Synthesis of 2′,4-diarylbenzophenones through site-selective suzuki-miyaura reactions of bis(triflates) of 2′,4-dihydroxybenzophenones

Article abstract of DOI:10.1002/ejoc.201100762

Palladium(0)-catalyzed Suzuki cross-coupling reactions of the bis(triflates) of 2′,4-dihydroxybenzophenones afforded 2′,4-diarylbenzophenones. The reactions proceeded with very good site selectivity in favour of the 4-position. Palladium(0)-catalyzed Suzuki cross-coupling reactions of the bis(triflates) of 2′,4- dihydroxybenzophenones afforded 2′,4-diarylbenzophenones. The reactions proceeded with very good site selectivity infavour of the 4-position. Copyright

Full text of DOI:10.1002/ejoc.201100762

FULL PAPER
DOI: 10.1002/ejoc.201100762
Synthesis of 2Ј,4-Diarylbenzophenones through Site-Selective Suzuki–Miyaura
Reactions of Bis(triflates) of 2Ј,4-Dihydroxybenzophenones
Muhammad Nawaz,[a] Ihsan Ullah,[a] Obaid-Ur-Rahman Abid,[a] Alexander Villinger,[a] and
Peter Langer*[a,b]
Keywords: Palladium / Regioselectivity / Benzophenones / Cross-coupling
Palladium(0)-catalyzed Suzuki cross-coupling reactions of
2Ј,4-diarylbenzophenones. The reactions proceeded with
the bis(triflates) of 2Ј,4-dihydroxybenzophenones afforded
very good site selectivity in favour of the 4-position.
In recent years we have studied domino reactions be-
tween silyl enol ethers and chromones. In this context we
developed a new approach to 4-(2-hydroxybenzoyl)salicyl-
ates through cyclizations of 1,3-bis(silyloxy)buta-1,3-dienes
with 3-formylchromones.[4] Recently we reported[15] the syn-
thesis of 2Ј,4-diaryl-2-methoxycarbonylbenzophenones
based on site-selective[16] Suzuki–Miyaura cross-coupling
reactions of bis(triflates) of 2Ј,4-dihydroxy-2-methoxycar-
bonylbenzophenones. Here we report full details of these
studies and a comprehensive study of the scope of this ap-
proach. In addition, we report for the first time on site-
selective Suzuki–Miyaura reactions of the bis(triflate) of the
parent 2Ј,4-dihydroxybenzophenone.
Introduction
Benzophenones show a variety of useful pharmacologi-
cal and physical properties. 4-Arylbenzophenones, for in-
stance, exhibit interesting pharmacological activities such
as cytotoxic[1] and antibacterial activities,[2] as well as the
inhibition of various enzymes.[3] 4-(2-Hydroxybenzoyl)sali-
cylic acids were reported to show good in vitro activity as
selectin antagonists.[4] Structurally related benzoylfluor-
enones are also of biological relevance.[5] 4-Arylbenzo-
phenones are substructures of complex polycyclic frame-
works, such as anthraquinone and tetracycline natural
products.[6] 2-Hydroxy- and 2-aminobenzophenones are of
considerable importance in anticancer therapy, because they
act as antitubulin agents.[7] Benzophenones also have
technical applications. Functionalized benzophenones are
also widely used as photosensitizers and UV filters (sun
creams).[8] 2,2Ј-Dihydroxy-4,4Ј-dimethoxybenzophenone is
used as a sensitive fluorimetric reagent for the determi-
nation of the nitrate anion. This method has been applied
to the analysis of a variety of natural waters and sedi-
ments.[9] Several substituted benzophenones display phos-
phorescence.[10–12]
Classic syntheses of benzophenones are based on reac-
tions of aryllithium or magnesium reagents with aldehydes
and subsequent oxidation and on Friedel–Crafts acyl-
ations.[7b,13] For the synthesis of functionalized benzo-
phenones (e.g., containing hydroxy, halide or ester groups),
these methods often give unsatisfactory results, due to com-
peting side reactions. An alternative strategy is based on
SmI2-mediated reactions between benzaldehydes and benzyl
halides and subsequent oxidation.[14]
Results and Discussion
The TMSOTf-mediated domino “addition/retro-
Michael/Mukaiyama-aldol” reaction between 3-formyl-
chromone (2, Scheme 1) and 1,3-bis(trimethylsilyloxy)buta-
1,3-diene (1) afforded the 2Ј,4-dihydroxybenzophenone 3,
which was transformed into its bis(triflate) 4. The structure
of 4 was independently confirmed by X-ray crystal structure
analysis (Figure 1).[17]
Suzuki reactions between 4 and different boronic acids
afforded the novel 2Ј,4-diarylbenzophenones 5a–r 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 were employed, and when the
reaction was carried out in 1,4-dioxane (reflux, 4 h) with
K3PO4 as the base. The benzophenones 5g and 5r were pre-
pared from 4- and 3-bromophenylboronic acid, respectively,
in good yields. These experiments show that the presence
of the bromine moiety is compatible with the reaction con-
ditions.
[a] Institut für Chemie, Universität Rostock,
Albert-Einstein-Str. 3a, 18059 Rostock, Germany
Fax: +49-381-4986412
E-mail: peter.langer@uni-rostock.de
[b] Leibniz-Institut für Katalyse e. V. an der Universität Rostock,
Albert-Einstein-Str. 29a, 18059 Rostock, Germany
The structures of all products were confirmed by spectro-
scopic methods. The structure of 5a was independently con-
firmed by an X-ray crystal structure analysis (Figure 2).[17]
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2Ј,4-Diarylbenzophenones from Bis(triflates) of 2Ј,4-Dihydroxybenzophenones
Table 1. Synthesis of 5a–r.
5
R1
R2
R3
R4
Yield of 5[a]
[%]
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
p
q
r
H
H
H
H
H
H
H
H
H
H
H
H
H
OMe
OMe
H
H
H
H
H
H
Cl
H
H
H
OMe
H
OMe
H
OH
H
H
H
H
Me
Br
Me
H
C2H5
H
vinyl
Cl
Br
OMe
OH
OMe
F
H
CF3
H
H
H
H
H
H
H
H
H
H
OMe
H
H
H
OMe
H
H
Me
H
84
75
62
77
72
64
74
62
67
58
62
65
76
67
69
72
78
64
Scheme 1. Synthesis of 3 and 4. Reagents and conditions: (i) 1. 2
(1.0 equiv.), Me3SiOTf (0.3 equiv.), CH2Cl2, 0 °C, 2. 1 (1.1 equiv.),
0 Ǟ 20 °C, 12 h, 3. HCl (10%); (ii) 1. 3 (1.0 equiv.), pyridine
(4.0 equiv.), CH2Cl2, –78 °C, 10 min, 2. Tf2O (2.4 equiv.), –78 Ǟ
0 °C, 4 h.
H
tBu
H
H
[a] Yield of isolated product.
Figure 1. ORTEP plot of 4.
Figure 2. ORTEP plot of 5a.
Scheme 2. Synthesis of 5a–r. Reagents and conditions: (i) 1,4-diox-
ane (5 mL per 1 mmol of triflate), 4 (1.0 equiv.), boronic acids
(2.6 equiv.), K3PO4 (3.0 equiv.), Pd(PPh3)4 (6 mol-%), 110 °C, 4 h.
Suzuki reactions between 4 and only 1.3 equiv. of bo-
ronic acids afforded the 4-arylbenzophenones 6a–h with
very good site selectivity (Scheme 3, Table 2). Suzuki–Mi-
yaura reactions between 6a, 6c or 6e–h and 4-vinylphen-
ylboronic acid gave the 2Ј,4-diarylbenzophenones 7a–f,
each containing two different aryl groups (Scheme 3,
Table 3). The configurations of all products were again
studied by spectroscopic methods. The structures of 6d and
6g were independently confirmed by X-ray crystal structure
analyses (Figures 3 and 4).[17]
Scheme 3. Synthesis of 6a–h and 7a–f. Reagents and conditions:
(i) 4 (1.0 equiv.), boronic acid (1.3 equiv.), K3PO4 (3.0 equiv.),
Pd(PPh3)4 (3 mol-%), 1,4-dioxane, 110 °C, 4 h; (ii) 6a, 6c or 6e–h
(1.0 equiv.), 4-vinylphenylboronic acid (1.3 equiv.), K3PO4
(3.0 equiv.), Pd(PPh3)4 (3 mol-%), 1,4-dioxane, 110 °C, 4 h.
The site selectivities of palladium(0)-catalyzed reactions curs first at the most electron-deficient and sterically less
are generally controlled by electronic and steric parameters. hindered carbon atom. The site-selective formation of the
Oxidative addition of the palladium(0) catalyst usually oc- products 6a–h might therefore be explained by the fact that
Eur. J. Org. Chem. 2011, 6670–6684
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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6671

M. Nawaz, I. Ullah, O.-U.-R. Abid, A. Villinger, P. Langer
FULL PAPER
Table 2. Synthesis of 6a–h.
both an electron-withdrawing benzoyl group and an elec-
tron-withdrawing ester group are located para and ortho,
respectively, to C-4.
6
R1
R2
R3
R4
Yield of 6[a]
[%]
a
b
c
d
e
f
H
H
OEt
Br
H
H
H
Me
H
H
H
OMe
H
H
Cl
H
Me
H
H
H
H
H
OMe
H
78
45
89
78
44
63
43
72
H
OMe
OH
OMe
H
g
h
OMe
OH
H
[a] Yield of isolated product.
Scheme 4. Possible explanation for the site-selective formation of
the products 6a–h.
Table 3. Synthesis of 7a–f.
The Suzuki–Miyaura reaction between 6d, containing a
bromide and a triflate group both in ortho positions
(Scheme 5), and 4-vinylphenylboronic acid (2.6 equiv.) af-
forded the bisdiphenyl ketone 8 in 62% yield.
6
7
R1
R2
R3
R4
Yield of 7[a]
[%]
a
f
e
g
h
c
a
b
c
d
e
f
H
H
H
H
H
Me
H
OMe
OMe
OH
H
H
OH
OMe
OMe
H
Me
H
H
OMe
H
H
60
74
65
72
64
68
OEt
H
[a] Yield of isolated product.
Scheme 5. Synthesis of 8. Reagents and conditions: (i) 6d
(1.0 equiv.), 4-vinylphenylboronic acid (2.6 equiv.), K3PO4
(3.0 equiv.), Pd(PPh3)4 (6 mol-%), 1,4-dioxane, 110 °C, 4 h.
The Suzuki–Miyaura reaction between 4-vinylphenylbo-
ronic acid (2.6 equiv.) and 5g, containing two para-bro-
mophenyl moieties (Scheme 6) afforded the diphenyl tri-
phenyl ketone 9.
Figure 3. ORTEP plot of 6d.
Scheme 6. Synthesis of 9. Reagents and conditions: (i) 5g
(1.0 equiv.), 4-vinylphenylboronic acid (2.6 equiv.), K3PO4
(3.0 equiv.), Pd(PPh3)4 (6 mol-%), 1,4-dioxane, 110 °C, 4 h.
Figure 4. ORTEP plot of 6g.
The Suzuki–Miyaura reaction between 4-vinylphenylbor-
carbon atom C-4 is more electron-deficient and less steri- onic acid (2.6 equiv.) and 5r, containing two meta-bromo-
cally hindered than C-2Ј (Scheme 4). One electron-with- phenyl moieties (Scheme 7), afforded the diphenyl triphenyl
drawing benzoyl group is located ortho to C-2Ј. In contrast, ketone 10.
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Eur. J. Org. Chem. 2011, 6670–6684

2Ј,4-Diarylbenzophenones from Bis(triflates) of 2Ј,4-Dihydroxybenzophenones
Scheme 7. Synthesis of 10. Reagents and conditions: (i) 5r
(1.0 equiv.), 4-vinylphenylboronic acid (2.6 equiv.), K3PO4
(3.0 equiv.), Pd(PPh3)4 (3 mol-%), 1,4-dioxane, 110 °C, 4 h.
Figure 5. ORTEP plot of 13b.
Extending the scope of our study, we investigated reac-
tions of the bis(triflate) of the commercially available 2Ј,4-
dihydroxybenzophenone (11), which was transformed into
the bis(triflate) 12 in 88% yield (Scheme 8).
Suzuki reactions between 12 and smaller quantities of
the different boronic acids (1.3 equiv.) in the presence of
Pd(PPh3)4 (3 mol-%) proceeded with very good site selec-
tivities in favour of carbon atom C-4 to give the benzo-
phenones 14a–h (Scheme 10, Table 5). The pure products
were obtained after chromatographic purification. Treat-
ment of 14a–h with (4-vinylphenyl)boronic acid (1.3 equiv.)
gave the 2Ј,4-diarylbenzophenones 15a–h, each containing
two different aryl groups (Scheme 10, Table 5). The struc-
Scheme 8. Synthesis of 12. Reagents and conditions: (i) CH2Cl2, 11
(1.0 equiv.), –78 °C, pyridine (4.0 equiv.), Tf2O (2.4 equiv.), –78 Ǟ
0 °C, 4 h.
Suzuki reactions between 12 and different boronic acids
(2.6 equiv.) afforded the novel 2Ј,4-diarylbenzophenones
13a–d in good yields (Scheme 9, Table 4). The best yields
were obtained when Pd(PPh3)4 (6 mol-%) was used as the
catalyst, when 2.6 equiv. of the boronic acid were employed,
and when the reaction was carried out in 1,4-dioxane (re-
flux, 4 h) with K3PO4 as the base. The structures of all
products were established by spectroscopic methods. The
structure of 13b was independently confirmed by X-ray
crystallographic analysis (Figure 5).[17]
Scheme 10. Synthesis of 14a–h and 15a–h. Reagents and condi-
tions: (i) 12 (1.0 equiv.), boronic acids (1.3 equiv.), K3PO4
(3.0 equiv.), Pd(PPh3)4 (3 mol-%), 1,4-dioxane, 110 °C, 4 h; (ii) 14a–
h
(1.0 equiv.), 4-vinylphenylboronic acid (1.3 equiv.), K3PO4
(3.0 equiv.), Pd(PPh3)4 (3 mol-%), 1,4-dioxane, 110 °C, 4 h.
Scheme 9. Synthesis of 13a–d. Reagents and conditions: (i) 1,4-di-
oxane (5 mL per 1 mmol of triflate), 12 (1.0 equiv.), boronic acid
(2.6 equiv.), K3PO4 (3.0 equiv.), Pd(PPh3)4 (6 mol-%), 110 °C, 4 h.
Table 5. Synthesis of 14a–h and 15a–h.
14,15
R1
R2
R3
R4
R5
Yield [%]
14[a]
15[a]
Table 4. Synthesis of 13a–d.
a
b
c
d
e
f
H
OCH3
OCH3
OEt
H
H
H
OCH3
H
H
H
vinyl
H
H
H
H
H
H
tBu
H
Et
H
OCH3
H
H
H
H
CH3
H
H
H
OCH3
H
H
H
68
72
64
76
70
66
78
74
70
72
68
62
66
64
76
74
13
R1
R2
R3
Yield of 13[a]
[%]
a
b
c
H
F
H
H
OCH3
H
H
H
OCH3
vinyl
78
70
68
66
H
H
g
h
CH3
H
H
H
d
H
[a] Yield of isolated product.
[a] Yield of isolated product.
Eur. J. Org. Chem. 2011, 6670–6684
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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6673

