Scope and limitation of the nickel-catalyzed coupling reaction between lithium borates and mesylates

Article abstract of DOI:10.1016/S0022-328X(02)01174-9

Coupling reaction of aryl borates and mesylates derived from phenols and enols was studied. Mesylates with an electron-with-drawing group or ring were highly reactive at room temperature in the presence of NiCl₂(PPh₃)₂ to furnish the coupling products in good yields.

Full text of DOI:10.1016/S0022-328X(02)01174-9

Journal of Organometallic Chemistry 653 (2002) 91–97
www.elsevier.com/locate/jorganchem
Scope and limitation of the nickel-catalyzed coupling reaction
between lithium borates and mesylates
Yuichi Kobayashi *, Anthony D. William, Ryo Mizojiri
Department of Biomolecular Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501, Japan
Received 10 September 2001; received in revised form 26 November 2001; accepted 27 November 2001
Abstract
Coupling reaction of aryl borates and mesylates derived from phenols and enols was studied. Mesylates with an electron-with-
drawing group or ring were highly reactive at room temperature in the presence of NiCl (PPh ) to furnish the coupling products
2
3 2
in good yields. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Biaryl; Borate; Coupling; Mesylate; Nickel-catalyst
1. Introduction
coupling reaction, thus prompting an investigation of
alternative sulfonates.
Aryl bromides and iodides 1 (X=Br, I) are sub-
strates usually employed in the transition metal-cata-
lyzed coupling reaction with organometallics 2 (Eq.
1)). The reaction has provided successful results in
organic synthesis and material science, and is now
recognized as one of the most reliable carbonꢀcarbon
bond forming reactions [1]. Although aryl halides of a
simple structure are available by several methods or
directly from commercial sources, preparation of aryl
halides with a complex structure encounters difficulty.
Phenol derivatives such as sulfonates and phosphonates
are attractive alternatives for the halides as they can be
prepared under milder conditions
Aryl mesylates and tosylates are convenient substi-
tutes for triflates. So far, mesylate couplings were first
published by Percec et al. [4], then by Kobayashi and
Mizojiri [5], and recently by Miyaura and coworkers
[6]. Percec and Miyaura studied aryl boronic acids as
organometallics 2, the reagents developed by Suzuki
and Miyaura for coupling reactions using the various
types of substrates [7–9]. Among the palladium and
nickel complexes Percec examined, the latter showed a
somewhat higher catalytic activity, though the yields
are moderate in most cases with the best ligand of dppf
under forcing conditions of the higher temperatures
(65 °C in THF or 90–100 °C in dioxane). Later,
Miyaura improved the yields and provided a number of
entries of the mesylate coupling, though the high reac-
tion temperature was left unimproved. According to
Percec, the results are ascribed to the slow oxidative
addition of the mesylates 1 (X=OMs) to Ni(0) com-
plexes. However, there is likely to be slow transmetala-
tion with the boronic acids, which is responsible for the
requirement of the high reaction temperature.
(
ArꢀX+Rꢀm“ArꢀR
(1)
1
2
cat.
3
X:Br, I, OTf (standard substrates)
X:OMs, OTs (substrates of the present study)
than halides, and furthermore phenols allow flexibility
in their preparation and manipulation. Among them,
triflates 1 (X=OTf) have been studied well, and their
high reactivity in the coupling reaction has produced
successful applications [2,3]. However, the unstable na-
ture of the triflates and higher price of the triflating
reagents reduce the advantage of using triflates in the
Recently, we have found that lithium organoborates
T
5
with a transferring aryl or alkenyl group (R ) and a
dummy methyl ligand are more reactive reagents than
the classical reagents in the coupling with allyl esters 4
(
Scheme 1) [10]. Nickel complexes catalyze the reaction
much more efficiently than palladium complexes, and
overnight stirring at or below room temperature is
*
Corresponding author. Tel./fax: +81-45-9245789.
E-mail address: ykobayas@bio.titech.ac.jp (Y. Kobayashi).
0
022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(02)01174-9

9
2
Y. Kobayashi et al. / Journal of Organometallic Chemistry 653 (2002) 91–97
sufficient for completion of the allylic coupling. In
addition, the neutral and stable nature of boronate
esters 7, the precursors of 5, allows easy purification by
chromatography and/or distillation and storage for a
long period of time without any decomposition. We
envisioned that the inherent high reactivity of borates 5
coupled with a nickel-catalyst would accelerate the
transmetalation in the coupling reaction of mesylates
and tosylates derived from phenols and enols. As com-
municated previously [5], the coupling was found to
proceed at room temperature with the finding that the
modified borates 8 possessing the dummy Bu ligand
have the highest reactivity, whereas the original borates
the transmetalation is the rate-determining step in the
mesylate coupling as we have proposed above. Herein,
we report a full account of the coupling reaction.
