The Heck-type arylation of allylic alcohols with arenediazonium salts

Article abstract of DOI:10.1016/j.jorganchem.2005.05.020

The Heck coupling of ArN₂BF₄ with secondary allylic alcohols, carried out in methanol using Pd(dba)₂ as catalyst without extra ligands and base, leads to the corresponding β-arylated carbonyl compounds. Such conditions afford arylated acetals from primary allylic alcohols.

Full text of DOI:10.1016/j.jorganchem.2005.05.020

Journal of Organometallic Chemistry 690 (2005) 3822–3826
www.elsevier.com/locate/jorganchem
The Heck-type arylation of allylic alcohols with arenediazonium salts
b
a
Judit Masllorens a,b, Sandrine Bouquillon , Anna Roglans ,
b
Franc¸oise Henin , Jacques Muzart
b,
*
´
a
Department of Chemistry, Universitat de Girona, Campus de Montilivi, 17071 Girona, Spain
´ ´ ´ ´
Unite Mixte de Recherche ‘‘Reactions Selectives et Applications’’, CNRS – Universite de Reims Champagne-Ardenne, B.P. 1039,
b
51687 Reims Cedex 2, France
Received 29 March 2005; received in revised form 12 May 2005; accepted 13 May 2005
Available online 20 June 2005
Abstract
The Heck coupling of ArN2BF4 with secondary allylic alcohols, carried out in methanol using Pd(dba)2 as catalyst without extra
ligands and base, leads to the corresponding b-arylated carbonyl compounds. Such conditions afford arylated acetals from primary
allylic alcohols.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Arylation; Palladium; Allylic alcohols; Ketones; Acetals; Arenediazonium salts
R
1. Introduction
R
1 (cat.)
ArN2BF4
+
(1)
EtOH, rt
2
Some of us have recently reported the arylation of
styrene and a, b-unsaturated esters with arenediazonium
tetrafluoroborates using a palladium(0) complex of a 15-
membered macrocyclic triolefin (1) as the catalyst (Eq.
(1)) [1]. Such phosphine-free palladium(0) complexes
are air- and moisture-stable and recoverable catalysts
for a variety of reactions [2]. Our interest in the arylation
of allylic alcohols [3] urged us to use 1 as the catalyst
with ArN2BF4 (2) as arylating agents since we expected
the recovery of the catalyst [1]. Furthermore, the reac-
tion of 2 with carbon–carbon double bonds can occur
at ambient or moderate temperature in the absence of
a base [1,4]1 while the reaction of aryl halides with allylic
alcohols requires basic conditions and usually the heat-
ing of the mixture [3,6].
Ar
R= CO2Et, CO2t-Bu, Ph
SO2Tol
N
N
ð1Þ
1:
O2
S
Pd
N
Fe
SO2Tol
2. Results and discussion
Preliminary experiments carried out in ethanol using
5% of 1, a 1:1 mixture of PhN2BF4 (2a) and 3-methyl-
but-3-en-2-ol (3a) at room temperature led to both
1-phenyl-2-methylbutan-3-one (4aa) and 1-phenyl-2-
methylbut-1-en-3-ol (5aa) with low yields (Eq. (2),
*
Corresponding author. Tel.: +33 3 2691 3237; fax: +33 3 2691 3166.
E-mail addresses: anna.roglans@udg.es (A. Roglans), jacques.
muzart@univ-reims.fr (J. Muzart).
1
Some Heck reactions with arenediazonium tetrafluoroborates have
been carried in the presence of a base [5].
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.05.020

J. Masllorens et al. / Journal of Organometallic Chemistry 690 (2005) 3822–3826
3823
Table 1
Arylation of 3-methylbut-3-en-2-ol with ArN2BF4 using 1 (0.05 equiv.)
as the catalyst
the arylation of alcohols 3a, 3c and 3d, with 2 (2:3
ratio = 1:1.5) at 60 ꢁC in EtOH using Pd(OAc)2 as the
catalyst [9].