M. Nawaz, I. Ullah, O.-U.-R. Abid, A. Villinger, P. Langer
FULL PAPER
(EI, 70 eV), chemical ionization (CI, isobutane) or electrospray ion-
ization (ESI). For preparative scale chromatography silica gel 60
(0.063–0.200 mm, 70–230 mesh) was used.
tures of all products were verified by spectroscopic meth-
ods. The structures of 14f and 14h were independently con-
firmed by X-ray crystallography (Figures 6 and 7).[17]
Synthesis of the Triflates 4 and 12: Pyridine (4.0 equiv.) was added
at –78 °C under argon to a stirred solution of 3 or 11 (1.0 equiv.)
in CH2Cl2 (10 mLmmol–1). After 10 min, Tf2O (2.4 equiv.) was
added at –78 °C. The mixture was allowed to warm 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 by rapid column chromatography (flash silica gel,
heptanes/EtOAc).
Methyl 2-(Trifluoromethanesulfonyloxy)-5-[2-(trifluoromethanesulf-
onyloxy)benzoyl]benzoate (4): Compound 4 was obtained from 3
(120 mg, 0.44 mmol), pyridine (0.14 mL, 1.76 mmol) and Tf2O
(0.17 mL, 1.05 mmol) as a crystalline colourless solid (200 mg,
1
84%). M.p. 124–126 °C. H NMR (300 MHz, CDCl3): δ = 3.90 (s,
Figure 6. ORTEP plot of 14f.
3 H, OCH3), 7.39 (d, J = 8.7 Hz, 2 H, ArH), 7.45–7.54 (m, 2 H,
ArH), 7.66 (s, 1 H, ArH), 8.02 (dd, J = 2.4, 8.6 Hz, 1 H, ArH), 8.39
(d, J = 2.2 Hz, 1 H, ArH) ppm. 13C NMR (75.46 MHz, CDCl3): δ
= 53.0 (OCH3), 116.2 (q, JF,C = 320.0 Hz, CF3), 116.5 (C), 120.5
(q, JF,C = 321.2 Hz, CF3), 120.8 (C), 122.8, 123.4, 128.5, 131.2,
133.7, 134.4, 135.3 (CH), 136.4, 146.7, 151.1, 163.2 (C), 190.1
(C=O) ppm. 19F NMR (282 MHz, CDCl3): δ = –73.28 (CF) ppm.
IR (KBr): ν = 3117, 3076, 3040 (w), 1671, 1624 (s), 1582 (m), 1479,
˜
1341, 1237 (m), 1202 (s), 1164, 1087, 988 (m), 866, 793, 703 (s),
589, 537 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 536 [M]+ (89),
505 (40), 467 (06), 403 (09), 375 (23), 311 (100), 247 (61), 211 (20),
183 (30), 155 (34), 120 (29), 92 (16), 69 (50). HRMS (EI): calcd.
for C17H10F6O9S2 [M]+ 535.96649; found 535.966638.
2-[4-(Trifluoromethanesulfonyloxy)benzoyl]phenyl
Trifluorometh-
Figure 7. ORTEP plot of 14h.
anesulfonate (12): Compound 12 was obtained from 11 (168 mg,
0.78 mmol), pyridine (0.25 mL, 3.12 mmol) and Tf2O (0.31 mL,
1.87 mmol) as a yellow oil (yield 330 mg, 88%). 1H NMR
(300 MHz, CDCl3): δ = 7.31–7.38 (m, 3 H, ArH), 7.43–7.53 (m, 2
H, ArH), 7.58–7.64 (m, 1 H, ArH), 7.83 (d, J = 8.91 Hz, 2 H,
The site-selective formation of 14a–h can be explained by
the fact that carbon atom C-4Ј (located para to the keto
group) is less sterically hindered than C-1 (located ortho to
the keto group) (Scheme 11). Both centres are similar from
the electronic viewpoint.
ArH) ppm. 13C NMR (62.90 MHz, CDCl3): δ = 115.8 (q, JF,C
320.0 Hz, CF3), 120.9 (q, JF,C = 321.3 Hz, CF3), 121.6, 122.7,
128.3, 131.1, 132.2, 133.3 (CHAr), 133.3, 136.3, 146.6, 152.7 (CAr),
190.8 (C=O) ppm. 19F NMR (282 MHz, CDCl3): δ = –73.3, 72.6
=
(2 CF) ppm. IR (KBr): ν = 1598, 1589, 1580, (m), 1496, 1431, 1414,
˜
1319, 1291 (m), 1265 (s), 1165, 1077, 1028, 989, 976, 932 (m), 887,
787, 757 (s), 680, 595, 572 (m) cm–1. GC–MS (EI, 70 eV): m/z (%)
= 478 [M]+ (58), 345 (06), 317 (13), 281 (09), 253 (100), 212 (12),
184 (28), 155 (07), 128 (12), 92 (10), 69 (17), 63 (06). HRMS (EI):
calcd. for C15H8F6O7S2 [M]+ 477.96101 found 477.961813.
Scheme 11. Possible explanation for the site-selective formation of
products 14a–h.
General Procedure for the Synthesis of Benzophenones 5a–r and
13a–d: A 1,4-dioxane solution of the arylboronic acid, K3PO4,
Pd(PPh3)4 and the triflate 4 or 12 was stirred at 110 °C under argon
for 4 h. After the system had cooled to 20 °C, a saturated aqueous
solution of NH4Cl was added, the organic and aqueous layers were
separated, and the latter was extracted with CH2Cl2. The combined
organic layers were dried (Na2SO4) and filtered, and the filtrate
was concentrated in vacuo. The residue was purified by column
chromatography.
Conclusion
In conclusion, we report the synthesis of various 2Ј,4-
diarylbenzophenones based on palladium(0)-catalyzed Su-
zuki cross-coupling reactions of the bis(triflates) of 2Ј,4-di-
hydroxybenzophenones. These reactions proceed with very
good site selectivities.
Methyl 2-Hydroxy-5-(2-hydroxybenzoyl)benzoate (3): Compound 3
was obtained from 2 (1740 mg, 10 mmol), 1,3-bis(silyloxy)buta-1,3-
diene (1, 2860 mg, 11 mmol) and TMSOTf (0.54 mL, 3 mmol) as a
yellowish oil (1650 mg, 60%). 1H NMR (300 MHz, CDCl3): δ =
3.89 (s, 3 H, OCH3), 6.79–6.85 (m, 1 H, ArH), 6.94–6.98 (m, 1 H,
ArH), 7.02 (s, 1 H, ArH), 7.39–7.43 (m, 1 H, ArH), 7.49 (dd, J =
1.6, 7.9 Hz, 1 H, ArH), 7.77 (dd, J = 2.2, 8.7 Hz, 1 H, ArH), 8.18
(d, J = 2.2 Hz, 1 H, ArH), 11.1 (s, 1 H, OH), 11.7 (s, 1 H,
Experimental Section
General Comments: All solvents were dried by standard methods
1
and all reactions were carried out under inert atmosphere. For H
and 13C NMR spectra the deuterated solvents indicated were used.
Mass spectrometric data (MS) were obtained by electron ionization
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2Ј,4-Diarylbenzophenones from Bis(triflates) of 2Ј,4-Dihydroxybenzophenones
OH) ppm. 13C NMR (62.90 MHz, CDCl3): δ = 52.7 (OCH3), 117.8, (C=O) ppm. IR (KBr): ν = 3055, 3021, 2962 (w), 1721, 1663 (s),
˜
118.5, 118.7 (CHAr), 131.8 (CAr), 132.4, 132.9 (CHAr), 135.1, 135.6 1597 (m), 1552, 1515 (w), 1434, 1303 (m), 1229 (s), 1150, 1085, 939
(CAr), 136.1, 136.6 (CHAr), 161.9, 163.6 (CAr), 168.9 (COO), 197.9
(m), 829, 760 (s), 584 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 448
(100) [M]+, 419 (41), 387 (31), 359 (07), 267 (21), 209 (25), 165 (29),
152 (16). HRMS (EI): calcd. for C31H28O3 [M]+ 448.20330; found
448.203658.
(C=O) ppm. IR (KBr): ν = 3117, 3076, 3040 (w), 1671, 1624 (m),
˜
1582 (s), 1438, 1341, 1291 (m), 1237, 1202 (s), 1164, 1087, 988, 933,
819, 779 (m), 725, 678 (s), 537 (m) cm–1. GC–MS (EI, 70 eV): m/z
(%) = 272 (92) [M]+, 239 (25), 212 (06), 196 (02), 184 (11), 147 (38),
128 (04), 121 (96), 120 (100), 92 (20), 79 (07), 65 (13), 53 (05), 39
(06). HRMS (EI): calcd. for C15H12O5 [M + H]+ 272.07575; found
273.075251.
Methyl 3Ј-Chloro-4-(3Ј-chlorobiphenylcarbonyl)biphenyl-2-carboxyl-
ate (5d): Compound 5d was obtained from 4 (220 mg, 0.41 mmol),
K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 3-chlorophen-
ylboronic acid (165 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a colourless oil; yield 146 mg (77%). 1H NMR
(300 MHz, CDCl3): δ = 3.57 (s, 3 H, OCH3), 7.00–7.06 (m, 4 H,
Methyl
4Ј-Methyl-4-(4Ј-methylbiphenylcarbonyl)biphenyl-2-carb-
(220 mg,
oxylate (5a): Compound 5a was obtained from
4
0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), p- ArH), 7.15–7.20 (m, 4 H, ArH), 7.26 (s, 1 H, ArH), 7.39–7.45 (m,
tolylboronic acid (144 mg, 1.06 mmol) and 1,4-dioxane
(5 mLmmol–1 of triflate) as a colourless crystalline solid; yield
145 mg (84%). M.p. 114–116 °C. 1H NMR (300 MHz, CDCl3): δ
2 H, ArH), 7.52–7.58 (m, 2 H, ArH), 7.73 (dd, J = 1.9, 8.1 Hz, 1 H,
ArH), 7.94 (d, J = 1.9 Hz, 1 H, ArH) ppm. 13C NMR (75.46 MHz,
CDCl3): δ = 52.2 (OCH3), 126.3, 127.4, 127.5, 127.9, 128.1, 129.1,
= 2.17 (s, 3 H, CH3), 2.30 (s, 3 H, CH3), 3.56 (s, 3 H, OCH3), 6.95 129.2, 129.3, 129.5, 130.1 (CHAr), 130.5 (CAr), 130.7, 131.1, 131.7,
(d, J = 8.0 Hz, 2 H, ArH), 7.04–7.21 (m, 6 H, ArH), 7.35–7.53 (m, 132.0 (CHAr), 134.0, 134.2, 136.5, 138.1, 140.0, 141.8, 141.9, 145.0
5 H, ArH), 7.70 (dd, J = 2.9, 8.1 Hz, 1 H, ArH), 7.98 (d, J =
(CAr), 167.5 (COO), 196.8 (C=O) ppm. IR (KBr): ν = 3059, 3024
˜
1.9 Hz, 1 H, ArH) ppm. 13C NMR (62.89 MHz, CDCl3): δ = 21.0 (w), 1725, 1663, 1593 (s), 1557 (w), 1435 (m), 1303, 1231 (s), 1152,
(CH3), 21.2 (CH3), 52.1 (OCH3), 126.9, 127.9, 128.8, 128.9, 129.0 1087 (m), 987 (w), 851 (m), 786 (s), 538 (m) cm–1. GC–MS (EI,
(CHAr), 129.9 (CAr), 130.2, 130.6, 131.4, 132.1 (CHAr), 135.8, 70 eV): m/z (%) = 461 (47) [M]–, 460 (97), 429 (18), 399 (70), 365
137.1, 137.2, 137.7, 138.3, 141.3, 146.3 (CAr), 168.4 (COO), 197.4 (12), 338 (10), 302 (09), 273 (74), 215 (88) 197 (36), 165 (28), 152
(C=O) ppm. IR (KBr): ν = 3080, 3057, 3025 (w), 1724, 1659 (s),
(100). HRMS (EI): calcd. for C27H18Cl2O3 [M]+ 460.06275; found
˜
1613 (w), 1595 (m), 1574, 1518 (w), 1438, 1310, 1277 (m), 1231 (s), 460.062304.
1152, 1082, 972 (m), 819, 704 (s), 536 (m) cm–1. MS (EI, 70 eV):
Methyl 4Ј-Vinyl-4-(4Ј-vinylbiphenylcarbonyl)biphenyl-2-carboxylate
m/z (%) = 420 (100) [M]+, 405 (21), 373 (09), 359 (23), 332 (07),
253 (26), 210 (07), 195 (40), 165 (39) 152 (25). HRMS (EI): calcd.
for C29H24O3 [M]+ 420.17200; found 420.172525.
(5e): Compound 5e was obtained from 4 (220 mg, 0.41 mmol),
K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 4-vinylphen-
ylboronic acid (156 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a yellow solid; yield 132 mg (72%). M.p. 89–90 °C.
1H NMR (300 MHz, CDCl3): δ = 3.55 (s, 3 H, OCH3), 5.16 (ddd,
J = 0.8, 10.8, 24.2 Hz, 2 H, CH2 vinyl), 5.65 (ddd, J = 0.8, 17.5,
33.0 Hz, 2 H, CH2 vinyl), 6.59 (ddd, J = 10.9, 17.6, 28.5 Hz, 2 H, 2
CHvinyl), 7.00–7.12 (m, 4 H, ArH), 7.14–7.18 (m, 2 H, ArH), 7.21
Methyl 4-(Biphenylcarbonyl)biphenyl-2-carboxylate (5b): Com-
pound 5b was obtained from 4 (220 mg, 0.41 mmol), K3PO4
(261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), phenylboronic acid
(130 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate) as
a colourless solid; yield 120 mg (75%). M.p. 124–126 °C. 1H NMR
(300 MHz, CDCl3): δ = 3.51 (s, 3 H, OCH3), 7.06–7.19 (m, 8 H, (s, 1 H, ArH), 7.34 (d, J = 8.1 Hz, 2 H, ArH), 7.40–7.50 (m, 4 H,
ArH), 7.23 (s, 1 H, ArH), 7.37–7.54 (m, 6 H, ArH), 7.69 (dd, J =
ArH), 7.71 (dd, J = 1.8, 8.0 Hz, 1 H, ArH), 7.99 (d, J = 1.6 Hz, 1
2.2, 8.4 Hz, 1 H, ArH), 7.97 (d, J = 1.9 Hz, 1 H, ArH) ppm. 13C H, ArH) ppm. 13C NMR (75.46 MHz, CDCl3): δ = 52.1 (OCH3),
NMR (62.89 MHz, CDCl3): δ = 52.0 (OCH3), 115.3 (CAr), 127.3, 114.2, 114.4, (2 CH2 vinyl), 126.0, 126.2, 127.3, 128.3, 128.9, 129.2,
127.4, 127.8, 128.0, 128.1, 128.3, 128.9, 129.0, 130.2, 130.6, 130.8,
131.5, 132.1 (CHAr), 136.1, 138.3, 140.1, 140.2, 141.3, 146.3 (CAr),
130.1, 130.6, 130.8, 131.6, 132.2, 136.2, 136.3 (CHAr, CHvinyl),
136.7, 137.1, 138.2, 139.5, 139.6, 141.0, 146.1 (CAr), 168.2 (COO),
168.2 (COO), 197.3 (C=O) ppm. IR (KBr): ν = 3056, 3024, 2849
197.3 (C=O) ppm. IR (KBr): ν = 3435, 3057, 3021, 2948 (w), 1721,
˜
˜
(w), 1721, 1663 (s), 1596 (m), 1556 (w), 1433 (m), 1398 (w), 1303 1663 (s), 1597 (m), 1548, 1514 (w), 1435, 1305 (m), 1230 (s), 1151,
(m), 1230 (s), 1151, 1086, 939, 967 (m), 742 (s), 539 (m) cm–1. MS 1085, 939 (m), 838, 768 (s), 539 (m) cm–1. GC–MS (EI, 70 eV): m/z
(EI, 70 eV): m/z (%) = 392 (100) [M]+, 359 (11), 331 (41), 305 (11),
239 (39), 181 (54), 165 (06), 152 (51) 139 (04). HRMS (EI): calcd.
for C27H20O3 [M]+ 392.14070; found 392.140174.
(%) = 444 (100) [M]+, 417 (05), 383 (08), 356 (04), 265 (19), 222
(11), 178 (30), 152 (07). HRMS (EI): calcd. for C31H24O3 [M]+
444.17200; found 444.172615.
Methyl 4Ј-Ethyl-4-(4Ј-ethylbiphenylcarbonyl)biphenyl-2-carboxylate
(5c): Compound 5c was obtained from 4 (220 mg, 0.41 mmol),
Methyl 4Ј-Chloro-4-(4Ј-chlorobiphenylcarbonyl)biphenyl-2-carboxyl-
ate (5f): Compound 5f was obtained from 4 (220 mg, 0.41 mmol),
K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4, (6 mol-%), 4-ethylphen- K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 4-chlorophen-
yboronic acid (159 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1 ylboronic acid (165 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a yellow solid; yield 115 mg (62%). M.p. 93–94 °C. of triflate) as a colourless solid; yield 122 mg (64%). M.p. 49–50 °C.
1H NMR (300 MHz, CDCl3): δ = 1.06 (t, J = 7.6 Hz, 3 H,
CH3 ethyl), 1.18 (t, J = 7.6 Hz, 3 H, CH3 ethyl), 2.47 (q, J = 7.6 Hz,
1H NMR (300 MHz, CDCl3): δ = 3.56 (s, 3 H, OCH3), 7.11 (s, 5
H, ArH), 7.20 (d, J = 8.4 Hz, 1 H, ArH), 7.30 (d, J = 8.6 Hz, 2 H,
2 H, CH2 ethyl), 2.62 (q, J = 7.5 Hz, 2 H, CH2 ethyl), 3.56 (s, 3 H, ArH), 7.38–7.50 (m, 5 H, ArH), 7.72 (dd, J = 1.8, 8.0 Hz, 1 H,
OCH3), 6.96 (d, J = 8.1 Hz, 2 H, ArH), 7.02–712 (m, 4 H, ArH),
7.14–7.18 (m, 2 H, ArH), 7.21 (s, 1 H, ArH), 7.37–7.44 (m, 2 H,
ArH), 7.48–7.54 (m, 2 H, ArH), 7.68 (dd, J = 1.8, 7.7 Hz, 1 H,
ArH), 7.95 (d, J = 2.1 Hz, 1 H, ArH) ppm. 13C NMR (62.90 MHz,
CDCl3): δ = 15.3 (CH3), 15.4 (CH3), 28.4, 28.5 (2 CH2 ethyl), 52.0
(OCH3), 127.0, 127.6, 127.8, 128.0, 128.9, 129.0, 130.1, 130.5, 130.6
ArH), 7.98 (d, J = 1.8 Hz, 1 H, ArH) ppm. 13C NMR (62.89 MHz,
CDCl3): δ = 52.2 (OCH3), 127.6, 128.3, 128.5, 129.0, 129.4, 130.1,
130.3 (CHAr), 130.5 (CAr), 130.8, 130.9, 131.7, 132.2 (CHAr), 133.7,
134.1, 136.2, 138.1, 138.6, 140.1, 145.5 (CAr), 167.7 (COO), 196.9
(C=O) ppm. IR (KBr): ν = 3058, 3027, 2949 (w), 1724, 1663 (s),
˜
1599 (m), 1573, 1554 (w), 1472 (m), 1394 (w), 1230 (s), 1190 (w),
(CHAr), 130.7 (CAr), 131.4, 132.0 (CHAr), 135.9, 137.4, 138.3, 1152 (m), 1087 (s), 939 (m), 826 (s), 778, 535 (m) cm–1. GC–MS
141.4, 143.5, 143.9, 146.2, 147.2 (CAr), 168.4 (COO), 197.5
(70 eV): m/z (%) = 460 [M]+ (35Cl), 461 (46), 460 (100), 429 (15),
Eur. J. Org. Chem. 2011, 6670–6684
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6675