5
with the Me ligand show rather moderate reactivity
(
Scheme 2, Fig. 1, Eq. (2)). These results indicate that
2
. Results and discussion
Initially, p-methoxycarbonylphenyl mesylate (1a) [11]
was selected as a representative sulfonate, and the
T
coupling was investigated with the borates 5a (R =2-
T
furyl) and 5b (R =Ph). Methyllithium (three equiva-
lents) was added to a mixture of NiCl (PPh ) or
2
3 2
NiCl (dppf) (10 mol%) and the boronate precursor 7a
2
T
T
(
R =2-furyl) or 7b (R =Ph) (four equivalents) in
THF to generate the Ni(0) catalyst and borate 5a or 5b
15–30 min, 0 °C–room temperature), and, after addi-
Scheme 1. Allylic coupling with the highly reactive borates 5.
(
tion of 1a, reaction was carried out at room tempera-
ture overnight. Furylborate 5a underwent smooth
coupling
with
mesylate
1a
furnishing
p-
MeO CC H ꢀ(2-furyl) (3a) [12] in good yield (Table 1,
2
6
4
entries 1 and 2). To the best of our knowledge, this is
the first example that the oxidative addition of mesy-
lates to the Ni(0) species and the subsequent transmeta-
lation proceeded at room temperature at reasonable
rates. On the other hand, phenylborate 5b under similar
conditions to 1a resulted in incomplete coupling and
Scheme 2. Summary of the present study. aRT and RD in the
boronates 7a–e and borates 5a,b, 8b–e, 9, 10: see Eq. (2); 3a:
b
p-MeO CC H ꢀ(2-furyl), 3b: p-MeO CC H ꢀC H . For other 3, see
2
6
4
2
6
4
6
5
poor product-selectivity yielding p-MeO CC H ꢀC H
Table 2.
2
6
4
6
5
(
3b) 9e in 24–32% yield and the by-product 11a in
fairly large quantity (entries 3 and 4). Attempted reac-
tions at higher temperatures and/or in other solvents
such as DMF, MeCN did not improve the reactivity or
the product-selectivity. We imputed the unsatisfying
result to the poor transmetalating ability of the phenyl
group from boron to nickel.
Since the reactivity of the borates in the allylic cou-
pling was raised substantially by a more electron-donat-
ing dummy alkyl ligand than the Me ligand,
Fig. 1. Sulfonates 1 examined in Scheme 2.
phenylborates with the CH TMS, t-Bu, or n-Bu ligand
2

Y. Kobayashi et al. / Journal of Organometallic Chemistry 653 (2002) 91–97
93
Table 1
Nickel-catalyzed reaction of sulfonates (1a or 1b) with furylborate (5a) or phenylborate (5b, 8b, 9, or 10)
a
Entry Sulfonate
Borate b
Ni catalyst
Temperature
°C)
Time (h)
Yield c of product 3 e
Ratio d
(
Number RD
RT
3:11
f
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
1b
5a
5a
5b
5b
9
10
8b
8b
8b
8b
5a
5a
9
Me
Me
Me
Me
2-furyl
2-furyl
Ph
NiCl (PPh )
20
20
20
20
20
20
20
20
20
60
20
20
20
20
11
14
11
11
12
12
12
12
12
6
3a
3a
3b
3b
3b
3b
3b
3b
3b
3b
3a
3a
3b
3b
82
91
24
32
84
40
95
93
60
90
21
33
17
83
100:0
100:0
57:43
55:45
90:10
2
3 2
NiCl (dppf)
2
g
g
NiCl (PPh )
2
3 2
Ph
NiCl (dppf)
2
CH TMS Ph
NiCl (PPh )
2
2
3 2
t-Bu
n-Bu
n-Bu
n-Bu
n-Bu
Me
Ph
Ph
Ph
Ph
Ph
2-furyl
2-furyl
NiCl (PPh )
45:55
2
3 2
NiCl (PPh )
\95:B5
\95:B5
\95:B5
\95:B5
50:50
70:30
85:15
\95:B5
2
3 2
h
NiCl (PPh )
2
3 2
g
NiCl (dppf)
2
0
NiCl (PPh )
2
3 2
g
g
g
1
2
3
4
NiCl (PPh )
11
14
12
14
2
3 2
Me
NiCl (dppf)
2
CH TMS Ph
n-Bu
NiCl (PPh )
2
2
3 2
8b
Ph
NiCl (PPh )
2
3 2
a
Reactions were carried out at room temperature overnight using the sulfonate and three equivalents of the borate in the presence of 10 mol%
of the nickel-catalyst unless otherwise noted.
b
D
Borates were prepared in situ from the corresponding boronate esters (7a or 7b) and R ꢀLi (0 °C, 15 min).
c
d
e
f
Isolated yields.
