Synthesis of biaryl derivatives by using ruthenium-mediated [2+2+2] cyclotrimerization and Suzuki-Miyaura cross-coupling as key steps

Article abstract of DOI:10.1055/s-0030-1260009

Functionalized biaryl derivatives have been prepared by applying [2+2+2] cyclotrimerization with the aid of Grubbs first-generation catalyst (G-I). The trimerized products were subjected to the Suzuki-Miyaura cross-coupling reaction sequence to generate h

Full text of DOI:10.1055/s-0030-1260009

PAPER
1581
Synthesis of Biaryl Derivatives by Using Ruthenium-Mediated [2+2+2]
Cyclotrimerization and Suzuki–Miyaura Cross-Coupling as Key Steps
Synthesis of
B
a
iaryl
D
eriv
m
Department of Chemistry, Indian Institute of Technology-Bombay, Powai, Mumbai 400 076, India
Fax +91(22)25723480; E-mail: srk@chem.iitb.ac.in
Received 10 February 2011; revised 15 March 2011
our work in this area we are interested in designing biaryl
derivatives by cyclotrimerization using a ruthenium-
based catalyst.
Abstract: Functionalized biaryl derivatives have been prepared by
applying [2+2+2] cyclotrimerization with the aid of Grubbs’ first-
generation catalyst (G-I). The trimerized products were subjected to
the Suzuki–Miyaura cross-coupling reaction sequence to generate
highly functionalized biaryl derivatives.
Mes-N
Cl
N-Mes
Ph
PCy3
Ru
Key words: terphenyl, quinquephenyl, [2+2+2] cyclotrimeriza-
tion, Suzuki–Miyaura cross-coupling, metathesis
Ph
H
Cl
Cl
Ru
H
Cl
PCy3
(G-II)
PCy3
The biaryl unit occupies a unique position in synthetic or-
ganic chemistry. These compounds draw considerable at-
tention due to their broad applications, such as key
building blocks for pharmaceutically active molecules,1
ligands for catalysis,2 liquid crystals,3 organic semicon-
ductors,4 polymers,5 and sensors.6 Various methods have
been reported for aryl–aryl cross-coupling between two
different aryl groups. Most of these developments are
based on the transition-metal-catalyzed cross-coupling of
aryl halides with arylmetal species through Stille, Suzuki,
Negishi, Kharasch, and Hiyama coupling reactions.7 Late-
ly, attention has also been focused on strategies other than
cross-coupling, such as the Diels–Alder reaction,8
[2+2+2] cyclotrimerization,9 oxidative coupling,10 and
radical chain reaction of arenediazonium salts.11 Addi-
tionally, some other methodologies have also been report-
ed for the preparation of biaryl12 and terphenyl
derivatives.13 Various structurally related biaryl-contain-
ing cyclopeptide natural products such as biphenomycin14
and arylomycin15 represent interesting examples of biaryl
compounds used in medicinal chemistry.
(G-I)
1
2
Figure 1 Various Grubbs catalysts used in [2+2+2] cyclotrimeriza-
tions
Herein, we report the synthesis of biaryl derivatives based
on [2+2+2] cyclotrimerization and Suzuki–Miyaura
cross-coupling as key steps. The first step involves
[2+2+2] cyclotrimerization of phenylacetylene deriva-
tives with dimethyl acetylenedicarboxylate in the pres-
ence of Grubbs’ catalyst to generate biaryl derivatives.
Later on, these biaryl compounds were subjected to
Suzuki–Miyaura cross-coupling with various boronic
acids such as 4-formyl-, 4-acetoxy-, and 4-methoxyphe-
nylboronic acids in the presence of Pd(PPh3)4 catalyst in
tetrahydrofuran–toluene–water (1:1:1) to generate the ter-
phenyl systems (Scheme 1).
Ar1
O
O
Ar2
Ar2
OMe
OMe
OMe
OMe
Metal-catalyzed cyclotrimerization of an alkyne is one of
the most powerful methods for assembling substituted
benzene derivatives.16 In this regard, various transitional-
metal derivatives (e.g., Co, Pd, Cr, Ni, Rh, and Ta)17 have
been used for this transformation.
