Bismuth triflate-catalyzed rearrangement of acetates of the Baylis-Hillman adducts into (E)-trisubstituted alkenes

Article abstract of DOI:10.1016/j.tet.2008.03.053

In the presence of a catalytic amount of bismuth triflate, methyl 3-acetoxy-3-aryl-2-methylenepropanoates and 3-acetoxy-3-aryl-2-methylenepropanitriles were smoothly converted into methyl (2E)-2-(acetoxymethyl)-3-arylprop-2-enoates and (2E)-2-(acetoxymeth

Full text of DOI:10.1016/j.tet.2008.03.053

Tetrahedron 64 (2008) 5150–5155
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Bismuth triflate-catalyzed rearrangement of acetates
of the Baylis–Hillman adducts into (E)-trisubstituted alkenes
*
Thierry Ollevier , Topwe M. Mwene-Mbeja
De´partement de chimie, Universite´ Laval, Que´bec (Que´bec), Canada G1K 7P4
a r t i c l e i n f o
a b s t r a c t
Article history:
In the presence of
a catalytic amount of bismuth triflate, methyl 3-acetoxy-3-aryl-2-methyl-
Received 12 December 2007
Received in revised form 8 March 2008
Accepted 14 March 2008
enepropanoates and 3-acetoxy-3-aryl-2-methylenepropanitriles were smoothly converted into methyl
(2E)-2-(acetoxymethyl)-3-arylprop-2-enoates and (2E)-2-(acetoxymethyl)-3-arylprop-2-enenitriles,
respectively. A remarkable reversal in stereochemical directions from ester to nitrile was observed.
3-Aryl-3-hydroxy-2-methylenepropanoates and 3-aryl-3-hydroxy-2-methylenepropanitriles could be
easily obtained as Baylis–Hillman adducts from methyl acrylate and acrylonitrile, respectively. The
overall process is an efficient isomerization of the Baylis–Hillman adducts to the corresponding cinnamyl
derivatives. The isomerization reaction proceeded rapidly and afforded smoothly the cinnamyl acetates
in moderate to very good yields using catalytic amounts of Bi(OTf)3$4H2O (10 mol %).
Available online 21 March 2008
Keywords:
Bismuth
Lewis acids
Rearrangement
Claisen
Ó 2008 Elsevier Ltd. All rights reserved.
Morita–Baylis–Hillman
Green chemistry
1. Introduction
alternative as they have recently attracted attention due to their
low toxicity, low cost, and good stability.9 Bismuth salts have been
Morita–Baylis–Hillman reaction is a well-known carbon–carbon
bond forming reaction.1 The resultant a-methylene-b-hydroxy
adducts are key intermediates as they can be further derivatized.
The Morita–Baylis–Hillman adducts can be rearranged into the
primary allylic alcohols.2 The latter in the cinnamyl series are im-
portant because they constitute an important class of synthons for
the synthesis of many bioactive molecules.3 Esters of the rear-
ranged allylic alcohols have been obtained by various methods.4
The development of new methods for the isomerization of the
acetates of these a-methylene-b-hydroxy adducts is an important
area of synthetic efforts as allylic acetates are extremely important
as key synthetic intermediates. 5 Among the variety of mediators so
far reported for the isomerization of acetate derivatives are mont-
morillonite K10 clay or FeCl3 used in stoichiometric quantities.5,6
Catalytic rearrangement of the acetates has been reported in a few
cases, e.g., with DABCO, TMSOTf, or Pd(OAc)2/Ph3P as an efficient
method to prepare the corresponding isomeric allylic acetates.7
Recently, some precedents have been disclosed regarding
Yb(OTf)3 as a catalyst for the rearrangement.6c High catalytic
activity, low toxicity, and moisture and air tolerance make lantha-
nide triflates valuable catalysts.8 However, the high cost of these
catalysts restricts their use. Bismuth compounds provide a good
reported as catalysts for the Sakurai reaction,10 opening of epox-
ides,11 Mukaiyama-aldol reaction,12 Mannich-type reactions,13 for-
mation or deprotection of acetals,14 Friedel–Crafts reactions,15 and
Fries rearrangements.16 Bi(OTf)3 is particularly attractive because it
is commercially available or can be easily prepared from readily
available compounds.17
2. Results and discussion
As a part of our ongoing interest in bismuth(III)-catalyzed
Claisen rearrangements,18 we report herein our results in the
bismuth(III)-catalyzed rearrangement of the acetates of 3-aryl-3-
hydroxy-2-methylenepropanoates and 3-aryl-3-hydroxy-2-meth-
ylenepropanitriles easily obtained as the Baylis–Hillman adducts
from methyl acrylate and acrylonitrile, respectively. The adducts 1
and 2 were prepared using various aromatic aldehydes, DABCO, and
methyl acrylate or acrylonitrile,19 and then converted to their cor-
responding acetates 3 and 4 (Scheme 1). Due to the importance of
the cinnamyl series 5 and 6 (Tables 1 and 2) for the synthesis of
many bioactive molecules,3 only adducts 1 and 2 derived from
aromatic aldehydes were prepared.