M. Nawaz, I. Ullah, O.-U.-R. Abid, A. Villinger, P. Langer
FULL PAPER
401 (30), 372 (07), 273 (67), 215 (69), 197 (31), 180 (10) 165 (21),
152 (82). HRMS (EI): calcd. for C27H18Cl2O3 [M]+ (35Cl)
460.06275; found 460.062308.
Methyl
3Ј,4Ј,5Ј-Trimethoxy-4-(3Ј,4Ј,5Ј-trimethoxybiphenylcarb-
onyl)biphenyl-2-carboxylate (5j): Compound 5j was obtained from
4 (220 mg, 0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4
(6 mol-%),
3,4,5-trimethoxyphenylboronic
acid
(224 mg,
Methyl 4Ј-Bromo-4-(4Ј-bromobiphenylcarbonyl)biphenyl-2-carboxyl-
ate (5g): Compound 5g was obtained from 4 (220 mg, 0.41 mmol),
K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 4-bromophen-
ylboronic acid (212 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a yellow solid; yield 168 mg (74%). M.p. 49–51 °C.
1H NMR (300 MHz, CDCl3): δ = 3.6 (s, 3 H, OCH3), 7.12 (d, J =
5.9 Hz, 4 H, ArH), 7.43 (d, J = 6.1 Hz, 4 H, ArH), 7.40 (s, 1 H,
ArH), 7.50–7.80 (m, 4 H, ArH), 7.91 (dd, J = 2.0, 5.9 Hz, 1 H,
ArH), 8.19 (d, J = 1.7 Hz, 1 H, ArH) ppm. 13C NMR (75.46 MHz,
CDCl3): δ = 52.3 (OCH3), 122.7, 123.2, 126.7, 127.3, 128.2, 129.8,
130.2, 131.9, 132.5, 133.0, 133.7 (CHAr), 139.0, 139.3, 139.6, 146.3,
146.8, 147.0, 167.6 (CAr), 167.9, (COO), 191.3 (C=O) ppm. IR
1.06 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate) as a yellow
1
solid; yield 136 mg (58%). M.p. 138–140 °C. H NMR (300 MHz,
CDCl3): δ = 3.52 (s, 3 H, OCH3), 3.62 (s, 3 H, OCH3), 3.69 (s, 6
H, 2 OCH3), 3.78 (s, 6 H, 2 OCH3), 3.81 (s, 3 H, OCH3), 6.35 (s,
2 H, ArH), 6.39 (s, 2 H, ArH), 7.21 (dd, J = 1.1, 7.4 Hz, 1 H,
ArH), 7.42–7.47 (m, 2 H, ArH), 7.52–7.56 (m, 2 H, ArH), 7.71 (d,
J = 1.0 Hz, 2 H, ArH) ppm. 13C NMR (62.89 MHz, CDCl3): δ =
52.1 (OCH3), 55.9 (2 OCH3), 56.1 (2 OCH3), 60.6 (OCH3), 60.9
(OCH3), 105.2, 106.7, 127.6, 128.8, 129.4, 130.1, 130.8 (CHAr),
130.9 (CAr), 131.0, 131.1 (CHAr), 135.6, 135.8, 136.0, 137.3, 137.8,
138.4, 141.1, 145.6, 152.9, 153.0 (CAr), 168.7, (COO), 197.8
(C=O) ppm. IR (KBr): ν = 3057, 2921, 2851 (w), 1722 (m), 1661
˜
(KBr): ν = 3063, 3031, 2951 (w), 1727, 1669 (s), 1477 (m), 1422 (s),
˜
(s), 1583 (w), 1563 (s), 1461 (m), 1432 (s), 1377 (m), 1343, 1292,
1236, 1171 (s), 1067, 942 (m), 884, 875, 765, 679 (s), 532 (m) cm–1.
MS (EI, 70 eV): m/z (%) = 572 (100) [M]+, 556 (08), 525 (03), 286
(07), 240 (02), 197 (01), 127 (01), 69 (03). HRMS (EI): calcd. for
C33H32O9 [M]+ 572.20408; found 572.204330.
1307 (m), 1205 (s), 1167 (w), 1134 (m), 1086 (s), 944 (m), 884 (s),
781, 569 (m) cm–1. MS (70 eV): m/z (%) = 550 (100) [M]+ (81Br),
513 (16), 410 (07), 379 (16), 319 (37), 298 (25), 215 (13), 181 (09),
151 (28) 121 (21), 82 (21), 69 (51). HRMS (EI): calcd. for
C27H18Br2O3 [M]+ (81Br) 550.17200; found 550.172525.
Methyl 4Ј-Fluoro-4-(4Ј-fluorobiphenylcarbonyl)biphenyl-2-carboxyl-
ate (5k): Compound 5k was obtained from 4 (220 mg, 0.41 mmol),
K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 4-flourophenyl-
boronic acid (148 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a yellow oil; yield 110 mg (62%). 1H NMR
(300 MHz, CDCl3): δ = 3.55 (s, 3 H, OCH3), 6.82 (t, J = 8.7 Hz, 2
H, ArH), 6.9 (t, J = 8.6 Hz, 2 H, ArH), 7.10–7.17 (m, 4 H, ArH),
7.20 (s, 1 H, ArH), 7.38–7.50 (m, 4 H, ArH), 7.70 (dd, J = 2.2,
8.3 Hz, 1 H, ArH), 7.96 (d, J = 1.9 Hz, 1 H, ArH) ppm. 13C NMR
Methyl
4-(3Ј,4Ј-Dimethoxybiphenylcarbonyl)-3Ј,4Ј-dimethoxybi-
phenyl-2-carboxylate (5h): Compound 5h was obtained from 4
(220 mg, 0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4
(6 mol-%), 3,4-dimethoxyphenylboronic acid (192 mg, 1.06 mmol)
and 1,4-dioxane (5 mLmmol–1 of triflate) as a colourless solid;
1
yield 132 mg (62%). M.p. 65–67 °C. H NMR (300 MHz, CDCl3):
δ = 3.54 (s, 3 H, OCH3), 3.70 (s, 6 H, 2 OCH3), 3.80 (s, 3 H,
OCH3), 3.83 (s, 3 H, OCH3), 6.63 (d, J = 9.0 Hz, 1 H, ArH), 6.69–
6.72 (m, 2 H, ArH), 6.73 (d, J = 2.7 Hz, 2 H, ArH), 6.80 (d, J =
7.7 Hz, 1 H, ArH), 7.19 (d, J = 2.2 Hz, 2 H, ArH), 7.22 (s, 1 H,
ArH), 7.36–7.46 (m, 3 H, ArH), 7.69 (dd, J = 2.2, 8.2 Hz, 1 H,
ArH), 7.86 (d, J = 1.8 Hz, 1 H, ArH) ppm. 13C NMR (62.89 MHz,
CDCl3): δ = 52.1, 55.7, 55.8, 55.8, 55.9 (5OCH3), 110.8, 111.0,
111.4, 112.3, 120.6, 121.6, 127.1, 128.6, 129.8, 130.4, 130.6 (CHAr),
130.8 (CAr), 131.2, 131.6, (CHAr), 132.6, 132.8, 135.6, 138.4, 140.7,
145.7, 148.4, 148.6, 148.7, 148.9 (CAr), 168.7 (COO), 197.7
3
(62.89 MHz, CDCl3): δ = 52.1 (OCH3), 115.0 (d, JC,F = 7.5 Hz,
3
CHAr), 115.4 (d, JC,F = 7.1 Hz, CHAr), 127.4, 128.9, 129.7, 129.8,
3
130.1, 130.6 (CHAr), 130.8 (d, JC,F = 4.4 Hz, CHAr), 131.6, 132.0
4
(CHAr), 136.1 (d, JC,F = 3.7 Hz, CF), 136.2, 138.2, 140.1, 145.5,
160.4 (d, JC,F = 20.1 Hz, CF), 164.3 (d, JC,F = 21.1 Hz, CF), 167.9
(COO), 197.1 (C=O) ppm. 19F NMR (282 MHz, CDCl3): δ =
–73.34 (CF) ppm. IR (KBr): ν = 3062, 2950 (w), 1722, 1664 (s),
˜
1557 (w), 1476, 1394, 1305, 1220 (m), 1154, 1085, 987 (m), 833, 760
(s), 657, 547 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 428 (100)
[M]+, 395 (09), 367 (30), 340 (10), 257 (51), 214 (10), 199 (59), 170
(47), 120 (02) 59 (02). HRMS (EI): calcd. for C27H18F2O3 [M]+
428.12185; found 428.121344.
(C=O) ppm. IR (KBr): ν = 3057, 2998, 2950 (w), 1720 (m), 1662
˜
(s), 1569 (w), 1518 (s), 1480 (m), 1437 (s), 1325 (m), 1243, 1214,
1171 (s), 1086, 941 (m), 881, 850, 756, 699 (s), 597 (m) cm–1. MS
(EI, 70 eV): m/z (%) = 512 (100) [M]+, 496 (04), 465 (02), 299 (03),
241 (09), 210 (04), 167 (01), 126 (02) 91 (01), 43 (05). HRMS (EI):
calcd. for C31H28O7 [M]+ 512.18295; found 512.182285.
Methyl 3Ј-Hydroxy-4-(3Ј-hydroxybiphenylcarbonyl)biphenyl-2-carb-
Methyl 4Ј-Hydroxy-4-(4Ј-hydroxybiphenylcarbonyl)biphenyl-2-carb-
oxylate (5l): Compound 5l was obtained from
0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 3-
0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 4- hydroxyphenylboronic acid (146 mg, 1.06 mmol) and 1,4-dioxane
4 (220 mg,
oxylate (5i): Compound 5i was obtained from
4 (220 mg,
hydroxyphenylboronic acid (146 mg, 1.06 mmol) and 1,4-dioxane
(5 mLmmol–1 of triflate) as a colourless solid; yield 114 mg (65%).
(5 mLmmol–1 of triflate) as a yellow solid; yield 117 mg (67%). M.p. 48–49 °C. 1H NMR (300 MHz, CDCl3): δ = 3.63 (s, 3 H,
1
M.p. 134–136 °C. H NMR (300 MHz, CDCl3): δ = 3.64 (s, 3 H,
OCH3), 6.52 (s, 1 H, OH), 6.55 (s, 1 H, OH), 6.66 (d, J = 7.9 Hz,
2 H, ArH), 6.97–7.02 (m, 4 H, ArH), 7.15 (s, 1 H, ArH), 7.19 (d,
J = 2.2 Hz, 1 H, ArH), 7.39–7.41 (m, 3 H, ArH), 7.48–7.51 (m, 2
OCH3), 6.75–6.88 (m, 5 H, ArH), 7.02 (dd, J = 1.1, 8.5 Hz, 1 H,
ArH), 7.22 (d, J = 7.6 Hz, 2 H, ArH), 7.42–7.48 (m, 3 H, ArH),
7.54 (dd, J = 1.5, 8.0 Hz, 2 H, ArH), 7.75 (dd, J = 2.1, 7.7 Hz, 1
H, ArH), 8.02 (d, J = 1.8 Hz, 1 H, ArH), 11.84 (s, 2 H, OH) ppm.
H, ArH), 7.66 (dd, J = 1.8, 8.0 Hz, 1 H, ArH), 7.90 (d, J = 1.7 Hz, 13C NMR (62.89 MHz, CDCl3): δ = 52.4, (OCH3), 115.0, 115.2,
1 H, ArH) ppm. 13C NMR (75.46 MHz, CDCl3): δ = 52.5 (OCH3), 116.2, 117.1, 118.5, 118.9, 119.2, 120.6, 129.5, 130.7, 131.1, 131.6,
115.4, 115.5, 126.8, 129.1, 129.5, 130.1, 130.4, 130.7, 131.0, 131.4
(CHAr), 131.7, 132.2 (CAr), 132.3 (CHAr), 135.5, 137.9, 141.3, 149.1, 155.6, 163.2 (CAr), 168.3 (COO), 197.5 (C=O) ppm. IR
146.2, 155.6, 156.1 (CAr), 169.5 (COO), 198.4 (C=O) ppm. IR (KBr): ν = 3071, 3048, 2962, 2839, 2831 (w), 1721, 1662 (s), 1593,
132.2, 133.3, 136.7, (CHAr), 141.5, 142.2, 143.4, 144.2, 145.3, 147.2,
˜
(KBr): ν = 3352, 3060, 2951 (w), 1708, 1649 (m), 1589 (s), 1553 1582 (m), 1478, 1452 (m), 1391, 1343, 1301 (m), 1281, 1235, 1168
˜
(w), 1517 (s), 1476 (m), 1398 (w), 1232, 1172 (s), 1153 (m), 1087
(s), 1092, 941 (s), 892, 863, 774, 694 (s), 591, 572, 530 (m) cm–1.
(s), 941 (m), 832 (s), 761, 660, 539 (m) cm–1. GC–MS (70 eV): m/z
MS (EI, 70 eV): m/z (%) = 424 (50) [M]+, 410 (20), 390 (36), 380
(%) = 424 (96) [M]+, 392 (100), 372 (24), 255 (18), 223 (35), 212 (45), 341 (17), 312 (38), 285 (23), 249 (80), 221 (11), 134 (13), 110
(16), 197 (58), 168 (14), 139 (23) 115 (13), 89 (02). HRMS (EI):
(100), 91 (13), 64 (19). HRMS (EI): calcd. for C27H20O5 [M]+
424.03841; found 424.038844.
calcd. for C27H20O5 [M]+ 424.13053; found 424.130645.
6676
www.eurjoc.org
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 6670–6684