Run
2
2:3a ratio Solvent t (ꢁC) Time
Products, yield %
4.25 h 4aa, 21; 5aa, 11
3.5 h 4aa, 31; 5aa, 10
In our hands however, the coupling of 2b with 3a
using the Chinese procedure provided 4ba in no more
than 13% yield instead of the reported 58%; a similar re-
sult was obtained using MeOH as the solvent, or using
an excess of 2b and increasing the amount of the catalyst
from 2% to 5%. The use of other PdII catalysts, PdCl2
and PdCl2(MeCN)2, in MeOH at 50 ꢁC for 2 h yielded
35–39% of 4ba. Therefore, we tested various Pd0 cata-
lysts. Pd/C was inefficient, and no more than 38% yield
was attained with Pd(PPh3)4 or with palladium nanopar-
ticles prepared as previously described [10]. In contrast,
the yields were improved to 60–69% with Pd(dba)2 as
the catalyst (Table 2, runs 1 and 2). Consequently, the
use of this catalyst was retained to perform other
arylations.
Under Pd(dba)2-catalyzed conditions, the arylation
of the secondary alcohols with various arenediazonium
tetrafluoroborates led to the expected ketones with fair
to high yields (runs 3–7 and 9–14), except with the ary-
lating agent bearing a p-methoxy substituent (Entry 8).
The negative effect of the p-methoxy substituent has
already been reported by Matsuda et al. [7], but, in
contrast to this team, we obtained a fair yield instead
of trace with the p-nitro substituted arylating agent
(run 7).
1
2
3
4
5
6
7
8
2a 1:1
2a 1:1
EtOH
rt
MeOH rt
MeOH 45
MeOH 45
MeOH 45
MeOH 45
MeOH 45
MeOH 45
2a 1:1
2b 1:1
40 min 4aa, 46; 5aa, <3
40 min 4ba, 51
2a 1.5:1
2b 1.5:1
2c 1.5:1
2d 1.5:1
1 h
1 h
1 h
1 h
4aa, 51
4ba, 72
4ca, 60
4da, 47
Table 1, run 1). No reaction was observed in THF
while, in methanol, the yield increased, especially when
the reaction was performed at 45 ꢁC (runs 2 and 3). The
use of p-tolylN2 BF4 (2b) in MeOH at 45 ꢁC led selec-
tively to ketone 4ba (run 4). Further experiments car-
ried out in MeOH at 45 ꢁC, using an excess of
R1C6H4N2BF4 (R1 = H, p-Me, p-t-Bu, p-F) towards
the allylic alcohol, afforded the corresponding ketones
with yields up to 72% (runs 5–8). Unfortunately, 1
was decomplexed in the course of these experiments,
the macrocyclic ligand being almost quantitatively
recovered.
OH
N2BF4
Pd catalyst
+
R3
solvent
R1
R2
The arylation of primary alcohol 3c with 2a, 2e and
2f occured at the unsubstituted olefinic carbon and
provided acetals 7, while the arylation of 3d led to
acetals 7 and 8 (Eq. (3) and Table 3). From these pri-
mary alcohols, we never isolated the arylated alde-
hydes. That contrasts with the results of Cai et al.,
who reported exclusively the formation of arylated
aldehydes from primary allylic alcohols and arene-
diazonium tetrafluoroborates using EtOH as the sol-
vent [9].
2
3
O
OH
R3
R1
R3
+
R2
R2
R1
4
5
a: R1 = H; b: R1 = Me; c: R1 = t-Bu; d: R1 = F; e: R1 = NO2; f: R1 = MeO
a: R2 = R3 = Me; b: R2 = Me, R3 = CH2CHMe2; c: R2 = Me, R3 = H; d: R2 = R3 = H
ð2Þ
The instability of 1 in the course of the above reac-
tions and, consequently, its un-recyclability, urge us to
envisage the use of more common Pd catalysts. Actually,
a careful study of the literature reveals three reports
relating the Pd-catalysed arylation of allylic alcohols
