Pd-catalyzed threefold arylation of Baylis-Hillman bromides and acetates with triarylbismuth reagents

Article abstract of DOI:10.1002/ejoc.201200543

Functionalized alkyl 2-benzylacrylates and 2-benzylacrylonitriles were synthesized by means of atom-economic cross-couplings of Baylis-Hillman bromides or acetates with BiAr₃ under palladium-catalyzed conditions. These reactions, involving thre

Full text of DOI:10.1002/ejoc.201200543

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FULL PAPER
DOI: 10.1002/ejoc.201200543
Pd-Catalyzed Threefold Arylation of Baylis–Hillman Bromides and Acetates
with Triarylbismuth Reagents
Maddali L. N. Rao*[a] and Somnath Giri[a]
Dedicated to Professor Mariappan Periasamy on the occasion of his 60th birthday
Keywords: Bismuth / Palladium / Alkenes / Synthetic methods / C–C coupling
Functionalized alkyl 2-benzylacrylates and 2-benzylacrylo-
nitriles were synthesized by means of atom-economic cross-
couplings of Baylis–Hillman bromides or acetates with BiAr3
under palladium-catalyzed conditions. These reactions, in-
volving threefold aryl couplings using BiAr3 reagents with
bromides and acetates, are fast and are completed in 1–2 h
with high product yields.
such as the Suzuki, Negishi or similar couplings are usually
limited to one C–C bond formation using the respective
organoboron, zinc, or other reagents. Our sustained efforts
in this area using triarylbismuths as atom-economic three-
fold arylating organometallic reagents led to the develop-
ment of a new generation of coupling reactions with a vari-
ety of organic electrophiles under palladium catalysis.[9]
Allylic substrates are also important in cross-coupling re-
actions and considerable differences exist in the reactivity
of these substrates under metal-catalyzed conditions.[2,5] Re-
cently, we have demonstrated the novel cross-coupling reac-
tivity of triarylbismuths with various allylic coupling part-
ners under palladium-catalyzed conditions. For example,
(E)-cinnamyl acetates,[9d] (E)-cinnamyl carbonates,[9e] and
halide derivatives of Baylis–Hillman adducts[9f] reacted well
in couplings with triarylbismuths under palladium-cata-
lyzed thermal conditions. Therefore, it was of interest to
further explore the coupling reactivity of Baylis–Hillman
adducts derived from methyl 2-(bromomethyl)acrylate,
methyl 2-(acetoxymethyl)acrylate, and 2-(acetoxymethyl)-
acrylonitrile with triarylbismuth reagents. To our surprise,
for example, alkyl 2-(bromomethyl)acrylates showed re-
markable reactivity even at room temperature, whereas the
corresponding acetates reacted under thermal conditions
using palladium catalytic protocols. We report these studies
herein.
Introduction
Synthetic organic chemistry is profoundly enriched by
Baylis–Hillman applications in a variety of synthetic trans-
formations.[1] In particular, Baylis–Hillman adducts or their
derivatives are extremely useful even under metal-catalyzed
conditions.[2] Interestingly, Baylis–Hillman adduct deriva-
tives such as 2-(halomethyl)acrylates, 2-(acetoxymethyl)-
acrylates, or 2-(acetoxymethyl)acrylonitriles are important
substrates in organic synthesis.[3] For example, 2-halomethy-
lacrylates can be easily prepared through Baylis–Hillman/
halogenation procedure[4] and are used in several reac-
tions.[5] These substrates are employed (i) in the preparation
of organotin[5a–5c] or organozinc[5d–5f] derivatives and are
employed in metal-catalyzed reactions; (ii) in palladium-cat-
alyzed cascade reactions[5g] to synthesize 3,3-disubstituted-
2,3-dihydrobenzofurans; (iii) in couplings with arylzinc and
heteroarylzinc,[5h] vinylzinc,[5i] and organomagnesium[5j]
reagents, etc. Similarly, Baylis–Hillman acetates have also
been frequently utilized in various metal-catalyzed[6] and
other transformations.[7] The advantage of using these sub-
strates is that they provide a onetime installation of multi-
functional three-carbon skeleton of synthetic importance;
for these reasons the search for new applications is continu-
ing unabated.
Palladium-catalyzed cross-coupling reactions are promi-
nently employed in organic synthesis for C–C bond forma-
tion with a variety of organometallic reagents.[8] Reactions
Results and Discussion
[a] Department of Chemistry,
Initially, we chose the combination of methyl 2-bromo-
methylacrylate (4 equiv.) and BiPh3 (1 equiv.) to explore the
coupling conditions, as summarized in Table 1. We began
the coupling study with two different palladium catalysts
and found that [Pd(PPh3)4] was more effective, furnishing
Indian Institute of Technology Kanpur,
Kanpur 208016, India
Fax: +91-512-259-7532
E-mail: maddali@iitk.ac.in
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201200543.