2Ј,4-Diarylbenzophenones from Bis(triflates) of 2Ј,4-Dihydroxybenzophenones
Methyl 4Ј-(Trifluoromethyl)-4-[4Ј-(trifluoromethyl)biphenylcarb-
1452 (m), 1389, 1341, 1301 (m), 1281, 1231, 1164 (s), 1092, 941 (s),
891, 864, 779, 693 (s), 591, 573, 538 (m) cm–1. MS (EI, 70 eV): m/z
(%) = 452 (12) [M]+, 421 (100), 405 (01), 375 (01), 347 (08), 269
(03), 195 (09), 168 (05), 139 (05). HRMS (EI): calcd. for C29H24O5
[M]+ 452.16183; found 452.161882.
onyl]biphenyl-2-carboxylate (5m): Compound 5m was obtained
from 4 (220 mg, 0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd
(PPh3)4 (6 mol-%), 4-(trifluoromethyl)phenylboronic acid (201 mg,
1.06 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate) as a colour-
less oil; yield 165 mg (76%). 1H NMR (300 MHz, CDCl3): δ = 3.55
(s, 3 H, OCH3), 7.18–7.28 (m, 4 H, ArH), 7.31 (s, 1 H, ArH), 7.39–
7.44 (m, 4 H, ArH), 7.48–7.50 (m, 1 H, ArH), 7.54–7.58 (m, 3 H,
ArH), 7.74 (dd, J = 1.8, 8.0 Hz, 1 H, ArH), 8.02 (d, J = 1.8 Hz, 1
H, ArH) ppm. 13C NMR (75.46 MHz, CDCl3): δ = 52.2 (OCH3),
125.0 (q, JF,C = 3.6 Hz, CHAr), 125.2 (q, JF,C = 3.9 Hz, CHAr),
128.1, 128.4, 129.3, 129.4 (CHAr), 129.8 (CAr), 130.2 (CHAr), 130.4
(CAr), 130.8, 131.2, 131.8, 132.2 (CHAr), 136.7, 138.1, 140.1, 143.7,
143.9, 145.4, 146.2 (CAr), 167.7 (COO), 196.6 (C=O) ppm. 19F
Methyl
2Ј-Methoxy-4-(2Ј-methoxybiphenylcarbonyl)biphenyl-2-
carboxylate (5p): Compound 5p was obtained from 4 (220 mg,
0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 4-
tert-butylphenylboronic acid (188 mg, 1.06 mmol) and 1,4-dioxane
(5 mLmmol–1 of triflate) as a colourless solid; yield 150 mg (72%).
4
4
1
M.p. 131–133 °C. H NMR (300 MHz, CDCl3): δ = 1.13 (s, 9 H,
3 CH3), 1.26 (s, 9 H, 3 CH3), 3.53 (s, 3 H, OCH3), 7.06 (d, J =
8.6 Hz, 2 H, ArH), 7.10 (d, J = 4.2 Hz, 2 H, ArH), 7.14 (s, 1 H,
ArH), 7.16 (d, J = 2.0 Hz, 1 H, ArH), 7.30 (d, J = 8.8 Hz, 2 H,
ArH), 7.38–7.44 (m, 3 H, ArH), 7.48–7.53 (m, 2 H, ArH), 7.63 (dd,
J = 1.9, 8.1 Hz, 1 H, ArH), 7.89 (d, J = 1.8 Hz, 1 H, ArH) ppm.
13C NMR (75.47 MHz, CDCl3): δ = 31.3 (6 CH3), 34.6 (2 CtBu),
52.0 (OCH3), 125.1, 125.2 (CHAr), 126.3 (CAr), 127.0, 127.8, 128.9,
129.0, 130.0, 130.4 (CHAr), 130.6 (CAr), 130.8, 131.3, 131.9 (CHAr),
136.1, 137.2, 138.4, 141.4, 145.9, 150.4, 150.8 (CAr), 168.5 (COO),
NMR (282 MHz, CDCl ): δ = –73.30 (CF) ppm. IR (KBr): ν =
˜
3
3063, 2953, 2855 (w), 1727, 1666 (s), 1600 (w), 1437, 1321, 1233
(m), 1161, 1066, 940 (m), 838, 785, 705, (s), 671, 607, 539 (m) cm–1.
MS (EI, 70 eV): m/z (%) = 528 (10) [M]+, 291 (17), 290 (100), 271
(23), 240 (12), 201 (16), 162 (14), 97 (12), 84 (73) 71 (16), 57 (29).
HRMS (EI): calcd. for C29H18F6O3 [M]+ 528.11547; found
528.115737.
197.7 (C=O) ppm. IR (KBr): ν = 3068, 3049, 2969, 2842, 2829 (w),
˜
Methyl
4-(2Ј,5Ј-Dimethoxybiphenylcarbonyl)-2Ј,5Ј-dimethoxybi-
1721, 1663 (s), 1592, 1581 (m), 1472, 1452 (m), 1390, 1339, 1301
(m), 1279, 1235, 1162 (s), 1090, 941 (s), 891, 862, 771, 692 (s), 590,
572, 533 (m) cm–1. MS (EI, 70 eV): m/z (%) = 504 (100) [M]+, 490
(32), 489 (89), 457 (42), 447 (14), 401 (12), 359 (01), 295 (03), 252
(02), 237 (39), 181 (24), 152 (09), 126 (03), 57 (24), 41 (10). HRMS
(EI): calcd. for C35H36O3 [M]+ 504.26590; found 504.265979.
phenyl-2-carboxylate (5n): Compound 5n was obtained from 4
(220 mg, 0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4
(6 mol-%), 2,5-dimethoxyphenylboronic acid (192 mg, 1.06 mmol)
and 1,4-dioxane (5 mLmmol–1 of triflate) as a colourless solid;
yield 140 mg (67%). M.p. 150–152 °C. 1H NMR (300 MHz,
CDCl3): δ = 3.27 (s, 3 H, OCH3), 3.55 (s, 3 H, OCH3), 3.57 (s, 3
H, OCH3), 3.67 (s, 3 H, OCH3), 3.72 (s, 3 H, OCH3), 6.50 (d, J =
8.9 Hz, 1 H, ArH), 6.63 (dd, J = 3.6, 8.8 Hz, 1 H, ArH), 6.71–6.74
(m, 2 H, ArH), 6.78 (dd, J = 2.6, 7.7 Hz, 2 H, ArH), 7.23 (d, J =
7.9 Hz, 1 H, ArH), 7.37 (dd, J = 3.1, 7.3 Hz, 2 H, ArH), 7.46–7.52
(m, 2 H, ArH), 7.83 (dd, J = 1.8, 7.9 Hz, 1 H, ArH), 8.08 (d, J =
1.7 Hz, 1 H, ArH) ppm. 13C NMR (75.47 MHz, CDCl3): δ = 51.8
(OCH3), 54.8 (OCH3), 55.7 (2 OCH3), 55.8 (OCH3), 111.1, 111.5,
113.5, 113.8, 116.0, 116.8, 127.0, 128.7, 130.9, 131.0, 131.1, 131.2,
132.5, (CHAr), 136.1, 137.8, 138.5, 142.3, 149.5, 150.2, 153.6, 153.7,
153.8, 156.0, 158.8 (CAr), 167.8 (COO), 195.7 (C=O) ppm. IR
Methyl 4-(3Ј,5Ј-Dimethylbiphenylcarbonyl)-3Ј,5Ј-dimethylbiphenyl-
2-carboxylate (5q): Compound 5q was obtained from 4 (220 mg,
0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%),
3,5-dimethylphenylboronic acid (159 mg, 1.06 mmol) and 1,4-diox-
ane (5 mLmmol–1 of triflate) as a colourless solid; yield 144 mg
(78%). M.p. 109–111 °C. 1H NMR (300 MHz, CDCl3): δ = 2.11 (s,
6 H, 2 CH3), 2.26 (s, 6 H, 2 CH3), 3.55 (s, 3 H, OCH3), 6.69 (s, 1
H, ArH), 6.77 (d, J = 3.0 Hz, 2 H, ArH), 6.92 (s, 1 H, ArH), 7.16
(s, 1 H, ArH), 7.19 (d, J = 2.8 Hz, 1 H, ArH), 7.40 (d, J = 1.9 Hz,
1 H, ArH), 7.42 (s, 2 H, ArH), 7.49–7.54 (m, 2 H, ArH), 7.66 (dd,
J = 1.9, 7.8 Hz, 1 H, ArH), 7.84 (d, J = 2.7 Hz, 1 H, ArH) ppm.
13C NMR (62.90 MHz, CDCl3): δ = 21.0 (2 CH3), 21.2 (2 CH3),
52.0 (OCH3), 125.8, 127.1, 128.9, 129.0, 129.5, 129.9, 130.3, 130.7,
131.1, 131.5 (CHAr), 136.1, 137.6, 137.7, 138.3, 139.9, 140.1, 141.7,
(KBr): ν = 3070, 3050, 2970, 2842, 2832 (w), 1721, 1662 (s), 1594,
˜
1582 (m), 1475, 1452 (m), 1391, 1341, 1301 (m), 1281, 1233, 1164
(s), 1091, 940 (s), 891, 862, 773, 691 (s), 592, 574, 530 (m) cm–1.
MS (EI, 70 eV): m/z (%) = 512 (40) [M]+, 448 (19), 409 (31), 385
(04), 340 (15), 323 (33), 288 (20), 250 (81), 195 (01), 182 (38), 167
(40), 151 (10), 138 (25), 123 (36), 94 (68), 84 (100), 65 (10), 47 (21),
43 (44). HRMS (EI): calcd. for C31H29O7 [M + H]+ 513.19078;
found 513.190802.
146.1 (CAr), 168.5 (COO), 197.6 (C=O) ppm. IR (KBr): ν = 3068,
˜
3048, 2969, 2837, 2821 (w), 1721, 1659 (s), 1593, 1579 (m), 1481,
1461 (m), 1389, 1331, 1301 (m), 1282, 1239, 1164 (s), 1090, 941 (s),
893, 863, 776, 691 (s), 593, 575, 530 (m) cm–1. MS (EI, 70 eV): m/z
(%) = 448 (87) [M]+, 433 (100), 401 (32), 387 (17), 267 (12), 209
(37), 179 (19), 165 (36), 115 (01), 77 (01). HRMS (EI): calcd. for
C31H28O3 [M]+ 448.20330; found 448.203841.
Methyl
2Ј-Methoxy-4-(2Ј-methoxybiphenylcarbonyl)biphenyl-2-
carboxylate (5o): Compound 5o was obtained from 4 (220 mg,
0.41 mmol), K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 2-
methoxyphenylboronic acid (161 mg, 1.06 mmol) and 1,4-dioxane
(5 mLmmol–1 of triflate) as a colourless solid; yield 128 mg (69%).
Methyl 3Ј-Bromo-4-(3Ј-bromobiphenylcarbonyl)biphenyl-2-carboxyl-
ate (5r): Compound 5r was obtained from 4 (220 mg, 0.41 mmol),
K3PO4 (261 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 3-bromophen-
ylboronic acid (212 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a colourless oil; yield 144 mg (64%). 1H NMR
(300 MHz, CDCl3): δ = 3.57 (s, 3 H, OCH3), 6.80 (d, J = 7.1 Hz,
2 H, ArH), 6.90 (t, J = 6.2 Hz, 2 H, ArH), 7.06 (d, J = 5.1 Hz, 2
1
M.p. 139–140 °C. H NMR (300 MHz, CDCl3): δ = 3.32 (s, 3 H,
OCH3), 3.56 (s, 3 H, OCH3), 3.61 (s, 3 H, OCH3), 6.58 (d, J =
7.2 Hz, 1 H, ArH), 6.80–6.89 (m, 3 H, ArH), 6.92–6.98 (m, 2 H,
ArH), 7.08–7.14 (m, 2 H, ArH), 7.16 (s, 1 H, ArH), 7.20–7.30 (m,
2 H, ArH), 7.37 (dd, J = 3.0, 7.7 Hz, 1 H, ArH), 7.46–7.52 (m, 1
H, ArH), 7.82 (dd, J = 2.0, 8.4 Hz, 1 H, ArH), 8.10 (d, J = 1.86 Hz, H, ArH), 7.26 (s, 1 H, ArH), 7.39–7.58 (m, 6 H, ArH), 7.73 (dd, J
1 H, ArH) ppm. 13C NMR (62.90 MHz, CDCl3): δ = 51.8 (OCH3), = 2.5, 8.3 Hz, 1 H, ArH), 7.94 (d, J = 1.9 Hz, 1 H, ArH) ppm. 13
C
54.4 (OCH3), 55.2, (OCH3), 109.9, 110.1, 110.3, 126.8, 128.6, 129.1, NMR (75.46 MHz, CDCl3): δ = 52.2 (OCH3), 126.3, 127.9, 128.1,
129.4, 129.7, 130.8, 131.0, 131.1, 131.2, 132.5, 132.8 (CHAr), 135.1 128.7, 129.1, 129.3, 129.5, 130.1, 130.7, 131.1, 131.6. 131.7, 132.0
(CAr), 136.8 (CHAr), 138.0, 138.5, 142.6, 144.2, 146.8, 155.2, 155.9, (CHAr), 134.0, 135.2, 136.5, 137.1, 138.1, 139.9, 141.8, 141.9, 145.0
164.5 (CAr), 167.9 (COO), 195.8 (C=O) ppm. IR (KBr): ν = 3072,
(CAr), 167.5 (COO), 196.8 (C=O) ppm. IR (KBr): ν = 3059, 3024
˜
˜
3049, 2968, 2842, 2832 (w), 1719, 1664 (s), 1593, 1581 (m), 1475, (w), 1725, 1663, 1593 (s), 1557 (w), 1435 (m), 1303, 1231 (s), 1152,
Eur. J. Org. Chem. 2011, 6670–6684
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6677

M. Nawaz, I. Ullah, O.-U.-R. Abid, A. Villinger, P. Langer
1087 (m), 987 (w), 851 (m), 786 (s), 538 (m) cm–1. GC–MS (EI, 463 (38), 448 (64), 415 (38), 315 (78), 287 (18), 271 (42), 253 (18),
FULL PAPER
70 eV): m/z (%) = 550 (47) [M]+ (81Br, 79Br), 510 (46), 489 (48), 456
(21), 461 (92), 427 (16), 398 (72), 362 (10), 336 (12), 302 (09), 271
(72), 212 (86), 195 (32), 162 (26), 150 (100), 120 (45), 102 (36), 89
(42), 62 (46), 48 (28). HRMS (EI): calcd. for C27H18Br2O3 [M]+
(81Br, 79Br) 550.24062; found 550.240120.
223 (46), 139 (28), 121 (14), 69 (10). HRMS (EI): calcd. for
C24H19F3O7S [M]+ 508.07981; found 508.079693.
Methyl 2Ј-Bromo-4-[2-(trifluoromethanesulfonyloxy)benzoyl]biphen-
yl-2-carboxylate (6d): Compound 6d was obtained from 4 (150 mg,
0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd (PPh3)4 (3 mol-%), 2-
bromophenylboronic acid (70 mg, 0.35 mmol) and 1,4-dioxane
(5 mLmmol–1 of triflate) as a colourless solid; yield 119 mg (78%).
Methyl 3Ј,5Ј-Dimethyl-4-[2-(trifluoromethanesulfonyloxy)benzoyl]bi-
phenyl-2-carboxylate (6a): Compound 6a was obtained from 4
(150 mg, 0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4
(3 mol-%), 3,5-dimethylphenylboronic acid (52 mg, 0.35 mmol) and
1,4-dioxane (5 mLmmol–1 of triflate) as a colourless oil; yield
107 mg (78%). 1H NMR (300 MHz, CDCl3): δ = 2.28 (s, 6 H, 2
CH3), 3.58 (s, 3 H, OCH3), 6.88 (s, 2 H, ArH), 6.96 (s, 1 H, ArH),
7.36 (s, 1 H, ArH), 7.47–7.61 (m, 4 H, ArH), 7.89 (dd, J = 2.1,
8.3 Hz, 1 H, ArH), 8.11 (d, J = 2.4 Hz, 1 H, ArH) ppm. 13C NMR
1
M.p. 124–126 °C. H NMR (300 MHz, CDCl3): δ = 3.58 (s, 3 H,
OCH3), 7.13 (s, 1 H, ArH), 7.28–7.40 (m, 4 H, ArH), 7.48–7.62
(m, 4 H, ArH), 7.94 (dd, J = 2.1, 8.1 Hz, 1 H, ArH), 8.36 (d, J =
2.1 Hz, 1 H, ArH) ppm. 13C NMR (75.46 MHz, CDCl3): δ = 52.3
(OCH3), 122.7 (q, JF,C = 321.4 Hz, CF3), 127.1, 128.3, 129.2, 129.7,
129.8, 130.2, 131.3, 131.8, 132.3, 132.9, 133.2, (CHAr), 134.9, 135.0,
136.0, 141.5, 146.7, 146.8, 147.2 (CAr), 166.2 (COO), 191.4
(62.90 MHz, CDCl3): δ = 21.2 (2 CH3), 52.2 (OCH3), 110.8 (C), (C=O) ppm. 19F NMR (282 MHz, CDCl3): δ = –73.29 (CF) ppm.
121.0 (q, JF,C = 320.7 Hz, CF3), 122.6, 125.9, 128.1, 129.8, 131.0, IR (KBr): ν = 3053, 2953, 2923 (w), 1728, 1672 (s), 1567 (m), 1482
˜
131.1, 131.3 (CHAr), 131.5, 132.0 (CAr), 132.2, 132.9 (CHAr), 135.0, (w), 1309, 1294 (m), 1241, 1203 (s), 1168 (m), 1087 (s), 948 (m),
137.1, 139.8, 146.8, 147.6 (CAr), 168.4 (COO), 191.4 (C=O) ppm. 887, 769, 592 (s) cm–1. MS (EI, 70 eV): m/z (%) = 543 (100) [M]+,
19F NMR (282 MHz, CDCl ): δ = –73.34 (CF) ppm. IR (KBr): ν 489 (19), 462 (21), 402 (13), 389 (29), 347 (31), 331 (12), 301 (48),
˜
3
= 3065, 3004, 2950 (w), 1724 (m), 1669 (s), 1560 (w), 1422 (s), 1308
(m), 1245, 1205, 1135 (s), 1092, 944 (m), 886, 855, 593 (s) cm–1. MS
(EI, 70 eV): m/z (%) = 492 (100) [M]+, 461 (19), 359 (03), 327 (31),
300 (14), 267 (19), 255 (07), 209 (03), 165 (09). HRMS (EI): calcd.
for C24H19F3O6S [M]+ 492.08490; found 492.084987.
271 (24), 242 (75), 215 (7), 183 (5), 151 (11), 69 (15). HRMS (EI):
calcd. for C22H14BrF3O6S [M]+ (79Br) 543.96471; found
543.964520.
Methyl 3Ј,4Ј-Dimethoxy-4-[2-(trifluoromethanesulfonyloxy)benzo-
yl]biphenyl-2-carboxylate (6e): Compound 6e was obtained from 4
Methyl 4Ј-Chloro-4-[2-(trifluoromethanesulfonyloxy)benzoyl]biphen- (150 mg, 0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4
yl-2-carboxylate (6b): Compound 6b was obtained from 4 (150 mg,
(3 mol-%), 3,4-dimethoxyphenylboronic acid (63 mg, 0.35 mmol)
0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4 (3 mol-%), 4- and 1,4-dioxane (5 mLmmol–1 of triflate) as a yellow solid; yield
1
chlorophenylboronic acid (54 mg, 0.35 mmol) and 1,4-dioxane
65 mg (44%). M.p. 116–118 °C. H NMR (300 MHz, CDCl3): δ =
(5 mLmmol–1 of triflate) as a yellow solid; yield 63 mg (45%). M.p.
3.61 (s, 3 H, OCH3), 3.83 (s, 3 H, OCH3), 3.86 (s, 3 H, OCH3),
105–106 °C. 1H NMR (300 MHz, CDCl3): δ = 3.61 (s, 3 H, OCH3), 6.81 (s, 1 H, ArH), 6.86 (d, J = 6.2 Hz, 1 H, ArH), 7.19 (s, 1 H,
7.21 (d, J = 8.5 Hz, 2 H, ArH), 7.32 (s, 1 H, ArH), 7.35–7.42 (m, ArH), 7.37 (d, J = 6.9 Hz, 1 H, ArH), 7.45–7.85 (m, 4 H, ArH),
3 H, ArH), 7.48 (dd, J = 1.0, 7.3 Hz, 1 H, ArH), 7.53–7.63 (m, 2
7.91 (dd, J = 3.9, 7.2 Hz, 1 H, ArH), 8.1 (d, J = 1.9 Hz, 1 H,
H, ArH), 7.90 (dd, J = 1.9, 8.0 Hz, 1 H, ArH), 8.20 (d, J = 1.8 Hz, ArH) ppm. 13C NMR (62.89 MHz, CDCl3): δ = 52.3, 55.8, 55.9,
1 H, ArH) ppm. 13C NMR (75.46 MHz, CDCl3): δ = 52.3 (OCH3), (3 OCH3), 110.9, 111.4 (CHAr), 120.7 (q, JF,C = 320.1 Hz, CF3),
116.3 (CAr), 120.5 (q, JF,C = 321.1 Hz, CF3), 122.7, 123.0, 128.2,
122.6, 123.0, 128.1, 130.9, 131.1, 131.4, 132.2, 132.9, (CHAr), 133.9,
128.5, 129.5, 131.1, 131.8 (CHAr), 131.9 (CAr), 132.5, 133.1, 134.3, 134.8, 144.8, 146.8, 146.9, 148.7, 149.1 (CAr), 168.6 (COO),
(CHAr), 134.3, 135.5, 138.5, 146.3, 146.8 (CAr), 167.6 (COO), 191.3 191.3 (C=O) ppm. 19F NMR (282 MHz, CDCl3): δ = –73.30
(C=O) ppm. 19F NMR (282 MHz, CDCl3): δ = –73.29 (CF) ppm.
(CF) ppm. IR (KBr): ν = 3064, 2994, 2924 (w), 1726 (s), 1668,
˜
IR (KBr): ν = 3066, 3033, 2952 (w), 1727, 1670 (s), 1603 (m), 1573, 1520, 1482 (m), 1421 (s), 1308 (m), 1243, 1206, 1170, 1086 (s), 944
˜
1554 (w), 1475, 1308 (m), 1245, 1134, 1084 (s), 1040 (w), 944 (m),
827, 767, 592 (s) cm–1. GC–MS (70 eV): m/z (%) = 498 (100) [M]+,
467 (30), 333 (26), 306 (14), 273 (32), 253 (07), 215 (06), 151 (07), 69
(06). HRMS (EI): calcd. for C22H14ClF3O6S [M]+ (35Cl) 498.01462;
found 498.014917.
(m), 891 (s), 830 (m), 763 (s), 732, 655 (m), 602 (s), 592 (m) cm–1.
MS (EI, 70 eV): m/z (%) = 524 (100) [M]+, 493 (03), 392 (11), 359
(29), 332 (07), 289 (04), 218 (02), 189 (02), 121 (04), 69 (05). HRMS
(EI): calcd. for C24H19F3O8S [M]+ 524.07472; found 524.074184.
Methyl 4Ј-Hydroxy-4-[2-(trifluoromethanesulfonyloxy)benzoyl]bi-
Methyl 2Ј-Ethoxy-4-[2-(trifluoromethanesulfonyloxy)benzoyl]biphen- phenyl-2-carboxylate (6f): Compound 6f was obtained from 4
yl-2-carboxylate (6c): Compound 6c was obtained from 4 (150 mg, (150 mg, 0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4
0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4 (3 mol-%), 2- (3 mol-%), 4-hydroxyphenylboronic acid (48 mg, 0.35 mmol) and
ethoxyphenylboronic acid (58 mg, 0.35 mmol) and 1,4-dioxane
1,4-dioxane (5 mLmmol–1 of triflate) as a colourless oil; yield
(5 mLmmol–1 of triflate) as a yellow oil; yield 127 mg (89%). 1H
85 mg (63%). 1H NMR (300 MHz, CDCl3): δ = 3.60 (s, 3 H,
NMR (300 MHz, CDCl3): δ = 1.32 (t, J = 3.1 Hz, 3 H, CH3), 3.89 OCH3), 6.78 (d, J = 6.9 Hz, 2 H, ArH), 7.13 (d, J = 6.2 Hz, 2 H,
(s, 1 H, OCH3), 4.05 (q, J = 4.1 Hz, 2 H, OCH2), 6.82 (s, 1 H,
ArH), 6.90–7.76 (m, 8 H, ArH), 7.91 (dd, J = 1.8, 8.1 Hz, 1 H,
ArH), 8.21 (d, J = 1.8 Hz, 1 H, ArH) ppm. 13C NMR (75.46 MHz,
ArH), 7.18 (s, 1 H, OH), 7.37 (s, 1 H, ArH), 7.40–7.62 (m, 4 H,
ArH), 7.89 (dd, J = 4.6, 6.9 Hz, 1 H, ArH), 8.13 (d, J = 5.8 Hz, 1
H, ArH) ppm. 13C NMR (62.89 MHz, CDCl3): δ = 52.3 (OCH3),
CDCl3): δ = 14.8 (CH3), 51.8 (OCH3), 63.9 (OCH2), 111.2 (CH), 115.3 (CHAr), 122.7 (q, JF,C = 321.2 Hz, CF3), 128.1, 129.6, 131.0,
120.8 (q, JF,C = 320.1 Hz, CF3), 122.6, 128.2, 129.6, 129.7, 131.1,
131.1, 131.6, 132.4, 132.9, 133.0 (CHAr), 133.8, 134.2, 134.8, 145.1,
131.3, 131.8, 132.6, 132.9, 133.0 (CHAr), 135.0, 136.8, 137.5, 144.5,
146.8, 147.1, 155.9 (CAr), 168.5 (COO), 191.4 (C=O) ppm. 19F
146.8, 155.3, 163.9 (CAr), 167.6 (COO), 191.6 (C=O) ppm. 19F NMR (282 MHz, CDCl ): δ = –73.71 (CF) ppm. IR (KBr): ν =
˜
3
NMR (282 MHz, CDCl ): δ = –73.34 (CF) ppm. IR (KBr): ν = 3377, 3060, 2952 (w), 1715, 1667 (s), 1599 (m), 1555, 1520 (w),
˜
3
3497, 3067, 3032 (w), 1725, 1669 (s), 1599 (m), 1575, 1500 (w), 1480, 1310 (m), 1245, 1134, 1086 (s), 1040 (w), 944 (m), 884, 767,
1445, 1309, 1282 (m), 1245, 1206 (s), 1083, 945 (m), 884, 751 (s), 656, 592 (s) cm–1. GC–MS (70 eV): m/z (%) = 480 (22) [M]+, 449
569 (m) cm–1. MS (EI, 70 eV): m/z (%) = 508 (100) [M]+, 477 (04),
(05), 348 (100), 315 (45), 289 (87), 272 (22), 255 (57), 228 (24), 197
6678
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 6670–6684