with diazonium salts [7–9]. In 1977 and 1981, a Japanese
team disclosed the room temperature reaction of pri-
mary allylic alcohols, 3c and 3d, with R1C6H4N2Cl
(6a: R1 = H; 6b: p-Me; 6e: p-NO2 ; 6f: p-MeO) in aque-
ous acetonitrile using a base, NaOAc, and a Pd0 catalyst
(6:3 ratio = 1:2); the reaction of 3c was performed only
with 6a yielding 64% of 4ac and 3% of 2-phenyl-2-meth-
ylpropionaldehyde, while no more than 41% yield of
mixtures of cinnamaldehyde and the a- and b-arylated
aldehydes was obtained from the reaction of 3d with
6a or 6b, this yield dropping to 20% and virtually 0%
with 6f and 6e, respectively [7,8]. In 2001, an article in
the Chinese literature reported yields up to 63% for
Table 2
Arylation of secondary allylic alcohols with ArN2BF4 (1.5 equiv.) in
MeOH using Pd(dba)2 (0.05 equiv.) as the catalyst
Run
2
3
t (ꢁC)
Time
Product, yield %
1
2
2b
2b
2a
2a
2c
2d
2e
2f
3a
3a
3a
3a
3a
3a
3a
3a
3b
3b
3b
3b
3b
3b
rt
15 h
2 h
4ba, 60
4ba, 69
4aa, 33
4aa, 43
4ca, 63
4da, 49
4ea, 52
4fa, <15
4ab, 59
4bb, 65
4cb, 72
4cb, 83
4db, 65
4db, 75
50
rt
3
24 h
2 h
4
50
rt
5
23 h
24 h
25 h
29 h
6.5 h
7.5 h
7.5 h
2.5 h
7.5 h
2.5 h
6
rt
7
rt
8
rt
9
2a
2b
2c
2c
2d
2d
rt
10
11
12
13
14
rt
rt
50
rt
50

3824
J. Masllorens et al. / Journal of Organometallic Chemistry 690 (2005) 3822–3826
Table 3
Arylation of primary allylic alcohols with ArN2BF4 (1.5 equiv.) in
MeOH using Pd(dba)2 (0.05 equiv.) as the catalyst
Reaction of arenediazonium salts with allylic alcohols,
general procedure: A solution of the allylic alcohol
(0.70 mmol) in methanol (2 mL) was added to a magnet-
ically stirred mixture of the arenediazonium salt
(1.05 mmol) and Pd(dba)2 (0.035 mmol) in methanol
(20 mL). The reaction mixture was stirred under the
conditions depicted in Tables. After addition of satu-
rated NaHCO3 aqueous solution (20 mL), the resulting
Run
2
3
t (ꢁC)
Time
Products, yield %
1
2
2a
2a
2e
2e
2f
3c
3c
3c
3c
3c
3c
3d
3d
3d
3d
3d
3d
rt
10 h
2 h
9 h
2 h
9 h
2 h
9 h
2 h
9 h
2 h
9 h
2 h
7ac, 61
7ac, 67
50
rt
3
7ec, 79
7ec, 83
7fc, 53
4
50
rt
5
mixture
was
extracted
with
dichloromethane
6
2f
50
rt
7fc, 60
7
2a
2a
2e
2e
2f
7ad + 8ad, 32 (87/13)a
7ad + 8ad, 40 (84/16)a
7ed, 73;8ed,12
7ed,76; 8ed,13
7fd + 8fd,34 (62/38)a
7fd + 8fd,40 (62/38)a
(2 · 15 mL). The combined organic fractions were
washed with water, dried over anhydrous sodium sul-
fate, and evaporated. The products were purified by
flash chromatography.
The NMR data of 4aa [15], 4ca [16], 4fa [17], 7ac [18],
7ad [19], 8ad [20], 7fd [21], 8fd [22] were in agreement
with literature.
8
50
rt
9
10
11
12
a
50
rt
2f
50
An inseparable mixture of 7 and 8 was obtained, the ratio was
calculated via 1H NMR integration.
4.1. 3-Methyl-4-(p-tolyl)butan-2-one (4ba)
OH
Colorless oil. 1H NMR (CDCl3, 250 MHz): d 1.09 (d,
J = 6.8 Hz, 3H), 2.10 (s, 3H), 2.31 (s, 3H), 2.52 (dd,
J = 12.4 and 6.5 Hz, 1H), 2.81 (sext, J = 6.5 Hz, 1H),
2.96 (dd, J = 12.4 and 6.5 Hz, 1H), 7.20 (d, J = 6.8 Hz,
2H), 7.6 (d, J = 6.8 Hz, 2H). 13C NMR (CDCl3,
62.5 MHz): d 16.2, 21.0, 28.8, 38.5, 48.9, 128.8, 129.1,
135.7, 136.5, 212.3. IR (neat) m (cmꢀ1): 2926, 1713. Anal.
Calc. for C12H16O (176.0): C, 81.80; H, 9.10. Found: C,
81.96; H, 9.12%.
N2BF4
Pd(dba)2 (0.05 equiv.)