Ruthenium catalysts have broad application18,19 in the
synthesis of various natural and non-natural products.20
Limited reports are available for [2+2+2] cyclotrimeriza-
tion using ruthenium catalysts. Our group has extensively
used ruthenium catalysts (Figure 1) for metathesis reac-
tions.21 Additionally, Suzuki–Miyaura cross-coupling22
and [2+2+2] cyclotrimerization23 have been used to gen-
erate diverse polycyclic compounds.24 In continuation of
O
O
Ar1
O
X
X
Scheme 1 Retrosynthetic analysis of biaryl derivatives
For the synthesis of biaryl derivatives, we started with
commercially available acetophenone derivatives 3.
These acetophenones were converted into acetylene de-
rivatives 5 using the Vilsmeier reaction as a key step.
Thus, treatment of acetophenone 3 with phosphorus oxy-
chloride and a slightly excess of N,N-dimethylformamide
SYNTHESIS 2011, No. 10, pp 1581–1586
x
x.
x
x
.
2
0
1
1
Advanced online publication: 19.04.2011
DOI: 10.1055/s-0030-1260009; Art ID: Z18311SS
© Georg Thieme Verlag Stuttgart · New York

1582
S. Kotha et al.
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gave the corresponding b-chloro-a,b-unsaturated alde-
hyde 4 in 76% yield. Although we obtained two regioiso-
meric aldehydes, only one isomer is shown in Scheme 2.
Hydrolysis of the b-chloro-a,b-unsaturated aldehyde in-
termediates with aqueous sodium hydroxide in dioxane
gave the required acetylene derivatives 5 in 78% yield
(Scheme 2).25
O
Cl
DMF, POCl3
NaOH
78%
CHO
76%
X
X
X
3
4
5
Scheme 2 Preparation of various phenylacetylene derivatives
The acetylenes 5 were subjected to [2+2+2] cyclotrimer-
ization with dimethyl acetylenedicarboxylate (6) in the
presence of Grubbs first-generation catalyst 1 (5 mol%) in
toluene under reflux to deliver the terphenyl systems 7
(Scheme 3).
Figure 2 ORTEP diagram of 7b at 50% probability
Table 1 List of Various [2+2+2] Cyclotrimerized Products Pre-
pared
Entry Substrate
Producta
Yield
(%)
X
O
CO2Me
1 (5 mol%)
OMe
OMe
Cl
+
O
2 ×
CO2Me
OMe
OMe
7
O
1
75
67
62
64
X
6
X
Cl
X = Cl, Br, I, OMe
O
O
5
5a
Cl
Br
Scheme 3 [2+2+2] Cyclotrimerization with dimethyl acetylenedi-
carboxylate
7a
7b
7c
7d
OMe
OMe
When we replaced dimethyl acetylenedicarboxylate (6)
with other acetylenic partners, such as 1,4-dibromobut-2-
yne, 1,4-diacetylbut-2-yne, 1,4-dihydroxybut-2-yne, the
desired [2+2+2] cyclotrimerized product was not ob-
served. From the above reaction conditions we assumed
that acetylene derivatives with electron-withdrawing
groups like dimethyl acetylenedicarboxylate are required
for the successful implementation of the [2+2+2] cyclo-
trimerization reaction with phenylacetylene derivatives.
2
3
4
Br
O
5b
5c
5d
Br
I
O
OMe
OMe
I
O
The structures of the trimerized products 7a–d were char-
I
acterized using H and 13C NMR and HRMS data. 13C
1
NMR data clearly indicated the symmetrical nature of the
product. Finally, an X-ray crystal structure of 7b unam-
biguously established the structure of [2+2+2] trimerized
product (Figure 2).26 We also observed a minor amount of
dimethyl acetylenedicarboxylate self-trimerized product
(~15%).
MeO
O
OMe
OMe
MeO
O
MeO
Our detailed studies indicated that the catalyst G-I (1) is
more suitable for cyclotrimerization than G-II (2). Vari-
ous phenylacetylene derivatives 5 were subjected to
[2+2+2] cyclotrimerization reaction with dimethyl acety-
lenedicarboxylate in presence of G-I (1) to deliver trimer-
ized products 7a–d in good yield (Table 1).
a Reaction conditions: 5, DMAD (1.25 equiv), 1 (5 mol%), toluene,
reflux, 36 h.