2Ј,4-Diarylbenzophenones from Bis(triflates) of 2Ј,4-Dihydroxybenzophenones
(16), 139 (22), 121 (88), 93 (18), 65 (13). HRMS (EI): calcd. for
C22H15F3O7S[M]+ 480.04851; found 480.048783.
(m), 864, 786 (s), 694, 647, 575, 540 (m) cm–1. GC–MS (EI, 70 eV):
m/z (%) = 446 (100) [M]+, 414 (16), 385 (16), 358 (08), 267 (29),
207 (20), 194 (08), 178 (49), 152 (14), 77 (01). HRMS (EI): calcd.
for C31H26O3 [M]+ 446.18765; found 446.187064.
Methyl 3Ј,4Ј,5Ј-Trimethoxy-4-[2-(trifluoromethanesulfonyloxy)benz-
oyl]biphenyl-2-carboxylate (6g): Compound 6g was obtained from
4 (150 mg, 0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4
(3 mol-%), 3,4,5-trimethoxyphenylboronic acid (74 mg, 0.35 mmol)
and 1,4-dioxane (5 mLmmol–1 of triflate) as a crystalline yellow
solid; yield 68 mg (43%). M.p. 103–104 °C. 1H NMR (300 MHz,
CDCl3): δ = 3.61 (s, 9 H, 3 OCH3), 3.83 (s, 3 H, OCH3), 6.49 (s, 2
H, ArH), 7.40 (s, 1 H, ArH), 7.45–7.63 (m, 4 H, ArH), 7.91 (dd, J
Methyl
4Ј-Hydroxy-4-(4Ј-vinylbiphenylcarbonyl)biphenyl-2-carb-
oxylate (7b): Compound 7b was obtained from 6f (150 mg,
0.31 mmol), K3PO4 (197 mg, 0.93 mmol), Pd(PPh3)4 (3 mol-%), 4-
vinylphenylboronic acid (59 mg, 0.40 mmol) and 1,4-dioxane
(5 mLmmol–1 of triflate) as a colourless oil; yield 100 mg (74%).
1H NMR (300 MHz, CDCl3): δ = 3.59 (s, 3 H, OCH3), 5.15 (dd, J
= 3.9, 7.2 Hz, 1 H, CH2 vinyl), 5.63 (dd, J = 2.2, 8.2 Hz, 1 H,
= 4.2, 6.4 Hz, 1 H, ArH), 8.08 (d, J = 6.2 Hz, 1 H, ArH) ppm. 13
C
NMR (75.46 MHz, CDCl3): δ = 52.4 (OCH3), 56.2 (2 OCH3), 60.9 CH2 vinyl), 6.60 (dd, J = 1.6, 6.8 Hz, 1 H, CHvinyl), 6.72 (d, J =
(OCH3), 105.5 (CHAr), 122.7 (q, JF,C = 320.1 Hz, CF3), 128.2, 6.2 Hz, 2 H, ArH), 6.90 (d, J = 6.8 Hz, 2 H, ArH), 7.01 (d, J =
129.0, 130.8, 131.1, 131.2, 132.2, 133.0 (CHAr), 134.1, 135.1, 135.9,
136.8, 137.6, 138.0, 146.8, 153.1 (CAr), 168.5 (COO), 191.3
6.4 Hz, 2 H, ArH), 7.14 (d, J = 6.7 Hz, 2 H, ArH), 7.31–7.56 (m,
4 H, ArH), 6.73 (dd, J = 1.4, 8.2 Hz, 2 H, ArH), 7.97 (d, J =
(C=O) ppm. 19F NMR (282.40 MHz, CDCl3):
δ =
–73.27 1.9 Hz, 1 H, ArH), 9.43 (s, 1 H, OH) ppm. 13C NMR (62.89 MHz,
(CF) ppm. IR (KBr): ν = 3074, 3052, 2972, 2846, 2835 (w), 1723,
CDCl3): δ = 52.1 (OCH3), 114.1 (CH2 vinyl), 115.2, 126.2, 127.2
(CHAr), 127.9, 128.0, 128.1 (CAr), 128.8, 129.2, 130.1, 130.6, 130.7,
131.5, 132.1, 135.2, 136.2 (CHAr, CHvinyl), 136.7, 138.2, 139.5,
140.9, 146.1, 155.7 (CAr), 168.6 (COO), 197.4 (C=O) ppm. IR
˜
1667 (s), 1597, 1586 (m), 1479, 1454 (m), 1394, 1344, 1300 (m),
1287, 1237, 1169 (s), 1093, 942 (s), 890, 865, 776, 696 (s), 593, 579,
532 (m) cm–1. MS (EI, 70 eV): m/z (%) = 554 (100) [M]+, 539 (08),
422 (04), 389 (17), 347 (09), 319 (04), 203 (03), 69 (07). HRMS
(EI): calcd. for C25H21F3O9S [M]+ 554.08529; found 554.085710.
(KBr): ν = 3417, 3060, 3022, 2946 (w), 1715, 1692 (s), 1597 (m),
˜
1555, 1519 (w), 1434, 1306 (m), 1233 (s), 1153, 1087, 987, 939 (m),
831, 769 (s), 699, 607, 571, 539 (m) cm–1. GC–MS (EI, 70 eV): m/z
(%) = 434 (100) [M]+, 401 (07), 373 (09), 347 (04), 255 (20), 212
(09), 178 (30), 152 (07), 91 (03). HRMS (EI): calcd. for C29H22O4
[M]+ 434.15126; found 434.151613.
Methyl 3Ј-Hydroxy-4-[2-(trifluoromethanesulfonyloxy)benzoyl]bi-
phenyl-2-carboxylate (6h): Compound 6h was obtained from 4
(150 mg, 0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4
(3 mol-%), 3-hydroxyphenylboronic acid (48 mg, 0.35 mmol) and
1,4-dioxane (5 mLmmol–1 of triflate) as a yellow oil; yield 97 mg
(72%). 1H NMR (300 MHz, CDCl3): δ = 3.62 (s, 3 H, OCH3), 6.91
(s, 1 H, ArH), 7.11 (s, 1 H, ArH), 7.32 (d, J = 6.2 Hz, 1 H, ArH),
Methyl
3Ј,4Ј-Dimethoxy-4-(4Ј-vinylbiphenylcarbonyl)biphenyl-2-
carboxylate (7c): Compound 7c was obtained from 6e (150 mg,
0.28 mmol), K3PO4 (178 mg, 0.84 mmol), Pd(PPh3)4 (3 mol-%), 4-
7.34 (t, J = 2.2 Hz, 1 H, ArH), 7.53 (d, J = 7.0 Hz, 1 H, ArH), vinylphenylboronic acid (53 mg, 0.36 mmol) and 1,4-dioxane
7.54 (m, 4 H, ArH), 7.81 (dd, J = 6.4, 2.1 Hz, 1 H, ArH), 8.15 (d,
(5 mLmmol–1 of triflate) as a yellow solid; yield 90 mg (65%). M.p.
1
J = 6.2 Hz, 1 H, ArH), 11.80 (s, 1 H, OH) ppm. 13C NMR 75–76 °C. H NMR (300 MHz, CDCl3): δ = 3.57 (s, 3 H, OCH3),
(62.90 MHz, CDCl3): δ = 52.4, (OCH3), 118.8, (CAr), 118.6, 119.0
(CHAr), 120.6 (q, JF,C = 320.1 Hz, CF3), 121.3, 128.2, 130.0, 130.9,
131.0, 131.8, 132.0, 133.2, 136.8, (CHAr), 137.6 141.1, 142.9, 143.6,
144.2, 149.2 (CAr), 168.5 (COO), 199.8 (C=O) ppm. 19F NMR
3.79 (s, 3 H, OCH3), 3.84 (s, 3 H, OCH3), 5.15 (dd, J = 1.6, 7.2 Hz,
1 H, CH2 vinyl), 5.64 (dd, J = 3.2, 6.2 Hz, 1 H, CHvinyl), 6.60 (dd,
J = 7.2, 6.4 Hz, 1 H, CH2 vinyl), 6.69 (d, J = 6.4 Hz, 1 H, ArH),
6.83 (d, J = 7.2 Hz, 1 H, ArH), 6.90 (d, J = 6.4 Hz, 2 H, ArH),
7.00 (s, 1 H, ArH), 7.12, (d, J = 6.1 Hz, 2 H, ArH), 7.21 (s, 1 H,
(282.40 MHz, CDCl ): δ = –73.27 (CF) ppm. IR (KBr): ν = 3071,
˜
3
3049, 2965, 2832, 2826 (w), 1716, 1654 (s), 1582, 1578 (m), 1462, ArH), 7.38–7.56 (m, 4 H, ArH), 7.73 (dd, J = 1.8, 8.0 Hz, 1 H,
1448 (m), 1389, 1339, 1301 (m), 1282, 1234, 1164 (s), 1091, 940 (s), ArH), 7.94 (d, J = 1.6 Hz, 1 H, ArH) ppm. 13C NMR (75.47 MHz,
897, 862, 771, 692 (s), 591, 575, 531 (m) cm–1. MS (EI, 70 eV): m/z
(%) = 480 (40) [M]+, 448 (19), 421 (31), 387 (04), 347 (15), 315 (33),
287 (20), 255 (81), 226 (15), 139 (14), 121 (100), 93 (18), 69 (19), 44
(04). HRMS (EI): calcd. for C22H15F3O7S [M]+ 480.04851; found
480.048846.
CDCl3): δ = 52.2, 55.9, 55.9 (3 OCH3), 111.4 (CHvinyl), 114.1
(CH2 vinyl), 120.7, 126.2, 127.2, 128.8, 129.2, 130.1, 130.5, 130.7,
131.3, 132.0, 135.2, 136.2 (CHAr, CHvinyl), 136.7, 138.3, 139.5,
140.9, 141.1, 142.3, 143.6, 145.9, 148.6, 149.0 (CAr), 168.7 (COO),
197.2 (C=O) ppm. IR (KBr): ν = 3056, 2999 (w), 1720, 1663 (s),
˜
1596 (m), 1554, 1519 (w), 1436, 1306 (m), 1232 (s), 1140, 1086, 940
(m), 843, 765 (s), 699, 606, 539 (m) cm–1. GC–MS (EI, 70 eV): m/z
(%) = 478 (100) [M]+, 418 (02), 387 (03), 300 (05), 225 (12), 178
(20), 145 (06), 96 (03), 74 (02). HRMS (ESI+): calcd. for C31H26O5
[M]+ 478.18539; found 478.185821.
Methyl 3Ј,5Ј-Dimethyl-4-[2-(trifluoromethanesulfonyloxy)benzoyl]bi-
phenyl-2-carboxylate (7a): Compound 7a was obtained from 6a
(100 mg, 0.20 mmol), K3PO4 (127 mg, 0.60 mmol), Pd(PPh3)4
(3 mol-%), 4-vinylphenylboronic acid (38 mg, 0.26 mmol) and 1,4-
dioxane (5 mLmmol–1 of triflate) as a colourless solid; yield 54 mg
(60%). M.p. 123–125 °C. 1H NMR (300 MHz, CDCl3): δ = 2.24 (s, Methyl 3Ј,4Ј,5Ј-Trimethoxy-4-(4Ј-vinylbiphenylcarbonyl)biphenyl-2-
6 H, 2 CH3), 3.54 (s, 3 H, OCH3), 5.14 (dd, J = 2.3, 6.8 Hz, 1 H, carboxylate (7d): Compound 7d was obtained from 6g (150 mg,
CH2 vinyl), 5.63 (dd, J = 1.5, 8.1 Hz, 1 H, CHvinyl), 6.59 (dd, J = 0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4 (3 mol-%), 4-
1.2, 6.8 Hz, 1 H, CH2 vinyl), 6.76 (s, 2 H, ArH), 6.91 (s, 1 H, ArH), vinylphenylboronic acid (51 mg, 0.35 mmol) and 1,4-dioxane
7.13 (s, 1 H, ArH), 7.21 (d, J = 7.2 Hz, 2 H, ArH), 7.37 (d, J = (5 mLmmol–1 of triflate) as a colourless oil; yield 100 mg (72%).
6.2 Hz, 2 H, ArH), 7.54–7.65 (m, 4 H, ArH), 7.71 (dd, J = 1.9,
1H NMR (300 MHz, CDCl3): δ = 3.57 (s, 3 H, OCH3), 3.77 (s, 6
H, 2 OCH3), 3.81 (s, 3 H, OCH3), 5.15 (dd, J = 5.9, 6.2 Hz, 1 H,
8.0 Hz, 1 H, ArH), 7.95 (d, J = 1.8 Hz, 1 H, ArH) ppm. 13C NMR
(75.47 MHz, CDCl3): δ = 21.3 (2 CH3), 52.0 (OCH3), 113.1 CH2 vinyl), 5.64 (dd, J = 4.6, 7.5 Hz, 1 H, CH2 vinyl), 6.37 (s, 2 H,
(CH2 vinyl), 124.8, 125.0, (CAr), 125.9, 126.2, 127.2, 128.9, 129.6, ArH), 6.60 (dd, J = 7.1, 6.7 Hz, 1 H, CHvinyl), 7.14 (d, J = 7.5 Hz,
130.6, 131.3, 132.2, 133.4, 134.3, 136.3 (CHAr, CHvinyl), 137.1,
137.3, 138.5, 139.0, 139.9, 145.6 (CAr), 167.4 (COO), 196.3
2 H, ArH), 7.30 (d, J = 6.2 Hz, 2 H, ArH), 7.41–7.61 (m, 4 H,
ArH), 7.73 (dd, J = 4.2, 7.2 Hz, 2 H, ArH), 7.93 (d, J = 6.2 Hz, 1
H, ArH) ppm. 13C NMR (75.46 MHz, CDCl3): δ = 52.2, 56.1, 60.9
(C=O) ppm. IR (KBr): ν = 3057, 3019, 2948 (w), 1720, 1663 (s),
˜
1596 (m), 1556, 1513 (w), 1435, 1306 (m), 1231 (s), 1151, 1099, 940 (3 OCH3), 114.1 (CH2 vinyl), 127.2 (CHAr), 127.9, 128.5 (CAr),
Eur. J. Org. Chem. 2011, 6670–6684
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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6679