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methyl 2-benzylacrylate in 73% yield (Table 1, entries 1–2). ized conditions involving [Pd(PPh3)4] catalyst with K3PO4
This demonstrated the facile reactivity of three equivalents base in N,N-dimethylformamide (DMF) solvent at room
of methyl 2-bromomethylacrylate with one equivalent of temperature to obtain high yields of cross-coupling product
BiPh3, resulting in threefold phenyl couplings with high (Table 1, entry 9). These conditions were used for further
product yield. We then proceeded to examine the reaction studies.
under different sets of conditions. For example, the reac-
The high cross-coupling reactivity of BiPh3 even at room
tions with a range of carbonate bases provided yields up to temperature in threefold couplings with three equivalents of
61–70% (Table 1, entries 3–5). From this, it was pleasing to allylic substrate was pleasantly surprising and encouraged
note that the couplings with K3PO4 base was more pro- us to extend our study to the corresponding acetates under
ductive and gave relatively higher yield (Table 1, entry 2). palladium-catalyzed conditions (Table 2). The cross-cou-
The effect of temperature was then studied (Table 1, en- pling of Baylis–Hillman acetate was initially carried out
tries 6–8). Interestingly, the cross-coupling was facile even using the conditions established above (Table 2, entry 1).
at room temperature, with 83% product yield being ob- However, this attempt did not furnish the desired couplings
tained (Table 1, entry 8). Encouragingly, coupling with with acetate at room temperature. Furthermore, the cou-
3.3 equivalents of methyl 2-bromomethylacrylate afforded pling reaction with [Pd(PPh3)4] and K3PO4 base in DMF
the desired product in 91% yield (Table 1, entry 9). Hence, under thermal conditions at 60 °C furnished the product in
it was decided to use 3.3 equivalents of methyl 2-bromo- only 61% yield (Table 2, entry 2).
methylacrylate for further screenings.
Table 2. Screening with Baylis–Hillman acetate.[a,b]
Table 1. Screening with Baylis–Hillman bromide.[a,b]
Entry
Catalyst
Base
Solvent
T
[°C]
Yield
[%]
Entry
1
Catalyst/
ligand
1
Base Solvent
K3PO4 DMF
T
[°C]
Yield
[%]
[equiv.]
[c]
1
2
3
4
5
6
7
8
Pd(PPh3)4
Pd(PPh3)4
PdCl2(PPh3)2
K3PO4
K3PO4
K3PO4
DMF
DMF
DMF
DMF
DMF
DMA
NMP
THF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
25
60
60
60
60
60
60
60
40
90
60
60
60
60
60
–
Pd(OAc)2
/2PPh3
4
90
65
61
81
68
64
69
72
–
73
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
none
4
4
4
4
4
4
4
3.3
3.3
3.3
3.3
3.3
3.3
3.3
K3PO4 DMF
Cs2CO3 DMF
K2CO3 DMF
Na2CO3 DMF
K3PO4 DMF
K3PO4 DMF
K3PO4 DMF
K3PO4 DMF
K3PO4 NMP
K3PO4 THF
K3PO4 MeCN
K3PO4 DMF
90
90
90
90
60
40
25
25
25
25
25
25
60
60
73
70
64
61
88
86
83
91
75
PdCl2(PPh3)2 Cs2CO3
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
none
K2CO3
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
none
9
10
11
12
13
14
15
63
76[d]
61[e]
69[f]
72
(34)[g]
70
68[c]
[h]
K3PO4
–
none
DMF
55[d]
[a] Reaction
conditions:
Methyl
2-(acetoxymethyl)acrylate
[e]
K3PO4 DMF
–
(1.0 mmol, 4.0 equiv.), BiPh3 (0.25 mmol, 1.0 equiv.), Pd catalyst
(0.0225 mmol, 0.09 equiv.), base (0.50 mmol, 2.0 equiv.), solvent
(3 mL), 2 h. [b] Isolated yield of product. [c] Reaction with
methyl 2-(acetoxymethyl)acrylate (0.825 mmol, 3.3 equiv.), base
(0.25 mmol, 1 equiv.), 1 h. [d] Methyl 2-(acetoxymethyl)acrylate
(0.825 mmol, 3.3 equiv.), 1 h. [e] With 3 mol-% catalyst. [f] With
1 equiv. K3PO4 base. [g] Control reaction without base, GC conver-
sion shown in parentheses. [h] Control reaction without catalyst.
[a] Reaction conditions: BiPh3 (0.25 mmol, 1.0 equiv.), Pd catalyst
(0.0225 mmol, 0.09 equiv.), methyl 2-(bromomethyl)acrylate
(1 mmol or 0.825 mmol,
1.0 equiv.), solvent (3 mL), 1 h. [b] Isolated yield. [c] With 1 mol-%
catalyst. [d] Control without base. [e] Control without catalyst.
