Synthesis of functionalized para -and meta -terphenyls based on site-selective Suzuki cross-coupling reactions of bis(triflates) of methyl 2,5-dihydroxybenzoate and methyl 2,4-dihydroxybenzoate

Article abstract of DOI:10.1139/cjc-2013-0201

The palladium(0)-catalyzed Suzuki cross-coupling reaction of the bis(triflates) of methyl 2,5-dihydroxybenzoate and methyl 2,4-dihydroxybenzoate afforded para-and meta-terphenyls, respectively. The reactions proceeded with very good site selectivity in fa

Full text of DOI:10.1139/cjc-2013-0201

1048
ARTICLE
Synthesis of functionalized para- and meta-terphenyls based on
site-selective Suzuki cross-coupling reactions of bis(triflates) of
methyl 2,5-dihydroxybenzoate and methyl 2,4-dihydroxybenzoate
Muhammad Nawaz, Ihsan Ullah, Obaid-ur-Rahman Abid, Asad Ali, Tamás Patonay, Ashot S. Saghyan, Tariel V. Ghochikan, Alexander Villinger,
and Peter Langer
Abstract: The palladium(0)-catalyzed Suzuki cross-coupling reaction of the bis(triflates) of methyl 2,5-dihydroxybenzoate and
methyl 2,4-dihydroxybenzoate afforded para- and meta-terphenyls, respectively. The reactions proceeded with very good site
selectivity in favor of the sterically less hindered carbon atom.
Key words: terphenyls, cross-coupling, palladium, site selectivity, Suzuki reaction.
Résumé : La réaction de couplage croisé de Susuki des bis(triflates) de méthyl 2,5-dihydroxybenzoate et de méthyl 2,
4-dihydroxybenzoate catalysée au palladium(0) a donné les para- et méta-terphényles, respectivement. Les réactions se sont déroulées
avec une très bonne sélectivité de site en faveur de l’atome de carbone stériquement le moins encombré. [Traduit par la Rédaction]
Mots-clés : terphényles, couplage croisé, palladium, sélectivité de site, réaction de Suzuki.
reactions. Recently, we have reported preliminary results related
Introduction
to Suzuki−Miyaura reactions of this substrate.12 Herein, we report
Functionalized p-terphenyls occur in a great variety of pharma-
full details of these studies related to the preparative scope. In
cologically relevant natural products. Examples include terphen-
addition, we report, for the first time, Suzuki−Miyaura reactions
yllin,1 terprenin,2 curtisian A,3 leucomentin-6,4 thelephorin A,5
of the bis(triflate) of methyl 2,4-dihydroxybenzoate. These reac-
ganbajunin D,6 and thelephantin A.7 Symmetrical and unsymmet-
tions result in the formation of meta-terphenyls. The chemical
rical terphenyls, functionalized with electron donor or acceptor
groups, are the main constituents of a large number of natural
core structure of meta-terphenyls occurs in a great variety of phar-
macologically relevant natural products. Examples include vari-
products of mushrooms belonging to the Thelephoraceae
ous simple hydroxylated and alkylated meta-terphenyls, such as
family. Several synthetic p-terphenyl derivatives have been de-
trifucolnonaacetate, dunnianol, and mulberrofuran R.13 Other de-
signed as selective inhibitors for dihydroortate dehydrogenase
rivatives, such as pusilatin A, are incorporated in cyclophanes.14
and cyclooxygenase enzymes.
In recent years, site-selective palladium-catalyzed reactions of
The meta-terphenyl unit of various other natural products is incor-
porated in bis(anthracene)15 or bis(carbazole)16 frameworks. The
meta-terphenyl substructure is also found in complex macrocyclic
natural products, such as acutissimin B, castalagin, and roburin
A.17,18 Sonogashira reactions of the bis(triflate) of dimethyl 4,6-
dihydroxy-isophthalate have been previously reported.19
polyhalogenated substrates have been studied.8 We have reported
site-selective reactions of various polyhalogenated heterocycles
and of poly(triflates) of various arenes.9 Polyhalogenated benzoic
acid derivatives are interesting substrates for site-selective
palladium(0)-catalyzed cross-coupling reactions. Tschierske and
co-workers reported the synthesis of p-terphenyls by double
Suzuki reactions of methyl 2,5-dibromobenzoate.10 As two equiv-
alents of the same boronic acid were employed in this study, no
issue of site selectivity arose. Mioskowski et al. reported site-
selective Sonogashira reactions of 2,5-diiodobenzoic acid.11a The
scope of this approach is limited by the fact that polyhalogenated
benzene derivatives are often not readily available. Reactions of
the bis(triflate) of diethyl 2,5-bis-hydroxy-terephthalate have been
previously reported.11b We envisaged that the bis(triflate) of
methyl 2,5-dihydroxybenzoate, which represents a commercially
available and inexpensive substrate, could be of considerable
preparative usefulness in palladium-catalyzed cross-coupling
Results and discussion
Methyl 2,5-dihydroxybenzoate (1) was transformed into bis(tri-
flate) 2 in 84% yield (Scheme 1). The Suzuki reaction of 2 with
different boronic acids (2.6 equiv.) afforded the novel 2,5-
diarylbenzoates 3a–3f in good yields (Scheme 2; Table 1). The best
yields were obtained when Pd(PPh3)4 (6 mol%) was used as the
catalyst, when 2.6 equiv. of the boronic acid was employed, and
when the reaction was carried out in 1,4-dioxane (reflux, 4 h) using
K3PO4 as the base. The structures of all products were established
by spectroscopic methods. The structures of 1, 2, and 3d were
independently confirmed by X-ray crystal structure analyses
Received 6 April 2012. Accepted 10 December 2012.
M. Nawaz and A. Villinger. Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany.
I. Ullah and A. Ali. Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany; Department of Chemistry, Abdul Wali Khan University, Mardan, KPK, Pakistan.
O.-u.-R. Abid. Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany; Department of Chemistry, Hazara University, Mansehra, KPK, Pakistan.
T. Patonay. Department of Organic Chemistry, University of Debrecen, H-4032 Debrecen, Egyetem tér 1, Hungary.
A.S. Saghyan. Scientific and Production Center “Armbiotechnology” of NAS RA, Gyurjyan str. 14, 0056 Yerevan, Armenia; Department of Chemistry, Yerevan State University, Alex
Manoogian 1, 0025 Yerevan, Armenia.
T.V. Ghochikan. Department of Chemistry, Yerevan State University, Alex Manoogian 1, 0025 Yerevan, Armenia.
P. Langer. Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany; Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a,
18059 Rostock, Germany.
Corresponding author: P. Langer (e-mail: peter.langer@uni-rostock.de).
Can. J. Chem. 91: 1048–1058 (2013) dx.doi.org/10.1139/cjc-2013-0201
Published at www.nrcresearchpress.com/cjc on 9 November 2012.

Nawaz et al.
1049
Scheme 1. Synthesis of 2. Reagents and conditions: (i) CH2Cl2, 1
Fig. 1. Ortep plot of 1.
(1.0 equiv.), –78 °C, pyridine (4.0 equiv.), –78 °C, Tf2O (2.4 equiv), 4 h.
Scheme 2. Synthesis of 3a–3f. Reagents and conditions: (i) 2
(1.0 equiv.), boronic acids (2.6 equiv.), K3PO4 (3.0 equiv.), Pd(PPh3)4
(6 mol%), 1,4-dioxane (5 mL per 1 mmol of 2), 110 °C, 4 h.
obtained when Pd(PPh3)4 (6 mol%) was used as the catalyst, when
2.6 equiv. of the boronic acid was employed, and when the reac-
tion was carried out in 1,4-dioxane (reflux, 4 h) using K3PO4 as the
base.
The Suzuki reaction of 7 with different boronic acids (1.3 equiv.)
in the presence of Pd(PPh3)4 (3 mol%) proceeded with very good
site selectivity at carbon atom C-4 and afforded the biaryls 9a–9e
(Scheme 7; Table 4). In some cases, a small amount of the bis-
coupled product could be detected in the crude product (by
1H NMR and GC-MS). The pure monocoupled products were
again obtained after chromatographic purification. The reac-
tion of 9a–9e with vinyl phenyl boronic acid (1.3 equiv.) gave
2,4-diarylbenzoates 10a–10d containing two different aryl groups.
The structure of 9c was independently confirmed by X-ray crystal
structure analysis (Fig. 4).20
As mentioned above, the oxidative addition of palladium usually
occurs first at the most electron-deficient carbon atom. Carbon at-
oms C-2 and C-4 of bis(triflate) 7 are equally electron deficient. The
site-selective formation of 9a–9e can be explained by the fact that
carbon atom C-4 is less sterically hindered (Scheme 8).
Table 1. Synthesis of 3a−3f.
3
R1
R2
R3
% (3)a
a
b
c
d
e
f
OMe
H
H
H
H
H
H
OMe
H
Cl
H
H
78
75
56
77
67
54
tBu
OMe
Vinyl
H
H
H
aYields of isolated products.
In conclusion, we have reported the synthesis of para- and
meta-terphenyls based on Suzuki cross-coupling reactions of the
bis(triflates) of methyl 2,5- dihydroxybenzoate and methyl
2,4-dihydroxybenzoate, respectively. The reactions proceed with
very good site selectivity.
(Figs. 1–3) (see Supplementary material section). The X-ray crystal
structure analysis of 3b was already published in our preliminary
communication.12
The Suzuki reaction of 2 with different boronic acids (1.3 equiv.)
in the presence of Pd(PPh3)4 (3 mol%) occurred site selectively at
carbon atom C-5 and afforded the biaryls 4a−4g (Scheme 3;
Table 2). The reaction of 4a–4g with vinylphenyl boronic acid
(1.3 equiv.) gave 2,5-diarylbenzoates 5a–5g containing two differ-
ent aryl groups.
Experimental section
General comments
All solvents were dried by standard methods and all reactions
were carried out under an inert atmosphere. For 1H and 13C NMR
spectra, the deuterated solvents indicated were used. MS data
were obtained by electron ionization (EI, 70 eV), chemical ioniza-
tion (isobutane), or electrospray ionization. For preparative scale
chromatography, silica gel 60 (0.063–0.200 mm, 70–230 mesh)
was used. X-ray crystal structure analysis: crystallographic data
were collected on a Bruker X8Apex diffractometer with CCD-
Kamera (MoKa und Graphit Monochromator, = 0.71073 Å). The
structures were solved by direct methods using SHELXS-97 and
refined against F2 on all data by full matrix least-squares with
SHELXL-97.
In some cases, a small amount of the bis-coupled product and of
the other regioisomer could be detected in the crude product (by
1H NMR and GC−MS). For example, 10% of the bis-coupled product
1
was detected by H NMR in the crude product of 4a. The pure
monocoupled products were obtained after chromatographic pu-
rification. The oxidative addition of palladium usually occurs first
at the less steric-hindered and more electron-deficient carbon
atom. Carbon atom C-2 of bis(triflate) 2 is more electron deficient
than C-5 due to the electronic influence of the ester group. On the
other hand, carbon C-5 is less sterically hindered than C-2. There-
fore, the site-selective formation of 4a–4g seems to be mainly
influenced by steric parameters (Scheme 4).
Extending the scope of our study, we have investigated Suzuki
reactions of the bis(triflate) of commercially available methyl
2,4-dihydroxybenzoate to give meta-terphenyls. Methyl 2,4-
dihydroxybenzoate (6) was transformed into its bis(triflate) 7 in
88% yield (Scheme 5). The Suzuki reaction of 7 with different
boronic acids (2.6 equiv.) afforded the novel 2,5-diarylbenzoates
8a–8j in good yields (Scheme 6; Table 3). The best yields were
Synthesis of triflates 2 and 7
To a stirred solution of 1 and 6 (1.0 equiv) in CH2Cl2 (10 mL/mmol)
was added pyridine (4.0 equiv.) at –78 °C under an argon atmo-
sphere. After 10 min, Tf2O (2.4 equiv.) was added at –78 °C. The
mixture was allowed to warm up to 0 °C and stirred for 4 h. The
reaction mixture was filtered and the filtrate was concentrated
in vacuo. The products of the reaction mixture were isolated
Published by NRC Research Press

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Can. J. Chem. Vol. 91, 2013
Fig. 2. Ortep plot of 2.