Determined by 1H-NMR (300 MHz) spectroscopy.
3
a: p-MeO CC H ꢀ(2-furyl). 3b: p-MeO CC H ꢀC H .
2 6 4 2 6 4 6 5
One of 11a–d.
g
h
Starting mesylate was recovered.
Reaction was carried out with 1.5 equivalents of 8b.
were investigated for the phenylation of mesylate 1a.
mesylates with an electron-withdrawing or -donating
substituent at the p-position (1d–f, 1g), 1-naphthalenyl
mesylate 1h, 2-pyridyl mesylate 1i. In addition, mesy-
lates 1j–1l derived from the enols were also studied.
Results of the coupling of these mesylates with 2-furyl-
borate 5a, phenylborate 8b, and/or substituted phenylb-
orates 8c–e are presented in Table 2. Reaction of
mesylate 1a with borates 8c and 8d proceeded at room
temperature to furnish 3c and 3d, respectively, with
good efficiency (the yield and the product-selectivity)
The CH TMS ligand considerably improved the yield
2
and the product-selectivity (entry 5), while only the
yield was increased moderately by the t-Bu ligand
(
entry 6). The best results were provided by borate 8b
with the n-Bu ligand, furnishing 3b in 95% yield with
high product-selectivity of 3b–11d (\95:B5) (entry
7
). Although the reaction was run with three equiva-
lents of borate 8b, similar efficiency was recorded with
.5 equivalents of 8b (entry 8). Regarding the catalyst,
NiCl (PPh ) provided a better result than NiCl (dppf)
1
(
entries 1 and 2). The substituent (CO Me) near the
2
2
3 2
2
reaction site in mesylate 1c did not interfere with the
efficiency producing 3e–g (entries 3–5). Product 3g
would be a precursor of the angiotensin II receptor
antagonists such as DuP 753 [13].
(
entry 7 vs. 9). In the examination with borate 8b,
methyl benzoate (12), a likely product via b-hydride
elimination of the n-Bu ligand, was not detected by
1
H-NMR spectroscopy. Even at an elevated tempera-
ture the side reaction was not observed at all (entry 10).
Coupling of tosylate 1b with furylborate 5a and
phenylborates 8b and 9 was investigated under similar
conditions described above. Among the entries exam-
ined (entries 11–14), NiCl (PPh ) showed higher cata-
2
3 2
lytic activity than NiCl (dppf), and the best result was
2
obtained with phenylborate of the n-Bu ligand (8b)
(
entry 14). However, tosylate 1b was somewhat less
Mesylates with an electron-withdrawing substituent
such as acetyl (Ac) and cyano (CN) groups were shown
to be good mesylates (entries 6–8) as 1a and 1c. On the
other hand, fluorine–mesylate 1f required a high tem-
perature of 60 °C for the completion of the coupling
(entry 9), while methoxy–mesylate 1g was a poor sub-
reactive than mesylate 1a.
Next, the best conditions explored for production of
a and 3b were applied to other combinations of mesy-
3
lates and borates. The aryl mesylates we investigated
were 1a, sterically more congested mesylate 1c, phenyl

9
4
Y. Kobayashi et al. / Journal of Organometallic Chemistry 653 (2002) 91–97
−
1
1
13
strate even at 60 °C (entry 10). These results indicate
that the electron-withdrawing nature is indispensable
for a mesylate being a reactive substrate. With this
conclusion, it is not surprising that mesylates 1h and 1i
produced 3m and 3o in 93 and 91% yields, respectively
wave numbers (cm ). H-NMR (300 MHz) and C-
NMR (75 MHz) spectra were measured on a Varian
Gemini-300 in CDCl using Me Si (l=0 ppm) and the
3
4
center line of CDCl triplet (l=77.1 ppm) as internal
3
standards, respectively.
(
entries 11 and 12) because of the presence of the
Methyllithium (MeLi) in Et O and n-butyllithium
2
electron-withdrawing ring.
(n-BuLi) in C H were prepared as a 0.75–2.76 M
6
14
Finally, mesylates derived from enols were subjected
to the reaction at room temperature overnight. The
coupling products 3o as a mixture of Z and E isomers
solution by the usual procedures and stocked under Ar.