4 or 3.3 equiv.), base (0.25 mmol,
At this stage, a coupling study with a range of solvents
such as acetonitrile, tetrahydrofuran, and N-methyl-2-
pyrrolidinone (NMP), furnished 70–75% yield (Table 1, en-
Additional investigations with [PdCl2(PPh3)2] as catalyst
tries 10–12), whereas employing 1 mol-% catalyst afforded produced 81% yield (Table 2, entry 3). Different bases such
68% yield of the desired product (Table 1, entry 13). Two as Cs2CO3 and K2CO3 afforded moderate yields (Table 2,
independent control experiments without base and catalyst entries 4 and 5), whereas the use of N,N-dimethylacetamide
gave moderate or no coupling, respectively (Table 1, en- (DMA) or N-methyl-2-pyrrolidinone (NMP) as solvents
tries 14 and 15). During this screening, a biphenyl side gave 69 and 72% yield, respectively (Table 2, entries 6 and
product was formed in 10–15% yield, through a known 7). Tetrahydrofuran (THF) solvent was found to be ineffec-
homocoupling of triarylbismuths under palladium cataly- tive for this reaction (Table 2, entry 8). Conducting the cou-
sis.[10] The present screening studies led us to the standard- pling reactions either at 40 or 90 °C did not furnish high
2
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Arylation of Baylis–Hillman Bromides and Acetates
yields (Table 2, entries 9 and 10) in comparison to the yield yields in these reactions, and this amount was higher in re-
obtained at 60 °C (Table 2, entry 3). The reaction with actions for which there was no cross-coupling reaction.
3.3 equivalents of acetate gave inferior coupling yield From the above study, the Baylis–Hillman bromide was
(Table 2, entry 11). Low catalyst loading and the use of shown to be more reactive at room temperature than the
1 equivalent of base furnished moderate yields (Table 2, en- corresponding acetate and, hence, demonstrated high reac-
tries 12 and 13). Expectedly, performing the reaction with- tivity under palladium catalytic conditions.
out base or catalyst gave poor or no conversion, respectively
To evaluate the generality of the method, methyl 2-
(Table 2, entries 14 and 15). These efforts revealed that the bromomethylacrylate was treated with a range of BiAr3 rea-
conditions with [PdCl2(PPh3)2] as catalyst and K3PO4 gents under the established room temperature conditions
(2 equiv.) as base in DMF solvent was high yielding for (Table 3). It is noteworthy that the coupling reaction of
coupling reactions involving acetates (Table 2, entry 3). Bi- methyl 2-bromomethylacrylate showed high reactivity with
phenyl as a minor side product was formed in 10–15% electronically different BiAr3 reagents. This evaluation
Table 4. Couplings of acetate with BiAr3 reagents.[a]
Table 3. Couplings of bromide with BiAr3 reagents.[a]
[a] Reaction conditions: 2-(bromomethyl)acrylate (0.825 mmol,
3.3 equiv.), BiAr3 (0.25 mmol, 1 equiv.), K3PO4 (0.25 mmol,
1 equiv.), [Pd(PPh3)4] (0.0225 mmol, 0.09 equiv.), DMF (3 mL),
25 °C, 1 h. Biaryls as a minor homocoupling product was formed
in all reactions. All products were identified by 1H NMR, 13C
NMR, and IR spectroscopy and additionally by ESI-HRMS or EI-
HRMS. [b] Isolated yield.
[a] Reaction conditions: methyl 2-(acetoxymethyl)acrylate (1 mmol,
4 equiv.), BiAr3 (0.25 mmol, 1 equiv.), K3PO4 (0.50 mmol,
2 equiv.), [PdCl2(PPh3)2] (0.0225 mmol, 0.09 equiv.), DMF (3 mL),
60 °C, 2 h. Biaryls as a minor side homocoupling product was
1
formed in all reactions. All products were identified by H NMR,
13C NMR, and IR spectroscopy and additionally by ESI-HRMS
or EI-HRMS. [b] Isolated yield.
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using both electron-rich and electron-deficient BiAr3 rea- thiophene and methyl acrylate was earlier reported to give a
gents gave the corresponding functionalized methyl 2-benz- mixture of products and required a longer reaction time.[11]
ylacrylates products in excellent yields. It is particularly
Further elaboration of the coupling reactivity of Baylis–
noteworthy to mention that tris-2-thiophenylbismuth also Hillman acetate was carried out with BiAr3 reagents under
afforded the corresponding cross-coupled product methyl 2- the optimized conditions (Table 4). The couplings of dif-
(thiophen-2-yl)acrylate in high yield. Importantly, synthesis ferent BiAr3 reagents were facile and gave the correspond-
of this product through Heck couplings involving 2-bromo- ing arylated products in moderate to high yields in all cases.