Fig. 3. Ortep plot of 3d.
by rapid column chromatography (flash silica gel, heptanes/
EtOAc).
␯˜ = 3121, 3088, 2961 (w), 1736, 1618 (s), 1586, 1485, 1300, 1279 (m),
1244 (s), 1124, 1075, 977 (m), 875, 781, 759 (s), 698, 581, 543 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 432 (M +, 70), 401(40), 363(06), 337(02),
299(32), 273(13), 235(98), 205(27), 179(24), 135(62), 107(33), 79(26),
69(100), 53(28). HRMS (EI) calcd. for C10H6F6O8S2 [M +]: 431.94028;
found: 431.940891.
Methyl 2,5-bis(trifluoromethylsulfonyloxy)benzoate (2)
Starting with 1 (168 mg, 1.0 mmol), pyridine (0.32 mL, 4.0 mmol),
and Tf2O (0.39 mL, 2.4 mmol), 2 was isolated as a colorless crystal-
1
line solid; yield 364 mg (84%), mp 152–154 °C. H NMR (300 MHz,
CDCl3): ␦ = 3.92 (s, 3H, OCH3), 7.36 (s, 1H, ArH), 7.47 (d, 1H, J =
Methyl 2,4-bis(trifluoromethylsulfonyloxy)benzoate (7)
3.0 Hz, ArH), 7.92 (d, 1H, J = 3.2 Hz, ArH). 13C NMR (75.46 MHz,
Starting with 6 (168 mg, 1.0 mmol), pyridine (0.32 mL,
4.0 mmol), and Tf2O (0.39 mL, 2.4 mmol), 7 was isolated as a
colorless oil (382 mg, 88%). 1H NMR (300 MHz, CDCl3): ␦ = 3.92 (s,
3H, OCH3), 7.19 (s, 1H, ArH), 7.35 (d, 1H, J = 8.2 Hz, ArH), 8.17 (d, 1H,
CDCl3): ␦ = 53.2 (OCH3), 116.5 (q, JC,F = 320.0 Hz, CF3), 120.2 (q, JC,F
=
318.0 Hz, CF3), 125.0, 125.6, 127.0 (CHAr), 147.1, 147.9, 148.0 (CAr),
162.3 (C=O). 19F NMR (282 MHz, CDCl3): ␦ = –73.3 (CF). IR (KBr):
Published by NRC Research Press

Nawaz et al.
1051
Scheme 3. Synthesis of 4a–4g and 5a–5g. Reagents and conditions:
(i) 2 (1.0 equiv.), boronic acids (1.3 equiv.), K3PO4 (1.5 equiv.),
Pd(PPh3)4 (3 mol%), 1,4-dioxane (5 mL per 1 mmol of 2), 110 °C, 4 h;
(ii) 4a–4g (1.0 equiv.), vinylphenyl boronic acids (1.3 equiv.), K3PO4
(1.5 equiv), Pd(PPh3)4 (3 mol%), 1,4-dioxane (5 mL per 1 mmol of 2),
110 °C, 4 h.
Scheme 5. Synthesis of 7. Reagents and conditions: (i) CH2Cl2,
6 (1.0 equiv.), –78 °C, pyridine (4.0 equiv.), –78 °C, Tf2O (2.4 equiv.),
4 h.
Scheme 6. Synthesis of 8a–8j. Reagents and conditions:
(i) 7 (1.0 equiv.), boronic acids (2.6 equiv.), K3PO4 (3.0 equiv.),
Pd(PPh3)4 (6 mol%), 1,4-dioxane (5 mL per 1 mmol of 7), 110 °C, 4 h.
Table 3. Synthesis of 8a–8j.
8
R1
R2
R3
R4
% (8)a
a
b
c
d
e
f
g
h
i
H
OMe
H
H
H
Br
F
H
H
H
H
H
H
H
OH
H
H
H
CF3
H
Cl
H
H
tBu
H
H
H
F
H
CF3
H
OMe
H
H
H
H
H
H
H
72
78
65
79
62
74
68
77
63
69
Table 2. Synthesis of 4a−4g and 5a−5g
4, 5
R1
R2
R3
R4
% (4)a
% (5)a
a
b
c
d
e
f
H
OMe
H
H
H
Me
H
H
OMe
H
H
H
H
Me
OMe
H
H
H
83
72
64
67
63
73
59
72
78
68
64
62
67
72
Me
OMe
Br
OMe
Cl
OMe
H
H
H
j
H
g
H
aYields of isolated products.
aYields of isolated products.
Scheme 4. Possible explanation for the site-selective formation of
products 4a–4g.
51(16), 39(03). HRMS (EI) calcd. for C10H6F6O8S2 [M+]: 431.94028;
found: 431.941432.
2,2== -Dimethoxy-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid methyl
ester (3a)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol),
Pd(PPh3)4 (6 mol%), 2-methoxyphenylboronic acid (180 mg,
1.19 mmol), and 1,4-dioxane (5 mL/mmol triflate), 3a was isolated
1
as a colorless viscous oil; yield 126 mg (78%). H NMR (300 MHz,
CDCl3): ␦ = 3.57 (s, 3H, OCH3), 3.65 (s, 3H, OCH3), 3.74 (s, 3H, OCH3),
6.82 (d, 2H, J = 8.2 Hz, ArH), 6.90–6.99 (m, 3H, ArH), 7.20–7.29 (m,
3H, ArH), 7.32 (d, 1H, J = 6.9 Hz, ArH), 7.64 (dd, 1H, J = 1.9, 7.9 Hz,
ArH), 7.95 (d, 1H, J = 1.7 Hz, ArH). 13C NMR (62.90 MHz, CDCl3): ␦ =
51.6 (OCH3), 55.2 (OCH3), 55.5 (OCH3), 110.0, 111.2, 120.7, 120.9,
128.7, 129.0 (CHAr), 129.4 (CAr), 130.0, 130.4 (CHAr), 130.5 (CAr), 130.8,
130.9 (CHAr), 131.3 (CAr), 132.6 (CHAr), 137.1, 137.4, 156.1, 156.5 (CAr),
168.7 (C=O). IR (KBr): ␯˜ = 3055, 3024, 2945, 2834 (w), 1720 (m), 1597,
1508 (w), 1492, 1479, 1433, 1311 (m), 1242 (s), 1179, 1120, 1086, 1053,
1003, 969, 910, 857, 789 (m), 748 (s), 686, 672, 576 (m) cm−1. GC−MS
(EI, 70 eV): m/z (%): 348 (M +, 72), 317(100), 302(16) 255(27), 231(06),
215(07), 166(08), 101(05). HRMS (EI) calcd. for C22H20O4 [M+]:
348.13561; found: 348.135865.
J = 8.6 Hz, ArH). 13C NMR (75.46 MHz, CDCl3): ␦ = 53.1 (OCH3), 116.1
(CHAr), 116.8 (q, JF,C = 320.2 Hz, CF3), 120.8 (CHAr), 121.4 (q, JF,C
=
321.2 Hz, CF3), 124.7 (CAr), 133.8 (CHAr), 148.6, 151.8 (CAr), 162.7
(C=O). 19F NMR (282 MHz, CDCl3): ␦ = –72.4, –73.1 (2CF3). IR (KBr): ␯˜ =
3117, 3085, 2960 (w), 1733, 1617 (s), 1583 (m), 1481, 1302, 1277 (m),
1241 (s), 1123, 1073, 975 (m), 873, 780, 758 (s), 697, 580, 541 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 432 (M+, 61), 401(61), 363(06), 337(52),
273(77), 207(53), 179(15), 138(10), 107(34), 95(06), 79(22), 69(100),
Published by NRC Research Press

1052
Can. J. Chem. Vol. 91, 2013
Scheme 7. Synthesis of 9a–9e and 10a–10d. Reagents and
conditions: (i) 7 (1.0 equiv.), boronic acids (1.3 equiv.), K3PO4 (1.5 equiv.),
Pd(PPh3)4 (3 mol%), 1,4-dioxane (5 mL per 1 mmol of 7), 110 °C, 4 h;
(ii) 9a–9e (1.0 equiv.), vinylphenyl boronic acids (1.3 equiv.), K3PO4
(1.5 equiv.), Pd(PPh3)4 (3 mol%), 1,4-dioxane (5 mL per 1 mmol of 9),
110 °C, 4 h.
3H, OCH3), 3.87 (s, 3H, OCH3), 3.90 (s, 3H, OCH3), 6.81 (s, 1H, ArH),
6.85 (s, 2H, ArH), 6.90 (d, 1H, J = 8.3 Hz, ArH), 7.07 (d, 1H, J = 6.2 Hz,
ArH), 7.12 (dd, 1H, J = 2.4, 8.6 Hz, ArH), 7.37 (d, 1H, J = 8.0 Hz, ArH),
7.63 (dd, 1H, J = 2.0, 8.0 Hz, ArH), 7.87 (d, 1H, J = 1.9 Hz, ArH).
13C NMR (62.90 MHz, CDCl3): ␦ = 52.1 (OCH3), 55.8 (OCH3), 56.0
(OCH3), 110.2, 111.9, 111.5, 111.7, 119.4, 120.6, 127.7, 129.2, 130.9
(CHAr), 131.5, 132.6, 133.5, 139.7, 140.1, 148.4, 148.6, 149.0, 149.6
(CAr), 169.7 (C=O). IR (KBr): ␯˜ = 2922, 2848 (w), 1724 (s), 1598, 1524,
1488, 1461, 1430, 1321, 1297 (m), 1240, 1215, 1174, 1137, 1090, 1020 (s),
960, 901, 864, 855, 807, 746, 671, 630, 578 (m) cm−1. GC−MS (EI,
70 eV): m/z (%): 408 (M+, 100), 393(05), 333(04), 204(06), 145(05).
HRMS (EI) calcd. for C24H24O6 [M+]: 408.15674; found: 408.157243.
4,4== -Divinyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid methyl
ester (3d)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol),
Pd(PPh3)4 (6 mol%), 4-vinylphenylboronic acid (176 mg, 1.19 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 3d was isolated as a yellow
solid; yield 121 mg (77%), mp 156–158 °C. 1H NMR (300 MHz, CDCl3):
␦ = 3.61 (s, 3H, OCH3), 5.9 (dd, 1H, J = 1.8, 6.2 Hz, CH2vinyl), 5.23 (dd,
1H, J = 1.6, 6.9 Hz, CH2vinyl), 5.70 (dd, 1H, J = 1.9, 7.6 Hz, CH2vinyl), 5.76
(dd, 1H, J = 1.8, 6.9 Hz, CH2vinyl), 6.66 (d, 1H, J = 10.8 Hz, CHvinyl), 6.72
(d, 1H, J = 10.2 Hz, CHvinyl), 7.17 (s, 1H, ArH), 7.35–7.47 (m, 4H, ArH),
7.54 (d, 1H, J = 8.3 Hz, ArH), 7.66–7.72 (m, 4H, ArH), 7.98 (d, 1H, J =
1.8 Hz, ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 52.0 (OCH3), 114.4,
114.6 (2CH2vinyl), 126.0, 126.7, 127.1, 128.2, 128.5, 129.5, 131.1, 136.2,
136.4 (CHAr, CHvinyl), 136.8, 137.1, 138.9, 139.6, 140.3, 140.8, 141.3
(CAr), 169.2 (C=O). IR (KBr): ␯˜ = 3085, 3032, 2947, 2923 (w), 1719 (s),
1626, 1481, 1426, 1309, 1298 (m), 1237, 1139 (s), 1088, 1049, 991, 972,
898 (m), 823 (s), 783, 700, 672, 568 (m) cm−1. GC−MS (EI, 70 eV):
m/z (%): 340 (M+, 100), 309(09), 281(04), 265(12), 162(08), 133(05).