The boronate esters were prepared by the method pub-
lished [10a].
[
14], 3p with the E stereochemistry [15], and 3q were
isolated in high yields (entries 13–15).
4.1. General procedure for the preparations of aryl
mesylates and tosylate
3
. Conclusions
To an ice-cold suspension of NaH (0.72 g, 50% in
mineral oil, 15 mmol) in THF (10 ml) was added the
corresponding phenol or enol (10 mmol) in THF (5 ml).
After 15 min, MsCl (1.55 ml, 20 mmol) or a THF (5
ml) solution of TsCl (3.8 g, 20 mmol) was added and
the reaction mixture was stirred at room temperature
(r.t.) for 3–7 h. The reaction was quenched by addition
In conclusion, we have shown that the coupling of
aryl mesylates with lithium borates takes place effi-
ciently at room temperature in the presence of a nickel-
catalyst, furnishing coupling products in high yields.
Although the mesylates we examined possess an elec-
tron-withdrawing group or ring, the mesylate method-
ology will open economical routes to biologically
important biaryl compounds.
of saturated NH Cl, and the product was extracted
4
with EtOAc several times. The combined organic layers
were dried over MgSO and concentrated in vacuo to
4
afford the crude product, which was purified by chro-
matography on silica gel and/or recrystallization from a
1
4. Experimental
solvent indicated. The H-NMR spectra of the products
1
13
a–g [11], 1h [16], and 1i [17] as well as the C-NMR
Infrared (IR) spectra were determined using a
spectra of 1a, 1c, 1e, 1f, and 1i were in good agreement
JASCO FT/IR-230 spectrometer and are reported in
with the data reported in the literatures.
Table 2
a
Nickel-catalyzed coupling of mesylates with borates
b
Entry
Mesylate
Borate
Temperature (°C)
Time (h)
Product 3
Number
RD
RT
Number
Yield (%) c
85 d
1
2
3
4
5
6
7
8
9
1a
1a
1c
1c
1c
1d
1d
1e
1f
8c
8d
5a
8b
8e
5a
8b
8b
8c
8d
8c
8b
8b
8b
8b
n-Bu
n-Bu
Me
n-Bu
n-Bu
Me
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
C H (p-OMe)
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
60
12
12
12
12
12
12
12
12
13
41
13
13
13
13
13
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
3o
3p
3q
6
4
d
C H (p-Me)
85
6
4
2-furyl
Ph
94
83
88
d
d
C H (p-CH OTBS)
6
4
2
2-furyl
Ph
Ph
80
95
80
82
d
d
d
C H (p-OMe)
6
4
d,e
10
11
12
13
14
15
1g
1h
1I
1j
1k
1l
C H (p-Me)
60
58
6
4
C H (p-OMe)
r.t.
r.t.
r.t.
r.t.
r.t.
93
91
95
6
4
Ph
f
Ph
Ph
Ph
g
93
97
a
b
c
d
e
f
Reactions were carried out using the mesylates and three equivalents of the borates with NiCl (PPh ) (10 mol%).
2
3 2
T
3
: ArꢀR of Scheme 2.
Isolated yields.
A trace amount (B5%) of the butyl-coupling product was detected by 1H-NMR spectroscopy.
g was recovered in 38% yield.
Product 3o was a 1:2 mixture of the (E)- and (Z)-stereoisomers.
1
g
(E)-Stereoisomer was obtained exclusively.

Y. Kobayashi et al. / Journal of Organometallic Chemistry 653 (2002) 91–97
95
4
.1.1. Ethyl (Z)-3-(methylsulfonyloxy)-2-butenoate (1j)
Yield: 53%. Colorless oil. b.p. 160–165 °C (0.5
Torr). IR (neat): w 1726, 1676, 1219, 1169, 1136,
4.2.2. Methyl 4-phenylbenzoate (3b)
White crystals. m.p. 115–116 °C (C H ) (lit. [4]
6
14
116–117 °C) IR (nujol): w
1726, 1606, 1277, 1113,
max
max
−
1
1
−1 13
1
2
2
3
049, 930 cm . H-NMR l=1.28 (t, J=7 Hz, 3H),
752 cm
.
C-NMR l=52.1, 126.9, 127.1, 128.0,
.21 (d, J=1 Hz, 3H), 3.31 (s, 3H), 4.17 (q, J=7 Hz,
128.9, 130.0, 139.8, 145.4, 166.7.
