Suzuki coupling of 2-chloroacrylonitrile, methyl 2-chloroacrylate, or 2-chloroprop-1-en-3-ol with arylboronic acids catalyzed by a palladium-tetraphosphine complex

Article abstract of DOI:10.1080/00397910600773866

The tetraphosphine all-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl) cyclopentane (Tedicyp) in combination with [Pd(C₃H ₅)Cl]₂ affords an efficient catalyst of the coupling of 2-chloroacrylonitrile with arylboronic acids.

Full text of DOI:10.1080/00397910600773866

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Suzuki Coupling of 2‐Chloroacrylonitrile,
Methyl 2‐Chloroacrylate, or
2‐Chloroprop‐1‐en‐3‐ol with
Arylboronic Acids Catalyzed by a
Palladium‐Tetraphosphine Complex
Florian Berthiol a , Henri Doucet a & Maurice Santelli a
a UMR 6180 CNRS and Université d'Aix‐Marseille III, Laboratoire de Synthèse
Organique , Faculté des Sciences de Saint Jérôme , Marseille, France
Published online: 16 Feb 2007.
To cite this article: Florian Berthiol , Henri Doucet & Maurice Santelli (2006) Suzuki Coupling of
2‐Chloroacrylonitrile, Methyl 2‐Chloroacrylate, or 2‐Chloroprop‐1‐en‐3‐ol with Arylboronic Acids Catalyzed
by a Palladium‐Tetraphosphine Complex, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 36:20, 3019-3027, DOI: 10.1080/00397910600773866
To link to this article: http://dx.doi.org/10.1080/00397910600773866
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Synthetic Communicationsw, 36: 3019–3027, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600773866
Suzuki Coupling of 2-Chloroacrylonitrile,
Methyl 2-Chloroacrylate, or 2-Chloroprop-
1-en-3-ol with Arylboronic Acids Catalyzed
by a Palladium-Tetraphosphine Complex
Florian Berthiol, Henri Doucet, and Maurice Santelli
´
UMR 6180 CNRS and Universite d’Aix-Marseille III,
`
´
Laboratoire de Synthese Organique, Faculte des
´ ˆ
Sciences de Saint Jerome, Marseille, France
Abstract: The tetraphosphine all-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclo-
pentane (Tedicyp) in combination with [Pd(C3H5)Cl]2 affords an efficient catalyst of
the coupling of 2-chloroacrylonitrile with arylboronic acids. In the presence of 1%
catalyst, the 2-arylacrylonitrile derivatives were obtained in medium to good yields.
A variety of substituents such as alkyl, methoxy, fluoro, trifluoromethyl, formyl, or
nitro on the arylboronic acid are tolerated. The cross-coupling reactions of methyl
2-chloroacrylate with arylboronic acids give simple access to 2-phenylacrylate deriva-
tives, which are useful precursors for the synthesis of biologically active compounds
such as ibuprofen, ketoprofen, and naproxen.
Keywords: Arylboronic acids, catalysis, palladium, tetraphosphine, vinyl chlorides
The palladium-catalyzed Suzuki reaction is one of the most powerful methods
for the formation of C–C bonds.[1] In recent years, several palladium catalysts
have been successfully used for this reaction, but most of them have not been
tested for synthesis of styrene derivatives by coupling of vinyl chlorides with
arylboronic acids. In fact, only a few examples of the coupling of vinyl
Received in Poland March 16, 2006
Address correspondence to Henri Doucet, UMR 6180 CNRS and Universite
d’Aix-Marseille III, “Chirotechnologies: catalyse et biocatalyse,” Laboratoire
´
`
´
´ ˆ
´
de Synthese Organique, Faculte des Sciences de Saint Jerome, Universite d’Aix-
Marseille III, Avenue Escadrille Normandie-Niemen, 13397, Marseille Cedex 20,
France. E-mail: henri.doucet@univ.u-3mrs.fr
3019