+
R1
MeOH
R2
2
3
OMe
Me
R2
OMe
OMe
+
R1
R2
OMe
R1
4.2. 4-(p-Fluorophenyl)-3-methylbutan-2-one (4da)
7
8
a: R1 = H; e: R1 = NO2; f: R1 = MeO
c: R2 = Me; d: R2 = H
Colorless oil. 1H NMR (CDCl3, 250 MHz): d 1.09 (d,
J = 6.9 Hz, 3H), 2.09 (s, 3H), 2.54 (dd, J = 13.4 and
7.3 Hz, 1H), 2.80 (sext, J = 7.0 Hz, 1H), 2.97 (dd,
J = 13.4 and 6.9 Hz, 1H), 6.91–7.02 (m, 2H), 7.06–7.19
(m, 2H). 13C NMR (CDCl3, 62.5 MHz): d 16.7, 29.3,
38.4, 49.3, 115.6 (d, 2JCF = 21 Hz), 130.7 (d,
ð3Þ
4
3. Conclusion
3JCF = 7.7 Hz), 135.7 (d, JCF = 3.2 Hz), 161.9 (d,
1JCF = 242.6 Hz), 212.4. IR (neat) m (cmꢀ1): 2971,
2933, 1713, 1510, 1222. MS (EI) m/z (%): 180 (M+,
39), 165 (44), 137 (21), 109 (100), 83 (23), 43 (89). Anal.
Calc. for C11H13FO (180.2): C, 73.31; H, 7.27. Found:
C, 72.96; H, 7.62%.
The arylation of allylic alcohols with arenediazonium
tetrafluoroborates can be carried out in MeOH using
Pd(dba)2 as the catalyst. The expected ketones are ob-
tained from secondary alcohols while the primary alco-
hols led to protected aldehydes.
4.3. 3-Methyl-4-(p-nitrophenyl)butan-2-one (4ea)
4. Experimental
Pale yellow solid. M.p. 64 ꢁC. 1H NMR (CDCl3,
250 MHz): d 1.14 (d, J = 7.0 Hz, 3H), 2.13 (s, 3H),
2.66 (dd, J = 13.4 and 7.0 Hz, 1H), 2.87 (sext,
J = 7.0 Hz, 1H), 3.12 (dd, J = 13.4 and 7.0 Hz, 1H),
7.32 (d, J = 8.5 Hz, 2H), 8.15 (d, J = 8.5 Hz, 2H). 13C
NMR (CDCl3, 62.5 MHz): d 17.4, 29.6, 39.0, 49.1,
124.5, 130.6, 147.4, 148.5, 211.9. IR (neat) m (cmꢀ1):
2971, 2930, 1703, 1602, 1508, 1345. MS (EI) m/z (%):
207 (M+, 2), 192 (3), 165 (5), 136 (11), 115 (70), 89
(100), 78 (82). Anal. Calc. for C11H13NO3 (207.2): C,
General: Arenediazonium tetrafluoroborates were
prepared from commercial aromatic amines according
to published methods [11]. 3-Methylbut-3-en-2-ol [12],
2,5-dimethylhex-1-en-3-ol [13] and Pd(dba)2 [14] were
prepared according to reported procedures. 1H and
13C NMR (250 and 62.5 MHz or 200 and 50 MHz) spec-
tra were obtained on Bruker AC spectrometers using
TMS as internal standard and CDCl3 as solvent.

J. Masllorens et al. / Journal of Organometallic Chemistry 690 (2005) 3822–3826
3825
4
1
63.76; H, 6.32; N, 6.76. Found: C, 63.86; H, 6.37; N,
6.71%.
136.0 (d, JCF = 3.2 Hz), 161.9 (d, JCF = 242.1 Hz),
214.1. IR (neat) m (cmꢀ1): 2959, 2872, 1711, 1510. MS
(CI) m/z (%): 240 ([M + NH4]+, 100), 223 ([M + H]+,
59), 109 (82), 85 (78). Anal. Calc. for C14H19 FO
(222.3): C, 75.64; H, 8.61. Found: C, 75.90; H, 8.69%.