Initial investigations involved the Baylis–Hillman adducts
derived from methyl acrylate (Scheme 2, Table 1). The benzalde-
hyde derived adduct 3a was smoothly isomerized into methyl
2-(acetoxymethyl)-3-phenylprop-2-enoate 5a with a good yield
* Corresponding author. Tel.: þ1 418 656 5034; fax: þ1 418 656 7916.
E-mail address: thierry.ollevier@chm.ulaval.ca (T. Ollevier).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.03.053

T. Ollevier, T.M. Mwene-Mbeja / Tetrahedron 64 (2008) 5150–5155
5151
O
OH
OAc
R'
DABCO, LiI, NaI
H
AcCl, Pyr
+
R
R
R
H2O, 25 °C, 8-216 h
R'
CH2Cl2, 25 °C, 1-4 h
R'
31-96%
70-96%
1 (R' = CO2Me)
2 (R' = CN)
3 (R' = CO2Me)
4 (R' = CN)
Scheme 1.
using 10 mol % of Bi(OTf)3$4H2O as the catalyst (Table 1, entry 1). The
isomerized product was obtained as the major E isomer, (2E)-
2-(acetoxymethyl)-3-phenylprop-2-enoate 5a (E/Z¼83:17). The
stereochemistry of 5a was unambiguously confirmed from the 1H
and 13C NMR data.7d No rearrangement occurred when the reactant
was submitted to the thermal conditions without catalyst (3a,
MeCN, 82 ꢀC, 28 h). Several examples of Bi(OTf)3$4H2O-catalyzed
isomerization of Baylis–Hillman adducts’ acetates are summarized
Table 1
Bi(OTf)3-catalyzed rearrangement of 3-acetoxy-3-aryl-2-methylenepropanoates 3
Entry
Reactant 3
Product (E)-5a
CO2CH3
OAc
CO2CH3
OAc
Time (h)
28
E/Z ratiob
Yield 5c (%)
OAc
1
83:17 (5a)
77
CO2CH3
OAc
2
3
17
23
82:18 (5b)
88:12 (5c)
67
73
CO2CH3
OAc
CO2CH3
OAc
CO2CH3
OAc
CO2CH3
OAc
4
5
6
7
25
36
26
36
88:12 (5d)
86:14 (5e)
75:25 (5f)
75:25 (5g)
74
62
80
80
CO2CH3
OAc
CO2CH3
OAc
CO2CH3
OAc
CO2CH3
OAc
F
CO2CH3
OAc
F
CO2CH3
OAc
Cl
Br
CO2CH3
OAc
Cl
Br
CO2CH3
OAc
8
36
34
28
81:19 (5h)
80:20 (5i)
92:8 (5j)
70
60
CO2CH3
OAc
CO2CH3
OAc
9
F
CO2CH3
F
OAc
CO2CH3
OAc
10
65
CO2CH3
Cl
Cl
(continued on next page)

5152
T. Ollevier, T.M. Mwene-Mbeja / Tetrahedron 64 (2008) 5150–5155
Table 1 (continued )
Entry
Reactant 3
Product (E)-5a
CO2CH3
OAc
Time (h)
35
E/Z ratiob
98:2 (5k)
Yield 5c (%)
OAc
11
82
CO2CH3
Br
Br
OAc
CO2CH3
OAc
12
38
75:25 (5l)
83
F3C
CO2CH3
F3C
a
All compounds were characterized by 1H NMR and 13C NMR.
b
c
Ratio determined by 1H NMR. E and Z isomers could not be purified by silica gel chromatography.