3020
F. Berthiol, H. Doucet, and M. Santelli
Figure 1. Structure of Tedicyp ligand.
chlorides with arylboronic acids have been reported.[2–9] Vinyl chlorides are
less reactive substrates than vinyl bromides or iodides. The most popular
ligand for this reaction is triphenylphosphine.[2–4] We found also four
examples of the formation of styrene derivatives using vinyl chlorides via
Suzuki reaction using other ligands than triphenylphosphine. Good results
were obtained using P(tBu)3 as the ligand associated with Pd2(dba)3 or
PdBr2(PhCN)2; however, with these catalytic systems, 6% of ligands were
used.[5,6] Two other monodentate ligands have also been employed success-
fully for the coupling of vinyl chlorides with arylboronic acids: (t-
Bu)2P(O H)[7] and a bulky phenanthryl N-heterocyclic carbene ligand.[8] To
our knowledge, the efficiency of polydentate phosphine ligands for this
reaction has not been described; moreover, Suzuki coupling reactions using
arylboronic acids with 2-chloroacrylonitrile, methyl 2-chloroacrylate, or
2-chloroprop-1-en-3-ol have not been reported.
To obtain a highly stable palladium catalyst, we have prepared the tetra-
phosphine ligand, all-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclo-
pentane or Tedicyp[10] (Fig. 1). We have already reported several results
obtained for Suzuki cross-coupling with aryl halides and arylboronic acids
using Tedicyp as ligand.[11] We have also recently reported some results
obtained for the coupling of vinyl halides with several arylboronic acids.[12]
To further establish the requirements for a successful Suzuki reaction with
our catalyst, we herein report on the reaction of 2-chloroacrylonitrile,
methyl 2-chloroacrylate, or 2-chloroprop-1-en-3-ol with arylboronic acids.
For this study, based on our previous results,[11,12] xylene was chosen as
the solvent and potassium carbonate as the base. The reactions were
performed at 100–1108C, under argon, in the presence of a 1:2 ratio of
[Pd(C3H5)Cl]2/Tedicyp as catalyst.
First, we studiedthereactivity of 2-chloroacrylonitrile witharylboronic acids
(Scheme 1, Table 1). We observed that, in most cases, the reactions performed
Scheme 1.

Suzuki Coupling by Palladium-Tetraphosphine Complex
3021
Table 1. Palladium-catalyzed coupling reactions of arylboronic acids with 2-chloro-
acrylonitrile, methyl 2-chloroacrylate, or 2-chloroprop-1-en-3-ol (Scheme 1)
Ratio
substrate/
catalyst
Entry
1
Vinyl chloride
Arylboronic acid Product
Yielda
79
2-Chloroacrylonitrile Benzeneboronic
acid
1
2
3
3
4
5
100
2
3
4
5
6
2-Chloroacrylonitrile 4-Methylbenze-
neboronic acid
100
100
100
100
100
66
74
53b
57
67
2-Chloroacrylonitrile 4-Methoxybenze-
neboronic acid
2-Chloroacrylonitrile 4-Methoxybenze-
neboronic acid
2-Chloroacrylonitrile 4-Fluorobenzene-
boronic acid
2-Chloroacrylonitrile 4-Trifluoro-
methylbenze-
neboronic acid
7
8
2-Chloroacrylonitrile 3-Nitrobenzene-
boronic acid
6
7
100
50
34
86
2-Chloroacrylonitrile 3-Formylbenze-
neboronic acid
9
2-Chloroacrylonitrile 1-Naphthalene-
boronic acid
8
100
250
100
100
100
50
79
10
11
12
13
14
15
16
2-Chloroacrylonitrile 1-Naphthalene-
boronic acid
8
(12)
62
2-Chloroacrylonitrile 2-Methylbenze-
neboronic acid
9
2-Chloroacrylonitrile 2-Phenylbenzene-
boronic acid
10
11
12
13
14
78
2-Chloroacrylonitrile 2-Methoxybenze-
neboronic acid
71
2-Chloroacrylonitrile 3-Thiophene-
boronic acid
15
Methyl
2-chloroacrylate
Methyl
2-chloroacrylate
Benzeneboronic
acid
100
100
60c
54c
6-Methoxy-2-
naphthylboro-
nic acid
17
18
19
Methyl
2-chloroacrylate
2-Chloroprop-1-en-
1-Naphthalene-
boronic acid
4-Methoxybenze-
neboronic acid
4-Fluorobenzene-
boronic acid
15
16
17
100
100
100
50c
25d
32d
3-ol
2-Chloroprop-1-en-
3-ol
(continued)