HRMS (EI) calcd. for C24H20O2 [M+]: 340.14578; found: 340.146235.
Table 4. Synthesis of 9a−9e and 10a−10d.
3,3== -Dichloro-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid methyl
ester (3e)
9, 10
R1
R2
R3
R4
% (9)a
% (10)a
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol),
Pd(PPh3)4 (6 mol%), 3-chlorophenylboronic acid (185 mg, 1.19 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 3e was isolated as a colorless
viscous oil; yield 110 mg (67%). 1H NMR (300 MHz, CDCl3): ␦ = 3.61
(s, 3H, OCH3), 7.10–7.14 (m, 1H, ArH), 7.18–7.24 (m, 2H, ArH), 7.26
(s, 1H, ArH), 7.27–7.29 (m, 1H, ArH), 7.31 (d, 1H, J = 6.9 Hz, ArH), 7.42
(t, 1H, J = 1.8 Hz, ArH), 7.44 (t, 1H, J = 1.6 Hz, ArH), 7.52–7.55 (m, 1H,
ArH), 7.63 (dd, 1H, J = 2.0, 8.0 Hz, ArH), 7.96 (d, 1 H, J = 1.95 Hz, ArH).
13C NMR (62.90 MHz, CDCl3): ␦ = 52.0 (OCH3), 125.2, 126.6, 127.2,
127.5, 128.4, 128.4, 129.2, 130.2, 131.2, 133.5, 133.8 (CHAr), 134.9,
135.2, 136.0 139.2, 140.5, 141.3, 142.5 (CAr), 168.3 (C=O). IR (KBr): ␯˜ =
3057, 2947, 2848 (w), 1719 (s), 1594, 1566, 1463, 1435, 1311, 1294 (m),
1235 (s), 1192, 1146, 1092, 1054, 1022, 997, 970, 873 (m), 779, 691 (s),
673, 618, 559 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 356 (M+, 35Cl,
35Cl)(100), 325(71), 290(20), 262(40), 200(04), 160(19), 131(05), 113(21),
75(03). HRMS (EI) calcd. for C20H14Cl2O2 [M+, 35Cl, 35Cl]: 356.03654;
found: 356.036229.
a
b
c
d
e
OMe
H
OMe
OMe
H
H
OMe
H
H
Me
H
OMe
H
OMe
H
OMe
H
H
H
Me
78
72
76
67
60
76
72
64
69
b
—
aYields of isolated products.
bExperiment was not carried out.
4,4== -Di-tert-butyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid methyl
ester (3b)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol),
Pd(PPh3)4 (6 mol%), 4-tert-butylphenylboronic acid (211 mg,
1.19 mmol), and 1,4-dioxane (5 mL/mmol triflate), 3b was isolated
as a colorless crystalline solid; yield 140 mg (75%), mp 148–150 °C.
1H NMR (300 MHz, CDCl3): ␦ = 1.28 (s, 18H, 6CH3), 3.58 (s, 3H, OCH3),
7.15–7.25 (m, 4H, ArH), 7.28–7.42 (m, 4H, ArH), 7.49 (s, 1H, ArH),
7.63 (d, 1H, J = 5.0 Hz, ArH), 7.94 (d, 1H, J = 6.9 Hz, ArH). 13C NMR
(75.46 MHz, CDCl3): ␦ = 31.3 (6CH3), 34.5 (2 CtBu), 51.9 (OCH3), 125.0,
125.8, 126.7, 127.0, 128.2, 129.2, 131.2 (CHAr), 131.7, 132.0, 135.3,
136.8, 137.9, 140.8, 150.8 (CAr), 168.9 (C=O). IR (KBr): ␯˜ = 3031, 2951,
2902 (w), 1727, 1605 (s), 1483 (m), 1461, 1362, 1267 (m), 1234 (s), 1180,
1085, 959 (m), 895, 788, 765 (s), 698, 572, 554 (m) cm−1. GC−MS (EI,
70 eV): m/z (%): 400 (M+, 58), 385(100), 357(02), 297(03), 252(02),
185(14), 157(09), 141(04), 57(06), 41(03). HRMS (EI) calcd. for
C28H32O2 [M+]: 400.23968; found: 400.239581.
[1,1=;4=,1== ]Terphenyl-2=-carboxylic acid methyl ester (3f)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol),
Pd(PPh3)4 (6 mol%), phenylboronic acid (145 mg, 1.19 mmol), and
1,4-dioxane (5 mL/mmol triflate), 3f was isolated as a colorless
1
viscous oil; yield 72 mg (54%). H NMR (300 MHz, CDCl3): ␦ = 3.51
(s, 3H, OCH3), 7.22–7.25 (m, 4H, ArH), 7.26 (s, 1H, ArH), 7.27–7.30
(m, 3H, ArH), 7.46–7.50 (m, 4H, ArH), 7.79 (dd, 1H, J = 1.7, 7.7 Hz,
ArH). 13C NMR (62.89 MHz, CDCl3): ␦ = 51.9 (OCH3), 125.7, 127.3,
127.4, 128.0, 128.1, 128.4, 128.9 (CHAr), 129.3 (CAr), 129.6, 130.6
(CHAr), 139.8, 141.5, 143.3, 144.1 (CAr), 168.8 (C=O). IR (KBr): ␯˜ = 3052,
2927, 2842 (w), 1716 (s), 1591, 1567, 1467, 1439, 1313, 1295 (m), 1231 (s),
1191, 1143, 1091, 1051, 1027, 993, 970, 873 (m), 779, 691 (s), 673, 618,
559 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 288 (M+, 75), 257(100),
228(34), 202(08), 152(05), 128(04), 113(08). HRMS (EI) calcd. for
C20H16O2 [M+]: 288.11448; found: 288.114296.
3,4,3== ,4== -Tetramethoxy-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid
methyl ester (3c)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol),
Pd(PPh3)4 (6 mol%), 3,4-dimethoxyphenylboronic acid (216 mg,
1.19 mmol), and 1,4-dioxane (5 mL/mmol triflate), 3c was isolated
1
as a reddish solid; yield 106 mg (56%), mp 140–142 °C. H NMR
(300 MHz, CDCl3): ␦ = 3.62 (s, 3H, OCH3), 3.82 (s, 3H, OCH3), 3.86 (s,
Published by NRC Research Press

Nawaz et al.
1053
Fig. 4. Ortep plot of 9c.
as a yellow solid; yield 140 mg (72%), mp 148–150 °C. 1H NMR
(300 MHz, CDCl3): ␦ = 3.69 (s, 3H, OCH3), 3.74 (s, 3H, OCH3), 3.90 (s,
3H, OCH3), 6.81 (s, 1H, ArH), 6.83–6.86 (m, 2H, ArH), 7.24 (d, 1H, J =
8.5 Hz, ArH), 7.71 (dd, 1H, J = 2.4, 8.5 Hz, ArH), 8.14 (d, 1H, J = 2.3 Hz,
ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 52.6 (OCH3), 55.8 (OCH3),
56.1 (OCH3), 112.6, 114.3, 116.4 (CHAr), 120.0 (q, JF,C = 320.0 Hz, CF3),
122.2 (CHAr), 123.8, 128.3 (CAr), 133.5, 135.1 (CHAr), 138.9, 147.0, 150.5,
153.8 (CAr), 164.2 (C=O). 19F NMR (282 MHz, CDCl3): ␦ = –73.5 (CF).
IR (KBr): ␯˜ = 3001, 2953, 2837 (w), 1728 (m), 1681, 1606, 1582 (w),
1504, 1464 (m), 1422 (s), 1307, 1248, 1171, 1074, 1051, 973, 905, 839,
804, 760, 693, 647, 572 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 420 (M+,
100), 389(08), 287(46), 257(19), 227(14), 185(12), 162(06), 113(06),
69(08). HRMS (EI) calcd. for C17H15F3O7S [M+]: 420.04851; found:
420.049146.
Scheme 8. Possible explanation for the site-selective formation of
products 9a–9e.
Methyl 4=-methyl-4-(trifluoromethylsulfonyloxy)biphenyl-
3-carboxylate (4c)
Methyl 3=,5=-dimethyl-4-(trifluoromethylsulfonyloxy)biphenyl-
3-carboxylate (4a)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (146 mg, 0.69 mmol),
Pd(PPh3)4 (3 mol%), 4-methylphenylboronic acid (80 mg, 0.59 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 4c was isolated as a colorless
solid; yield 112 mg (64%), mp 152–154 °C. 1H NMR (300 MHz, CDCl3):
␦ = 2.26 (s, 3H, CH3), 3.61 (s, 3H, OMe), 6.45 (dd, 2H, J = 8.3, 18.5 Hz,
ArH), 7.24 (d, 1 H, J = 7.5 Hz, ArH), 7.27–7.31 (m, 1H, ArH), 7.47 (s, 1H,
ArH), 7.52 (dd, 1H, J = 1.4, 8.1 Hz, ArH), 8.00 (d, 1H, J = 8.1 Hz, ArH).
13C NMR (62.89 MHz, CDCl3): ␦ = 21.2 (CH3), 52.3 (OCH3), 111.7
(CHAr), 120.0 (q, JF,C = 320.0 Hz, CF3), 123.0 (CAr), 124.1, 129.3, 130.7
(CHAr), 131.0 (CAr), 132.5 (CHAr), 145.2, 147.9, 156.3 (CAr), 167.1 (C=O).
19F NMR (282 MHz, CDCl3): ␦ = –73.4 (CF). IR (KBr): ␯˜ = 3012, 2952,
2926 (w), 1714, 1602 (s), 1493 (m), 1469, 1328, 1271 (m), 1243 (s), 1137,
1099, 978 (m), 863, 785, 751 (s), 699, 577, 540 (m) cm−1. GC−MS (EI,
70 eV): m/z (%): 374 (M+, 66), 361(07), 257(100), 223(12), 148(15),
113(03), 69(08).
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (146 mg, 0.69 mmol),
Pd(PPh3)4 (3 mol%), 3,5-dimethylphenylboronic acid (88 mg,
0.59 mmol), and 1,4-dioxane (5 mL/mmol triflate), 4a was isolated
1
as a colorless solid; yield 150 mg (83%), mp 160–162 °C. H NMR
(300 MHz, CDCl3): ␦ = 2.27 (s, 6H, 2CH3), 3.61 (s, 3H, OCH3), 6.82 (s,
1H, ArH), 6.95 (s, 1H, ArH), 7.17 (s, 1H, ArH), 7.35 (d, 1H, J = 3.4 Hz,
ArH), 7.36 (s, 1H, ArH), 7.63 (d, 1H, J = 3.4 Hz, ArH). 13C NMR
(62.89 MHz, CDCl3): ␦ = 21.2 (2CH3), 52.3 (OCH3), 120.0 (q, JF,C
=
320 Hz, CF3), 122.4, 123.8, 126.1, 129.6, 132.6 (CHAr), 137.7, 139.2,
141.1, 143.0, 148.0 (CAr), 167.1 (C=O). 19F NMR (282 MHz, CDCl3): ␦ =
–73.4 (CF). IR (KBr): ␯˜ = 3018, 2951, 2920 (w), 1723, 1601 (s), 1489 (m),
1467, 1328, 1271 (m), 1243 (s), 1137, 1099, 978 (m), 863, 785, 751 (s),
699, 577, 540 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 388 (M +, 66),
357(07), 255(100), 227(12), 152(15), 115(03), 69(08). HRMS (EI) calcd.
for C17H15F3O5S [M +]: 388.05868; found: 388.058373.