M. Nawaz, I. Ullah, O.-U.-R. Abid, A. Villinger, P. Langer
FULL PAPER
128.9, 129.2, 130.1, 130.4, 130.8, 131.2, 131.9, 134.9, 135.0, 136.2
(CHAr, CHvinyl), 136.1, 136.7, 138.2, 139.5, 140.9, 141.7, 145.9,
CHvinyl), 6.86 (d, J = 6.4 Hz, 4 H, ArH), 6.95 (d, J = 6.9 Hz, 4 H,
ArH), 7.12 (d, J = 5.7 Hz, 2 H, ArH), 7.20 (t, J = 4.9 Hz, 2 H,
ArH), 7.31 (s, 1 H, ArH), 7.40 (dd, J = 4.5, 6.7 Hz, 1 H, ArH),
7.43–7.52 (m, 4 H, ArH), 7.94 (d, J = 6.8 Hz, 1 H, ArH) ppm.
153.0 (CAr), 168.6 (COO), 197.2 (C=O) ppm. IR (KBr): ν = 3055,
˜
2925, 2850 (w), 1722, 1663 (s), 1583 (m), 1556, 1512 (w), 1433,
1397, 1342 (m), 1296, 1233 (s), 1151, 1122, 1094, 1028, 940 (m), 13C NMR (62.89 MHz, CDCl3): δ = 52.0 (OCH3), 113.8, 114.3 (2
880, 831, 769 721, (s), 693, 644, 539 (m) cm–1. GC–MS (EI, 70 eV):
m/z (%) = 508 (100) [M]+, 493 (35), 277 (09), 262 (21), 219 (35), 130.0, 130.7, 131.3, 131.9, 132.0, 133.2, 134.6, 136.2, 136.4 (CHAr
CH2 vinyl), 115.4 (CAr), 125.7, 126.1, 127.3, 128.9, 129.2, 129.8,
,
201 (11), 183 (31), 152 (13), 108 (19), 57 (18), 44 (29). HRMS (EI):
CHvinyl), 136.6, 138.2, 138.9, 139.5, 139.8, 140.0, 140.7, 141.2,
calcd. for C32H28O6 [M]+ 508.18704; found 508.187819.
143.4, 146.9 (CAr), 167.2 (COO), 197.4 (C=O) ppm. IR (KBr): ν =
˜
3056, 3019, 2948 (w), 1724, 1662 (s), 1596 (m), 1555, 1514 (w),
1435, 1399, 1305 (m), 1258, 1230 (s), 1152, 1085, 988, 941 (m), 843,
765 (s), 694, 633, 596, 540 (m) cm–1. GC–MS (EI, 70 eV): m/z (%)
= 520 (16) [M]+, 488 (100), 417 (14), 386 (32), 357 (07), 309 (20),
262 (48), 207 (50), 179 (77), 152 (20), 108 (13). HRMS (EI): calcd.
for C37H28O3 [M]+ 520.20330; found 520.203889.
Methyl
3Ј-Hydroxy-4-(4Ј-vinylbiphenylcarbonyl)biphenyl-2-carb-
oxylate (7e): Compound 7e was obtained from 6h (150 mg,
0.31 mmol), K3PO4 (197 mg, 0.93 mmol), Pd(PPh3)4 (3 mol-%), 4-
vinylphenylboronic acid (59 mg, 0.40 mmol) and 1,4-dioxane
(5 mLmmol–1 of triflate) as a yellow oil; yield 87 mg (64%). 1H
NMR (300 MHz, CDCl3): δ = 3.61 (s, 3 H, OCH3), 4.12 (dd, J =
2.6, 8.1 Hz, 1 H, CH2 vinyl), 5.19 (dd, J = 2.8, 8.6 Hz, 1 H, CH2 vi-
Methyl
4ЈЈ-Vinyl-4-(4ЈЈ-vinyl[1,1Ј;4Ј,1ЈЈ]terphenyl-2-carbonyl)-
nyl), 5.77 (dd, J = 2.4, 8.2 Hz, 1 H, CHvinyl), 6.72 (d, J = 6.2 Hz, 1 [1,1Ј;4Ј,1ЈЈ]terphenyl-2-carboxylate (9): Compound 9 was obtained
H, ArH), 6.90 (d, J = 6.8 Hz, 1 H, ArH), 7.11 (s, 1 H, ArH), 7.20
(t, J = 6.7 Hz, 1 H, ArH), 7.30 (s, 1 H, ArH), 7.35–7.45 (m, 4 H,
ArH), 7.54–7.65 (m, 4 H, ArH), 7.73 (dd, J = 5.4, 6.2 Hz, 1 H,
ArH), 7.97 (d, J = 2.9 Hz, 1 H, ArH) ppm. 13C NMR (62.89 MHz,
CDCl3): δ = 51.5 (OCH3), 114.3 (CH2 vinyl), 115.2, 117.2, 118.3,
126.2, 127.2 (CHAr), 127.9, 128.0, 128.1 (CAr), 128.8, 129.2, 130.1,
130.6, 130.7, 131.5, 132.1, 136.2 (CHAr, CHvinyl), 136.5, 138.1,
from 5g (150 mg, 0.27 mmol), K3PO4 (171 mg, 0.81 mmol),
Pd(PPh3)4 (6 mol-%), 4-vinylphenylboronic acid (103 mg,
0.70 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate) as a colour-
less solid; yield 118 mg (72%). M.p. 169–171 °C. 1H NMR
(300 MHz, CDCl3): δ = 3.58 (s, 3 H, OCH3), 5.05 (dd, J = 6.2,
5.4 Hz, 2 H, CH2 vinyl), 5.16 (dd, J = 5.2, 6.4 Hz, 2 H, CH2 vinyl),
5.23 (d, J = 6.4, 5.8 Hz, 2 H, CHvinyl), 5.48 (d, J = 6.4 Hz, 8 H,
139.2, 140.4, 146.0, 155.2 (CAr), 168.2 (COO), 197.2 (C=O) ppm. ArH), 7.44 (d, J = 6.4 Hz, 4 H, ArH), 7.59 (d, J = 6.2 Hz, 4 H,
IR (KBr): ν = 3415, 3029, 3021, 2943 (w), 1719, 1691 (s), 1596 (m), ArH), 7.65–8.00 (m, 7 H, ArH) ppm. 13C NMR (62.89 MHz,
˜
1553, 1517 (w), 1431, 1303 (m), 1231 (s), 1159, 1083, 981, 938 (m), CDCl3): δ = 52.1 (OCH3), 114.1 (CH2 vinyl), 126.2, 127.0, 127.9,
833, 767 (s), 691, 605, 573, 534 (m) cm–1. GC–MS (EI, 70 eV): m/z 128.0, 128.9, 129.2, 130.1, 130.7, 131.1, 131.8, 132.2, 133.0 (CHAr
,
(%) = 434 (100) [M]+, 401 (16), 375 (40), 341 (07), 314 (09), 281 CHvinyl), 134.9, 135.0, 136.1, 136.8, 138.2, 139.7, 140.1, 141.0, 146.0
(33), 255 (33), 207 (87), 191 (09), 133 (06), 121 (46), 93 (10), 65
(09), 44 (15). HRMS (EI): calcd. for C29H22O4 [M]+ 434.15180;
found 434.151680.
(CAr), 168.2 (COO), 197.3 (C=O) ppm. IR (KBr): ν = 3427, 2948
˜
(w), 1722, 1666 (s), 1596 (m), 1556, 1514 (w), 1434, 1305 (m), 1231
(s), 1152, 1093, 999, 939 (m), 843, 818, 768 (s), 726, 691, 649, 540
(m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 596 (10) [M]+, 540 (30),
502 (12), 480 (21), 439 (15), 414 (16), 385 (16), 358 (08), 267 (29),
207 (20), 194 (08), 178 (49), 152 (14), 77 (10). HRMS (EI): calcd.
for C43H32O3 [M]+ 596.71216; found 596.712403.
Methyl 2Ј-Ethoxy-4-(4Ј-vinylbiphenylcarbonyl)biphenyl-2-carboxyl-
ate (7f): Compound 7f was obtained from 6c (150 mg, 0.29 mmol),
K3PO4 (184 mg, 0.87 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphen-
ylboronic acid (55 mg, 0.37 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a colourless solid; yield 93 mg (68%). M.p. 143–
145 °C. 1H NMR (300 MHz, CDCl3): δ = 1.32 (t, J = 3.1 Hz, 3 H,
Methyl 4-([1,1Ј;3Ј,1ЈЈ]Terphenyl-2-carbonyl)[1,3Ј;1Ј,1ЈЈ]terphenyl-2-
carboxylate (10): Compound 10 was obtained from 5r (150 mg,
CH3), 3.54 (s, 1 H, OCH3), 3.82 (q, J = 4.1 Hz, 2 H, OCH2), 6.82 0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4 (6 mol-%),
(s, 1 H, ArH), 6.907.12 (m, 4 H, ArH), 7.20–7.30 (m, 4 H, ArH), phenylboronic acid (85 mg, 0.70 mmol) and 1,4-dioxane
7.42 (d, J = 2.4, 8.2 Hz, 2 H, ArH), 7.52–7.62 (m, 2 H, ArH), 7.91
(dd, J = 2.8, 7.2 Hz, 1 H, ArH), 8.21 (d, J = 6.8 Hz, 1 H,
ArH) ppm. 13C NMR (75.46 MHz, CDCl3): δ = 14.4 (CH3), 51.7
(5 mLmmol–1 of triflate) as a yellow oil; yield 90 mg (60%). 1H
NMR (300 MHz, CDCl3): δ = 3.46 (s, 3 H, OCH3), 7.10 (s, 1 H,
ArH), 7.23 (s, 2 H, ArH), 7.25–7.50 (m, 17 H, ArH), 7.57 (t, J =
(OCH3), 63.8 (OCH2), 111.3 (CHvinyl), 114.0 (CH2 vinyl), 120.7, 5.9 Hz, 1 H, ArH), 7.65 (d, J = 6.2 Hz, 2 H, ArH), 7.73 (dd, J =
126.2, 127.2 (CHAr), 128.0 (CAr), 128.9, 129.2, 129.7, 130.1, 131.0,
131.4, 132.3, 133.2, 134.6, 136.2 (CHAr, CHvinyl), 136.6, 137.2,
138.4, 139.5, 140.9, 141.1, 143.4, 144.2, 155.2 (CAr), 167.7 (COO),
6.2, 4.6 Hz, 1 H, ArH), 7.94 (d, J = 6.8 Hz, 1 H, ArH) ppm. 13C
NMR (62.89 MHz, CDCl3): δ = 52.0 (OCH3), 126.2, 127.0, 127.5,
127.9, 128.1, 128.7, 129.0, 130.9, 131.5, 131.8, 134.9, 135.0, 135.8
197.5 (C=O) ppm. 19F NMR (282 MHz, CDCl3): δ = –73.34 (CHAr), 136.3, 138.5, 140.6, 141.1, 142.0, 143.0, 146.2, 166.3 (CAr),
(CF) ppm. IR (KBr): ν = 3491, 3062, 3029 (w), 1723, 1661 (s), 1592
168.1 (COO), 197.5 (C=O) ppm. IR (KBr): ν = 3055, 3028, 2947
˜
˜
(m), 1571, 1504 (w), 1442, 1307, 1281 (m), 1241, 1202 (s), 1081, (w), 1720, 1662 (s), 1595 (m), 1572, 1487, (w), 1434, 1303 (m), 1210
942 (m), 883, 750 (s), 567 (m) cm–1. MS (EI, 70 eV): m/z (%) = 462 (s), 1151, 1086, 1031, 940 (m), 896, 783 (s), 696, 628, 539 (m) cm–1.
(100) [M]+, 430 (07), 417 (21), 401 (46), 373 (30), 357 (04), 313 (04), GC–MS (EI, 70 eV): m/z (%) = 544 (20) [M]+, 520 (20), 490 (10),
283 (06), 223 (21), 201 (27), 178 (67), 139 (19). HRMS (EI): calcd.
465 (12), 430 (19), 414 (16), 385 (16), 358 (08), 267 (29), 207 (20),
194 (08), 178 (49), 152 (14), 77 (01). HRMS (EI): calcd. for
C39H28O3 [M]+ 544.29380; found 544.293634.
for C31H26O4 [M]+ 462.18256; found 462.182193.
Methyl
4ЈЈ-Vinyl-4-(4Ј-vinylbiphenyl-2-carbonyl)[1,1Ј;2Ј,1ЈЈ]ter-
phenyl-2-carboxylate (8): Compound 8 was obtained from 6d
(150 mg, 0.27 mmol), K3PO4 (171 mg, 0.81 mmol), Pd(PPh3)4
(3Ј-Methoxybiphenyl-2-yl)(3Ј-methoxybiphenyl-4-yl)methanone (13a):
Compound 13a was obtained from 12 (200 mg, 0.41 mmol), K3PO4
(6 mol-%), 4-vinylphenylboronic acid (103 mg, 0.70 mmol) and 1,4- (260 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 3-methoxyphenyl-
dioxane (5 mLmmol–1 of triflate) as a yellow oil; yield 90 mg
(62%). 1H NMR (300 MHz, CDCl3): δ = 3.45 (s, 3 H, OCH3), 5.15
(ddd, J = 0.8, 5.7, 10.9 Hz, 2 H, CH2 vinyl), 5.62 (ddd, J = 0.8, 5.0,
17.6 Hz, 2 H, CH2 vinyl), 6.57 (ddd, J = 1.9, 10.9, 17.6 Hz, 2 H, 2
boronic acid (162 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a colourless solid; yield 128 mg (78%). M.p. 152–
154 °C. 1H NMR (300 MHz, CDCl3): δ = 3.61, 3.78 (s, 6 H, 2
OCH3), 6.61–6.64 (m, 2 H, ArH), 6.75–6.86 (m, 3 H, ArH), 6.99–
6680
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 6670–6684