3022
F. Berthiol, H. Doucet, and M. Santelli
Table 1. Continued
Ratio
substrate/
catalyst
Entry
20
Vinyl chloride
Arylboronic acid Product
Yielda
30d
2-Chloroprop-1-en-
3-ol
1-Naphthalene-
boronic acid
18
19
19
100
21
22
2-(2-Chloroallyloxy)- 1-Naphthalene-
tetrahydropyran boronic acid
2-(2-Chloroallyloxy)- 1-Naphthalene-
tetrahydropyran boronic acid
50
50
25d
(38)b,d
Note: Conditions: [ClPd(C3H5)]2/Tedicyp ¼ 1:2, 2-chloroacrylonitrile: 2 mmol,
arylboronic acid: 1 mmol, K2CO3: 2 mmol, xylene, 1008C, 20 h, argon, isolated yields.
aYields in parentheses are GC yields.
b0.05 mmol of hydroquinone was added.
cMethyl 2-chloroacrylate: 1 mmol, arylboronic acid: 2 mmol, 1108C.
d2-Chloroprop-1-en-3-ol or 2-(2-chloroallyloxy)-tetrahydropyran: 1 mmol, aryl-
boronic acid: 2 mmol.
with this vinyl chloride proceed smoothly. Quite similar yields were observed in
the presence of electron-poor and electron-rich arylboronic acids. For example,
yields of 67% and 74% were obtained respectively for the coupling of 2-chloroa-
crylonitrile using 4-trifluoromethylbenzeneboronic acid or 4-methoxybenzene-
boronic acid employing 1% catalyst (Table 1, entries 3 and 6). Benzeneboronic
acid, 4-methylbenzeneboronic acid, 4-fluorobenzeneboronic acid, or 3-formyl-
benzeneboronic acid gave the 2-arylacrylonitrile derivatives 1, 2, 4, and 7 in
57–86% yields (Table 1, entries 1, 2, 5, and 8). A lower yield was obtained
using 3-nitrobenzeneboronic acid as reactant. With this substrate, the formation
of side products was observed (Table 1, entry 7). Then, we studied the
influence of the presence of ortho-substituents on the arylboronic acid on the
yield of the reaction. Similar yields to those obtained with para-substituted aryl-
boronic acids were obtained using the sterically congested 1-naphthaleneboronic
acid, 2-methylbenzeneboronic acid, 2-phenylbenzeneboronic acid, and 2-meth-
oxybenzeneboronic acid with 2-chloroacrylonitrile (Table 1, entries 9–13). We
have also investigated this reaction in the presence of the heteroaryl substrate,
3-thiopheneboronic acid, but with this reagent, in the presence of 2% catalyst,
a very low yield of product 12 was obtained (Table 1, entry 14). Palladium(II)
complexes possess strong thiophilicity. This result suggests that with 3-thiophe-
neboronic acid, a possible interaction between the sulphur atom and the
palladium complex has a poisoning effect.
Methyl 2-chloroacrylate has been reacted with benzeneboronic acid and
1-naphthaleneboronic acid (Table 1, entries 15 and 17). The 2-arylacrylate deriva-
tives 13 and 15 were obtained in 60 and 50% yields respectively using 1%
catalyst. Application of this cross-coupling reaction to the synthesis of the