4.4. 2,5-Dimethyl-1-phenylhexan-3-one (4ab)
Colorless oil. 1H NMR (CDCl3, 250 MHz): d 0.75 (d,
J = 6.5, 3H), 0.76 (d, J = 6.5, 3H), 0.98 (d, J = 6.9 Hz,
3H), 1.89–2.27 (3H), 2.45 (dd, J = 13.2 and 7.3 Hz,
1H), 2.74 (sext, J = 6.9 Hz, 1H), 2.90 (dd, J = 13.2 and
7.0 Hz, 1H), 7.02–7.24 (m, 5H). 13C NMR (CDCl3,
63.5 MHz): d 15.0, 21.1, 21.2, 22.7, 37.5, 46.9, 49.6,
124.7, 126.9, 127.6, 138.4, 212.5. IR (neat) m (cmꢀ1):
2957, 2930, 1711, 1454, 1366. MS (CI) m/z (%): 222
([M + NH4]+, 100), 205 ([M + H]+, 91), 91 (38). Anal.
Calc. for C14H20O (204.3): C, 82.30; H, 9.87. Found:
C, 82.14; H, 10.36%.
4.8. 1-(3,3-Dimethoxy-2-methyl-1-propyl)-4-
nitrobenzene (7ec)
1
Pale yellow oil. H NMR (CDCl3, 200 MHz): d 0.85
(d, J = 6.8, 3H), 1.98–2.15 (m, 1H), 2.46 (dd, J = 13.4
and 9.6 Hz, 1H), 3.01 (dd, J = 13.4 and 4.5 Hz, 1H),
3.38 (s, 3H), 3.40 (s, 3H), 4.06 (d, J = 5.8 Hz, 1H),
7.32 (d, J = 8.6 Hz, 2H), 8.14 (d, J = 8.6 Hz, 2H). 13C
NMR (CDCl3, 50 MHz): d 14.6, 38.4, 38.5, 54.7, 55.3,
108.6, 124.0, 130.5, 146.9, 149.5. IR (neat) m (cmꢀ1):
2916, 2845, 1601, 1519, 1346. MS (EI) m/z (%): 208
([M ꢀ OCH3]+, 30), 192 (20), 136 (19), 115 (29), 89
(49), 75 (100). Anal. Calc. for C12H17NO4 (239.3): C,
60.24; H, 7.16; N, 5.85. Found: C, 60.39; H, 7.38; N,
5.77%.
4.5. 2,5-Dimethyl-1-(p-tolyl)hexan-3-one (4bb)
Colorless oil. 1H NMR (CDCl3, 250 MHz): d 0.84 (d,
J = 6.4 Hz, 6H), 1.05 (d, J = 6.8 Hz, 3H), 2.00–2.38
(3H), 2.31 (s, 3H), 2.49 (dd, J = 13.3 and 7.4 Hz, 1H),
2.77 (sext, J = 7.0 Hz, 1H), 2.93 (dd, J = 13.3 and
6.9 Hz, 1H), 7.03 (d, J = 8.2 Hz, 2H), 7.08 (d,
J = 8.2 Hz, 2H). 13C NMR (CDCl3, 62.5 MHz): d 16.7,
21.4, 23.0, 23.1, 24.5, 38.9, 48.8, 51.4, 129.3, 129.5,
136.0, 137.1, 214.4. IR (neat) m (cmꢀ1): 2957, 2930,
1712. MS (EI) m/z (%): 218 (M+, 61), 161 (64), 133
(70), 117 (36), 105 (100), 85 (92), 57 (84). Anal. Calc.
for C15H22O (218.3): C, 82.52; H, 10.16. Found: C,
82.65; H, 10.67%.
4.9. 1-(3,3-Dimethoxy-2-methylpropyl)-4-
methoxybenzene (7fc)
Colorless oil. 1H NMR (CDCl3, 200 MHz): d 0.84 (d,
J = 6.8, 3H), 1.98–2.10 (m, 1H), 2.29 (dd, J = 13.4 and
9.2 Hz, 1H), 2.83 (dd, J = 13.4 and 4.6 Hz, 1H), 3.37
(s, 3H), 3.38 (s, 3H), 3.80 (s, 3H), 4.05 (d, J = 6.0 Hz,
1H), 6.82 (d, J = 8.6 Hz, 2H), 7.08 (d, J = 8.6 Hz, 2H).
13C NMR (CDCl3, 50 MHz): d 14.3, 37.6, 38.3, 54.5,
54.7, 55.6, 108.7, 114.0, 130.5, 133.0, 158.2. IR (neat) m
(cmꢀ1): 2933, 2829, 1611, 1512, 1247. MS (EI) m/z
(%): 224 ([M]+, 20), 192 (90), 177 (78), 161 (70), 121
(100), 91 (46), 75 (98). Anal. Calc. for C13H20O3
(224.3): C, 69.61; H, 8.99. Found: C, 69.52; H, 9.33%.