boronic acids such as 4-acetyl-, 4-formyl-, and 4-methoxy-
phenylboronic acid using Pd(PPh3)4 catalyst (5–9 mol%)
in tetrahydrofuran–toluene–water (1:1:1) and using sodi-
um carbonate as a base. We found that Suzuki–Miyaura
The trimerized products 7b and 7c were subjected to
Suzuki–Miyaura cross-coupling reaction with different
Synthesis 2011, No. 10, 1581–1586 © Thieme Stuttgart · New York

PAPER
Synthesis of Biaryl Derivatives
1583
Table 2 Various Reaction Conditions Studied for the Suzuki–
cross-coupling products were hydrolyzed in the course of
the coupling sequence (Scheme 4). The presence of two
aromatic rings in the para positions may be responsible
for facial hydrolysis of the ester functionalities under mild
reaction conditions
Miyaura Cross-Coupling Reactiona
Entry Solventsa
Base
Product Yieldb (%)
1
2
3
4
5
6
7
8
THF–toluene–H2O (1:1:1) Na2CO3
THF–toluene–H2O (1:1:1) K2CO3
8b
8c
8a
8c
8b
8a
8c
8b
64
63
66
49
63
58
48
52
R
toluene
toluene
DME
DMF
K2CO3
Cs2CO3
K2CO3
K2CO3
Na2CO3
K3PO4
X
O
O
4-RC6H4B(OH)2
Pd(PPh3)4, base
OMe
OMe
OH
OH
O
8
O
X
7b X = Br
7c X = I
THF
R
DMF
R = CHO, COMe, OMe
a Reaction conditions: 7b or 7c, 4-RC6H4B(OH)2, Pd(PPh3)4 (5–9
mol%), 90–120 °C, 6–12 h.
Scheme 4 Suzuki–Miyaura cross-coupling reactions
b Cross-coupling products isolated as the products of hydrolysis of the
ester groups.
Table 3 Suzuki–Miyaura Cross-Coupling Reaction of Trimerized Products
Starting compound
Productsa
Yield
OHC
O
O
OH
OH
X = I, 74%
X = Br, 63%
OHC
O
8a
X
X
O
O
O
OMe
OMe
OH
X = I, 83%
X = Br, 68%
OH
O
X = Br (7b)
X = I (7c)
O
8b
MeO
O
OH
OH
X = I, 53%
X = Br, 48%
O
MeO
8c
a Reaction conditions: 7b,c, 4-RC6H4B(OH)2, Pd(PPh3)4 (5–9 mol%), THF–toluene–H2O (1:1:1), Na2CO3, 90 °C, 6 h.
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Dimethyl 4,4¢¢-Diiodo-1,1¢:2¢,1¢¢-terphenyl-4¢,5¢-dicarboxylate
To avoid the hydrolysis of the ester functionality, we stud-
ied the coupling reaction with substrate 7b and 7c with
various solvents and bases (Table 2); all reaction condi-
tions gave the ester-hydrolyzed Suzuki coupling products
8.
(7c)
Following the typical procedure for 7a using 5c (100 mg, 0.43
mmol), Grubbs catalyst 1 (18 mg, 5 mol%), and DMAD (6, 152 mg,
1.07 mmol) gave 7c (160 mg, 62%) as a solid; mp 149–150 °C.
IR (KBr): 1350, 1594, 1726, 2924 cm–1.
We have prepared biaryl derivatives 7a–d via [2+2+2] cy-
clotrimerization reaction by using Grubbs first-generation
catalyst under toluene at reflux. The trimerized products
7b,c were subjected Suzuki–Miyaura cross-coupling re-
action to generate highly functionalized biaryl derivatives
8a–c (Table 3). This methodology may be useful for the
preparation of carbon-rich polycyclic derivatives with ox-
idative coupling as a key step.27
1H NMR (400 MHz, CDCl3): d = 3.93 (s, 6 H), 6.86 (d, J = 4.8 Hz,
4 H), 7.60 (d, J = 4.8 Hz, 4 H), 7.73 (s, 2 H).
13C NMR (100.5 MHz, CDCl3): d = 53.0, 94.1, 131.3, 131.4, 131.5,
137.7, 138.8, 142.2, 167.7.
HRMS (Q-ToF): m/z [M + H]+ calcd for C22H17I2O4: 421.1627;
found: 421.1646.
Dimethyl 4,4¢¢-Dimethoxy-1,1¢:2¢,1¢¢-terphenyl-4¢,5¢-dicarboxy-
late (7d)
Following the typical procedure for 7a using 5d (100 mg, 0.73
mmol), Grubbs catalyst 1 (30 mg, 5 mol%), and DMAD (6, 266 mg,
1.87 mmol) gave 7d (195 mg, 64%) as a liquid.