Suzuki Coupling by Palladium-Tetraphosphine Complex
3023
precursor of the nonsteroidal anti-inflammatory agent naproxene is also reported.
6-Methoxy-2-naphthylboronic acid with methyl 2-chloroacrylate gave methyl
2-(6-methoxy-2-naphthyl)acrylate 14 in 54% yield (Table 1, entry 16).
Cross-coupling reactions using 2-chloroprop-1-en-3-ol with arylboronic
acids gave the corresponding 2-arylallyl alcohol derivatives 16–18 in low
yields (25–32%) (Table 1, entries 18–20). Even in the presence of the
protected substrate 2-(2-chloroallyloxy)-tetrahydropyran, a low yield of
adduct 19 was obtained (Table 1, entries 21 and 22). The oxidative addition
to palladium of this nonactivated vinyl chloride is probably very slow.
These results seems to indicate that with this catalyst, as expected, the
rate-limiting step for the coupling of arylboronic acid with 2-chloroacryloni-
trile, methyl 2-chloroacrylate, or 2-chloroprop-1-en-3-ol is the oxidative
addition of the vinyl chloride to the palladium complex.
CONCLUSION
The use of the tetradentate ligand Tedicyp associated to [ClPd(C3H5)]2
provides a convenient catalyst for the coupling reaction of 2-chloroacryloni-
trile or methyl 2-chloroacrylate with substituted arylboronic acids. A range
of functions such as methoxy, fluoro, formyl, nitro, or trifluoromethyl on the
arylboronic acid is tolerated. If the function of the arylboronic acids has an
influence on the yield of the reaction, their electronic properties have a
minor influence. The cross-coupling reaction of 2-chloroprop-1-en-3-ol with
arylboronic acids led to the 2-arylprop-1-en-3-ol derivatives in medium
yield. As expected, lower turnover numbers were observed for the coupling
of these vinyl chlorides than those observed with vinyl bromides such as
ethyl 2-bromoacrylate,[12] but in most cases with these substrates the
expected arylated adducts were obtained in satisfactory yields with only
1–2% catalyst. We believe that this system compares favorably with the
other catalysts that have been reported for the Suzuki reaction with vinyl
chlorides. These cross-coupling reactions should give a simple access to non-
steroidal anti-inflammatory agents such as naproxen or ibuprofen. Moreover,
2-chloroacrylonitrile, methyl 2-chloroacrylate, and 2-chloroprop-1-en-3-ol
are commercially available, and this is a practical advantage of these reactions.
EXPERIMENTAL
General
Xylene (analytical grade), vinyl chlorides, and arylboronic acids were not
purified before use. Potassium carbonate 99þ was used. All reactions were
run under argon using vacuum lines in Schlenk tubes in oven-dried glassware.
1H (300-MHz) and 13C (75-MHz) spectra were recorded in CDCl3 solutions.

3024
F. Berthiol, H. Doucet, and M. Santelli
Chemical shifts (d) are reported in parts per million (ppm) relative to CDCl3.
Flash chromatographies were performed on silica gel (230–400 mesh).
Preparation of the Pd-Tedicyp Catalyst[10]
An oven-dried 40-mL Schlenk tube equipped with a magnetic stirring
bar, under an argon atmosphere, was charged with [Pd(C3H5)Cl]2
(4.2 mg, 11.6 mmol) and Tedicyp (20 mg, 23.2 mmol). Anhydrous DMF
(2.5 mL) was added, and then the solution was stirred at room temperature
for 10 min.
General Procedure
As a typical experiment, the reaction of arylboronic acid (1 or 2 mmol, see
Table 1), vinyl chloride (1 or 2 mmol, see Table 1), and K2CO3 (0.276 g,
2 mmol) at 100 or 1108C (see Table 1) during 20 h in xylene (4 mL) in
the presence of cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclo-
pentane–12 [PdCl(C3 H5)]2 complex under argon affords the corresponding
products after addition of water, extraction with ether or dichloromethane,
separation, drying (MgSO4), evaporation, and chromatography on silica gel.
Data
2-Phenylacrylonitrile (1). 1H NMR (CDCl3, 300 MHz): d ¼ 7.63–7.57
(m, 2H), 7.46–7.38 (m, 3H), 6.33 (s, 1H), 6.10 (s, 1H).
2-( p-Tolyl)acrylonitrile (2). 1H NMR (CDCl3, 300 MHz): d ¼ 7.48
(d, J ¼ 8.0 Hz, 2H), 7.22 (d, J ¼ 8.0 Hz, 2H), 6.27 (s, 1H), 6.03 (s, 1H),
2.34 (s, 3H).
2-(4-Methoxyphenyl)acrylonitrile (3). 1H NMR (CDCl3, 300 MHz):
d ¼ 7.53 (d, J ¼ 8.9 Hz, 2H), 6.92 (d, J ¼ 8.9 Hz, 2H), 6.18 (s, 1H), 5.96
(s, 1H), 3.83 (s, 3H).
2-(4-Fluorophenyl)acrylonitrile (4). 1H NMR (CDCl3, 300 MHz): d ¼ 7.57
(dd, J ¼ 8.8, 5.1 Hz, 2H), 7.09 (t, J ¼ 8.8 Hz, 2H), 6.25 (s, 1H), 6.06 (s, 1H).
13C NMR (75 MHz, CDCl3): d ¼ 163.5 (d, JC-F ¼ 250.9 Hz), 128.5
4
3
(d, JC-F ¼ 3.3 Hz), 127.7, 127.6 (d, JC-F ¼ 8.3 Hz), 121.8, 117.5, 116.0
2
(d, JC-F ¼ 22.5 Hz). Anal. calcd. for C9H6FN: C, 73.46; H, 4.11. Found: C,
73.61; H, 4.19.
2-(4-Trifluoromethylphenyl)-acrylonitrile (5). 1H NMR (CDCl3,
300 MHz): d ¼ 7.73–7.67 (m, 4H), 6.43 (s, 1H), 6.23 (s, 1H).