1
3
H), 5.60 (d, J=1 Hz, 1H). C-NMR l=14.0, 22.3,
9.5, 60.3, 110.2, 157.2, 163.1.
4.2.3. Methyl 4-(4%-methoxyphenyl)benzoate (3c)
White crystals. m.p. 165–167 °C (C H –C H ). IR
6
6
−
6
1 1
14
(
nujol): wmax 1712, 1290, 833, 773, 721 cm . H-NMR
l=3.86 (s, 3H), 3.93 (s, 3H), 7.00 (d, J=9 Hz, 2H),
.57 (d, J=9 Hz, 2H), 7.62 (d, J=8.5 Hz, 2H), 8.08 (d,
4
.1.2. (Z)-4-(Methylsulfonyloxy)-3-penten-2-one (1k)
Yield: 38%. Colorless oil. b.p. 95–98 °C (0.5 Torr).
7
IR (neat): w
3024, 1705, 1633, 1358, 1174, 1140, 972,
06, 789 cm . H-NMR l=2.21 (q, J=0.9 Hz, 3H),
max
−
13
1
1
J=8.5 Hz, 2H). C-NMR l=52.1, 55.4, 114.5, 126.6,
9
2
1
4
28.4, 128.5, 130.3, 132.5, 145.4, 160.0, 167.3.
.27 (s, 3H), 3.29 (t, J=0.9 Hz, 3H), 5.84 (s, 1H).
C-NMR l=22.2, 31.5, 39.8, 117.7, 154.1, 194.8.
1
3
.2.4. Methyl 4-(4%-methylphenyl)benzoate (3d)
White crystals. m.p. 111–112 °C (C H ) (lit. [21]
6
14
4
.1.3. Methyl 1-(2%-(methylsulfonyloxy)-1%-cyclo-
1
8
(
15–116 °C). IR (nujol): w
18, 769 cm . H-NMR (revised data of lit. [6]) l 2.41
1730, 1606, 1275, 1111,
max
pentene)carboxylate (1l)
−
1 1
Yield: 69%. Colorless oil. b.p. 125–128 °C (0.5
s, 3H), 3.94 (s, 3H), 7.27 (d, J=8 Hz, 2H), 7.53 (d,
Torr). IR (neat): w
cm . H-NMR l=1.92–2.04 (m, 2H), 2.60–2.69 (m,
3022, 1718, 1657, 1165, 816
max
J=8 Hz, 2H), 7.65 (d, J=9 Hz, 2H), 8.09 (d, J=9 Hz,
−
1 1
13
2
1
H). C-NMR l=21.1, 52.1, 127.0, 127.3, 128.8,
2
H), 2.76–2.85 (m, 2H), 3.25 (s, 3H), 3.75 (s, 3H).
C-NMR l=19.1, 29.1, 33.7, 39.1 and 39.4, 51.4 and
1.6, 119.9, 156.8, 163.6.
29.8, 130.2, 137.3, 138.3, 145.8, 167.3.
1
3
5
4
.2.5. Methyl 2-(2%-furyl)benzoate (3e)
Colorless oil. IR (neat): w
60 cm . H-NMR l=3.85 (s, 3H), 6.49 (dd, J=3.5,
Hz, 1H), 6.58 (dd, J=3.5, 1 Hz, 1H), 7.36 (dt,
3022, 1726, 1604, 1261,
max
4
.2. General procedure for the coupling reaction
−1 1
7
2
To an ice-cold suspension of the boronate ester 7
J=1.5, 8 Hz, 1H), 7.46–7.53 (m, 2H), 7.58–7.68 (m,
(
1.08 mmol) and the nickel-catalyst (0.027 mmol) in
13
2
H). C-NMR l=52.4, 108.1, 111.7, 127.8, 128.3,
THF (2 ml) was added the lithium reagent (0.81 mmol)
dropwise over 5 min under Ar. The ice bath was
removed and the solution was stirred at r.t. for 15 min.
The mesylate or tosylate 1 (0.27 mmol) in THF (1 ml)
was added to the solution. The reaction was continued
at r.t. overnight, and quenched by addition of saturated
1
29.4, 130.0, 130.3, 131.1, 142.9, 152.7, 169.8.
4.2.6. Methyl 2-phenylbenzoate (3f)
Colorless oil. IR (neat): w
1732, 1282, 1248, 1126,
max
−1 13
1
092, 746, 700 cm
.