Isolated yield.
in Table 1. A variety of differently substituted aryl derivatives were
reacted in acetonitrile in our optimized conditions. With both
electron-poor, electron-rich and o-substituted benzaldehyde ad-
ducts 3, the corresponding cinnamyl acetates 5 were obtained in
moderate to good yields (Table 1, entries 1–12). E/Z ratios in all cases
weregreaterthan 75:25 (Table 1). E and Z isomers of 5 could neverbe
separated by column chromatography. Chemical yields of the pro-
cess are moderate togood (62–83% range, Table 1) due to incomplete
conversion. No by-products were isolated and unreacted starting
materialcould beobserved. Thestereochemistryof the productswas
assigned on the basis of the 1H NMR chemical shifts values of the
olefinic protons by comparison with the values reported in the lit-
erature.7d,e The yields and stereoselectivity of the Bi(OTf)3-catalyzed
process compares well with the ones obtained with montmoril-
lonite K10 used as catalyst.5,6b However, our conditions are less ef-
ficient than the ones involving Yb(OTf)3, TMSOTf or Pd(OAc)2/Ph3P
as a catalyst. When Yb(OTf)3 was used as a catalyst, slight better
chemical yields and E/Z ratios could be obtained.6c The two latest
methods involving TMSOTf and Pd(OAc)2/Ph3P appeared to be su-
perior since they give the rearranged product in similar yields as in
our conditions but affording the E isomer only, albeit longer reaction
times were required with Bi(OTf)3.7c,e Overall, no significant im-
provement could be obtained using Bi(OTf)3 with the acetates of 3-
aryl-3-hydroxy-2-methylenepropanoates as substrates.
Table 2
Bi(OTf)3-catalyzed rearrangement of 3-acetoxy-3-aryl-2-methylenepropanitriles 4
Entry
Reactant 4
Product (E)-6a
Time (h) 6 Yield 6b (%)
We then synthesized various (2E)-2-(acetoxymethyl)-3-aryl-
prop-2-enenitriles 6 via the Bi(OTf)3$4H2O-catalyzed isomerization
of 3-acetoxy-3-aryl-2-methylenepropanitriles 4 (Scheme 3). Using
our standard conditions, (2E)-2-(acetoxymethyl)-3-phenylprop-
2-enenitrile 6a could be obtained in moderateyield (Table 2, entry 1).
Our results in the nitrile series are summarized in Table 2. With both
electron-rich (Table 2, entries 2–5), electron-poor (Table 2, entries 6
and 7) and o-substituted benzaldehyde adducts 4 (Table 2, entry 5),
the corresponding cinnamyl acetates 6 were obtained in moderate to
verygood yields (Table 2, entries 2–7). Exclusive formationof the (E)-
isomer was observed in all cases (Table 2, entries 1–7). In this series,
the cyano group was cis to the aryl group giving rise again to (E)-form
due to inversion of priorityof the substituents. The assignmentof the
(E)-stereochemistry of compounds 6 was based on the 1H and 13C
NMR chemical shift values of the allylic methylene group in com-
parison with the published ones.5,7d,e We could not isolate the
(Z)-isomer, which might be present in trace amounts in the reaction
mixtures. Chemical yields were usually moderate, mostly due to
incomplete conversion. The stereoselectivity of the present method
appears to be as good as the one obtained using TMSOTf, except for
the reaction time required, since 2 h is sufficient for the TMSOTf-
catalyzed reaction to proceed.7c However, our method appears to be
superior compared to other methods (e.g., montmorillonite K10 clay
or Pd(OAc)2/Ph3P) leading to the formation of the product with E/Z
ratio of 80:20–95:5 and 81:19–86:14, respectively.5,6b,7e Z isomer has
never been detected using our method.
OAc
OAc
1
24
6
6a 64
6b 63
6c 77
6d 81
CN
CN
OAc
OAc
2
3
4
CN
CN
OAc
OAc
36
28
CN
CN
OAc
OAc
CN
CN
OAc
OAc
5
6
45
70
6e 60
6f 59
CN
CN
OAc
OAc
OAc
CN
The remarkable reversal in stereochemical directions from ester
to nitrile in these reactions is consistent with earlier work.7d This
can possibly be explained through a Claisen-type rearrangement
(Scheme 4).7c In the case of compounds 3, there is a quasi-eclipsed
1,2-interaction between the Ar group and the pseudo-equatorial
CO2CH3 group (transition state TS I). This interaction is likely to be
stronger than the ones present in transition state TS II, where the
ester group occupies a pseudo-axial position, leading to (E)-5 as the
major product. However, in the nitrile series, the corresponding
Cl
F
CN
Cl
F
OAc
7
19
6g 87
CN
CN
All compounds were characterized by 1H NMR and 13C NMR.