Table 5. Couplings of different bromides and acetates with BiAr3 reagents.[a,b]
[a] Reaction conditions for bromides: 2-(Bromomethyl)acrylate (0.825 mmol, 3.3 equiv.), BiAr3 (0.25 mmol, 1 equiv.), K3PO4 (0.25 mmol,
1 equiv.), [Pd(PPh3)4] (0.0225 mmol, 0.09 equiv.), DMF (3 mL), 25 °C, 1 h. Reaction conditions for acetates: 2-(Acetoxymethyl)-
acrylate (or) 2-(acetoxymethyl)acrylonitrile (1 mmol, 4 equiv.), BiAr3 (0.25 mmol, 1 equiv.), K3PO4 (0.50 mmol, 2 equiv.), [PdCl2(PPh3)2]
(0.0225 mmol, 0.09 equiv.), DMF (3 mL), 60 °C, 2 h. Biaryls as a minor side homocoupling product was formed in all reactions. All
1
products were identified by H NMR, 13C NMR, and IR spectroscopy and additionally by ESI-HRMS or EI-HRMS. [b] Isolated yield.
4
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Arylation of Baylis–Hillman Bromides and Acetates
The demonstrated novel and efficient coupling reactivity methyl)acrylates, and 2-(acetoxymethyl)acrylonitrile in
of both Baylis–Hillman bromide and acetate with a range threefold couplings with BiAr3 reagents under the estab-
of triarylbismuths under different conditions, prompted fur- lished palladium-catalyzed coupling conditions for easy
ther studies with alkyl 2-(bromomethyl)acrylates, alkyl 2- preparation of the functionalized alkyl 2-benzylacrylates
(acetoxymethyl)acrylates, and 2-(acetoxymethyl)acryloni- and 2-benzylacrylonitriles in an atom-economic manner
trile, as summarized in Table 5. Ethyl and n-butyl deriva- and in a one-pot operation. The reactions involving three-
tives of 2-bromomethylacrylates that were required for this fold aryl couplings using BiAr3 reagents are fast (completed
study were synthesized by using literature procedures.[4] The in 1–2 h) and high-yielding. This study demonstrated a ge-
corresponding benzyl derivative was also prepared by litera- neral approach to the synthesis of various functionalized
ture methods.[12a,12b] Alkyl 2-(acetoxymethyl)acrylates and alkyl 2-benzylacrylates and 2-benzylacrylonitriles, which
2-(acetoxymethyl)acrylonitriles were also obtained by using are useful for further applications in synthetic organic
known methods.[12c] Thus, a series of coupling reactions chemistry.
conducted using alkyl 2-(bromomethyl)acrylates with ethyl,
n-butyl and benzyl derivatives and different BiAr3 reagents
demonstrated promising reactivity under established palla- Experimental Section
dium catalytic protocols. Encouragingly, BiAr3 reagents in
General Methods: Triarylbismuth compounds were prepared either
all cases provided three aryl groups for threefold couplings
through aryllithium or Grignard reagents according to the litera-
in reactions with bromides under room temperature condi-
tions to give the corresponding 2-benzylacrylates in short
reaction times. The corresponding reactivity of alkyl 2-(ace-
ture procedures.[10b] All solvents employed were dried according
to standard procedures. Analytical thin layer chromatography was
performed on precoated aluminium plates with GF254 silica (Spec-
toxymethyl)acrylates is also noteworthy because these sub- trochem, Mumbai). Products were isolated by column chromatog-
raphy on 100–200 mesh silica gel by using a mixture of EtOAc and
petroleum ether as eluent. GC analyses were performed with a Per-
kin Elmer (Clarus 500) gas chromatograph. 1H NMR and 13C
NMR spectra were recorded with a JEOL-Delta (500 MHz) spec-
trometer by using CDCl3 as solvent. Chemical shift values (δ) for
protons and carbon atoms are expressed in parts per million (ppm)
with respect to TMS. IR spectra were recorded with a Bruker Vec-
tor 22 FT-IR spectrometer. HR mass spectra were measured with
a Waters HAB213 instrument by using the electrospray (ES) tech-
nique and with a CAB155 micromass spectrometer by using the
strates reacted with a range of BiAr3 reagents under ther-
mal conditions with high yields. Further couplings with a
different class of 2-(acetoxymethyl)acrylonitrile also dem-
onstrated high reactivity with BiAr3 reagents. Overall, these
attempts demonstrated the atom-efficient multiple-coupling
reaction of triarylbismuth reagents in threefold couplings
with three equivalents of different allylic coupling partners
in short reaction time in a palladium-catalyzed one-pot op-
eration.
In this context, it should be mentioned that the pre- electroionization (EI) technique.
viously known coupling reactions of allylic acetates,[9d] all-
Coupling of 2-(Bromomethyl)acrylates with BiAr3 Reagents; Typical
ylic carbonates,[9e] and halide derivatives of Baylis–Hillman
adducts[9f] and allylic bromides[13] reacted under thermal
conditions. Indeed, to the best of our knowledge, the pres-
ent study is the first report on the room temperature cou-
pling reactions of alkyl 2-bromomethylacrylates with BiAr3
under palladium-catalyzed conditions. The reactivity of the
corresponding acetates under thermal conditions was in ac-
cordance with earlier findings.