Suzuki Coupling by Palladium-Tetraphosphine Complex
3025
1
2-(3-Nitrophenyl)acrylonitrile (6). H NMR (CDCl3, 300 MHz): d ¼ 8.43
(s, 1H), 8.25 (d, J ¼ 7.8 Hz, 1H), 7.93 (d, J ¼ 7.8 Hz, 1H), 7.64
(t, J ¼ 7.5 Hz, 1H), 6.52 (s, 1H), 6.30 (s, 1H). 13C NMR (75 MHz, CDCl3):
d ¼ 148.6, 134.0, 131.7, 130.9, 130.3, 124.5, 121.1, 120.4, 116.6. Anal.
calcd. for C9H6N2O2: C, 62.07; H, 3.47. Found: C, 62.14; H, 3.59.
2-(3-Formylphenyl)acrylonitrile (7). 1H NMR (CDCl3, 300 MHz):
d ¼ 10.03 (s, 1H), 8.06 (t, J ¼ 1.6 Hz, 1H), 7.90 (dt, J ¼ 7.8, 1.3 Hz, 1H),
7.83 (dt, J ¼ 7.8, 1.6 Hz, 1H), 7.59 (t, J ¼ 7.8 Hz, 1H), 6.44 (s, 1H), 6.21
(s, 1H). 13C NMR (75 MHz, CDCl3): d ¼ 191.3, 136.9, 133.3, 131.4, 130.8,
127.8, 129.7, 126.4, 121.8, 117.1. Anal. calcd. for C10H7NO: C, 76.42; H,
4.49. Found: C, 76.60; H, 4.31.
2-(1-Naphthyl)acrylonitrile (8). 1H NMR (CDCl3, 300 MHz): d ¼ 8.12
(d, J ¼ 8.3 Hz, 1H), 7.95–7.87 (m, 2H), 7.63–7.51 (m, 2H), 7.48 (m, 2H),
6.44 (s, 1H), 6.20 (s, 1H).
2-(o-Tolyl)acrylonitrile (9). 1H NMR (CDCl3, 300 MHz): d ¼ 7.35–7.16
(m, 4H), 6.26 (s, 1H), 6.00 (s, 1H), 2.46 (s, 3H). 13C NMR (75 MHz, CDCl3):
d ¼ 135.8, 133.7, 133.6, 130.8, 129.5, 128.9, 126.4, 123.3, 117.9, 20.0. Anal.
calcd. for C10H9 N: C, 83.88; H, 6.34. Found: C, 83.74; H, 6.39.
2-Biphenyl-2-yl-acrylonitrile (10). 1H NMR (CDCl3, 300 MHz): d ¼ 7.50–
7.30 (m, 9H), 6.07 (s, 1H), 5.90 (s, 1H).
2-(2-Methoxyphenyl)acrylonitrile (11). 1H NMR (CDCl3, 300 MHz):
d ¼ 7.41 (dd, J ¼ 7.6, 1.6 Hz, 1H), 7.35 (td, J ¼ 7.6, 1.6 Hz, 1H), 6.98
(td, J ¼ 7.6, 1.0 Hz, 1H), 6.93 (d, J ¼ 8.6 Hz, 1H), 6.39 (s, 1H), 6.18
(s, 1H), 3.88 (s, 3H).
1
2-(3-Thienyl)acrylonitrile (12). H NMR (CDCl3, 300 MHz): d ¼ 7.56 (dd,
J ¼ 3.0, 1.2 Hz, 1H), 7.37 (dd, J ¼ 5.2, 3.0 Hz, 1H), 7.26 (dd, J ¼ 5.2, 1.2 Hz,
1H), 6.16 (s, 1H), 5.99 (s, 1H). 13C NMR (75 MHz, CDCl3): d ¼ 135.0, 127.6,
126.3, 124.9, 124.0, 117.8, 117.6. Anal. calcd. for C7H5NS: C, 62.19; H, 3.73.
Found: C, 61.94; H, 3.70.
Methyl 2-phenylacrylate (13). 1H NMR (CDCl3, 300 MHz): d ¼ 7.50–7.26
(m, 5H), 6.36 (s, 1H), 5.89 (s, 1H), 3.82 (s, 3H).
Methyl 2-(6-methoxy-2-naphthyl)acrylate (14). 1H NMR (CDCl3,
300 MHz): d ¼ 7.83 (s, 1H), 7.71 (m, 2H), 7.49 (dd, J ¼ 8.4, 1.7 Hz, 1H),
7.12 (m, 2H), 6.39 (s, 1H), 5.98 (s, 1H), 3.93 (s, 3H), 3.84 (s, 3H).
2-Naphthalen-1-yl-acrylic acid methyl ester (15). 1H NMR (CDCl3,
300 MHz): d ¼ 7.84 (m, 2H), 7.72 (m, 1H), 7.45 (m, 3H), 7.35 (dd,
J ¼ 7.0, 1.1 Hz, 1H), 6.71 (s, 1H), 5.88 (s, 1H), 3.71 (s, 3H).