IR (neat): 1265, 1602, 1725, 2953, 3056 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.79 (s, 6 H), 3.92 (s, 6 H), 6.78
(d, J = 4.4 Hz, 4 H), 7.06 (d, J = 4.8 Hz, 4 H), 7.73 (s, 2 H).
13C NMR (100.5 MHz, CDCl3): d = 52.8, 55.4, 113.8, 130.5, 130.6,
130.9, 131.3, 132.3, 159.1, 168.1.
HRMS (Q-ToF): m/z [M + H]+ calcd for C24H23O6: 407.1495;
found: 407.1507.
Analytical TLC was performed on 10 × 5 cm glass plates coated
with silica gel g or GF254 (containing 13% CaSO4 as a binder). Vi-
sualization was achieved by exposure to either iodine vapor or UV
light. Column chromatography was performed using silica gel
(100–200 mesh) and the column was usually eluted with a mixture
of EtOAc and PE (petroleum ether; bp 60–80 °C). 1H NMR and 13
C
NMR spectral data were recorded on a Varian VXR 400 spectrom-
eter using TMS as an internal standard and CDCl3 as a solvent. Cou-
pling constants (J) are given in hertz (Hz). HRMS data were
recorded on a Q-ToF micro mass instrument. Boronic acids were
purchased from Lancaster Chemical Company (UK) and Aldrich
Chemical Company (USA). (PPh3)4Pd catalyst was purchased from
Strem Chemicals, Inc. (USA).
4,4¢¢¢¢-Diformyl-1,1¢:2¢,1¢¢;4¢¢¢,1¢¢¢¢-quinquephenyl-4¢¢,5¢¢-dicar-
boxylic Acid (8a); Typical Procedure
Dimethyl 4,4¢¢-Dichloro-1,1¢:2¢,1¢¢-terphenyl-4¢,5¢-dicarboxy-
late (7a); Typical Procedure
To a soln of 7c (100 mg, 0.16 mmol) in THF–toluene–H2O (1:1:1)
mixture, 4-formylphenylboronic acid (118 mg, 0.79 mmol), aq
Na2CO3 (83 mg, 0.78 mmol, degassed with N2 for 20 min), and
Pd(PPh3)4 (9.3 mg, 4 mol%) were added; the mixture was heated at
90 °C for 6 h. When the reaction was complete (TLC monitoring),
the mixture was diluted with H2O and extracted with CH2Cl2 (4 ×
50 mL). The combined organic layers were washed with H2O and
brine and dried (Na2SO4). The solvent was evaporated and the crude
product was charged on a column (silica gel, EtOAc–PE, 1:4) to
give 8a (62 mg, 74%) as a white solid; mp 155–158 °C.
IR (KBr): 960, 1352, 1384, 1601, 1677, 2811, 3428 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.44–7.51 (m, 6 H), 7.62–7.68 (m,
4 H), 7.74–7.77 (m, 4 H), 7.94–7.97 (m, 4 H), 10.06 (s, 2 H).
13C NMR (100.5 MHz, CDCl3): d = 127.4, 127.5, 127.5, 128.4,
129.1, 130.9, 136.0, 136.1, 140.1, 146.6, 171.1, 198.1.
4-Chlorophenylacetylene (5a, 100 mg, 0.73 mmol) in anhyd toluene
was degassed with N2 for 10 min. Then, Grubbs catalyst 1 (30 mg,
5 mol%) was added and the mixture was stirred for 15 min. DMAD
(6, 259 mg, 1.82 mmol) in toluene was added to the mixture and it
was refluxed under N2 for 36 h. When the reaction was complete
(TLC monitoring), the mixture was cooled to r.t. and the solvent
was removed under reduced pressure and the residue was purified
by column chromatography (EtOAc–PE) to give 7a (228 mg, 75%);
mp 180–182 °C.
IR (KBr): 836, 1247, 1594, 1736, 2954 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.94 (s, 6 H), 7.05 (d, J = 4.4 Hz,
4 H), 7.24 (d, J = 4.4 Hz, 4 H), 7.75 (s, 2 H).
13C NMR (100.5 MHz, CDCl3): d = 52.9, 128.8, 131.0, 131.3,
134.1, 137.8, 142.2, 167.7.
HRMS (Q-ToF): m/z [M + Na]+ calcd for C22H16Cl2NaO4:
437.0322; found: 437.0323.