Methyl 2=,5=-dimethoxy-4-(trifluoromethylsulfonyloxy)biphenyl-
3-carboxylate (4b)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (146 mg, 0.69 mmol),
Pd(PPh3)4 (3 mol%), 2,5-dimethoxyphenylboronic acid (107 mg,
0.59 mmol), and 1,4-dioxane (5 mL/mmol triflate), 4b was isolated
Methyl 3=,4=-dimethoxy-4-(trifluoromethylsulfonyloxy)biphenyl-
3-carboxylate (4d)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (146 mg, 0.69 mmol),
Pd(PPh3)4 (3 mol%), 3,4-dimethoxyphenylboronic acid (107 mg,
0.59 mmol), and 1,4-dioxane (5 mL/mmol triflate), 4d was isolated
Published by NRC Research Press

1054
Can. J. Chem. Vol. 91, 2013
1
as a reddish solid; yield 131 mg (67%), mp 166–168 °C. H NMR
(300 MHz, CDCl3): ␦ = 3.59 (s, 3H, OCH3), 3.64 (s, 3H, OCH3), 3.80 (s,
3H, OCH3), 6.79 (s, 1H, ArH), 6.84–6.87 (m, 2H, ArH), 7.26 (d, 1H, J =
8.2 Hz, ArH), 7.671 (dd, 1H, J = 2.6, 8.2 Hz, ArH), 8.16 (d, 1H, J = 2.3 Hz,
ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 52.4 (OCH3), 55.2 (OCH3),
56.4 (OCH3), 112.3, 114.6, 116.8 (CHAr), 121.0 (q, JF,C = 320.2 Hz, CF3),
122.4 (CHAr), 123.4, 127.2 (CAr), 133.4, 136.1 (CHAr), 137.9, 146.0, 150.1,
152.4 (CAr), 168.2 (C=O). 19F NMR (282 MHz, CDCl3): ␦ = –73.2 (CF). IR
(KBr): ␯˜ = 2999, 2952, 2849 (w), 1726 (m), 1603, 1588 (w), 1520, 1463
(m), 1421 (s), 1325, 1289, 1171, 1080, 1052, 974, 905, 883, 827, 806,
755, 684, 664, 573 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 420 (M+, 51),
389(04), 287(100), 257(15), 229(17), 213(04), 185(05), 157(04), 114(05),
69(06).
3== ,5== -Dimethyl-4-vinyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid
methyl ester (5a)
Starting with 4a (100 mg, 0.25 mmol), K3PO4 (78 mg, 0.37 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (47 mg, 0.32 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 5a was isolated as colorless
solid; yield 64 mg (72%), mp 144–146 °C. 1H NMR (300 MHz, CDCl3):
␦ = 2.28 (s, 6H, 2CH3), 3.60 (s, 3H, OCH3), 5.20 (dd, 1H, J = 7.5, 3.2 Hz,
CH2vinyl), 5.24 (dd, 1H, J = 7.3, 4.2 Hz, CH2vinyl), 5.71 (dd, 1H, J = 6.48,
3.2 Hz, CHvinyl), 6.65 (d, 2H, J = 4.0 Hz, ArH), 6.90 (s, 1H, ArH), 7.18 (s,
1H, ArH), 7.45 (s, 2H, ArH), 7.65 (d, 2H, J = 2.4 Hz, ArH), 7.68 (d, 1H,
J = 2.4 Hz, ArH), 7.94 (d, 1H, J = 2.4 Hz, ArH). 13C NMR (75.46 MHz,
CDCl3): ␦ = 21.3 (2CH3), 52.0 (OCH3), 113.9 (CH2vinyl), 126.1, 126.7,
127.1, 127.9, 128.4, 129.3, 131.2, 130.1 (CHAr, CHvinyl), 132.1, 133.6,
136.4, 137.0, 138.4, 139.4, 140.7 (CAr), 169.4 (C=O). IR (KBr): ␯˜ = 3029,
2947, 2900 (w), 1723, 1604 (s), 1479 (m), 1459, 1361, 1264 (m), 1231 (s),
1179, 1081, 957 (m), 893, 785, 762 (s), 693, 571, 551 (m) cm−1. GC−MS
(EI, 70 eV): m/z (%): 342 (M+, 100), 326(01), 311(22), 296(06), 267(08),
253(07), 202(01), 163(10), 133(05).
Methyl 4=-bromo-4-(trifluoromethylsulfonyloxy)biphenyl-
3-carboxylate (4e)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol),
Pd(PPh3)4 (3 mol%), 4-bromophenylboronic acid (118 mg, 0.59 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 4e was isolated as a colorless
viscous oil; yield 129 mg (63%). 1H NMR (300 MHz, CDCl3): ␦ = 3.92
(s, 3H, OCH3), 7.33–7.41 (m, 2H, ArH), 7.44 (d, 1H, J = 6.2 Hz, ArH),
7.48–7.52 (m, 2H, ArH), 7.59 (s, 1H, ArH), 7.93 (d, 1H, J = 6.2 Hz, ArH).
2== ,5== -Dimethoxy-4-vinyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid
methyl ester (5b)
Starting with 4b (100 mg, 0.23 mmol), K3PO4 (72 mg, 0.34 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (42 mg, 0.29 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 5b was isolated as colorless
solid; yield 70 mg (78%), mp 156–158 °C. 1H NMR (300 MHz, CDCl3):
␦ = 3.59 (s, 3H, OCH3), 3.71 (s, 3H, OCH3), 3.74 (s, 3H, OCH3), 5.52
(dd, 1H, J = 1.5, 7.2 Hz, CH2vinyl), 5.62 (dd, 1H, J = 2.3, 6.2 Hz, CH2vinyl),
5.72 (dd, 1H, J = 1.8, 6.2 Hz, CHvinyl), 6.82–6.88 (m, 2H, ArH), 7.24 (d,
1H, J = 8.2 Hz, ArH), 7.30–7.40 (m, 4H, ArH), 7.60–7.66 (m, 2H, ArH),
7.92 (d, 1H, J = 1.8 Hz, ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 51.9
(OCH3), 55.8 (OCH3), 56.3 (OCH3), 113.8 (CH2vinyl), 116.1, 116.5, 125.9,
128.0, 128.5, 130.4, 132.3, 133.0, 134.9 (CHAr, CHvinyl), 135.0, 135.1,
136.4, 136.5, 137.4, 140.6, 150.8, 153.8 (CAr), 169.1 (C=O). IR (KBr): ␯˜ =
2922, 2850 (w), 1715, 1604, 1462, 1391, 1275 (m), 1227 (s), 1176, 1118,
1041, 1024, 998, 907, 877, 800, 788, 722, 639, 540 (m) cm−1. GC−MS
(EI, 70 eV): m/z (%): 374 (M+, 100), 327(07), 300(19), 285(07), 257(07),
228(04), 202(06), 150(06), 101(04), 59(06). HRMS (EI) calcd. for
C24H22O4 [M+]: 374.15126; found: 374.150994.
13C NMR (62.90 MHz, CDCl3): ␦ = 52.7 (OCH3), 120.0 (q, JF,C
=
320.0 Hz, CF3), 125.0, 125.6, 127.5, 128.6, 132.0 (CHAr), 133.0, 134.9,
136.0, 147.1, 147.8 (CAr), 168.3 (C=O). IR (KBr): ␯˜ = 3119, 2959, 2872
(w), 1725 (s), 1613, 1586, 1479, 1461 (m), 1426 (s), 1300, 1278, 1244 (m),
1127 (s), 1076, 1001, 975, 921, 842, 782, 697, 665, 542 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 438 (M+, 79Br)(60), 383(71), 353(20),
307(100), 215(43), 170(08), 139(16), 69(05).
Methyl 2=,4=-dimethoxy-4-(trifluoromethylsulfonyloxy)biphenyl-
3-carboxylate (4f)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (146 mg, 0.69 mmol),
Pd(PPh3)4 (3 mol%), 2,4-dimethoxyphenylboronic acid (107 mg,
0.59 mmol), and 1,4-dioxane (5 mL/mmol triflate), 4f was isolated
1
as a colorless solid; yield 142 mg (73%), mp 168–170 °C. H NMR
(300 MHz, CDCl3): ␦ = 3.73 (s, 3H, OCH3), 3.78 (s, 3H, OCH3), 3.89 (s,
3H, OCH3), 6.48–6.52 (m, 2H, ArH), 7.15–7.22 (m, 2H, ArH), 7.67 (dd,
1H, J = 2.4, 8.5 Hz, ArH), 8.1 (d, 1H, J = 2.3 Hz, ArH). 13C NMR
(62.90 MHz, CDCl3): ␦ = 52.5 (OCH3), 55.4 (OCH3), 55.5 (OCH3), 99.0,
104.9 (CHAr), 120.0 (q, JF,C = 320.0 Hz, CF3), 122.1 (CHAr), 123.7 (CAr),
131.1, 133.4 (CHAr), 134.9 (CAr), 135.0 (CHAr), 139.0, 146.6, 157.4, 161.2
(CAr), 168.4 (C=O). 19F NMR (282 MHz, CDCl3): ␦ = –73.5 (CF). IR (KBr):
␯˜ = 2921, 2871 (w), 1727 (m), 1677, 1609, 1578 (w), 1512, 1463 (m), 1422
(s), 1305, 1281, 1160, 1074, 1053, 967, 905, 890, 835, 797, 761, 686,
638, 571 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 420 (M+, 38), 389(05),
287(100), 257(11), 229(04), 185(10), 128(06), 69(08). HRMS (EI) calcd.
for C17H15F3O7S [M+]: 420.04851; found: 420.049231.
4=-Methyl 4-vinyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid methyl
ester (5c)
Starting with 4c (100 mg, 0.26 mmol), K3PO4 (82 mg, 0.39 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (48 mg, 0.33 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 5c was isolated as colorless
solid; yield 60 mg (68%), mp 132–134 °C. 1H NMR (300 MHz, CDCl3):
␦ = 2.31 (s, 3H, CH3), 3.60 (s, 3H, OCH3), 5.19 (dd, 1H, J = 2.4, 9.4 Hz,
CH2vinyl), 5.71 (dd, 1 H, J = 3.8, 8.6 Hz, CH2vinyl), 6.67 (dd, 1H, J = 10.8,
17.6 Hz, CHvinyl), 7.15 (d, 2H, J = 6.2 Hz, ArH), 7.24 (s, 1H, ArH),
7.35–7.40 (m, 3H, ArH), 7.54–7.66 (m, 4H, ArH), 7.95 (d, 1H, J =
1.9 Hz, ArH). 13C NMR (75.47 MHz, CDCl3): ␦ = 21.2 (CH3), 52.0
(OCH3), 113.9 (CH2vinyl), 126.0, 126.8, 127.1, 128.1, 128.5, 129.5, 131.1,
136.2 (CHAr, CHvinyl), 136.3, 136.5, 137.1, 137.9, 139.0, 139.4, 140.8
(CAr), 169.3 (C=O). IR (KBr): ␯˜ = 3052, 2946, 2920 (w), 1722, 1604 (s),
1482 (m), 1434, 1308, 1254 (m), 1234 (s), 1164, 1072, 971 (m), 854, 783,
750 (s), 694, 567 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 328 (M+, 100),
297(24), 282(05), 253(11), 157(11), 126(06). HRMS (EI) calcd. for
C23H20O2 [M+]: 328.14578; found: 328.146151.
Methyl 4=-chloro-4-(trifluoromethylsulfonyloxy)biphenyl-
3-carboxylate (4g)
Starting with 2 (200 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol),
Pd(PPh3)4 (3 mol%), 4-chlorophenylboronic acid (92 mg, 0.59 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 4g was isolated as a yellow
solid; yield 107 mg (59%), mp 140–142 °C. 1H NMR (300 MHz, CDCl3):
␦ = 3.91 (s, 3H, OCH3), 7.12–7.15 (m, 1H, ArH), 7.27–7.33 (m, 1H, ArH),
7.36 (s, 1H, ArH), 7.47 (dd, 1H, J = 3.1, 9.0 Hz, ArH), 7.61–7.71 (m, 1H,
ArH), 7.92 (d, 1H, J = 3.0 Hz, ArH), 8.16 (d, 1H, J = 2.4 Hz, ArH).