Isolated yield.
a
b

T. Ollevier, T.M. Mwene-Mbeja / Tetrahedron 64 (2008) 5150–5155
5153
OAc
CO2CH3
Bi(OTf)3•4H2O (10 mol %)
OAc
CO2CH3
(Z)-5
R
+
R
R
CO2CH3
MeCN, reflux
OAc
3
(E)-5
Scheme 2.
spectra were obtained with complete proton decoupling. For 19F
NMR, CFCl3 was used as internal standard (d¼0). Infrared spectra
were recorded on a FT infrared spectrometer and are reported in
reciprocal centimeters (cmꢁ1). Column chromatography was per-
formed on silica gel (230–400 mesh) and analytical thin layer chro-
matography was carried out using 250 mm commercial silica gel
plates. Visualization of the developed chromatogram was performed
by UV absorbance or aqueous potassium permanganate. Acetonitrile
was distilled from calcium hydride. 3-Acetoxy-3-aryl-2-methyl-
enepropanoates 3 and 3-acetoxy-3-aryl-2-methylenepropanitriles 4
were synthesized according to known literature.19
OAc
Bi(OTf)3•4H2O (10 mol %)
MeCN, reflux
OAc
R
R
CN
CN
4
(E)-6
Scheme 3.
1,2-interaction (transition state TS III) may not result in such
a strong steric bias. Product (E)-6 is then produced exclusively.
3. Conclusions
4.2. Representative procedure for the bismuth triflate-
catalyzed rearrangement of the acetates of Morita–Baylis–
Hillman adducts
As an improvement over other catalytic systems, Bi(OTf)3$4H2O
is a versatile catalyst for the rearrangement of acetates of Morita–
Baylis–Hillman adducts. The reaction affords moderate to good
yields in isomeric acetates using 10 mol % of catalyst. This method
offers several advantages including mild reaction conditions,
catalytic process, and no formation of by-products. The conditions
are suitable for a variety of aromatic aldehydes. Also, the practical
use of Bi(OTf)3$4H2O is highly valuable as an environmentally be-
nign Lewis acid. Because of its numerous benefits, this method for
the synthesis of (E)-trisubstituted alkenes using Bi(OTf)3$4H2O
catalysis should find utility in the synthesis of biologically active
compounds. Whereas a good (E)-selectivity was obtained with the
methyl acrylate derived series, the isomerization in the nitrile
series occurred in complete (E)-stereoselectivity. Research is on
its way to demonstrate other significant applications of this
Bi(OTf)3$4H2O-catalyzed rearrangement.
The benzylic acetate 3 or 4 (2.0 mmol) and Bi(OTf)3$4H2O
(0.20 mmol) were mixed together in dry MeCN (4 mL) under argon
atmosphere. The solution was then brought up to 82 ꢀC (tempera-
ture of oil bath) for 6–70 h. The solvent was evaporated and the
residue was quenched with water, extracted with ether (three
times), dried over Na2SO4, and concentratedunder reduced pressure
to afford the crude product. The crude was then purified by column
chromatography (eluent: hexane/EtOAc80:20). Spectral data accord
exactly with those previously reported in the literature.5,7c–e
4.3. Spectroscopic data for cinnamyl acetates
4.3.1. Methyl 2-(acetoxymethyl)-3-phenylacrylate (5a)
4. Experimental
4.1. General
Spectral data were consistent with those previously reported.7c
4.3.2. Methyl 2-(acetoxymethyl)-3-p-tolylacrylate (5b)
Spectral data were consistent with those previously reported.7c
1H, 13C, and 19F spectra were recorded on a 400 MHz magnetic
resonance spectrometer in CDCl3. For 1H NMR, tetramethylsilane
(TMS) served as internal standard (d¼0) and data are reported
as follows: chemical shift, multiplicity (s¼singlet, d¼doublet,
dd¼doubletofdoublet, dt¼doubletof triplet, t¼triplet, m¼multiplet,
and br¼broad), coupling constant in hertz, integration, and assign-
ment. For 13C NMR, CDCl3 was used as internal standard (d¼77.0) and
4.3.3. Methyl 2-(acetoxymethyl)-3-(4-ethylphenyl)acrylate (5c)
Spectral data were consistent with those previously reported.7c
4.3.4. Methyl 2-(acetoxymethyl)-3-(4-isopropylphenyl)acrylate
(5d)
Spectral data were consistent with those previously reported.7c
CO2CH3
CH
CO2CH3
O
O
O 3
CH3
O
O
O
BiX3
BiX3
Ar
H3CO2C
CH3
Ar
(E)-5
Ar
TS I
TS II
major product
CN
CH
O 3
CH
O 3
CH3
O
O
O
O
BiX3
BiX3
Ar
Ar
NC
NC
Ar
(E)-6
only product
TS III
TS IV
Scheme 4.