C-NMR l=52.0, 127.3, 127.4,
1
28.2, 128.5, 129.9, 130.9, 131.0, 131.4, 141.5, 142.7,
NaHCO . The product was extracted with AcOEt sev-
3
169.4.
eral times. The combined organic layers were dried over
MgSO and concentrated in vacuo to afford the crude
product, which was purified by chromatography on
4
4.2.7. Methyl 2-(4%-((tert-butyldimethyl)-
silyloxymethyl)phenyl)benzoate (3g)
silica gel (C H –AcOEt) to afford the coupling
6
14
Colorless oil. IR (neat): w
090, 839 cm . H-NMR l=0.12 (s, 6H), 0.95 (s,
1724, 1599, 1284, 1253,
max
product 3 in the yield given in Tables 1 and 2. The
−1
1
1
9
7
1
H-NMR spectra of the products 3b [9e], 3f [9e], 3h
H), 3.62 (s, 3H), 4.78 (s, 2H), 7.25–7.28 (m, 2H),
[
12b], 3i [3a,3i,4,9e], 3j [9e], 3k [18], 3l [3g,6,9h,19], 3n
20], (E)-isomer of 3o [14], and 3p [15] as well as the
C-NMR spectra of 3l were in good agreement with
.30–7.42 (m, 4H), 7.53 (dt, J=1, 8 Hz, 1H), 7.80 (d,
[
13
J=8 Hz, 1H). C-NMR l= −5.3, 18.4, 25.9, 52.0,
1
3
6
1
4.8, 125.9, 127.2, 128.3, 129.9, 130.9, 131.0, 131.4,
40.0, 140.6, 142.5, 169.5.
the data reported and/or spectra attached in the
literatures.
4
.2.8. 1-(4%-(2¦-Furyl)phenyl)ethanone (3h)
4.2.1. Methyl 4-(2%-furyl)benzoate (3a)
White crystals. m.p. 100–101 °C (C H ) (lit. [12b]
6
14
White crystals. m.p. 120–121 °C (C H ) (lit. [12a]
102–103 °C). IR (nujol): w
1670, 1608, 1018, 839
6
14
max
−
1
13
1
1
3
1
8
1
19–120 °C; lit. [12b] 120–121 °C). IR (nujol): w
cm
.
C-NMR l=26.6, 107.5, 112.1, 123.6, 129.0,
max
−
1 1
716, 1277, 1109, 773, 740 cm . H-NMR l=3.95 (s,
H), 6.52 (dd, J=3.5, 2 Hz, 1H), 6.79 (d, J=3.5 Hz,
H), 7.53 (d, J=2 Hz, 1H), 7.74 (d, J=8.5 Hz, 2H),
135.0, 135.7, 143.3, 153.0, 197.3.
4.2.9. 1-(4%-Biphenyl)ethanone (3i)
White crystals. m.p. 120–121 °C (C H –C H ) (lit.
13
.03 (d, J=8.5 Hz, 2H). C-NMR l=52.1, 107.3,
6
14
6
6
12.1, 123.5, 128.7, 130.2, 134.9, 143.2, 153.2, 166.8.
[3a,4] 119–120 °C). IR (nujol): wmax 1680, 1263, 960,

9
6
Y. Kobayashi et al. / Journal of Organometallic Chemistry 653 (2002) 91–97
−
1
13
764, 721 cm
.
C-NMR (revised data of lit. [3i])
References
l=26.6, 127.37, 127.42, 128.4, 129.06, 129.10, 136.1,
[
1] Reviews: (a) F. Diederich, P.J. Stang, (Eds.), Metal-catalyzed
Cross-coupling Reactions, Wiley, New York, 1997;
1
4
40.1, 146.0, 197.9.
(
b) J. Tsuji, Palladium Reagents and Catalysts, Wiley, New
York, 1995;
c) F.J. McQuillin, D.G. Parker, G.R. Stephenson, (Eds.), Tran-
.2.10. 4-Phenylbenzenecarbonitrile (3j)
(
White crystals. m.p. 82–84 °C (C H ) (lit. [22]
6
14
sition Metal Organometallics for Organic Synthesis, Cambridge
University Press, New York, 1991;
8
cm
6 °C). IR (nujol): w
2225, 1604, 1113, 1078, 847
max
−
1 13
.
C-NMR l=111.1, 119.1, 127.4, 127.9, 128.8,
(
d) G. Bringmann, R. Walter, R. Weirich, Angew. Chem. Int.
1
29.3, 132.8, 139.4, 145.9.
Ed. Engl. 29 (1990) 977;
(
(
e) K. Ritter, Synthesis (1993) 735;
f) S.P. Stanforth, Tetrahedron 54 (1998) 263.