2Ј,4-Diarylbenzophenones from Bis(triflates) of 2Ј,4-Dihydroxybenzophenones
7.07 (m, 2 H, ArH), 7.26 (t, J = 7.95 Hz, 1 H, ArH), 7.39–7.51 (m,
7.31–7.38 (m, 4 H, ArH), 7.40–7.48 (m, 4 H, ArH), 7.54 (s, 1 H,
6 H, ArH), 7.63–7.66 (m, 2 H, ArH) ppm. 13C NMR (75.47 MHz, ArH), 7.66 (d, J = 8.5 Hz, 2 H, ArH) ppm. 13C NMR (75.47 MHz,
CDCl3): δ = 55.1, 55.3 (2 OCH3), 113.0, 113.2, 113.4, 114.4, 119.7,
121.5, 126.8, 127.1, 128.5, 129.3, 129.9, 130.2, 130.4, 131.0 (CHAr),
136.2, 139.0, 140.8, 141.3, 141.5, 145.2, 159.3, 160.0 (CAr), 198.2
CDCl3): δ = 114.2, 114.8 (2 CH2 vinyl), 125.3, 125.7, 126.3, 126.6,
126.9, 127.2, 128.6, 129.2, 129.7, 130.0, 130.3, 130.7 (CHAr), 136.1
(CAr), 136.3, 136.5 (CHAr, CHvinyl), 136.8, 138.3, 138.9, 139.7,
(C=O) ppm. IR (KBr): ν = 3058, 2998, 2834 (w), 1725 (w), 1661, 140.2, 140.7, 146.4 (CAr), 198.2 (C=O) ppm. IR (KBr): ν = 3043,
˜
˜
1581, 1477, 1435, 1398, 1307 (m), 1278, 1210 (s), 1170, 1150, 1049,
1027, 1019 (m), 929 (s), 844, 775 (m), 757, 689 (s), 672, 617, 565,
3029, 2952, 2847, 1721 (w), 1657, 1597 (s), 1579, 1513, 1475, 1447,
1403, 1317 (m), 1266, 1253, 1235 (s), 1187, 1153, 1041, 987 (m),
531 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 394 (100) [M]+, 363 925 (s), 861, 803, 783, 708, 665, 627, 543 (m) cm–1. GC–MS (EI,
(15), 281 (04), 211 (47), 168 (23), 139 (19), 44 (05). HRMS (EI):
70 eV): m/z (%) = 386 (100) [M]+, 369 (8), 281 (07), 253 (04), 207
(56), 193 (08), 178 (51), 152 (16). HRMS (EI): calcd. for C29H22O
[M]+ 386.16652; found 386.166535.
calcd. for C27H22O3 [M]+ 394.15689; found 394.156780.
(2Ј-Fluorobiphenyl-2-yl)(2Ј-fluorobiphenyl-4-yl)methanone
(13b):
Compound 13b was obtained from 12 (200 mg, 0.41 mmol), K3PO4
(260 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 2-fluorophenylboronic
acid (148 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate)
2-(3Ј-Methoxybiphenylcarbonyl)phenyl Trifluoromethanesulfonate
(14a): Compound 14a was obtained from 12 (200 mg, 0.41 mmol),
K3PO4 (260 mg, 1.23 mmol), Pd (PPh3)4 (3 mol-%), 3-methoxy-
as a colourless crystalline solid; yield 108 mg (70%). M.p. 146– phenylboronic acid (80 mg, 0.53 mmol) and 1,4-dioxane
1
148 °C. H NMR (300 MHz, CDCl3): δ = 6.80 (t, J = 8.67 Hz, 1 (5 mLmmol–1 of triflate) as a colourless oil; yield 124 mg (68%).
H, ArH), 6.93–7.00 (m, 2 H, ArH), 7.04–7.12 (m, 3 H, ArH), 7.17– 1H NMR (300 MHz, CDCl3): δ = 3.77 (s, 3 H, OCH3), 6.86 (dd, J
7.23 (m, 3 H, ArH), 7.34–7.42 (m, 3 H, ArH), 7.46–7.50 (m, 2 H,
= 1.8, 8.10 Hz, 1 H, ArH), 7.07–7.14 (m, 2 H, ArH), 7.27–7.38 (m,
2 H, ArH), 7.43 (d, J = 7.11 Hz, 1 H, ArH), 7.50–7.54 (m, 3 H,
ArH), 7.67 (d, 8.25 Hz,
J
=
2
H, ArH) ppm. 13C NMR
2
(75.47 MHz, CDCl3): δ = 115.5 (d, JC,F = 22.3 Hz, CHAr), 116.3 ArH), 7.61 (d, J = 8.31 Hz, 1 H, ArH), 7.80 (d, J = 8.28 Hz, 2 H,
2
4
(d, JC,F = 22.6 Hz, CHAr), 124.2 (d, JC,F = 3.6 Hz, CHAr), 124.5
ArH) ppm. 13C NMR (62.90 MHz, CDCl3): δ = 55.3 (OCH3),
4
4
(d, JC,F = 3.6 Hz, CHAr), 127.5 (CHAr), 128.7 (d, JC,F = 3.1 Hz, 113.1, 113.7, 119.8 (CHAr), 121.0 (q, JF,C = 320 Hz, CF3), 122.5,
3
CHAr), 129.2 (CHAr), 129.5 (d, JC,F = 8.1 Hz, CHAr), 129.7 (d, 127.2, 128.0, 130.0, 130.7, 131.1, 132.6 (CHAr), 135.2, 141.1, 146.3,
3JC,F = 8.3 Hz, CHAr), 130.1, 130.6, 131.2 (CHAr), 131.4 (d, JC,F
= 3.2 Hz, CHAr), 135.3, 136.3, 139.1, 140.1, 157.4, 158.1, 160.7,
161.4 (CAr), 197.0 (C=O) ppm. 19F NMR (282 MHz, CDCl3): δ =
146.7, 147.2, 160.0 (CAr), 198.2 (C=O) ppm. 19F NMR (282 MHz,
4
CDCl ): δ = –73.3 (CF ) ppm. IR (KBr): ν = 3066, 2921, 1727 (w),
˜
3
3
1665 (m), 1599 (s), 1479 (m), 1421 (s), 1400, 1309, 1293, 1274, 1247
(m), 1205, 1135 (s), 1086, 1051, 1028, 1013 (m), 936, 879, 845, 765
(s), 748, 691, 618, 568 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) =
436 (100) [M]+, 303 (40), 287 (08), 260 (18), 231 (07), 211 (22), 168
(06), 139 (13), 69 (04). HRMS (EI): calcd. for C21H15F3O5S [M]+
–117.3, –115.6 (2 CF) ppm. IR (KBr): ν = 3310, 3039, 2954, 2852,
˜
1728 (w), 1665 (s), 1606, 1593, 1567, 1447, 1404, 1313, 1280, 1260,
1201, 1187, 1156, 1103, 1079, 1036, 975, 963, 945, 883, 844, 790
(m), 728, 719 (s), 694, 638, 614, 559 (w) cm–1. GC–MS (EI, 70 eV):
m/z (%) = 370 (100) [M]+, 351 (26), 199 (72), 170 (48), 151 (10). 436.05868; found 436.058091.
HRMS (EI): calcd. for C25H16F2O [M]+ 370.11637; found
2-(2Ј,5Ј-Dimethoxybiphenylcarbonyl)phenyl Trifluoromethanesulfon-
370.116915.
ate (14b): Compound 14b was obtained from 12 (200 mg,
0.41 mmol), K3PO4 (260 mg, 1.23 mmol), Pd (PPh3)4 (3 mol-%),
2,5-dimethoxyphenylboronic acid (96 mg, 0.53 mmol) and 1,4-di-
oxane (5 mLmmol–1 of triflate) as a reddish solid; yield 140 mg
(72%). M.p. 138–140 °C. 1H NMR (300 MHz, CDCl3): δ = 3.66 (s,
6 H, 2 OCH3), 6.60 (d, J = 8.4 Hz, 2 H, ArH), 7.17–7.26 (m, 2 H,
ArH), 7.35–7.43 (m, 3 H, ArH), 7.52–7.58 (m, 2 H, ArH), 7.77 (d,
J = 8.37 Hz, 2 H, ArH) ppm. 13C NMR (75.47 MHz, CDCl3): δ =
(4Ј-Methoxybiphenyl-2-yl)(3Ј-methoxybiphenyl-4-yl)methanone (13c):
Compound 13c was obtained from 12 (200 mg, 0.41 mmol), K3PO4
(260 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 4-methoxyphenyl-
boronic acid (161 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a yellow solid; yield 112 mg (68%). M.p. 138–140 °C.
1H NMR (300 MHz, CDCl3): δ = 3.61, 3.78 (s, 6 H, 2 OCH3),
6.61–6.64 (m, 2 H, ArH), 6.75–6.86 (m, 3 H, ArH), 6.99–7.07 (m,
2 H, ArH), 7.26 (t, J = 7.95 Hz, 1 H, ArH), 7.39–7.51 (m, 6 H, 55.9 (2 OCH3), 104.2 (CHAr), 118.2 (CAr), 120.6 (q, JF,C = 320 Hz,
ArH), 7.63–7.66 (m, 2 H, ArH) ppm. 13C NMR (75.47 MHz,
CDCl3): δ = 55.1, 55.3 (2 OCH3), 113.0, 113.4, 114.4, 119.7, 121.5,
126.8, 127.1, 128.5, 129.9, 130.4 (CHAr), 136.1, 139.2, 140.6, 141.4,
CF3), 122.4, 127.8, 129.5, 129.6, 130.0, 131.3, 131.4, 132.3 (CHAr),
132.7, 133.0, 134.5, 140.6, 146.9, 157.5 (CAr), 192.3 (C=O) ppm.
19F NMR (282 MHz, CDCl ): δ = –74.6 (CF ) ppm. IR (KBr): ν
˜
3
3
141.8, 145.6, 159.8, 160.3 (CAr), 198.3 (C=O) ppm. IR (KBr): ν =
= 3068, 3002, 2839, 1726 (w), 1665, 1603, 1588 (m), 1471 (s), 1402,
1294, 1272 (m), 1204, 1135, 1103, 1087 (s), 1036, 935 (m), 878, 782,
725 (s), 693, 620, 569 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 466
(100) [M]+, 317 (25), 287 (15), 241 (12), 198 (05), 155 (04), 69 (04).
˜
3033, 2965, 2839 (w), 1671, 1594, 1526, 1480, 1442, 1399, 1297,
1267 (m), 1248, 1226, 1189, 1133, 1090, 1030 (m), 1010, 936, 876,
824, 768 (s), 743, 717, 690, 627, 616, 542 (m) cm–1. GC–MS (EI,
70 eV): m/z (%) = 394 (100) [M]+, 363 (15), 281 (04), 211 (47), HRMS (EI): calcd. for C22H17F3O6S [M]+ 466.06825; found
168 (23), 139 (19), 44 (05). HRMS (EI): calcd. for C27H22O3 [M]+
394.15689; found 394.156342.
466.068720.
2-(2Ј,6Ј-Dimethoxybiphenylcarbonyl)phenyl Trifluoromethanesulfon-
ate (14c): Compound 14c was obtained from 12 (200 mg,
0.41 mmol), K3PO4 (260 mg, 1.23 mmol), Pd(PPh3)4 (3 mol-%),
2,6-dimethoxyphenylboronic acid (96 mg, 0.53 mmol) and 1,4-di-
oxane (5 mLmmol–1 of triflate) as a colourless solid; yield 124 mg
(64%). M.p. 162–164 °C. 1H NMR (300 MHz, CDCl3): δ = 3.65 (s,
(4Ј-Vinylbiphenyl-2-yl)(4Ј-vinylbiphenyl-4-yl)methanone (13d): Com-
pound 13d was obtained from 12 (200 mg, 0.41 mmol), K3PO4
(260 mg, 1.23 mmol), Pd(PPh3)4 (6 mol-%), 4-vinylphenylboronic
acid (157 mg, 1.06 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate)
as a colourless oil; yield 107 mg (66%). 1H NMR (300 MHz,
CDCl3): δ = 5.01–5.11 (dd, J = 1.7, 10.8 Hz, 1 H, CH2 vinyl), 5.19– 6 H, 2 OCH3), 6.57 (d, J = 8.4 Hz, 2 H, ArH), 7.21 (t, J = 8.37 Hz,
5.24 (dd, J = 1.7, 11.2 Hz, 1 H, CH2 vinyl), 5.54–5.61 (dd, J = 1.7,
17.5 Hz, 1 H, CH2 vinyl), 5.68–5.74 (dd, J = 1.6, 17.5 Hz, 1 H,
1 H, ArH), 7.33–7.41 (m, 4 H, ArH), 7.50–7.56 (m, 2 H, ArH), 7.75
(d, J = 8.37 Hz, 2 H, ArH) ppm. 13C NMR (62.90 MHz, CDCl3): δ
CH2 vinyl), 6.47–6.57 (dd, J = 10.8, 17.5 Hz, 1 H, CHvinyl), 6.62– = 55.8 (2 OCH3), 104.2 (CHAr), 118.2 (CAr), 120.6 (q, JF,C
=
6.72 (dd, J = 10.8, 17.5 Hz, 1 H, CHvinyl), 7.18 (m, 4 H, ArH), 320 Hz, CF3), 122.4, 127.8, 129.5, 129.6, 131.3, 131.4, 132.3
Eur. J. Org. Chem. 2011, 6670–6684
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6681

M. Nawaz, I. Ullah, O.-U.-R. Abid, A. Villinger, P. Langer
FULL PAPER
(CHAr), 132.6, 134.5, 140.6, 146.9, 157.4 (CAr), 192.2 (C=O) ppm.
1300 (w), 1278, 1269 (m), 1197, 1142 (s), 1112, 1040, 1003, 937,
882, 864 (m), 831, 767, 735 (s), 700, 645, 596, 567 (w) cm–1. GC–
19F NMR (282 MHz, CDCl ): δ = –73.5 (CF ) ppm. IR (KBr): ν
˜
3
3
= 3065, 3004, 2841, 1721 (w), 1667, 1605, 1587 (m), 1473 (s), 1403, MS (EI, 70 eV): m/z (%) = 462 (43) [M]+, 447 (100), 313 (43), 299
1295, 1273 (m), 1205, 1137, 1105, 1081 (s), 1033, 931 (m), 877, 781, (09), 273 (04), 178 (04), 69 (04). HRMS (EI): calcd. for
722 (s), 693, 620, 569 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 466
(100) [M]+, 317 (23), 287 (14), 241 (11), 198 (05), 155 (04), 69 (04).
HRMS (EI): calcd. for C22H17F3O6S [M]+ 466.06925; found
466.069423.
C24H21F3O4S [M]+ 462.11172; found 462.111365.
2-(3Ј,5Ј-Dimethylbiphenylcarbonyl)phenyl Trifluoromethanesulfon-
ate (14g): Compound 14g was obtained from 12 (200 mg,
0.41 mmol), K3PO4 (260 mg, 1.23 mmol), Pd(PPh3)4 (3 mol-%),
2-(2Ј-Ethoxybiphenylcarbonyl)phenyl
Trifluoromethanesulfonate 3,5-dimethylphenylboronic acid (79 mg, 0.53 mmol) and 1,4-diox-
(14d): Compound 14d was obtained from 12 (200 mg, 0.41 mmol),
K3PO4 (260 mg, 1.23 mmol), Pd(PPh3)4 (3 mol-%), 2-ethoxyphen-
ylboronic acid (88 mg, 0.53 mmol) and 1,4-dioxane (5 mLmmol–1
ane (5 mLmmol–1 of triflate) as a colourless oil; yield 142 mg
(78%). 1H NMR (300 MHz, CDCl3): δ = 2.28 (s, 6 H, 2 CH3), 6.94
(s, 1 H, ArH), 7.14 (s, 2 H, ArH), 7.35 (dd, J = 8.25, 19.6 Hz, 2 H,
ArH), 7.47–7.51 (m, 2 H, ArH), 7.56 (d, J = 8.3 Hz, 2 H, ArH),
of triflate) as a colourless solid; yield 144 mg (76%). M.p. 150–
1
152 °C. H NMR (300 MHz, CDCl3): δ = 1.25 (t, J = 6.99 Hz, 3 7.75 (d, J = 8.3 Hz, 2 H, ArH) ppm. 13C NMR (75.47 MHz,
H, CH3), 3.97 (q, J = 6.9 Hz, 2 H, OCH2), 6.89–6.98 (m, 2 H,
ArH), 7.23–7.28 (m, 2 H, ArH), 7.34–7.44 (m, 2 H, ArH), 7.51–
7.61 (m, 4 H, ArH), 7.76 (d, J = 8.52 Hz, 2 H, ArH) ppm. 13C
NMR (75.47 MHz, CDCl3): δ = 14.7 (CH3), 64.1 (OCH2), 112.6
CDCl3): δ = 21.3 (2 CH3), 120.6 (q, JF,C = 321.0 Hz, CF3), 122.5,
125.2, 127.2, 128.0, 130.1, 130.7, 131.2, 132.6 (CHAr), 133.0, 135.0,
138.5, 139.6, 146.8, 146.9, (CAr), 192.2 (C=O) ppm. 19F NMR
(282 MHz, CDCl ): δ = –73.4 (CF ) ppm. IR (KBr): ν = 3032,
˜
3
3
(CHAr), 120.6 (q, JF,C = 321.0 Hz, CF3), 120.9, 122.4, 128.0 2850, 2850, 1725 (w), 1665, 1600 (m), 1560, 1480 (w), 1422 (s),
(CHAr), 129.3 (CAr), 129.6, 129.7, 129.8, 130.7, 131.2, 132.4 1294, 1246 (m), 1203, 1135 (s), 1084, 1038, 1016 (m), 936 (m), 879,
(CHAr), 132.7, 134.6, 144.5, 146.8, 155.9 (CAr), 192.3 (C=O) ppm.
850, 779 (s), 742, 639, 618, 568 (w) cm–1. GC–MS (EI, 70 eV): m/z
(%) = 434 (100) [M]+, 301 (57), 285 (06), 258 (07), 209 (30), 165
(19), 69 (05). HRMS (EI): calcd. for C22H17F3O4S [M]+ 434.07942;
19F NMR (282 MHz, CDCl ): δ = –73.4 (CF ) ppm. IR (KBr): ν
˜
3
3
= 3068, 3034, 2925, 1722 (w), 1665, 1602 (m), 1581, 1511, 1446 (w),
1422 (s), 1312, 1264 (m), 1204, 1135 (s), 1086, 1039, 935 (m), 879, found 434.079488.
750 (s), 693, 668, 646, 590 (m) cm–1. GC–MS (EI, 70 eV): m/z (%)
2-(4Ј-Ethylbiphenylcarbonyl)phenyl
Trifluoromethanesulfonate
(14h): Compound 14h was obtained from 12 (200 mg, 0.41 mmol),
K3PO4 (260 mg, 1.23 mmol), Pd(PPh3)4 (3 mol-%), 4-ethylphen-
ylboronic acid (79 mg, 0.53 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a colourless crystalline solid; yield 134 mg (74%).
M.p. 170–172 °C. 1H NMR (300 MHz, CDCl3): δ = 1.17 (t, J =
7.5 Hz, 3 H, CH3 ethyl), 2.59 (q, J = 7.5 Hz, 2 H, CH2 ethyl), 7.19 (d,
J = 8.1 Hz, 2 H, ArH), 7.35 (dd, J = 8.2, 18.5 Hz, 2 H, ArH), 7.44–
7.51 (m, 4 H, ArH), 7.57 (d, J = 8.4 Hz, 2 H, ArH), 7.77 (d, J =
= 450 (100) [M]+, 422 (28), 289 (30), 215 (08), 197 (21), 168 (13),
121 (17), 92 (04), 69 (05). HRMS (EI): calcd. for C22H17F3O5S [M]
+
450.07433; found 450.074512.
2-(3Ј-Vinylbiphenylcarbonyl)phenyl Trifluoromethanesulfonate (14e):
Compound 14e was obtained from 12 (200 mg, 0.41 mmol), K3PO4
(260 mg, 1.23 mmol), Pd(PPh3)4 (3 mol-%), 3-vinylphenylboronic
acid (78 mg, 0.53 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate)
1
as a yellow oil; yield 127 mg (70%). H NMR (300 MHz, CDCl3):
δ = 5.23 (d, J = 10.95 Hz, 1 H, CH2 vinyl), 5.74 (d, J = 17.55 Hz, 1 8.4 Hz, 2 H, ArH) ppm. 13C NMR (75.47 MHz, CDCl3): δ = 14.4
H, CH2 vinyl), 6.65–6.74 (dd, J = 10.8, 17.5 Hz, 1 H, CHvinyl), 7.33– (CH3), 28.6 (CH2), 120.6 (q, JF,C = 321.0 Hz, CF3), 122.5, 127.0,
7.38 (m, 3 H, ArH), 7.40–7.43 (m, 2 H, ArH), 7.50–7.55 (m, 3 H,
ArH), 7.61 (d, J = 8.43 Hz, 2 H, ArH), 7.80 (d, J = 8.40 Hz, 2 H,
ArH) ppm. 13C NMR (75.47 MHz, CDCl3): δ = 114.7 (CH2 vinyl),
120.6 (q, JC,F = 322.20 Hz, CF3), 122.5, 125.3, 126.1, 126.8, 127.2,
127.2, 128.0, 128.5, 130.8, 131.2, 132.6 (CHAr), 133.0, 134.8, 137.0,
144.8, 146.5, 146.8 (CAr), 192.1 (C=O) ppm. 19F NMR (282 MHz,
CDCl ): δ = –73.4 (CF ) ppm. IR (KBr): ν = 3065, 3031, 2923,
˜
3
3
1721 (w), 1663, 1605 (m), 1583, 1511, 1443 (w), 1421 (s), 1312, 1264
128.1, 129.2, 130.8, 131.2, 132.6 (CHAr), 135.2 (CAr), 136.5 (CHAr), (m), 1203, 1137 (s), 1083, 1037, 931 (m), 877, 751 (s), 691, 667, 645,
138.3, 139.4, 140.0, 146.4, 146.8 (CAr), 192.1 (C=O) ppm. 19F
NMR (282 MHz, CDCl ): δ = –73.3 (CF ) ppm. IR (KBr): ν =
591 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 434 (100) [M]+, 419
(08), 301 (41), 273 (17), 209 (21), 165 (13), 69 (05). HRMS (EI):
calcd. for C22H17F3O4S [M]+ 434.07942; found 434.079081.
˜
3
3
3085, 3060, 2957, 2854 (w), 1665, 1601 (m), 1579, 1559, 1480 (w),
1421 (s), 1294, 1274, 1246 (w), 1204, 1134 (s), 1087 (m), 1039, 1014,
955 (w), 878, 866, 778, 766 (s), 747, 710, 670, 617, 568, 545
(m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 432 (100) [M]+, 299 (35),
284 (14), 255 (09), 207 (42), 178 (23), 152 (09), 69 (05). HRMS
(EI): calcd. for C22H15F3O4S [M]+ 432.06377; found 432.063610.
(3Ј-Methoxybiphenyl-4-yl)(4Ј-vinylbiphenyl-2-yl)methanone (15a):
Compound 15a was obtained from 14a (100 mg, 0.23 mmol),
K3PO4 (146 mg, 0.69 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphen-
ylboronic acid (44 mg, 0.30 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a yellow oil; yield 63 mg (70%). 1H NMR (300 MHz,
CDCl3): δ = 3.76 (s, 3 H, OCH3), 5.08–5.12 (dd, J = 1.7, 10.8 Hz,
1 H, CH2 vinyl), 5.55–5.61 (dd, J = 1.2, 17.6 Hz, 1 H, CH2 vinyl),
2-(4Ј-tert-Butylbiphenylcarbonyl)phenyl Trifluoromethanesulfonate
(14f): Compound 14f was obtained from 12 (200 mg, 0.41 mmol),
K3PO4 (260 mg, 1.23 mmol), Pd(PPh3)4 (3 mol-%), 4-tert- 6.48–6.57 (dd, J = 10.8, 17.6 Hz, 1 H, CHvinyl), 6.81–6.85 (m, 1 H,
butylphenylboronic acid (94 mg, 0.53 mmol) and 1,4-dioxane
(5 mLmmol–1 of triflate) as a colourless crystalline solid; yield
128 mg (66%). M.p. 140–142 °C. 1H NMR (300 MHz, CDCl3): δ
ArH), 6.99 (t, J = 1.7 Hz, 1 H, ArH), 7.03–7.07 (m, 1 H, ArH),
7.18 (s, 4 H, ArH), 7.24 (t, J = 7.9 Hz, 1 H, ArH), 7.40–7.47 (m,
6 H, ArH), 7.66 (d, J = 8.4 Hz, 2 H, ArH) ppm. 13C NMR
= 1.27 (s, 9 H, 3 CH3), 7.32–7.42 (m, 4 H, ArH), 7.48–7.52 (m, 4 (75.47 MHz, CDCl3): δ = 55.3 (OCH3), 113.0, 113.5 (CHAr), 114.0
H, ArH), 7.60 (d, J = 8.28 Hz, 2 H, ArH), 7.78 (d, J = 8.25 Hz, 2
(CH2 vinyl), 119.7, 126.2, 126.9, 127.0, 128.7, 129.1, 129.9, 130.0,
130.3, 130.5 (CHAr), 136.2 (CAr), 136.3 (CHvinyl), 136.6, 138.9,
H, ArH) ppm. 13C NMR (75.47 MHz, CDCl3): δ = 31.3 (3 CH3),
34.6 (CtBu), 120.0 (q, JF,C = 320 Hz, CF3), 122.5, 126.0, 127.0, 139.6, 140.7, 141.3, 145.4, 160.0 (CAr), 198.1 (C=O) ppm. IR
127.1, 128.0, 130.8, 131.2, 132.5 (CHAr), 132.6, 134.9, 136.7, 146.4, (KBr): ν = 3054, 3001, 2953, 2851, 1725 (w), 1660, 1582, 1512,
146.8, 151.7 (CAr), 192.1 (C=O) ppm. 19F NMR (282 MHz, 1477, 1464, 1398, 1308 (m), 1212, 1170, 1116, 1050, 1012, 1003,
CDCl ): δ = –73.4 (CF ) ppm. IR (KBr): ν = 3070, 3030, 2929 (w),
992 (m), 927, 842, 767, 743, 690 (s), 667, 641, 568 (m) cm–1. GC–
1660, 1600 (m), 1550, 1521, 1495, 1443 (w), 1425 (s), 1393, 1366, MS (EI, 70 eV): m/z (%) = 390 (100) [M]+, 373 (09), 283 (04), 211
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3
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 6670–6684