Procedure: To an oven-dried Schlenk tube, BiPh3 (0.25 mmol,
110 mg, 1.0 equiv.), methyl 2-(bromomethyl)acrylate (0.825 mmol,
147.6 mg, 3.3 equiv.), K3PO4 (0.25 mmol, 53.0 mg, 1.0 equiv.),
[Pd(PPh3)4] (0.0225 mmol, 26.0 mg, 0.09 equiv.), and DMF (3 mL)
were added under an N2 atmosphere. The resulting mixture was
stirred at 25 °C for 1 h, then extracted with ethyl acetate and sub-
mitted to usual workup procedures.[9a] The pure product 1a was
obtained as a colorless liquid (0.12 g, 91%). The isolated yield was
calculated based on 3-phenyl couplings from BiPh3 (thus,
0.75 mmol of the product corresponds to a 100% yield).
As noted above, the majority of products in this study
were obtained in excellent yields. Known methods to syn-
thesize some of these products are cumbersome in many
ways,[14] whereas the present method is atom-economic,
with threefold arylations effected by nontoxic BiAr3 under
straightforward coupling conditions. Most importantly, the
coupling products obtained are highly sought-after as im-
portant building blocks for the synthesis of a variety of
compounds that are useful in medicinal applications,[15] for
hypoglycemic[15a] activity studies, human rennin inhibi-
tion[15b] studies, and HIV-1 protease inhibition[15c] studies.
These products are also useful precursors for various other
synthetic transformations.[16]
Coupling of 2-(Acetoxymethyl)acrylates with BiAr3 Reagents; Typi-
cal Procedure: The above representative procedure given for the
couplings of 2-(bromomethyl)acrylates was also followed for the
coupling reactions of 2-(acetoxymethyl)acrylates with the following
reaction conditions; BiPh3 (0.25 mmol, 110 mg, 1.0 equiv.), methyl
2-(acetoxymethyl)acrylate (1 mmol, 158.0 mg, 4.0 equiv.), K3PO4
(0.50 mmol, 106.1 mg, 2.0 equiv.), [PdCl2(PPh3)2] (0.0225 mmol,
15.8 mg, 0.09 equiv.) and DMF (3 mL), 60 °C, 2 h.
Methyl 2-Benzylacrylate (1a):[14g,17] Colorless liquid (0.12 g, 91%).
1H NMR (500 MHz, CDCl3): δ = 7.18–7.30 (m, 5 H, PhH), 6.22
(br. s, 1 H, C=CH2), 5.45 (br. s, 1 H, C=CH2), 3.73 (s, 3 H, OCH3),
3.62 (s, 2 H, CH2) ppm. 13C NMR (125 MHz, CDCl3): δ = 167.3,
140.0, 138.6, 129.0, 128.4, 126.3, 126.2, 51.8, 38.0 ppm. IR (film):
ν = 1722, 1631, 1438, 1255, 1203, 1137, 948, 701 cm–1. HRMS
˜
(ESI): calcd. for C11H12O2 [M + H]+ 177.0916; found 177.0916.
Conclusions
Methyl 2-(4-Methylbenzyl)acrylate (2a):[17] Colorless liquid
We have demonstrated novel cross-coupling reactions of
various alkyl 2-(bromomethyl)acrylates, alkyl 2-(acetoxy- (0.121 g, 85%). H NMR (500 MHz, CDCl3): δ = 7.07–7.09 (m, 4
1
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H, ArH), 6.21 (br. s, 1 H, C=CH2), 5.45 (br. s, 1 H, C=CH2), 3.73
H, C=CH2), 3.98 (q, J = 6.9 Hz, 2 H, OCH2CH3), 3.71 (s, 3 H,
(s, 3 H, OCH3), 3.59 (s, 2 H, CH2), 2.31 (s, 3 H, CH3) ppm. 13C OCH3), 3.54 (s,
2
H, CH2), 1.38 (t, J = 6.9 Hz, 3 H,
NMR (125 MHz, CDCl3): δ = 167.4, 140.2, 135.8, 135.5, 129.0,
128.8, 126.0, 51.8, 37.5, 21.0 ppm. IR (film): ν = 1722, 1631, 1437,
OCH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 167.4, 157.4,
140.4, 130.5, 129.9, 125.9, 114.3, 63.3, 51.8, 37.1, 14.8 ppm. IR
˜
1280, 1254, 1202, 1137, 947, 808 cm–1. HRMS (ESI): calcd. for (film): ν = 1722, 1632, 1511, 1246, 1136, 1048, 776 cm–1. HRMS
˜
C12H14O2 [M + H]+ 191.1072; found 191.1078.
(ESI): calcd. for C13H16NaO3 [M + Na]+ 243.0997; found 243.0997.