3== ,4== -Dimethoxy-4-vinyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid
methyl ester (5d)
13C NMR (62.90 MHz, CDCl3): ␦ = 53.1 (OCH3), 120.0 (q, JF,C
=
320.0 Hz, CF3), 124.1, 125.6, 127.0, 128.3, 129.2 (CHAr), 133.0, 134.9,
136.0, 147.1, 147.8 (CAr), 168.4 (C=O). IR (KBr): ␯˜ = 3119, 2959, 2872
(w), 1725 (s), 1613, 1586, 1479, 1461 (m), 1426 (s), 1300, 1278, 1244 (m),
1127 (s), 1076, 1001, 975, 921, 842, 782, 697, 665, 542 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 394 (M+, 35Cl, 66), 363(11), 261(100),
233(20), 198(13), 175(06), 155(05)), 139(35), 113(05), 69(16), 63(05).
HRMS (EI) calcd. for C15H10ClF3O5S [M+, 35Cl]: 393.98841; found:
393.987890.
Starting with 4d (100 mg, 0.23 mmol), K3PO4 (72 mg,
0.34 mmol), Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (42 mg,
0.29 mmol), and 1,4-dioxane (5 mL/mmol triflate), 5d was isolated
as yellow solid; yield 57 mg (64%), mp 138–140 °C. 1H NMR
(250 MHz, CDCl3): ␦ = 3.58 (s, 3H, OCH3), 3.69 (s, 3H, OCH3), 3.72 (s,
3H, OCH3), 5.50 (dd, 1H, J = 2.6, 6.4 Hz, CH2vinyl), 5.60 (dd, 1H, J = 2.4,
7.2 Hz, CH2vinyl), 5.70 (dd, 1H, J = 1.4, 7.8 Hz, CHvinyl), 6.80–6.86 (m,
2H, ArH), 7.22 (d, 1H, J = 6.2 Hz, ArH), 7.28–7.38 (m, 4H, ArH),
Published by NRC Research Press

Nawaz et al.
1055
7.58–7.64 (m, 2H, ArH), 7.88 (d, 1H, J = 4.6 Hz, ArH). 13C NMR
(62.90 MHz, CDCl3): ␦ = 52.1 (OCH3), 53.3 (OCH3), 55.8 (OCH3), 111.6,
113.4 (CHAr), 114.6 (CH2vinyl), 126.7, 127.1, 128.0, 130.5, 134.6, 135.0,
135.1 (CHAr, CHvinyl), 136.0, 136.1, 137.4, 138.5, 139.4, 140.6, 149.1,
151.4 (CAr), 168.1 (C=O). IR (KBr): ␯˜ = 3050, 2922, 2851 (w), 1721, 1602
(s), 1461, 1433, 1390, 1240, 1215, 1171, 1093, 967, 888, 788, 722 (s),
665, 539 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 374 (M+, 100), 325(03),
301(16), 281(05), 253(04), 226(06), 207(05), 153(08), 121(05), 57(10).
HRMS (EI) calcd. for C24H22O4 [M+]: 374.15126; found: 374.151338.
4,4== -Dichloro-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid methyl
ester (8a)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
2.07 mmol), Pd(PPh3)4 (6 mol%), 4-chlorophenylboronic acid
(280 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8a was
1
isolated as a yellow oil; yield 180 mg (72%). H NMR (300 MHz,
CDCl3): ␦ = 3.56 (s, 3H, OCH3), 7.06–7.09 (m, 1H, ArH), 7.19–7.23 (m,
4H, ArH), 7.32–7.34 (m, 2H, ArH), 7.37 (d, 1H, J = 3.2 Hz, ArH), 7.44
(d, 1H, J = 1.9 Hz, ArH), 7.45–7.47 (m, 1H, ArH), 7.82 (d, 1H, J = 8.1 Hz,
ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 52.2 (OCH3), 125.4, 126.7,
127.5, 128.2, 129.3 (CHAr), 129.6 (CAr), 130.2, 130.9 (CHAr), 133.9,
134.9, 141.3, 142.0, 142.8, 143.0 (CAr), 168.0 (C=O). IR (KBr): ␯˜ = 3053,
2945, 2847 (w), 1716 (s), 1593, 1567, 1461, 1432, 1317, 1291 (m), 1231
(s), 1193, 1147, 1091, 1053, 1021, 996, 971, 875 (m), 773, 693 (s), 671,
617, 541 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 356 (M+, 35Cl, 35Cl)(73),
325(100), 290(11), 262(38), 226(36), 200(04), 161(22), 131(05), 113(19).
HRMS (EI) calcd. for C20H14O2Cl2 [M+, 35Cl, 35Cl]: 356.03654; found:
356.036629.
4== -Bromo-4-vinyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid methyl
ester (5e)
Starting with 4e (100 mg, 0.22 mmol), K3PO4 (69 mg, 0.33 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (41 mg, 0.28 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 5e was isolated as a colorless
viscous oil; yield 56 mg (62%). 1H NMR (250 MHz, CDCl3): ␦ = 3.61 (s,
3H, OCH3), 5.22 (dd, 1H, J = 2.4, 8.4 Hz, CH2vinyl), 5.70 (dd, 1H, J = 2.8,
7.6 Hz, CH2vinyl), 5.77 (dd, 1H, J = 2.4, 8.6 Hz, CHvinyl), 7.24 (d, 2H, J =
6.2 Hz, ArH), 7.36–7.42 (m, 4H, ArH), 7.45 (s, 1H, ArH), 7.56 (d, 2H,
J = 6.8 Hz, ArH), 7.66–7.70 (dd, 1H, J = 2.4, 9.6 Hz, ArH), 7.98 (d, 1H,
J = 2.3 Hz, ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 52.0 (OCH3), 113.9
2,5,2== ,5== -Tetramethoxy-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid
methyl ester (8b)
(CH2vinyl), 126.0, 126.7, 127.1, 128.2, 128.5, 129.5, 131.1, 136.2 (CHAr
,
Starting with 7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
CHvinyl), 136.4, 136.6, 137.1, 138.9, 139.6, 140.3, 140.8 (CAr), 169.1
(C=O). IR (KBr): ␯˜ = 3084, 2946, 2921 (w), 1716 (s), 1604 (m), 1481 (m),
1455, 1389, 1256 (m), 1235 (s), 1185, 1090, 973 (m), 857, 781, 743 (s),
694, 653, 539 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 392 (M+, 79Br)
(100) 319(03), 279(10), 231(05), 201(04), 173(06), 126(11), 107(08),
77(05), 57(10).
2.07 mmol), Pd(PPh3)4 (6 mol%), 2,5-dimethoxyphenylboronic acid
(327 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8b was
isolated as colorless solid; yield 222 mg (78%), mp 148–150 °C.
1H NMR (300 MHz, CDCl3): ␦ = 3.59 (s, 6H, 2OCH3), 3.66 (s, 3H,
OCH3), 3.70 (s, 3H, OCH3), 3.71 (s, 3H, OCH3), 6.74 (d, 1H, J = 2.3 Hz,
ArH), 6.76 (s, 1H, ArH), 6.78 (d, 1H, J = 2.9 Hz, ArH), 6.82–6.83 (m,
2H, ArH), 6.85 (d, 1H, J = 2.8 Hz, ArH), 7.43 (d, 1H, J = 1.6 Hz, ArH),
7.50 (dd, 1H, J = 1.8, 8.0 Hz, ArH), 7.82 (d, 1H, J = 7.9 Hz, ArH).
13C NMR (62.90 MHz, CDCl3): ␦ = 51.6 (OCH3), 55.7 (OCH3), 55.8
(OCH3), 56.3 (OCH3), 111.1, 112.7, 113.0, 113.8, 116.1, 116.5, 128.3, 129.1
(CHAr), 130.0, 130.3, 131.5 (CAr), 132.2 (CHAr), 138.2, 141.7, 150.4,
150.8, 153.6, 153.8 (CAr), 168.4 (C=O). IR (KBr): ␯˜ = 2928, 2831 (w),
1721, 1601, 1585, 1498, 1461, 1378,1250 (m), 1213 (s), 1175, 1092, 1040,
964, 904, 860, 821, 789 (m), 723 (s), 694, 605, 539 (m) cm−1; GC−MS
(EI, 70 eV): m/z (%): 408 (M+, 100), 393(05), 377(71), 346(20), 204(08).
HRMS (EI) calcd. for C24H24O6 [M+]: 408.15674; found: 408.156969.
2== ,4== -Dimethoxy-4-vinyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid
methyl ester (5f)
Starting with 4f (100 mg, 0.23 mmol), K3PO4 (72 mg, 0.34 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (42 mg, 0.29 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 5f was isolated as a colorless
viscous oil; yield 67 mg (67%). 1H NMR (300 MHz, CDCl3): ␦ = 3.59 (s,
3H, OCH3), 3.75 (s, 3H, OCH3), 3.79 (s, 3H, OCH3), 5.20 (dd, 1H, J =
2.4, 10.8 Hz, CH2vinyl), 5.72 (dd, 1H, J = 2.4, 9.6 Hz, CH2vinyl), 6.69 (dd,
1H, J = 2.4, 10.6 Hz, CHvinyl), 7.21–7.24 (m, 3H, ArH), 7.26 (s, 1H, ArH),
7.30–7.39 (m, 4H, ArH), 7.60 (dd, 1H, J = 1.9, 7.9 Hz, ArH), 7.88 (d, 1H,
J = 1.6 Hz, ArH). 13C NMR (75.47 MHz, CDCl3): ␦ = 51.9 (OCH3), 55.4
(OCH3), 55.6 (OCH3), 99.0, 104.8 (CHAr), 113.8 (CH2vinyl), 125.9, 128.6,
130.3 (CHAr), 130.4 (CAr), 130.7, 131.2, 132.0, 136.5 (CHAr, CHvinyl),
136.6, 137.5, 138.9, 139.6, 140.0, 141.6, 142.0 (CAr), 169.1 (C=O). IR
(KBr): ␯˜ = 3052, 2921, 2848 (w), 1716, 1608 (s), 1463, 1435, 1391 (m),
1242, 1217 (s), 1173, 1095, 965, 887, 783, 721, 663, 537(m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 374 (M+, 100), 343(04), 285(06), 257(05),
179(06), 120(04). HRMS (EI) calcd. for C24H22O4 [M+]: 374.15126;
found: 374.151040.
[1,1=;3=,1== ]Terphenyl-4=-carboxylic acid methyl ester (8c)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
2.07 mmol), Pd(PPh3)4 (6 mol%), phenylboronic acid (219 mg,
1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8c was isolated
1
as a reddish solid; yield 130 mg (65%), mp 150–152 °C. H NMR
(300 MHz, CDCl3): ␦ = 3.51 (s, 3H, OCH3), 7.22–7.25 (m, 4H, ArH),
7.26 (s, 1H, ArH), 7.27–7.30 (m, 3H, ArH), 7.46–7.50 (m, 4H, ArH),
7.79 (dd, 1H, J = 1.7, 7.7 Hz, ArH). 13C NMR (62.89 MHz, CDCl3): ␦ =
51.9 (OCH3), 125.7, 127.3, 127.4, 128.0, 128.1, 128.4, 128.9 (CHAr),
129.3 (CAr), 129.6, 130.6 (CHAr), 139.8, 141.5, 143.3, 144.1 (CAr), 168.8
(C=O). IR (KBr): ␯˜ = 3052, 2927, 2842 (w), 1716 (s), 1591, 1567, 1467,
1439, 1313, 1295 (m), 1231 (s), 1191, 1143, 1091, 1051, 1027, 993, 970,
873 (m), 779, 691 (s), 673, 618, 559 (m) cm−1. GC−MS (EI, 70 eV): m/z
(%): 288 (M+, 75), 257(100), 228(34), 202(08), 152(05), 128(04), 113(08).
HRMS (EI) calcd. for C20H16O2 [M+]: 288.11448; found: 288.114296.