4.6. 1-(p-tert-Butylphenyl)-2,5-dimethylhexan-3-one
(4cb)
Colorless oil. 1H NMR (CDCl3, 250 MHz): d 0.82 (d,
J = 6.5, 6H), 1.06 (d, J = 6.8 Hz, 3H), 1.30 (s, 9H), 1.98–
2.34 (3H), 2.51 (dd, J = 13.2 and 7.3 Hz, 1H), 2.79 (sext,
J = 6.9 Hz, 1H), 2.93 (dd, J = 13.1 and 6.9 Hz, 1H), 7.07
(d, J = 8.2 Hz, 2H), 7.29 (d, J = 8.2 Hz, 2H). 13C NMR
(CDCl3, 62.5 MHz): d 16.8, 22.9, 23.0, 24.5, 31.8, 34.8,
38.9, 48.7, 51.4, 125.7, 129.1, 137.2, 149.4, 214.5. IR
(neat) m (cmꢀ1): 2960, 1712. MS (EI) m/z (%): 260
(M+, 6), 245 (14), 147 (36), 117 (31), 85 (48), 57 (100).
Anal. Calc. for C18H28O (260.4): C, 83.02; H, 10.84.
Found: C, 83.29; H, 11.04%.
4.10. 1-(3,3-Dimethoxy-1-propyl)-4-nitrobenzene (7ed)
Pale yellow oil. 1H NMR (CDCl3, 200 MHz): d 1.85–
2.00 (m, 2H), 2.79 (t, J = 8.0 Hz, 2H), 3.34 (s, 6H), 4.36
(t, J = 5.6 Hz, 1H), 7.35 (d, J = 8.7 Hz, 2H), 8.15 (d,
J = 8.7 Hz, 2H). 13C NMR (CDCl3, 50 MHz): d 31.1,
34.0, 53.4, 103.9, 124.1, 129.6, 147.0, 150.0. IR (neat) m
(cmꢀ1): 2919, 1601, 1519, 1345. MS (EI) m/z (%): 194
[M ꢀ OCH3]+, 37), 162 (30), 136 (43), 89 (42), 75
(100). Anal. Calc. for C11H15 NO4 (225.2): C, 58.66;
H, 6.71; N, 6.22. Found: C, 58.75; H, 6.48; N, 5.87%.
4.7. 1-(p-Fluorophenyl)-2,5-dimethylhexan-3-one (4db)
Colorless oil. 1H NMR (CDCl3, 250 MHz): d 0.83 (d,
J = 6.6, 6H), 1.06 (d, J = 6.8 Hz, 3H), 1.99–2.35 (m,
3H), 2.51 (dd, J = 13.3 and 7.0 Hz, 1H), 2.77 (sext,
J = 7.0 Hz, 1H), 2.95 (dd, J = 13.3 and 7.3 Hz, 1H),
6.90–7.00 (m, 2H), 7.05–7.13 (m, 2H). 13C NMR
(CDCl3, 62.5 MHz): d 16.9, 22.9, 23.0, 24.5, 38.5, 48.9,
4.11. 1-(1,1-Dimethoxy-2-propyl)-4-nitrobenzene (8ed)
1
Pale yellow oil. H NMR (CDCl3, 200 MHz): d 1.31
(d, J = 6.6 Hz, 3H), 3.00–3.22 (m, 1H), 3.28 (s, 3H),
3.39 (s, 3H), 4.36 (d, J = 6.2 Hz, 1H), 7.40 (d,
J = 8.0 Hz, 2H), 8.15 (d, J = 8.0 Hz, 2H). 13C NMR
(CDCl3, 50 MHz): d 17.1, 43.7, 54.9, 55.7, 108.7,
2
3
51.5, 115.5 (d, JCF = 21 Hz), 130.8 (d, JCF = 7.8 Hz),

3826
J. Masllorens et al. / Journal of Organometallic Chemistry 690 (2005) 3822–3826
124.0, 129.6, 147.3, 151.3. IR (neat) m (cmꢀ1): 2924,
1600, 1518, 1344. MS (EI) m/z (%): 194 ([M ꢀ OCH3]+,
48), 115 (22), 103 (26), 75 (100).
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Acknowledgement
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