Methyl 2-(3-Methoxybenzyl)acrylate (10a): Colorless liquid
(0.145 g, 94%). H NMR (500 MHz, CDCl3): δ = 7.18–7.24 (m, 1
Methyl 2-(4-Methoxybenzyl)acrylate (3a): Colorless liquid (0.133 g,
86%). H NMR (500 MHz, CDCl3): δ = 7.10 (d, J = 8.6 Hz, 2 H,
1
1
H, ArH), 6.74–6.78 (m, 3 H, ArH), 6.22 (br. s, 1 H, C=CH2), 5.47
(br. s, 1 H, C=CH2), 3.77 (s, 3 H, OCH3), 3.72 (s, 3 H, OCH3),
3.59 (s, 2 H, CH2) ppm. 13C NMR (125 MHz, CDCl3): δ = 167.3,
159.6, 140.2, 139.8, 129.3, 126.4, 121.4, 114.7, 111.6, 55.1, 51.9,
ArH), 6.82 (d, J = 8.9 Hz, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2),
5.43 (br. s, 1 H, C=CH2), 3.77 (s, 3 H, OCH3), 3.72 (s, 3 H, OCH3),
3.56 (s, 2 H, CH2) ppm. 13C NMR (125 MHz, CDCl3): δ = 167.5,
158.1, 140.5, 130.7, 130.1, 126.1, 113.9, 55.3, 52.0, 37.2 ppm. IR
38.0 ppm. IR (film): ν = 1722, 1631, 1437, 1258, 1203, 1136, 1050,
˜
(film): ν = 1722, 1631, 1437, 1258, 1203, 1136, 1050, 950, 785,
˜
817, 785, 754, 700 cm–1. HRMS (ESI): calcd. for C12H14NaO3 [M
+ Na]+ 229.0841; found 229.0841.
700 cm–1. HRMS (ESI): calcd. for C12H14NaO3 [M + Na]+
229.0841; found 229.0844.
Methyl 2-(4-sec-Butoxybenzyl)acrylate (11a): Colorless liquid
(0.146 g, 78%). H NMR (500 MHz, CDCl3): δ = 7.06–7.08 (m, 2
Methyl 2-(4-Fluorobenzyl)acrylate (4a): Colorless liquid (0.131 g,
90%). H NMR (500 MHz, CDCl3): δ = 7.13–7.15 (m, 2 H, ArH),
1
1
H, ArH), 6.80–6.81 (m, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2), 5.44
(br. s, 1 H, C=CH2), 4.21–4.27 (m, 1 H, OCH), 3.72 (s, 3 H, OCH3),
3.55 (s, 2 H, CH2), 1.68–1.76 (m, 1 H, CH), 1.55–1.63 (m, 1 H,
CH), 1.27 (d, J = 6.3 Hz, 3 H, CH3), 0.96 (t, J = 7.4 Hz, 3 H,
CH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 167.4, 156.7, 140.4,
130.3, 129.9, 125.9, 115.8, 75.0, 51.8, 37.1, 29.1, 19.2, 9.8 ppm. IR
6.94–6.98 (m, 2 H, ArH), 6.21 (br. s, 1 H, C=CH2), 5.45 (br. s, 1
H, C=CH2), 3.72 (s, 3 H, OCH3), 3.58 (s, 2 H, CH2) ppm. 13C
NMR (125 MHz, CDCl3): δ = 167.2, 161.5 (d, J = 243.2 Hz), 139.9,
134.2, 130.4 (d, J = 7.1 Hz), 126.3, 115.2 (d, J = 21.4 Hz), 51.9,
37.2 ppm. IR (film): ν = 1722, 1632, 1509, 1222, 1137, 841,
˜
818 cm–1. HRMS (ESI): calcd. for C11H11FO2 [M + H]+ 195.0821;
found 195.0826.
(film): ν = 1721, 1615, 1508, 1241, 1133, 816 cm–1. HRMS (ESI):
˜
calcd. for C15H20O3 [M + H]+ 249.1491; found 249.1494.
Methyl 2-(4-Chlorobenzyl)acrylate (5a):[17] Colorless liquid
Methyl 2-(Thiophen-2-ylmethyl)acrylate (12a): Brown liquid
1
(0.136 g, 86%). H NMR (500 MHz, CDCl3): δ = 7.24–7.25 (m, 2
1
(0.101 g, 74%). H NMR (500 MHz, CDCl3): δ = 7.14–7.15 (m, 1
H, ArH), 7.11–7.13 (m, 2 H, ArH), 6.22 (br. s, 1 H, C=CH2), 5.47
(br. s, 1 H, C=CH2), 3.72 (s, 3 H, OCH3), 3.58 (s, 2 H, CH2) ppm.
13C NMR (125 MHz, CDCl3): δ = 167.1, 139.5, 137.1, 132.1, 130.3,
H, ArH), 6.91–6.93 (m, 1 H, ArH), 6.82–6.83 (m, 1 H, ArH), 6.25
(br. s, 1 H, C=CH2), 5.59 (br. s, 1 H, C=CH2), 3.82 (s, 2 H, CH2),
3.75 (s, 3 H, CH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 166.9,
141.0, 139.4, 126.8, 126.4, 125.7, 124.0, 51.9, 32.0 ppm. IR (film):
128.5, 126.5, 51.9, 37.4 ppm. IR (film): ν = 1722, 1631, 1491, 1437,
˜
1203, 1137, 1090, 1016, 800 cm–1. HRMS (ESI): calcd. for
C11H11ClNaO2 [M + Na]+ 233.0345; found 233.0346.