4== -Chloro-4-vinyl-[1,1=;4=,1== ]terphenyl-2=-carboxylic acid methyl
ester (5g)
Starting with 4g (100 mg, 0.25 mmol), K3PO4 (78 mg, 0.37 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (47 mg, 0.32 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 5g was isolated as a reddish
solid; yield 64 mg (72%), mp 152–154 °C. 1H NMR (300 MHz, CDCl3):
␦ = 3.61 (s, 3H, OCH3), 5.22 (dd, 1H, J = 4.6, 10.8 Hz, CH2vinyl), 5.72 (dd,
1H, J = 4.3, 17.6 Hz, CH2vinyl), 6.69 (dd, 1H, J = 10.8, 17.5 Hz, CHvinyl),
7.21–7.25 (m, 2H, ArH), 7.35–7.41 (m, 2H, ArH), 7.44 (s, 1H, ArH),
7.54 (d, 2H, J = 8.2 Hz, ArH), 7.58–7.62 (m, 2 H, ArH), 7.68 (dd, 1H, J =
1.9, 8.6 Hz, ArH), 7.98 (d, 1H, J = 1.9 Hz, ArH). 13C NMR (75.47 MHz,
CDCl3): ␦ = 52.1 (OCH3), 114.0 (CH2vinyl), 126.0, 126.8, 127.1, 128.2,
129.5, 130.0, 131.1, 136.2 (CHAr, CHvinyl), 136.5, 137.1, 138.9, 139.7,
140.3, 140.8, 141.0 (CAr), 169.1 (C=O). IR (KBr): ␯˜ = 3054, 2922, 2852
(w), 1715, 1604 (m), 1501, 1462, 1391, 1306, 1275, 1241 (m), 1227 (s),
1176, 11181092, 1024, 998, 907, 877, 800, 788, 722, 639, 540 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 348 [M+], 35Cl, 100), 317(13), 282(31),
254(18), 226(07), 156(16), 126(10). HRMS (EI) calcd. for C22H17ClO2
[M+]: 348.09116; found: 348.091376.
4,4== -Di-tert-butyl-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid methyl
ester (8d)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
2.07 mmol), Pd(PPh3)4 (6 mol%), 4-tert-butylphenylboronic acid
(320 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8d was
isolated as a colorless solid; yield 220 mg (79%), mp 168–170 °C.
1H NMR (300 MHz, CDCl3): ␦ = 1.48 (s, 9H, 3CH3), 1.50 (s, 9H, 3CH3),
3.78 (s, 3H, OCH3), 7.44 (d, 1H, J = 8.3 Hz, ArH), 7.55–7.60 (m, 4H,
ArH), 7.68 (s, 1H, ArH), 7.70–7.75 (m, 4H, ArH), 8.00 (d, 1H, J = 8.1 Hz,
ArH). 13C NMR (75.46 MHz, CDCl3): ␦ = 31.4 (3CH3), 31.5 (3CH3), 34.5
(2 CtBu), 51.9 (OCH3), 125.0, 125.4, 125.9, 127.0, 128.2, 129.5, 130.6
(CHAr), 133.9, 137.0, 138.5, 143.2, 143.9, 150.1, 151.2 (CAr), 169.0 (C=O).
IR (KBr): ␯˜ = 3031, 2951, 2902 (w), 1727, 1605 (s), 1483 (m), 1461, 1362,
Published by NRC Research Press

1056
Can. J. Chem. Vol. 91, 2013
1267 (m), 1234 (s), 1180, 1085, 959 (m), 895, 788, 765 (s), 698, 572, 554
(m) cm−1. GC−MS (EI, 70 eV): m/z (%): 400 (M+, 36), 385(100), 357(05),
313(03), 252(04), 185(11), 157(07), 141(04), 57(04). HRMS (EI) calcd. for
4,4== -Difluoro-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid methyl
ester (8h)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
C
28H32O2 [M+]: 400.23968; found: 400.239954.
2.07 mmol), Pd(PPh3)4 (6 mol%), 4-flourophenylboronic acid
(252 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8h was
isolated as a colorless solid; yield 174 mg (77%), mp 156–158 °C.
1H NMR (300 MHz, CDCl3): ␦ = 3.58 (s, 3H, OCH3), 6.97–7.06 (m, 4H,
ArH), 7.19–7.23 (m, 2H, ArH), 7.40 (d, 1H, J = 1.8 Hz, ArH), 7.46–7.51
(m, 3H, ArH), 7.84 (d, 1H, J = 8.1 Hz, ArH). 13C NMR (62.90 MHz,
3,3== -Dihydroxy-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid methyl
ester (8e)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
2.07 mmol), Pd(PPh3)4 (6 mol%), 3-hydroxyphenylboronic acid
(248 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8e was
isolated as a colorless viscous oil; yield 138 mg (62%). 1H NMR
(300 MHz, CDCl3): ␦ = 3.56 (s, 3H, OCH3), 6.02 (s, 2H, 2OH), 6.68 (s,
1H, ArH), 6.70.6.75 (m, 3H, ArH), 6.90 (t, 1H, J = 1.8 Hz, ArH), 6.98 (d,
1H, J = 7.9 Hz, ArH), 7.08 (d, 1H, J = 7.5 Hz, ArH), 7.11 (m, 1H, ArH),
7.34 (s, 1H, ArH), 7.37 (d, 1H, J = 1.7 Hz, ArH), 7.68 (d, 1H, J = 7.9 Hz,
ArH). 13C NMR (75.47 MHz, CDCl3): ␦ = 52.3 (OCH3), 114.2, 114.5,
115.2, 115.4, 119.6, 120.8, 125.7, 129.2, 129.3, 130.1, 130.3 (CHAr),
139.0, 141.2, 142.5, 142.6, 143.7, 155.4, 156.0 (CAr), 169.9 (C=O). IR
(KBr): ␯˜ = 3058, 2941, 2927 (w), 1721, 1607 (s), 1481 (m), 1462, 1357,
1243 (m), 1221 (s), 1179, 1081, 957 (m), 891, 787, 761 (s), 697, 571, 541
(m) cm−1. GC−MS (EI, 70 eV): m/z (%): 320 (M+, 100), 289(75), 260(13),
231(08), 215(09), 202(08), 189(05), 152(06), 101(05). HRMS (EI) calcd.
for C20H16O4 [M+]: 320.10431; found: 320.104231.
CDCl3): ␦ = 51.9 (OCH3), 114.9 (d, 2JC,F = 21.5 Hz, CHAr), 115.8 (d, 2JC,F
=
21.5 Hz, CHAr), 125.7 (CHAr), 128.9 (d, 3JC,F = 8.2 Hz, CHAr), 129.1 (CAr),
3
129.4 (CHAr), 129.9 (d, JC,F = 8.1 Hz, CHAr), 130.8 (CHAr), 135.7 (d,
4JC,F = 3.2 Hz, CF), 137.2 (d, 4JC,F = 3.3 Hz, CF), 142.4 (CAr), 143.1 (CAr),
1
1
162.3 (d, JC,F = 246.4 Hz, CF), 162.9 (d, JC,F = 247.9 Hz, CF), 168.3
(C=O). IR (KBr): ␯˜ = 3043, 2927, 2843 (w), 1721 (s), 1617, 1603, 1573,
1497, 1431, 1389, 1277, 1221, 1189, 1117, 1051, 1011, 957, 923, 839 (m),
817, 757 (s), 689, 638, 543 (m) cm−1; GC−MS (EI, 70 eV): m/z (%): 324
(M+, 81), 293(100), 264(20), 244(25), 170(04), 122(08). HRMS (EI) calcd.
for C20H14F2O2 [M+]: 324.09564; found: 324.095444.
3,3== -Bis-trifluoromethyl-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid
methyl ester (8i)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
2.07 mmol), Pd(PPh3)4 (6 mol%), 3-trifluoromethylphenylboronic
acid (342 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8i
was isolated as a colorless viscous oil; yield 187 mg (63%). 1H NMR
(300 MHz, CDCl3): ␦ = 3.59 (s, 3H, OCH3), 7.44–7.48 (m, 4H, ArH),
7.54 (d, 2H, J = 7.6 Hz, ArH), 7.59 (dd, 2H, J = 1.8, 8.1 Hz, ArH), 7.72
(d, 1H, J = 7.6 Hz, ArH), 7.77 (s, 1H, ArH), 7.94 (d, 1H, J = 8.1 Hz, ArH).
2,2== -Dibromo-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid methyl
ester (8f)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
2.07 mmol), Pd(PPh3)4 (6 mol%), 2-bromophenylboronic acid
(360 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8f was
isolated as a yellow solid; yield 230 mg (74%), mp 138–140 °C.
1H NMR (300 MHz, CDCl3): ␦ = 3.60 (s, 3H, OCH3), 7.10–7.15 (m, 2H,
ArH), 7.22 (d, 1H, J = 1.9 Hz, ArH), 7.24 (d, 1H, J = 1.5 Hz, ArH),
7.26–7.30 (m, 2H, ArH), 7.43 (dd, 1H, J = 1.8, 8.1 Hz, ArH), 7.52–7.59
(m, 3H, ArH), 8.00 (d, 1H, J = 8.0 Hz, ArH). 13C NMR (62.90 MHz,
CDCl3): ␦ = 52.0 (OCH3), 122.3, 122.9 (CAr), 127.0, 127.5, 128.7, 128.8
(CHAr), 129.0 (CAr), 129.3, 130.0, 130.1, 131.1, 132.1, 132.6, 133.3
(CHAr), 141.1, 141.9, 142.4, 144.4 (CAr), 167.0 (C=O). IR (KBr): ␯˜ = 3052,
2946, 2839 (w), 1716 (s), 1605, 1562, 1474, 1430, 1387 (m), 1286 (s),
1189, 1118, 1060, 1004, 962, 904, 827, 788 (m), 749 (s), 697, 660, 587
(m) cm−1. GC−MS (EI, 70 eV): m/z (%): 446 (M+, 79Br, 81Br)(69), 370(12),
289(10), 257(100), 231(30), 202(08), 148(05), 128(04), 113(08).
13C NMR (62.90 MHz, CDCl3): ␦ = 52.0 (OCH3), 121.9 (q, JF,C
=
320.0 Hz, CF3), 122.0 (q, JF,C = 321.0 Hz, CF3), 124.0 (dq, JC,F = 3.8 Hz,
CHAr), 124.2 (dq, JF,C = 3.9 Hz, CHAr), 124.9 (q, JC,F = 3.7 Hz, CHAr),
125.3 (q, JC,F = 3.7 Hz, CHAr), 126.5, 128.4, 129.5 (CHAr), 129.8, 130.2
(CAr), 130.6 (CHAr), 130.7 (CAr), 131.2, 131.7, 132.0 (CHAr), 140.3, 141.9,
142.1, 142.9 (CAr), 167.8 (C=O). IR (KBr): ␯˜ = 3075, 2952, 2843 (w), 1725
(s), 1606, 1564, 1583, 1428, 1341, 1298 (m), 1244 (s), 1157 (m), 1125,
1071, 1035 (s), 965, 903, 844 (m), 803, 700 (s), 661, 612 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 424 (M+, 57), 405(09), 393(100), 373(10),
345(13), 325(07), 296(13), 275(05), 226(05). HRMS (EI) calcd. for
C22H14F6O2 [M+]: 424.08925; found: 424.088866.
4,4== -Bis-trifluoromethyl-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid
methyl ester (8j)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
2.07 mmol), Pd(PPh3)4 (6 mol%), 4-trifluoromethylphenylboronic
acid (342 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8j
was isolated as a yellow solid; yield 204 mg (69%), mp 142–144 °C.
1H NMR (300 MHz, CDCl3): ␦ = 3.61 (s, 3H, OCH3), 7.38 (d, 2H, J =
7.9 Hz, ArH), 7.46 (d, 1H, J = 1.7 Hz, ArH), 7.58 (d, 1H, J = 1.7 Hz, ArH),
7.62 (d, 2H, J = 1.8 Hz, ArH), 7.64 (m, 4H, ArH), 7.95 (d, 1H, J = 8.1 Hz,
2,2== -Difluoro-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid methyl
ester (8g)
Starting with
7 (300 mg, 0.69 mmol), K3PO4 (438 mg,
2.07 mmol), Pd(PPh3)4 (6 mol%), 2-flourophenylboronic acid
(252 mg, 1.80 mmol), and 1,4-dioxane (5 mL/mmol triflate), 8g was
isolated as a reddish solid; yield 154 mg (68%), mp 144–146 °C.