Anal. Calcd for C34H20O6: C, 77.85; H, 3.84. Found: C, 78.68; H,
4.14.
4,4¢¢¢¢-Diacetyl-1,1¢:2¢,1¢¢;4¢¢¢,1¢¢¢¢-quinquephenyl-4¢¢,5¢¢-dicar-
boxylic Acid (8b)
Following the typical procedure for 8a using 7c (50 mg, 0.08
mmol), 4-acetylphenylboronic acid (58 mg, 0.20 mmol), aq Na2CO3
(34 mg, 0.32 mmol degassed with N2 for 20 min), and Pd(PPh3)4
(9.7 mg, 4 mol%) gave 8b (37 mg, 83%) as a white solid; mp 160–
162 °C.
IR (KBr): 960, 1355, 1384, 1600, 2918, 3433 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.64 (s, 6 H), 7.40–7.49 (m, 6 H),
7.64–7.68 (m, 4 H), 7.68–7.70 (m, 4 H), 8.03–8.05 (m, 4 H).
Dimethyl4,4¢¢-Dibromo-1,1¢:2¢,1¢¢-terphenyl-4¢,5¢-dicarboxylate
(7b)
Following the typical procedure for 7a using 5b (100 mg, 0.55
mmol), Grubbs catalyst 1 (22 mg, 5 mol%), and DMAD (6, 195 mg,
1.37 mmol) gave 7b (186 mg, 67%) as a solid; mp 158–160 °C.
IR (KBr): 596, 1247, 1431, 1590, 1736, 2953 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.94 (s, 6 H), 6.99 (d, J = 8.4 Hz,
4 H), 7.40 (d, J = 8.4 Hz, 4 H), 7.74 (s, 2 H).
13C NMR (100.5 MHz, CDCl3): d = 52.8, 122.2, 131.1, 131.2,
131.5, 138.1, 142.0, 167.4.
HRMS (Q-ToF): m/z [M + H]+ calcd for C22H17Br2O4: 505.1825;
13C NMR (100.5 MHz, CDCl3): d = 26.7, 127.3, 127.4, 128.3,
129.0, 129.1, 135.9, 139.9, 145.8, 147.8, 178.4, 197.9.
found: 505.1842.
Anal. Calcd for C36H24O6: C, 78.25; H, 4.38. Found: C, 78.82; H,
3.67.
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Synthesis of Biaryl Derivatives
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4,4¢¢¢¢-Dimethoxy-1,1¢:2¢,1¢¢;4¢¢¢,1¢¢¢¢-quinquephenyl-4¢¢,5¢¢-dicar-
boxylic Acid (8c)
Following the typical procedure for 8a using 7c (50 mg, 0.08
mmol), 4-methoxyphenylboronic acid (58 mg, 0.33 mmol), aq
Na2CO3 (35 mg, 0.33 mmol, degassed with N2 for 20 min), and
Pd(PPh3)4 (8.7 mg, 9 mol%) gave 8c (23 mg, 54%) as a white solid;
mp 179–181 °C.
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2009, 4137. (b) Ullah, I.; Sher, M.; Khera, R. A.; Ali, A.;
Nawaz, M.; Shkoor, M.; Iqbal, I.; Imran, M.; Villinger, A.;
Fischer, C. Tetrahedron 2010, 66, 3824.
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H.; Imanaka, H. J. Antibiot. 1985, 38, 1462.
IR (KBr): 1351, 1384, 1605, 2924, 3432 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.65 (s, 6 H), 6.95–7.00 (m, 4 H),
7.28–7.32 (m, 4 H), 7.39–7.43 (m, 4 H), 7.46–7.49 (m, 2 H), 7.51–
7.56 (m, 4 H).
13C NMR (100.5 MHz, CDCl3): d = 52.8, 55.4, 113.8, 130.5, 130.6,
130.9, 131.3, 132.3, 159.1.
HRMS (ESI): m/z [M]+ calcd for C34H26O6: 530.5666; found:
530.6921.
Acknowledgment
We would like to acknowledge the DST for the financial support.
We also thank, SAIF-Mumbai for recording the spectral data. S.V.
thanks IIT-Bombay and UGC-New Delhi for the award of research
fellowship. S.K. thanks DST for the award of J. C. Bose fellowship.
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Sussmuth, R.; Muller, R. J.; Pukall, R.; Fiedler, H. P.
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