ν = 1722, 1632, 1438, 1203, 1151, 696 cm–1. HRMS (ESI): calcd.
˜
for C9H10O2S [M + H]+ 183.0480; found 183.0487.
Methyl 2-(3-Chlorobenzyl)acrylate (6a): Colorless liquid (0.138 g,
Methyl 2-(3-Fluorobenzyl)acrylate (13a): Colorless oil (0.0941 g,
61%). 1H NMR (500 MHz, CDCl3): δ = 7.22–7.27 (m, 1 H, ArH),
6.89–6.98 (m, 3 H, ArH), 6.26 (br. s, 1 H, C=CH2), 5.50–5.51 (m,
1 H, C=CH2), 3.75 (s, 3 H, OCH3), 3.62 (s, 2 H, CH2) ppm. 13C
NMR (125 MHz, CDCl3): δ = 167.1, 162.8 (d, J = 244.4 Hz), 141.2
(d, J = 7.1 Hz), 139.3, 129.8 (d, J = 8.3 Hz), 126.7, 124.6, 115.8 (d,
1
87%). H NMR (500 MHz, CDCl3): δ = 7.07–7.25 (m, 4 H, ArH),
6.25 (br. s, 1 H, C=CH2), 5.49 (br. s, 1 H, C=CH2), 3.72 (s, 3 H,
OCH3), 3.59 (s, 2 H, CH2) ppm. 13C NMR (125 MHz, CDCl3): δ
= 167.0, 140.7, 139.3, 134.1, 129.6, 129.0, 127.1, 126.7, 126.5, 51.9,
37.7 ppm. IR (film): ν = 1722, 1631, 1436, 1202, 1139, 1078, 951,
˜
725 cm–1. HRMS (ESI): calcd. for C11H11ClO2 [M + H]+ 211.0526;
found 211.0529.
J = 20.2 Hz), 113.2 (d, J = 21.4 Hz), 51.9, 37.8 ppm. IR (film): ν
˜
= 1722, 1616, 1590, 1487, 1445, 1250, 1144, 954 cm–1. HRMS
(ESI): calcd. for C11H11FO2 [M + H]+ 195.0821; found 195.0828.
Methyl 2-(4-Isopropoxybenzyl)acrylate (7a): Colorless liquid
1
(0.147 g, 83%). H NMR (500 MHz, CDCl3): δ = 7.06–7.08 (m, 2
Methyl 2-(3-Methylbenzyl)acrylate (14a): Colorless liquid (0.113 g,
79%). 1H NMR (500 MHz, CDCl3): δ = 7.17–7.20 (m, 1 H, ArH),
6.99–7.03 (m, 3 H, ArH), 6.23 (br. s, 1 H, C=CH2), 5.46–5.47 (m,
1 H, C=CH2), 3.73 (s, 3 H, OCH3), 3.59 (s, 2 H, CH2), 2.32 (s, 3
H, CH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 167.4, 140.1,
138.5, 137.9, 129.7, 128.2, 127.0, 126.2, 126.0, 51.8, 37.9, 21.3 ppm.
H, ArH), 6.79–6.81 (m, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2), 5.43
(br. s, 1 H, C=CH2), 4.46–4.53 (m, 1 H, OCH), 3.72 (s, 3 H, OCH3),
3.54 (s, 2 H, CH2), 1.31 [d, J = 6.1 Hz, 6 H, C(CH3)2] ppm. 13C
NMR (125 MHz, CDCl3): δ = 167.4, 156.4, 140.4, 130.4, 129.9,
125.8, 115.8, 69.8, 51.8, 37.1, 22.0 ppm. IR (film): ν = 1722, 1630,
˜
1509, 1242, 1136, 953 cm–1. HRMS (ESI): calcd. for C14H18O3 [M
+ H]+ 235.1334; found 235.1339.
IR (film): ν = 1722, 1631, 1437, 1201, 1135, 948 cm–1. HRMS
˜
(ESI): calcd. for C12H14NaO2 [M + Na]+ 213.0891; found 213.0892.
Methyl 2-(4-Isobutoxybenzyl)acrylate (8a): Colorless liquid
(0.153 g, 82%). H NMR (500 MHz, CDCl3): δ = 7.07–7.09 (m, 2
Methyl 2-[4-(Allyloxy)benzyl]acrylate (15a): Colorless oil (0.135 g,
77%). H NMR (500 MHz, CDCl3): δ = 7.09 (d, J = 8.5 Hz, 2 H,
1
1
H, ArH), 6.80–6.83 (m, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2), 5.43
(br. s, 1 H, C=CH2), 3.66–3.72 [m, 5 H, OCH3 and OCH2], 3.55
(s, 2 H, CH2), 2.02–2.09 (m, 1 H, OCH), 1.00 [d, J = 6.5 Hz, 6 H,
C(CH3)2] ppm. 13C NMR (125 MHz, CDCl3): δ = 167.4, 157.8,
140.5, 130.3, 129.9, 125.8, 114.4, 74.4, 51.8, 37.1, 28.2, 19.2 ppm.
