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