1H NMR (300 MHz, CDCl3): ␦ = 3.60 (s, 3H, OCH3), 6.95–7.10 (m, 4H,
ArH), 7.18–7.26 (m, 3H, ArH), 7.35 (dt, 1H, J = 1.8, 7.7 Hz, ArH), 7.43
(t, 1H, J = 1.5 Hz, ArH), 7.53 (dt, 1H, J = 1.7, 8.1 Hz, ArH), 7.95 (d, 1H,
J = 8.1 Hz, ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 52.0 (OCH3), 115.0
ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 52.0 (OCH3), 121.9 (q, JF,C
=
320.0 Hz, CF3), 122.0 (q, JF,C = 321.0 Hz, CF3), 124.0 (q, JC,F = 250.2 Hz,
CF3), 124.9 (q, JC,F = 3.8 Hz, CHAr), 125.9 (q, JF,C = 3.8 Hz, CHAr), 126.6,
127.6, 128.7, 129.6 (CHAr), 129.7, 129.8, 130.6 (CAr), 131.1 (CHAr), 142.3,
142.9, 143.0, 144.8 (CAr), 167.8 (C=O). IR (KBr): ␯˜ = 3071, 2947, 2841
(w), 1717 (s), 1607, 1563, 1579, 1421, 1343, 1293 (m), 1241 (s), 1161 (m),
1131, 1077, 1031 (s), 967, 907, 844 (m), 805, 703 (s), 661, 613 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 424 (M+, 56), 405(10), 393(100), 373(07),
345(11), 325(07), 296(20), 275(05), 226(05). HRMS (EI) calcd. for
C22H14F6O2 [M+]: 424.08925; found: 424.089297.
2
2
(d, JC,F = 22.2 Hz, CHAr), 116.2 (d, JC,F = 22.5 Hz, CHAr), 124.0 (d,
4JC,F = 3.5 Hz, CHAr), 124.5 (d, 4JC,F = 3.7 Hz, CHAr), 127.5 (d, 2JC,F
13.0 Hz, CF), 128.4 (d, JC,F = 3.3 Hz, CHAr), 128.9 (CAr), 129.1 (CAr),
=
4
3
3
129.3 (d, JC,F = 8.1 Hz, CHAr), 129.9 (d, JC,F = 8.3 Hz, CHAr), 130.4
(CHAr), 130.5 (d, 4JC,F = 3.3 Hz, CHAr), 130.6 (d, 4JC,F = 3.1 Hz, CHAr),
132.0 (d, 4JC,F = 2.9 Hz, CHAr), 136.3 (CAr), 139.4 (d, 4JC,F = 1.0 Hz, CF),
157.7 (d, 2JC,F = 11.5 Hz, CF), 161.6 (d, 2JC,F = 14.3 Hz, CF), 167.5 (C=O).
IR (KBr): ␯˜ = 3030, 2950, 2850 (w), 1722 (s), 1614, 1604, 1579, 1494,
1433, 1392, 1284, 1220, 1190, 1109, 1049, 1011, 960, 915, 842 (m), 817,
758 (s), 692, 638, 541 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 324 (M+,
81), 293(100), 264(17), 244(35), 170(04), 146(05), 122(12). HRMS (EI)
calcd. for C20H14F2O2 [M+]: 324.09564; found: 324.095647.
2=,5=-Dimethoxy-3-trifluoromethanesulfonyloxy-biphenyl-
4-carboxylic acid methyl ester (9a)
Starting with 7 (300 mg, 0.69 mmol), K3PO4 (218 mg, 1.03 mmol),
Pd(PPh3)4 (3 mol%), 2,5-dimethoxyphenylboronic acid (161 mg,
0.89 mmol), and 1,4-dioxane (5 mL/mmol triflate), 9a was isolated
1
as a colorless viscous oil; yield 228 mg (78%). H NMR (300 MHz,
CDCl3): ␦ = 3.67 (s, 3H, OCH3), 3.71 (s, 3H, OCH3), 3.88 (s, 3H, OCH3),
Published by NRC Research Press

Nawaz et al.
1057
6.80–6.84 (m, 3H, ArH), 7.47 (s, 1H, ArH), 7.52 (dd, 1H, J = 1.6, 8.3 Hz,
ArH), 8.00 (d, 1H, J = 8.1 Hz, ArH). 13C NMR (62.90 MHz, CDCl3): ␦ =
52.5 (OCH3), 55.8 (OCH3), 56.0 (OCH3), 112.8, 114.8, 116.3 (CHAr),
121.3 (q, JF,C = 320.0 Hz, CF3), 122.2 (CAr), 123.8 (CHAr), 127.9 (CAr),
129.0, 132.2 (CHAr), 145.0, 147.9, 150.6, 153.8 (CAr), 164.1 (C=O).
19F NMR (282 MHz, CDCl3): ␦ = –73.4 (CF). IR (KBr): ␯˜ = 3001, 2953,
2837 (w), 1725, 1614, 1553, 1510, 1464 (m), 1421 (s), 1387, 1270, 1246
(m), 1202, 1135, 1072 (s), 1022, 893, 824, 778, 730, 664, 571 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 420 (M+, 100), 389(06), 255(11), 240(15),
187(17), 162(05), 114(04), 69(05). HRMS (EI) calcd. for C17H15F3O7S
[M+]: 420.04851; found: 420.048583.
287(100), 257(11), 229(04), 185(10), 128(06), 69(08). HRMS (EI) calcd.
for C17H15F3O7S [M+]: 420.04851; found: 420.048507.
Methyl 3=,5=-dimethyl-3-(trifluoromethyl-sulfonyloxy)biphenyl-
4-carboxylate (9e)
Starting with 7 (300 mg, 0.69 mmol), K3PO4 (218 mg, 1.03 mmol),
Pd(PPh3)4 (3 mol%), 3,5-dimethylphenylboronic acid (133 mg,
0.89 mmol), and 1,4-dioxane (5 mL/mmol triflate), 9e was isolated
as colorless oil; yield 162 mg (60%). 1H NMR (300 MHz, CDCl3): ␦ =
2.25 (s, 6H, 2CH3), 3.59 (s, 3H, OCH3), 6.81 (s, 1H, ArH), 6.92 (s, 1H,
ArH), 7.15 (s, 1H, ArH), 7.34 (d, 1H, J = 3.4 Hz, ArH), 7.36 (s, 1H, ArH),
7.61 (d, 1H, J = 3.4 Hz, ArH). 13C NMR (62.89 MHz, CDCl3): ␦ = 21.1
(2CH3), 52.4 (OCH3), 120.0 (q, JF,C = 320 Hz, CF3), 122.6, 123.4, 126.0,
129.3, 132.4 (CHAr), 137.7, 139.2, 141.1, 143.0, 148.0 (CAr), 167.1 (C=O).
19F NMR (282 MHz, CDCl3): ␦ = –73.4 (CF). IR (KBr): ␯˜ = 3016, 2948,
2920 (w), 1723, 1600 (s), 1485 (m), 1462, 1324, 1268 (m), 1241 (s), 1136,
1099, 975 (m), 861, 785, 753 (s), 699, 577, 540 (m) cm−1. GC−MS (EI,
70 eV): m/z (%): 388 (M+, 66), 357(07), 255(100), 227(12), 152(15),
115(03), 69(08). HRMS (EI) calcd. for C17H15F3O5S [M+]: 388.05868;
found: 388.058632.
3=,4=-Dimethoxy-3-trifluoromethanesulfonyloxy-biphenyl-
4-carboxylic acid methyl ester (9b)
Starting with 7 (300 mg, 0.69 mmol), K3PO4 (218 mg, 1.03 mmol),
Pd(PPh3)4 (3 mol%), 3,4-dimethoxyphenylboronic acid (161 mg,
0.89 mmol), and 1,4-dioxane (5 mL/mmol triflate), 9b was isolated
1
as a colorless solid; yield 210 mg (72%); mp 148–150 °C. H NMR
(300 MHz, CDCl3): ␦ = 3.82 (s, 3H, OCH3), 3.85 (s, 3H, OCH3), 3.86 (s,
3H, OCH3), 6.97 (d, 1H, J = 2.1 Hz, ArH), 7.05 (dd, 1H, J = 2.1, 8.3 Hz,
ArH), 7.20 (s, 1H, ArH), 7.33 (d, 1H, J = 1.3 Hz, ArH), 7.52 (d, 1H, J = 1.7,
8.1 Hz, ArH), 8.00 (d, 1H, J = 8.2 Hz, ArH). 13C NMR (62.90 MHz,
CDCl3): ␦ = 52.4 (OCH3), 55.2 (OCH3), 56.4 (OCH3), 110.1, 111.6, 119.9
(CHAr), 120.2 (q, JF,C = 320.2 Hz, CF3), 120.6, 126.1 (CHAr), 127.7, 131.6
(CAr), 133.0 (CHAr), 147.5, 148.6, 149.5, 150.2 (CAr), 168.2 (C=O).
19F NMR (282 MHz, CDCl3): ␦ = –73.2 (CF). IR (KBr): ␯˜ = 2999, 2952,
2849 (w), 1726 (m), 1603, 1588 (w), 1520, 1463 (m), 1421 (s), 1325,
1289, 1171, 1080, 1052, 974, 905, 883, 827, 806, 755, 684, 664,
573 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 420 (M+, 100), 389(07),
259(62), 228(09), 185(05), 157(04), 114(06), 69(06). HRMS (EI) calcd.
for C17H15F3O7S [M+]: 420.04851; found: 420.048645.
2,5-Dimethoxy-4== -vinyl-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid
methyl ester (10a)
Starting with 9a (150 mg, 0.35 mmol), K3PO4 (110 mg, 0.52 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (66 mg, 0.45 mmol),
10a
and 1,4-dioxane (5 mL/mmol triflate),
was isolated as yellow
solid; yield 102 mg (76%), mp 156–158 °C. 1H NMR (300 MHz, CDCl3):
␦ = 3.59 (s, 3H, OCH3), 3.71 (s, 3H, OCH3), 3.74 (s, 3H, OCH3), 5.19 (d,
1H, J = 10.8 Hz, CH2vinyl), 5.71 (d, 1H, J = 17.5 Hz, CH2vinyl), 6.67 (d, 1H,
J = 6.3 Hz, CHvinyl), 6.82 (d, 3H, J = 6.4 Hz, ArH), 7.24 (d, 2H, J = 7.3 Hz,
ArH), 7.36 (d, 2H, J = 7.3 Hz, ArH), 7.46 (s, 1H, ArH), 7.50 (d, 1H, J =
7.8 Hz, ArH), 7.80 (d, 1H, J = 7.7 Hz, ArH). 13C NMR (62.90 MHz,
CDCl3): ␦ = 51.9 (OCH3), 55.8 (OCH3), 56.3 (OCH3), 112.7 (CHAr), 113.8
(CH2vinyl), 113.9, 116.5, 125.8, 128.3, 128.6, 129.7 (CHAr), 130.2 (CAr),
131.7 (CHAr), 136.4 (CAr), 136.5 (CHvinyl), 135.0, 140.9, 141.6, 142.0,
150.7, 153.8 (CAr), 168.9 (C=O). IR (KBr): ␯˜ = 2996, 2832 (w), 1716 (s),
1600, 1553, 1483, 1431, 1379 (m), 1266, 1211 (s), 1138 (m), 1095, 1021,
1012 (s), 989, 906, 877 (m), 843 (s), 827, 752, 688, 631, 542 (m) cm−1.
GC−MS (EI, 70 eV): m/z (%): 374 (M+, 100), 343(04), 327(06), 300(15),
285(10), 257(06), 227(04), 202(07), 180(04), 150(06), 101(04), 59(06).
HRMS (EI) calcd. for C24H22O4 [M+]: 374.15126; found: 374.151271.