4
.2.11. 4%-Methoxyphenyl-1-naphthalene (3m)
White crystals. m.p. 111–112 °C (EtOH) (lit. [23]
[2] Triflate couplings using organoboranes: (a) A. Huth, I. Beetz, I.
Schumann, Tetrahedron 45 (1989) 6679;
(
b) T. Oh-e, N. Miyaura, A. Suzuki, Synlett (1990) 221;
1
1
2
16–116.5 °C). IR (nujol): w
1608, 1244, 1174, 1107,
max
−
1 1
(c) J.-M. Fu, V. Snieckus, Tetrahedron Lett. 31 (1990) 1665;
032 cm . H-NMR l=3.91 (s, 3H), 7.06 (dt, J=9,
.5 Hz, 2H), 7.41–7.58 (m, 6H), 7.84–7.98 (m, 3H).
C-NMR l=55.4, 113.8, 125.6, 125.9, 126.1, 126.2,
27.1, 127.5, 128.4, 131.3, 132.0, 133.3, 134.0, 140.1,
59.1.
(
(
d) G. Marck, A. Villiger, R. Buchecker, Tetrahedron Lett. 35
1994) 3277;
1
3
(e) T. Oh-e, N. Miyaura, A. Suzuki, J. Org. Chem. 58 (1993)
2201;
1
1
(
(
f) Y.-Q. Mu, R.A. Gibbs, Tetrahedron Lett. 36 (1995) 5669;
g) T. Ishiyama, Y. Itoh, T. Kitano, N. Miyaura, Tetrahedron
Lett. 38 (1997) 3447;
h) M.A. Huffman, N. Yasuda, Synlett (1999) 471.
3] Triflate couplings using other organometallics: (a) A.M.
(
4
.2.12. 2-Phenylpyridine (3n)
[
Colorless oil. IR (neat): w
1585, 1468, 1448, 1425,
max
Echavarren, J.K. Stille, J. Am. Chem. Soc. 109 (1987) 5478;
−
1
13
746, 694 cm
.
C-NMR l=120.7, 122.2, 127.1,
(
(
b) R. McCague, Tetrahedron Lett. 28 (1987) 701;
c) A. Arcadi, A. Burini, S. Cacchi, M. Delmastro, F. Marinelli,
1
28.9, 129.1, 136.9, 139.6, 149.9, 157.7.
.2.13. Ethyl 3-phenyl-2-butenoate (3o)
.2.13.1. (E)-isomer. Colorless oil. IR (neat): w
B. Pietroni, Synlett (1990) 47;
(
(
(
(
d) Y. Hatanaka, T. Hiyama, Tetrahedron Lett. 31 (1990) 2719;
e) V. Farina, G.P. Roth, Tetrahedron Lett. 32 (1991) 4243;
f) G.P. Roth, C.E. Fuller, J. Org. Chem. 56 (1991) 3493;
g) V. Farina, B. Krishnan, D.R. Marshall, G.P. Roth, J. Org.
4
4
1
1712,
max
Chem. 58 (1993) 5434;
−
1 1
628, 1273, 1165, 1043, 768, 694 cm . H-NMR (up-
(h) T. Kamikawa, T. Hayashi, Synlett (1997) 163;
(i) M.E. Mowery, P. DeShong, J. Org. Chem. 64 (1999) 3266.
4] (a) V. Percec, J.-Y. Bae, D.H. Hill, J. Org. Chem. 60 (1995)
1060;(b) V. Percec, J.-Y. Bae, D.H. Hill, J. Org. Chem. 60 (1995)
dated data of lit. [14]) l=1.32 (t, J=7 Hz, 3H), 2.58
d, J=1 Hz, 3H), 4.22 (q, J=7 Hz, 2H), 6.14 (q, J=1
[
[
(
13
Hz, 1H), 7.34–7.43 (m, 3H), 7.45–7.52 (m, 2H). C-
NMR l=14.3, 17.9, 59.9, 117.3, 126.5, 128.7, 129.1,
6
895.
5] Y. Kobayashi, R. Mizojiri, Tetrahedron 37 (1996) 8531.
142.4, 155.7, 167.1.
[6] M. Ueda, A. Saitoh, S. Oh-tani, N. Miyaura, Tetrahedron 54
1998) 13079.
(
[
[
[
7] Reviews: (a) N. Miyaura, A. Suzuki, Chem. Rev. 95 (1995) 2457;
(b) D.W. Knight, in: B.M. Trost, I. Fleming, G. Pattenden
(Eds.), Comprehensive Organic Synthesis, Pergamon, New York,
vol. 3, 1991, p. 481.