5154
T. Ollevier, T.M. Mwene-Mbeja / Tetrahedron 64 (2008) 5150–5155
4.3.5. Methyl 2-(acetoxymethyl)-3-o-tolylacrylate (5e)
4.3.16. (E)-2-Cyano-3-(4-isopropylphenyl)allyl acetate (6d)
Spectral data were consistent with those previously reported.7c
Spectral data were consistent with those previously reported.7c
4.3.6. Methyl 2-(acetoxymethyl)-3-(4-fluorophenyl)acrylate (5f)
1H NMR (400 MHz, CDCl3): d¼7.39 (dd, J¼8.8, 8.8 Hz, 2H), 7.11 (t,
J¼8.6 Hz, 2H), 4.94 (s, 2H, E), 4.89 (s, 2H, Z), 3.85 (s, 3H, E), 3.71 (s, 3H,
Z), 2.11 (s, 3H, E), 2.10 (s, 3H, Z); 13C NMR (100 MHz, CDCl3): d¼170.9,
4.3.17. (E)-2-Cyano-3-(o-tolyl)allyl acetate (6e)
Spectral data were consistent with those previously reported.7c
4.3.18. (E)-2-Cyano-3-(4-chlorophenyl)allyl acetate (6f)
170.7, 167.4, 163.6 (d, JC–F¼251.6 Hz), 144.5, 138.6, 131.7 (d, JC–F
¼
Spectral data were consistent with those previously reported.7c
8.4 Hz), 130.7 (d, JC–F¼41.4 Hz), 130.5, 126.7, 116.1 (d, JC–F¼21.5 Hz),
115.4, 66.1, 59.4, 52.6, 52.1, 21.2; IR (film): 3074, 3000, 2954,
2907, 2848, 1747, 1718, 1637, 1601, 1509, 1437, 1236, 1118, 1026,
845 cmꢁ1;HRMS: calcd for C13H13FO4 ([MþNH4]þ): 270.1136, found:
270.1140.
4.3.19. Methyl 2-(acetoxymethyl)-3-(4-fluorophenyl)acrylate (6g)
1H NMR (400 MHz, CDCl3): d¼7.81 (dd, J¼7.1, 7.1 Hz, 2H), 7.19 (s,
1H), 7.14 (t, J¼8.7 Hz, 2H), 4.81 (s, 2H), 2.15 (s, 3H); 13C NMR
(100 MHz, CDCl3): d¼170.5, 164.3 (d, JC–F¼253.9 Hz), 146.3, 131.6 (d,
JC–F¼9.2 Hz), 129.0, 117.4, 116.4 (d, JC–F¼21.5 Hz), 105.7, 65.4, 21.0; IR
(film): 3109, 3076, 3045, 2958, 2892, 2217, 1743, 1600, 1509, 1444,
1419, 1224, 732 cmꢁ1; HRMS: calcd for C12H10FNO2 ([MþNH4]þ):
237.1034, found: 237.1035.