3026
F. Berthiol, H. Doucet, and M. Santelli
2-(4-Methoxyphenyl)allylalcohol (16). 1H NMR (CDCl3, 300 MHz):
d ¼ 7.40 (d, J ¼ 8.7 Hz, 2H), 6.88 (d, J ¼ 8.7 Hz, 2H), 5.38 (s, 1H), 5.25
(q, J ¼ 1.3 Hz, 1H), 4.51 (s, 2H), 3.81 (s, 3H).
2-(4-Fluorophenyl)allylalcohol (17). 1H NMR (CDCl3, 300 MHz): d ¼ 7.41
(dd, J ¼ 8.8, 5.5 Hz, 2H), 7.02 (t, J ¼ 8.8 Hz, 2H), 5.40 (s, 1H), 5.32 (s, 1H),
4.49 (s, 2H), 1.89 (s, 1H).
1
2-(1-Naphthyl)allylalcolol (18). H NMR (CDCl3, 300 MHz): d ¼ 8.07–
7.99 (m, 1H), 7.89–7.83 (m, 1H), 7.80 (d, J ¼ 8.3 Hz, 1H), 7.52–7.42
(m, 3H), 7.32 (dd, J ¼ 7.0, 1.2 Hz, 1H), 5.71 (q, J ¼ 1.7 Hz, 1H), 5.26
(q, J ¼ 1.4 Hz, 1H), 4.46 (s, 2H), 1.95 (s, 1H).
2-(2-Naphthalen-1-yl-allyloxy)-tetrahydropyran (19). 1H NMR (CDCl3,
300 MHz): d ¼ 8.09 (m, 1H), 7.87 (m, 1H), 7.78 (d, J ¼ 8.3 Hz, 1H), 7.52–
7.45 (m, 2H), 7.44 (d, J ¼ 8.3 Hz, 1H), 7.33 (dd, J ¼ 7.0, 1.2 Hz, 1H), 5.76
(q, J ¼ 1.8 Hz, 1H), 5.29 (q, J ¼ 1.8 Hz, 1H), 4.76 (t, J ¼ 3.4 Hz, 1H), 4.57
(dt, J ¼ 14.2 and 1.6 Hz, 1H), 4.32 (dt, J ¼ 14.2 and 1.6 Hz, 1H), 4.90–
4.75 (m, 1H), 3.50–3.40 (m, 1H), 2.00–1.45 (m, 6H). 13C NMR (75 MHz,
CDCl3): d ¼ 145.0, 138.4, 133.6, 131.5, 128.2, 127.6, 125.8, 125.6, 125.5;
125.4, 125.1, 115.8, 97.8, 69.9, 61.9, 30.4, 25.4, 19.2. Anal. calcd. for
C18H20O2: C, 80.56; H, 7.51. Found: C, 80.44; H, 7.42.
ACKNOWLEDGMENT
We thank the CNRS for providing financial support.
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