2=-Methoxy-3-trifluoromethanesulfonyloxy-biphenyl-4-carboxylic
acid methyl ester (9c)
Starting with 7 (300 mg, 0.69 mmol), K3PO4 (218 mg, 1.03 mmol),
Pd(PPh3)4 (3 mol%), 2-methoxyphenylboronic acid (135 mg,
0.89 mmol), and 1,4-dioxane (5 mL/mmol triflate), 9c was isolated
as a colorless crystalline solid; yield 206 mg (76%); mp 150–152 °C.
1H NMR (300 MHz, CDCl3): ␦ = 3.74 (s, 3H, OCH3), 3.89 (s, 3H, OCH3),
6.91–7.00 (m, 2H, ArH), 7.22–7.32 (m, 2H, ArH), 7.47 (s, 1H, ArH),
7.53 (dd, 1H, J = 1.6, 8.7 Hz, ArH), 8.03 (d, 1H, J = 8.1 Hz, ArH).
13C NMR (62.89 MHz, CDCl3): ␦ = 52.5 (OCH3), 55.4 (OCH3), 111.4,
121.1 (CHAr), 122.0 (q, JF,C = 321.0 Hz, CF3), 123.8, 129.0 (CHAr), 127.1
(CAr), 130.4, 130.6, 132.2 (CHAr), 145.2, 146.1, 147.9, 156.3 (CAr), 164.2
(C=O). 19F NMR (282 MHz, CDCl3): ␦ = –73.5 (CF3). IR (KBr): ␯˜ = 3072,
2954, 2918 (w), 1726 (s), 1687 (w), 1615 (m), 1582 (w), 1483 (m), 1422
(s), 1397, 1292 (m), 1245 (s), 1136, 1073 (s), 969 (w), 914 (s), 858 (w),
826 (s), 783 (m), 752 (s), 695, 568 (m) cm−1. GC−MS (EI, 70 eV): m/z (%):
390 (M+, 100), 359(19), 225(27), 197(11), 169(21), 155(10), 69(07). HRMS
(EI) calcd. for C16H13F3O6S [M+]: 390.03794; found: 390.037761.
3,4-Dimethoxy-4== -vinyl-[1,1=;3=,1== ]terphenyl-4=-carboxylic
acid methyl ester (10b)
Starting with 9b (150 mg, 0.35 mmol), K3PO4 (110 mg, 0.52 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (66 mg, 0.45 mmol),
10b
and 1,4-dioxane (5 mL/mmol triflate),
was isolated as white
solid; yield 96 mg (72%), mp 142–144 °C. 1H NMR (300 MHz, CDCl3):
␦ = 3.57 (s, 3H, OCH3), 3.81 (s, 3H, OCH3), 3.83 (s, 3H, OCH3), 5.17 (d,
1H, J = 11.1 Hz, CH2vinyl), 5.69 (d, 1H, J = 17.5 Hz, CH2vinyl), 6.66 (dd, 1H,
J = 10.9, 17.6 Hz, CHvinyl), 6.84 (d, 1H, J = 8.3 Hz, ArH), 7.03 (d, 1H, J =
1.8 Hz, ArH), 7.10 (dd, 1H, J = 2.0, 8.3 Hz, ArH), 7.22 (d, 2H, J = 8.1 Hz,
ArH), 7.36 (d, 1H, J = 8.1 Hz, ArH), 7.44 (d, 2H, J = 1.5 Hz, ArH), 7.48
(dd, 1H, J = 1.7, 8.0 Hz, ArH), 7.82 (d, 1H, J = 8.0 Hz, ArH). 13C NMR
(62.90 MHz, CDCl3): ␦ = 52.1 (OCH3), 55.9 (OCH3), 56.0 (OCH3), 111.3,
111.5 (CHAr), 113.9 (CH2vinyl), 119.7 125.4, 125.9, 128.6, 129.0, 130.7
(CHAr), 132.6 (CAr), 136.4 (CHvinyl), 136.6, 137.0, 138.2, 141.0, 142.9,
143.9, 149.3 (CAr), 168.6 (C=O). IR (KBr): ␯˜ = 2998, 2835 (w), 1715 (s),
1600, 1518, 1485, 1462, 1432, 1379, 1283 (m), 1246 (s), 1212, 1170, 1097,
1041, 990, 905, 843, 808, 784, 732, 682, 620, 541 (m) cm−1. GC−MS
(EI, 70 eV): m/z (%): 374 (M+, 100), 359(04), 331(07), 301(12), 281(06),
253(08), 226(06), 207(05), 153(08), 121(05), 57(10). HRMS (EI) calcd.
for C24H22O4 [M+]: 374.15126; found: 374.151281.
2=,4=-Dimethoxy-3-trifluoromethanesulfonyloxy-biphenyl-
4-carboxylic acid methyl ester (9d)
Starting with 7 (300 mg, 0.69 mmol), K3PO4 (218 mg, 1.03 mmol),
Pd(PPh3)4 (3 mol%), 2,4-dimethoxyphenylboronic acid (161 mg,
0.89 mmol), and 1,4-dioxane (5 mL/mmol triflate), 9d was isolated
as a colorless crystalline solid; yield 196 mg (67%), mp 150–152 °C.
1H NMR (300 MHz, CDCl3): ␦ = 3.73 (s, 3H, OCH3), 3.78 (s, 3H, OCH3),
3.89 (s, 3H, OCH3), 6.48–6.52 (m, 2H, ArH), 7.15–7.22 (m, 2H, ArH),
7.67 (dd, 1H, J = 2.4, 8.5 Hz, ArH), 8.1 (d, 1H, J = 2.3 Hz, ArH). 13C NMR
(62.90 MHz, CDCl3): ␦ = 52.5 (OCH3), 55.4 (OCH3), 55.5 (OCH3), 99.0,
104.9 (CHAr), 120.0 (q, JF,C = 320.0 Hz, CF3), 122.1 (CHAr), 123.7 (CAr),
131.1, 133.4 (CHAr), 134.9 (CAr), 135.0 (CHAr), 139.0, 146.6, 157.4, 161.2
(CAr), 168.4 (C=O). 19F NMR (282 MHz, CDCl3): ␦ = –73.5 (CF). IR (KBr):
␯˜ = 2921, 2871 (w), 1727 (m), 1677, 1609, 1578 (w), 1512, 1463 (m), 1422
(s), 1305, 1281, 1160, 1074, 1053, 967, 905, 890, 835, 797, 761, 686,
638, 571 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 420 (M+, 38), 389(05),
2-Methoxy-4== -vinyl-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid methyl
ester (10c)
Starting with 9c (150 mg, 0.38 mmol), K3PO4 (120 mg, 0.57 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (72 mg, 0.49 mmol),
Published by NRC Research Press

1058
Can. J. Chem. Vol. 91, 2013
Mitsumori, S.; Inagaki, M.; Nakatani, T.; Tamura, Y.; Takechi, S.; Taishi, T.;
Kishino, J.; Ohtani, M. Angew. Chem. 1998, 110, 1015. doi:10.1002/(SICI)1521-
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Ed. Engl. 1998, 37, 973. doi: doi:10.1002/(SICI)1521-3773(19980420)37:7<973::
AID-ANIE973>3.0.CO;2-T.
and 1,4-dioxane (5 mL/mmol triflate), 10c was isolated as off white
solid; yield 85 mg (64%), mp 160–162 °C. 1H NMR (250 MHz, CDCl3):
␦ = 3.58 (s, 3H, OCH3), 3.72 (s, 3H, OCH3), 5.17 (d, 1H, J = 10.9 Hz,
CH2vinyl), 5.68 (d, 1H, J = 17.6 Hz, CH2vinyl), 6.67 (dd, 1H, J = 10.9,
17.6 Hz, CHvinyl), 6.94 (dd, 2H, J = 7.9, 14.0 Hz, ArH), 7.22–7.29 (m,
4H, ArH), 7.36 (d, 1H, J = 8.1 Hz, ArH), 7.46 (d, 1H, J = 1.2 Hz, ArH),
7.50 (dd, 1H, J = 1.6, 8.0 Hz, ArH), 7.42 (s, 1H, ArH), 7.80 (d, 1H, J =
8.0 Hz, ArH). 13C NMR (62.90 MHz, CDCl3): ␦ = 51.9 (OCH3), 55.5
(OCH3), 111.3 (CHAr), 113.8 (CH2vinyl), 120.9, 125.8, 128.3, 128.6 (CHAr),
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128.8 (CAr), 129.4, 129.7, 130.7, 131.8 (CHAr), 136.4 (CAr), 136.5 (CHvi
-
nyl), 141.0, 141.8, 141.9, 142.6, 156.4 (CAr), 168.9 (C=O). IR (KBr): ␯˜ =
3002, 2947, 2835 (w), 1716 (s), 1627, 1580, 1513, 1498, 1461, 1386 (m),
1243 (s), 1180, 1137, 1120, 1055, 1024, 1005, 904, 786 (m), 750 (s), 715,
637, 574, 541 (m) cm−1. GC−MS (EI, 70 eV): m/z (%): 344 (M+, 100),
313(24), 285(06), 270(10), 239(10), 164(06), 119(04). HRMS (EI) calcd.
for C23H20O3 [M+]: 344.14070; found: 344.140881.
2,4-Dimethoxy-4== -vinyl-[1,1=;3=,1== ]terphenyl-4=-carboxylic acid
methyl ester (10d)
Starting with 9d (150 mg, 0.35 mmol), K3PO4 (110 mg, 0.52 mmol),
Pd(PPh3)4 (3 mol%), 4-vinylphenylboronic acid (66 mg, 0.45 mmol),
and 1,4-dioxane (5 mL/mmol triflate), 10d was isolated as a color-
1
less solid; yield 92 mg (69%), mp 160–162 °C. HNMR (300 MHz,
CDCl3): ␦ = 3.59 (s, 3H, OCH3), 3.75 (s, 3H, OCH3), 3.79 (s, 3H, OCH3),
5.20 (dd, 1H, J = 2.4, 10.8 Hz, CH2vinyl), 5.72 (dd, 1H, J = 2.4, 9.6 Hz,
CH2vinyl), 6.69 (dd, 1H, J = 2.4, 10.6 Hz, CHvinyl), 7.21–7.24 (m, 3H,
ArH), 7.26 (s, 1H, ArH), 7.30–7.39 (m, 4H, ArH), 7.60 (dd, 1H, J = 1.9,
7.9 Hz, ArH), 7.88 (d, 1H, J = 1.6 Hz, ArH). 13CNMR (75.47 MHz,
CDCl3): ␦ = 51.9 (OCH3), 55.4 (OCH3), 55.6 (OCH3), 99.0, 104.8 (CHAr),
113.8 (CH2vinyl), 125.9, 128.6, 130.3 (CHAr), 130.4 (CAr), 130.7, 131.2,
132.0, 136.5 (CHAr, CHvinyl), 136.6, 137.5, 138.9, 139.6, 140.0, 141.6,
142.0 (CAr), 169.1 (C=O). IR (KBr): ␯˜ = 3052, 2921, 2848 (w), 1716,
1608 (s), 1463, 1435, 1391 (m), 1242, 1217 (s), 1173, 1095, 965, 887, 783,
721, 663, 537(m) cm−1. GC−MS (EI, 70 eV): m/z (%): 374 (M+, 100),
343(04), 285(06), 257(05), 179(06), 120(04). HRMS (EI) calcd. for
C24H22O4 [M+]: 374.15126; found: 374.151040.
Supplementary material
Supplementary material is available with the article through
the journal Web site at http://nrcresearchpress.com/doi/suppl/
10.1139/cjc-2013-0201. CCDC 894261–894264 contain all crystallo-
graphic details of this publication and are available, free of
charge, via www.ccdc.cam.ac.uk/conts/retrieving.html (or from
the Cambridge Crystallographic Data Centre, 12 Union Road, GB-
Cambridge CB21EZ; Fax: (+44)1223-336-033 or e-mail: deposit@
ccdc.cam.ac.uk.
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Acknowledgements
Financial support by the DAAD (scholarships for M.N., I.U., and
O.-u.-R.A.) and by the State of Pakistan (scholarship for O.-u.-R.A.)
is gratefully acknowledged.
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