4.3.7. Methyl 2-(acetoxymethyl)-3-(4-chlorophenyl)acrylate (5g)
Spectral data were consistent with those previously reported.7c
4.3.8. Methyl 2-(acetoxymethyl)-3-(4-bromophenyl)acrylate (5h)
1H NMR (400 MHz, CDCl3): d¼7.86 (s, 1H, E), 7.52 (d, J¼8.6 Hz,
2H, E), 7.42 (d, J¼8.6 Hz, 2H, Z), 7.21 (d, J¼8.2 Hz, 2H, E), 7.15 (d,
J¼8.2 Hz, 2H, Z), 4.87 (s, 2H, E), 4.85 (s, 2H, Z), 3.82 (s, 3H, E), 3.76
(3H, Z), 2.07 (s, 3H, E); 13C NMR (100 MHz, CDCl3): d¼171.4, 170.9,
167.3, 144.4, 138.4, 138.3, 133.9, 133.2, 132.2, 131.6, 131.2, 130.5,
128.9, 127.5, 124.3, 123.2, 65.9, 65.8, 64.2, 59.4, 59.2, 52.7, 52.6, 52.2,
25.5, 21.2; IR (film): 3025, 2999, 2952, 2905, 2846, 1740, 1720, 1637,
Acknowledgements
This work was financially supported by the Natural Sciences and
Engineering Research Council of Canada (NSERC), the Fonds Que-
´
´
becois de la Recherche sur la Nature et les Technologies (FQRNT,
´
Quebec, Canada), the Canada Foundation for Innovation (CFI), and
´
Universite Laval. We thank Rhodia (Lyon, France) and Sidech s.a.
1587, 1488, 1436, 1230 cmꢁ1
; HRMS: calcd for C13H13BrO4
(Tilly, Belgium) for generous gift of chemicals.
([MþNH4]þ): 330.0336, found: 330.0334.
References and notes
4.3.9. Methyl 2-(acetoxymethyl)-3-(2-fluorophenyl)acrylate (5i)
1H NMR (400 MHz, CDCl3): d¼8.0 (s,1H), 7.29–7.41 (m, 3H), 7.09–
7.20 (m, 3H), 4.92 (s, 2H, Z), 4.91 (s, 2H, E), 3.86 (s, 3H, E), 3.69 (s, 3H,
Z), 2.12 (s, 3H, Z), 2.08 (s, 3H, E); 13C NMR (100 MHz, CDCl3): d¼170.9,
1. Basavaiah, D.; Rao, A. J.; Satyanarayana, T. Chem. Rev. 2003, 103, 811–891.
2. Kim, H. S.; Kim, T. Y.; Lee, K. Y.; Chung, Y. M.; Lee, H. J.; Kim, J. N. Tetrahedron
Lett. 2000, 41, 2613–2616.
3. Mohapatra, D. K.; Datta, A. J. Org. Chem. 1998, 63, 642–646.
4. Charette, A. B.; Coˆte´, B.; Monroc, S.; Prescott, S. J. Org. Chem. 1995, 60, 6888–
6894.
5. Shanmugam, P.; Rajasingh, P. Tetrahedron 2004, 60, 9283–9295.
6. (a) Kabalka, G. W.; Venkataiah, B.; Dong, G. Tetrahedron Lett. 2003, 44, 4673–
4675; (b) Shanmugam, P.; Singh, P. R. Synlett 2001, 1314–1316; (c) Krishna, P. R.;
Kannan, V.; Sharma, G. V. M. Synth. Commun. 2004, 34, 55–64.
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A.; El Guemmout, F. Bull. Soc. Chim. Fr. 1989, 403–408; (c) Basavaiah, D.;
Muthukumaran, K.; Sreenivasulu, B. Synthesis 2000, 545–548; (d) Basavaiah, D.;
Padmaja, K.; Satyanarayana, T. Synthesis 2000, 1662–1664; (e) Park, J. B.; Ko, S.
H.; Kim, B. G.; Hong, W. P.; Lee, K.-J. Bull. Korean Chem. Soc. 2004, 25, 27–28.
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2227–2302.
170.7, 169.5, 166.9, 165.4, 160.7 (d, JC–F¼250.8 Hz), 160.2 (d, JC–F
¼
249.3 Hz), 138.3 (d, JC–F¼41.0 Hz), 132.6, 131.7, 131.6, 130.7, 130.6,
130.4, 129.1, 129.0, 127.1, 124.3, 123.9, 123.2, 122.4, 116.3, 116.1,
115.9, 115.7, 115.5, 65.6, 59.7, 52.6, 52.1, 21.1; IR (film): 3069, 3002,
2955, 2848, 1748, 1728, 1636, 1617, 1590, 1493, 1458, 1439, 1222,
761 cmꢁ1; HRMS: calcd for C13H13FO4 ([MþNH4]þ): 270.1136, found:
270.1140.