4
1
.2.13.2. (Z)-isomer. Colorless oil. IR (neat): w
639, 1275, 1230, 1161, 1047, 768, 698 cm . H NMR
1724,
max
−
1 1
l=1.08 (t, J=7 Hz, 3H), 2.17 (d, J=1 Hz, 3H), 4.00
8] (a) N. Miyaura, T. Yanagi, A. Suzuki, Synth. Commun. 11
(
q, J=7 Hz, 2H), 5.91 (q, J=1 Hz, 1H), 7.17–7.23 (m,
(
(
1981) 513;
13
2
1
H), 7.29–7.33 (m, 3H). C-NMR l=13.9, 27.1, 59.8,
b) N. Miyaura, K. Yamada, H. Suginome, A. Suzuki, J. Am.
17.9, 126.9, 127.9, 128.0, 141.0, 155.6, 166.1.
Chem. Soc. 107 (1985) 972.
9] Recent applications of the Suzuki coupling: (a) T.I. Wallow,
B.M. Novak, J. Org. Chem. 59 (1994) 5034;
4.2.14. (E)-4-Phenyl-3-penten-2-one (3p)
(
b) R. Frenette, R.W. Friesen, Tetrahedron Lett. 35 (1994) 9177;
(c) S. Saito, M. Sakai, N. Miyaura, Tetrahedron Lett. 37 (1996)
993;
Colorless oil. IR (neat): w
1682, 1601, 1356, 1182,
max
−
1 13
2
758, 696 cm
.
C-NMR l=18.3, 32.3, 124.7, 126.6,
(
(
d) T.R. Hoye, L. Mi, Tetrahedron Lett. 37 (1996) 3097;
e) S. Saito, S. Oh-tani, N. Miyaura, J. Org. Chem. 62 (1997)
128.7, 129.3, 142.7, 154.1, 199.2.
8
(
024;
f) A.F. Indolese, Tetrahedron Lett. 38 (1997) 3513;
(g) C. Zhang, M.L. Trudell, Tetrahedron Lett. 41 (2000) 595;
h) A.F. Littke, C. Dai, G.C. Fu, J. Am. Chem. Soc. 122 (2000)
4020.
10] (a) Y. Kobayashi, R. Mizojiri, E. Ikeda, J. Org. Chem. 61 (1996)
391;
b) Y. Kobayashi, Y. Nakayama, R. Mizojiri, Tetrahedron 54
(1998) 1053;
4.2.15. Methyl 1-(2%-phenyl-1%-cyclopentene)carboxylate
(
3q)
Colorless oil. IR (neat): w
(
1720, 1435, 1354, 1228,
max
−
1 1
1
7
047, 756, 696 cm . H-NMR l=1.99 (quintet, J=
.5 Hz, 2H), 2.79–2.90 (m, 4H), 3.62 (s, 3H), 7.36–7.41
[
5
(
1
3
(m, 5H). C-NMR l=21.9, 35.1, 40.1, 51.2 (br peak),
1
27.8, 127.9, 128.0, 128.9, 137.1, 153.8, 166.8.

Y. Kobayashi et al. / Journal of Organometallic Chemistry 653 (2002) 91–97
97
(
3
(
3
c) Y. Kobayashi, E. Takahisa, S.B. Usmani, Tetrahedron Lett.
9 (1998) 597;
d) S.B. Usmani, E. Takahisa, Y. Kobayashi, Tetrahedron Lett.
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P.C. Wong, R.R. Wexler, P.B.M.W.M. Timmermans, Med. Res.
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Org. Chem. 50 (1985) 873.
(
(
(
(
(
(
(
(
e) Y. Kobayashi, Recent Res. Devel. Org. Chem. 3 (1999) 61;
f) Y. Nakayama, G.B. Kumar, Y. Kobayashi, J. Org. Chem. 65
2000) 707;
g) Y. Kobayashi, M. Ito, Eur. J. Org. Chem. (2000) 3393;
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[17] M.R.D. Giudice, G. Settimj, M. Delfini, Tetrahedron 40 (1984)
4067.
[18] Y. Hatanaka, K. Goda, Y. Okahara, T. Hiyama, Tetrahedron 50
(1994) 8301.
[19] M. Lourak, R. Vanderesse, Y. Fort, P. Caub e` re, J. Org. Chem.
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[
[
11] V. Percec, J.-Y. Bae, M. Zhao, D.H. Hill, J. Org. Chem. 60
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13] J.V. Duncia, D.J. Carini, A.T. Chiu, A.L. Johnson, W.A. Price,
(
(
1
[