2Ј,4-Diarylbenzophenones from Bis(triflates) of 2Ј,4-Dihydroxybenzophenones
(42), 178 (24), 152 (13), 101 (05). HRMS (EI): calcd. for C28H22O2
[M]+ 390.16143; found 390.161279.
(4Ј-Vinylbiphenyl-2-yl)(3Ј-vinylbiphenyl-4-yl)methanone (15e): Com-
pound 15e was obtained from 14e (100 mg, 0.23 mmol), K3PO4
(146 mg, 0.69 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphenylboronic
acid (44 mg, 0.30 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate)
as a colourless oil; yield 59 mg (66%). 1H NMR (300 MHz,
CDCl3): δ = 5.01–5.11 (dd, J = 1.7, 10.8 Hz, 1 H, CH2 vinyl), 5.19–
5.24 (dd, J = 1.7, 11.2 Hz, 1 H, CH2 vinyl), 5.54–5.61 (dd, J = 1.7,
17.5 Hz, 1 H, CH2 vinyl), 5.68–5.74 (dd, J = 1.6, 17.5 Hz, 1 H,
CH2 vinyl), 6.47–6.57 (dd, J = 10.8, 17.5 Hz, 1 H, CHvinyl), 6.62–
6.72 (dd, J = 10.8, 17.5 Hz, 1 H, CHvinyl), 7.18 (s, 4 H, ArH), 7.31–
7.38 (m, 4 H, ArH), 7.40–7.48 (m, 5 H, ArH), 7.66 (d, J = 8.5 Hz,
2 H, ArH) ppm. 13C NMR (75.47 MHz, CDCl3): δ = 114.0, 114.6
(2 CH2 vinyl), 125.2, 125.9, 126.2, 126.7, 126.9, 127.0, 128.7, 129.0,
129.1, 130.0, 130.3, 130.5 (CHAr), 136.1 (CAr), 136.3, 136.5
(CHvinyl), 136.6, 138.2, 138.9, 139.6, 140.2, 140.7, 145.4 (CAr), 198.2
(2Ј,5Ј-Dimethoxybiphenyl-4-yl)(4Ј-vinylbiphenyl-2-yl)methanone (15b):
Compound 15b was obtained from 14b (100 mg, 0.21 mmol),
K3PO4 (133 mg, 0.63 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphen-
ylboronic acid (40 mg, 0.27 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a colourless oil; yield 65 mg (72%). 1H NMR
(300 MHz, CDCl3): δ = 3.61 (s, 6 H, 2 OCH3), 5.12 (d, J = 11.3 Hz,
1 H, CH2 vinyl), 5.58–5.64 (dd, J = 1.4, 17.6 Hz, 1 H, CH2 vinyl),
6.56 (d, J = 8.4 Hz, 1 H, CHvinyl), 7.17 (s, 1 H, ArH), 7.22 (s, 4 H,
ArH), 7.24–7.27 (m, 3 H, ArH), 7.34–7.48 (m, 5 H, ArH), 7.68 (d,
J = 8.3 Hz, 2 H, ArH) ppm. 13C NMR (75.47 MHz, CDCl3): δ =
55.9 (2 OCH3), 104.2, 104.4 (CHAr), 113.8 (CH2 vinyl), 118.5 (CAr),
126.1, 126.8, 128.8, 128.9, 129.2, 129.3, 129.4, 130.1, 130.6, 130.9
(CHAr), 135.5 (CAr), 136.4 (CHvinyl), 136.6, 139.0, 139.5, 139.8,
(C=O) ppm. IR (KBr): ν = 3043, 3029, 2952, 2847, 1721 (w), 1657,
˜
141.0, 157.5 (CAr), 198.1 (C=O) ppm. IR (KBr): ν = 3056, 3002,
˜
1597 (s), 1579, 1513, 1475, 1447, 1403, 1317 (m), 1266, 1253, 1235
(s), 1187, 1153, 1041, 987 (m), 925 (s), 861, 803, 783, 708, 665, 627,
543 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 386 (100) [M]+, 359
(10), 281 (04), 207 (50), 193 (07), 178 (53), 152 (16). HRMS (EI):
calcd. for C29H22O [M]+ 386.16652; found 386.166803.
2954, 2851, 1724 (w), 1661, 1601, 1587, 1514, 1441, 1432, 1401,
1330, 1277 (m), 1244 (s), 1183, 1171, 1033, 1001, 953, 879, 798,
768, 755, 693, 638, 611, 572 (m) cm–1. GC–MS (EI, 70 eV): m/z (%)
= 420 (100) [M]+, 403 (07), 241 (40), 198 (10), 178 (23), 152 (07),
127 (05). HRMS (EI): calcd. for C29H24O3 [M]+ 420.17200; found
420.172846.
(4Ј-tert-Butylbiphenyl-4-yl)(4Ј-vinylbiphenyl-2-yl)methanone (15f):
Compound 15f was obtained from 14f (100 mg, 0.21 mmol),
K3PO4 (133 mg, 0.63 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphen-
ylboronic acid (41 mg, 0.28 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a yellow oil; yield 58 mg (64%). 1H NMR (300 MHz,
CDCl3): δ = 1.26 (s, 9 H, 3 CH3), 5.07–5.11 (dd, J = 1.8, 10.8 Hz,
1 H, CH2 vinyl), 5.54–5.60 (dd, J = 1.8, 17.5 Hz, 1 H, CH2 vinyl),
6.47–6.57 (dd, J = 10.8, 17.6 Hz, 1 H, CHvinyl), 7.17 (s, 4 H, ArH),
7.35–7.39 (m, 4 H, ArH), 7.42–7.49 (m, 6 H, ArH), 7.66 (d, J =
10.2 Hz, 2 H, ArH) ppm. 13C NMR (62.90 MHz, CDCl3): δ = 31.2
(3 CH3), 34.6 (C), 125.8, 126.2, 126.6, 126.9, 127.0, 128.6, 129.1,
130.0, 130.2, 130.5 (CHAr), 135.8 (CAr), 136.3 (CHvinyl), 136.5,
136.9, 139.0, 139.6, 140.7, 145.3, 151.4 (CAr), 198.2 (C=O) ppm.
(2Ј,6Ј-Dimethoxybiphenyl-4-yl)(4Ј-vinylbiphenyl-2-yl)methanone (15c):
Compound 15c was obtained from 14c (100 mg, 0.21 mmol),
K3PO4 (133 mg, 0.63 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphen-
ylboronic acid (40 mg, 0.27 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a yellow oil; yield 62 mg (68%). 1H NMR (300 MHz,
CDCl3): δ = 3.59 (s, 6 H, 2 OCH3), 5.08–5.12 (dd, J = 1.7, 10.8 Hz,
1 H, CH2 vinyl), 5.57–5.63 (dd, J = 1.8, 17.6 Hz, 1 H, CH2 vinyl),
6.54 (d, J = 8.4 Hz, 1 H, CHvinyl), 7.14–7.21 (m, 6 H, ArH), 7.24
(d, J = 8.4 Hz, 2 H, ArH), 7.33–7.36 (m, 1 H, ArH), 7.41–7.46
(m, 4 H, ArH), 7.66 (d, J = 8.4 Hz, 2 H, ArH) ppm. 13C NMR
(62.90 MHz, CDCl3): δ = 55.9 (2 OCH3), 104.4 (CHAr), 113.8
(CH2 vinyl), 118.5 (CAr), 126.1, 126.7, 128.9, 129.2, 129.3, 129.4,
130.1, 130.6, 130.9 (CHAr), 135.5 (CAr), 136.4 (CHvinyl), 136.5,
139.0, 139.5, 139.8, 141.0, 157.5 (CAr), 198.1 (C=O) ppm. IR
IR (KBr): ν = 3055, 3030, 2956 (w), 1724, 1661, 1600 (m), 1573,
˜
1514, 1476, 1440, 1392, 1311 (w), 1276 (s), 1242, 1183, 1150, 1112,
1070, 1018, 987, 951 (w), 927 (s), 907, 861, 842, 781 (m), 756, 722
(s), 696, 649, 570 (w) cm–1. GC–MS (EI, 70 eV): m/z (%) = 416
(100) [M]+, 401 (92), 383 (05), 281 (05), 237 (10), 207 (20), 178 (37),
152 (09), 41 (05). HRMS (EI): calcd. for C31H28O [M]+ 416.21247;
found 416.212861.
(KBr): ν = 3054, 3029, 2951, 2857, 1726 (w), 1667, 1623, 1593,
˜
1517, 1443, 1435, 1403, 1332, 1279 (m), 1245 (s), 1187, 1173, 1035,
1003, 957, 881, 783, 761, 757, 689, 632, 609, 571 (m) cm–1. GC–
MS (EI, 70 eV): m/z (%) = 420 (100) [M]+, 403 (08), 241 (35), 198
(09), 178 (23), 152 (07), 127 (05). HRMS (EI): calcd. for C29H24O3
[M]+ 420.17200; found 420.172372.
(3Ј,5Ј-Dimethylbiphenyl-4-yl)(4Ј-vinylbiphenyl-2-yl)methanone (15g):
Compound 15g was obtained from 14g (100 mg, 0.23 mmol),
K3PO4 (146 mg, 0.69 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphen-
ylboronic acid (44 mg, 0.30 mmol) and 1,4-dioxane (5 mLmmol–1
of triflate) as a colourless viscous oil; yield 68 mg (76%). 1H NMR
(250 MHz, CDCl3): δ = 2.28 (s, 6 H, 2 CH3), 5.10 (d, J = 11.5 Hz,
1 H, CH2 vinyl), 5.54–5.62 (dd, J = 1.6, 17.6 Hz, 1 H, CH2 vinyl),
6.47–6.58 (dd, J = 10.8, 17.6 Hz, 1 H, CHvinyl), 6.93 (s, 1 H, ArH),
7.08 (s, 2 H, ArH), 7.18 (s, 4 H, ArH), 7.36–7.48 (m, 6 H, ArH),
7.64 (d, J = 8.4 Hz, 2 H, ArH) ppm. 13C NMR (62.90 MHz,
CDCl3): δ = 21.3 (2 CH3), 113.9 (CH2 vinyl), 125.1, 126.2, 126.8,
127.0, 128.6, 129.1, 129.8, 130.0, 130.2, 130.4 (CHAr), 135.8 (CAr),
136.3 (CHvinyl), 136.5, 138.4, 139.0, 139.6, 139.8, 140.7, 145.8 (CAr),
(2Ј-Ethoxybiphenyl-4-yl)(4Ј-vinylbiphenyl-2-yl)methanone
(15d):
Compound 15d was obtained from 14d (100 mg, 0.22 mmol),
K3PO4 (139 mg, 0.66 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphen-
ylboronic acid (42 mg, 0.29 mmol) and 1,4-dioxane (5 mLmmol–1
1
of triflate) as a pink oil; yield 56 mg (62%). H NMR (300 MHz,
CDCl3): δ = 1.21 (t, J = 6.9 Hz, 3 H, CH3), 3.92 (q, J = 6.9 Hz, 2
H, OCH2), 5.09–5.13 (dd, J = 1.7, 10.8 Hz, 1 H, CH2 vinyl), 5.56–
5.62 (dd, J = 1.8, 17.6 Hz, 1 H, CH2 vinyl), 6.49–6.59 (dd, J = 10.8,
17.6 Hz, 1 H, CHvinyl), 6.86–6.59 (m, 2 H, ArH), 7.15–7.21 (m, 6
H, ArH), 7.40–7.46 (m, 6 H, ArH), 7.65 (d, J = 8.5 Hz, 2 H,
ArH) ppm. 13C NMR (75.47 MHz, CDCl3): δ = 14.7 (CH3), 64.1
(OCH2), 112.8 (CHAr), 113.9 (CH2 vinyl), 118.5 (CAr), 120.9, 126.1,
126.9, 128.8, 129.1, 129.3, 129.4, 129.7, 130.0, 130.2, 130.7 (CHAr),
135.5 (CAr), 136.3 (CHvinyl), 136.5, 139.1, 139.7, 140.8, 143.5, 155.8
198.2 (C=O) ppm. IR (KBr): ν = 3019, 2916, 1724 (w), 1661 (m),
˜
1598 (s), 1556, 1475, 1440, 1397, 1313 (m), 1277 (s), 1209, 1184,
1150, 1117, 1071, 1033, 1002, 987 (m), 928 (s), 907, 781, 768, 695,
646, 581 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 388 (100) [M]+,
371 (10), 209 (28), 194 (05), 178 (21), 165 (22), 152 (06). HRMS
(EI): calcd. for C29H24O [M]+ 388.18217; found 388.182014.
(CAr), 198.3 (C=O) ppm. IR (KBr): ν = 3056, 3031, 2954, 2850,
˜
1724 (w), 1661, 1599 (s), 1580, 1511, 1473, 1446, 1401, 1311 (m),
1277, 1260, 1237 (s), 1185, 1150, 1039, 988 (m), 927 (s), 860, 803,
785, 708, 666, 628, 541 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) =
404 (100) [M]+, 375 (18), 357 (10), 225 (23), 197 (14), 178 (44), 168
(13), 139 (12), 115 (06). HRMS (EI): calcd. for C29H24O2 [M]+
404.17708; found 404.177499.
(4Ј-Ethylbiphenyl-4-yl)(4Ј-vinylbiphenyl-2-yl)methanone (15h): Com-
pound 15h was obtained from 14h (100 mg, 0.23 mmol), K3PO4
Eur. J. Org. Chem. 2011, 6670–6684
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6683

M. Nawaz, I. Ullah, O.-U.-R. Abid, A. Villinger, P. Langer
FULL PAPER
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(146 mg, 0.69 mmol), Pd(PPh3)4 (3 mol-%), 4-vinylphenylboronic
acid (44 mg, 0.30 mmol) and 1,4-dioxane (5 mLmmol–1 of triflate)
as a colourless oil; yield 66 mg (74%). 1H NMR (250 MHz,
CDCl3): δ = 1.16 (t, J = 7.6 Hz, 3 H, CH3), 2.58 (q, J = 7.6 Hz, 2
H, CH2CH3), 5.06 (d, J = 11.5 Hz, 1 H, CH2 vinyl), 5.52–5.60 (dd,
J = 1.7, 17.6 Hz, 1 H, CH2 vinyl), 6.45–6.56 (dd, J = 10.8, 17.5 Hz,
1 H, CHvinyl), 7.17 (s, 4 H, ArH), 7.32 (d, J = 6.2 Hz, 2 H, ArH),
7.37 (d, J = 6.8 Hz, 2 H, ArH), 7.39–7.49 (m, 6 H, ArH), 7.64 (d,
J = 8.4 Hz, 2 H, ArH) ppm. 13C NMR (62.90 MHz, CDCl3): δ =
15.5 (CH3), 28.5 (CH2 ethyl), 114.0 (CH2 vinyl), 126.2, 126.6, 127.0,
127.1, 128.4, 128.6, 129.1, 130.0, 130.2, 130.5 (CHAr), 135.8 (CAr),
136.3 (CHvinyl), 136.5, 137.1, 139.0, 139.6, 140.7, 144.5, 145.5 (CAr),
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198.1 (C=O) ppm. IR (KBr): ν = 3053, 2926, 1725 (w), 1660, 1598
˜
(s), 1574, 1523, 1514, 1476, 1440, 1399, 1310 (m), 1277 (s), 1189,
1118, 1060, 1032, 1003, 987 (m), 928 (s), 908, 842, 780 (m), 735 (s),
700, 654, 539 (m) cm–1. GC–MS (EI, 70 eV): m/z (%) = 388 (100)
[M]+, 371 (09), 209 (28), 178 (20), 152 (17). HRMS (EI): calcd. for
C29H24O [M]+ 388.18217; found 388.182058.
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Financial support by the Deutscher Akademischer Austausch
Dienst (DAAD) and by the Higher Education Commission (HEC),
Pakistan for M. N., I. U., and O.-u.-R. A. is gratefully acknowl-
edged.
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[17] CCDC-837693, -837694, -837695, -837696, -837697, -837698,
and -837699 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Received: May 30, 2011
Published Online: September 21, 2011
6684
www.eurjoc.org
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 6670–6684