4.3.10. Methyl 2-(acetoxymethyl)-3-(2-chlorophenyl)acrylate (5j)
Spectral data were consistent with those previously reported.7e
9. (a) Suzuki, H.; Matano, Y. Organobismuth Chemistry; Elsevier: Amsterdam,
2001; (b) Gaspard-Iloughmane, H.; Le Roux, C. Eur. J. Org. Chem. 2004,
2517–2532; (c) Leonard, N. M.; Wieland, L. C.; Mohan, R. S. Tetrahedron 2002,
58, 8373–8397.
4.3.11. Methyl 2-(acetoxymethyl)-3-(2-bromophenyl)acrylate (5k)
Spectral data were consistent with those previously reported.7e
10. (a) Anzalone, P. W.; Baru, A. R.; Danielson, E. M.; Hayes, P. D.; Nguyen, M. P.;
Panico, A. F.; Smith, R. C.; Mohan, R. S. J. Org. Chem. 2005, 70, 2091–2096; (b)
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12. (a) Le Roux, C.; Ciliberti, L.; Laurent-Robert, H.; Laporterie, A.; Dubac, J. Synlett
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Hamada, T.; Manabe, K. Org. Lett. 2005, 7, 4729–4731; (c) Ollevier, T.; Desyroy,
V.; Debailleul, B.; Vaur, S. Eur. J. Org. Chem. 2005, 4971–4973; (d) Ollevier, T.;
Desyroy, V.; Catrinescu, C.; Wischert, R. Tetrahedron Lett. 2006, 47, 9089–9092;
(e) Ollevier, T.; Desyroy, V.; Nadeau, E. ARKIVOC (Gainesville, FL, U.S.) 2007, x,
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331–334.
4.3.12. Methyl 2-(acetoxymethyl)-3-(4-(trifluoromethyl)phenyl)-
acrylate (5l)
1H NMR (400 MHz, CDCl3): d¼7.97 (s, 1H), 7.68 (d, J¼8.2 Hz, 2H,
E), 7.60 (d, J¼8.2 Hz, 2H, Z), 7.50 (d, J¼8.6 Hz, 2H, E), 7.41 (d,
J¼8.6 Hz, 2H, Z), 7.05 (s, 1H), 4.91 (s, 2H, E), 3.87 (s, 3H, E), 3.70 (s,
3H, Z), 2.12 (s, 3H, Z), 2.10 (s, 3H, E); 13C NMR (100 MHz, CDCl3):
d¼170.7, 167.0, 143.7, 137.9, 137.7, 131.4 (q, JC–F¼32.2 Hz), 130.4,
129.7, 129.1, 129.0, 125.9 (q, JC–F¼3.8 Hz), 125.3, 124.0 (q, JC–F
¼
271.5 Hz), 65.5, 59.1, 52.7, 52.2, 21.1; IR (film): 3002, 2954, 2915,
2852, 1723, 1630, 1572, 1435, 1246, 735 cmꢁ1; HRMS: calcd for
C
14H13F3O4 ([MþNH4]þ): 320.1104, found: 320.1108.
4.3.13. (E)-2-Cyano-3-phenylallyl acetate (6a)
Spectral data were consistent with those previously reported.7c
13. (a) Ollevier, T.; Nadeau, E. J. Org. Chem. 2004, 69, 9292–9295; (b) Ollevier, T.;
Nadeau, E.; Eguillon, J.-C. Adv. Synth. Catal. 2006, 348, 2080–2084; (c) Ollevier,
´
T.; Nadeau, E. Synlett 2006, 219–222; (d) Ollevier, T.; Nadeau, E.; Guay-Begin,
4.3.14. (E)-2-Cyano-3-p-tolylallyl acetate (6b)
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D.; Smith, R. C.; Wieland, L. C.; Mohan, R. S. J. Org. Chem. 2002, 67, 1027–
1030.
Spectral data were consistent with those previously reported.7c
4.3.15. (E)-2-Cyano-3-(4-ethylphenyl)allyl acetate (6c)
Spectral data were consistent with those previously reported.7c

T. Ollevier, T.M. Mwene-Mbeja / Tetrahedron 64 (2008) 5150–5155
5155
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´
´
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