ArH), 6.84 (d, J = 8.8 Hz, 2 H, ArH), 6.20 (br. s, 1 H, C=CH2),
6.01–6.08 (m, 1 H, C=CH2), 5.38–5.44 (m, 2 H), 5.26–5.29 (m, 1
H), 4.50–4.52 (m, 2 H), 3.73 (s, 3 H, OCH3), 3.56 (s, 2 H,
CH2) ppm. 13C NMR (125 MHz, CDCl3): δ = 167.4, 157.1, 140.4,
133.3, 130.8, 129.9, 125.9, 117.5, 114.6, 68.8, 51.8, 37.1 ppm. IR
IR (film): ν = 1723, 1631, 1512, 1245, 1135, 1035, 817 cm–1. HRMS
(film): ν = 1721, 1630, 1510, 1243, 1136, 1024, 997, 839 cm–1.
˜
˜
(ESI): calcd. for C15H20NaO3 [M + Na]+ 271.1310; found 271.1314.
HRMS (ESI): calcd. for C14H16NaO3 [M + Na]+ 255.0997; found
255.0998.
Methyl 2-(4-Ethoxybenzyl)acrylate (9a): Colorless liquid (0.138 g,
83%). H NMR (500 MHz, CDCl3): δ = 7.06–7.08 (m, 2 H, ArH),
Ethyl 2-Benzylacrylate (16a):[18,14i] Colorless liquid (0.102 g, 71%).
1
6.79–6.81 (m, 2 H, ArH), 6.18 (br. s, 1 H, C=CH2), 5.41 (br. s, 1
1H NMR (500 MHz, CDCl3): δ = 7.18–7.30 (m, 5 H, ArH), 6.22
6
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20543
/KAP1
Date: 05-07-12 16:22:42
Pages: 11
Arylation of Baylis–Hillman Bromides and Acetates
(br. s, 1 H, C=CH2), 5.44 (br. s, 1 H, C=CH2), 4.18 (q, J = 7.0 Hz,
695 cm–1. HRMS (ESI): calcd. for C10H12O2S [M + H]+ 197.0636;
2 H, OCH2CH3), 3.62 (s, 2 H, CH2), 1.25 (t, J = 7.2 Hz, 3 H, found 197.0637.
OCH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 166.9, 140.3,
Ethyl 2-(4-Isobutoxybenzyl)acrylate (23a): Colorless oil (0.163 g,
83%). H NMR (500 MHz, CDCl3): δ = 7.09 (d, J = 8.2 Hz, 2 H,
138.7, 129.0, 128.3, 126.2, 125.9, 60.7, 38.0, 14.1 ppm. IR (film): ν
˜
1
= 1717, 1631, 1201, 1134, 1026, 747, 701 cm–1. HRMS (EI): calcd.
for C12H14O2 [M – H]+ 189.0916; found 189.0917.
ArH), 6.82 (d, J = 8.5 Hz, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2),
5.42 (br. s, 1 H, C=CH2), 4.17 (q, J = 7.2 Hz, 2 H, OCH2CH3),
3.68 [d, J = 6.4 Hz, 2 H, OCH2CH(CH3)2], 3.55 (s, 2 H, CH2),
2.01–2.11 [m, 1 H, OCH2CH(CH3)3], 1.26 (t, J = 7.0 Hz, 3 H,
OCH2CH3), 1.01 [d, J = 6.7 Hz, 6 H, C(CH3)2] ppm. 13C NMR
Ethyl 2-(4-Methylbenzyl)acrylate (17a): Colorless liquid (0.115 g,
75%). 1H NMR (500 MHz, CDCl3): δ = 7.06–7.08 (m, 4 H, ArH),
6.20 (br. s, 1 H, C=CH2), 5.43 (br. s, 1 H, C=CH2), 4.17 (q, J =
7.2 Hz, 2 H, OCH2CH3), 3.58 (s, 2 H, CH2), 2.31 (s, 3 H, CH3), (125 MHz, CDCl3): δ = 167.0, 157.7, 140.8, 130.5, 129.9, 125.5,
1.26 (t, J = 7.0 Hz, 3 H, OCH2CH3) ppm. 13C NMR (125 MHz, 114.4, 74.4, 60.6, 37.2, 28.2, 19.2, 14.1 ppm. IR (film): ν = 1718,
˜
CDCl3): δ = 166.9, 140.5, 135.7, 135.6, 129.0, 128.9, 125.7, 60.6,
1512, 1245, 1134, 1034, 785 cm–1. HRMS (ESI): calcd. for
37.6, 21.0, 14.1 ppm. IR (film): ν = 1718, 1632, 1514, 1278, 1195, C16H22O3 [M + H]+ 263.1647; found 263.1649.
˜
1134, 947, 806, 764 cm–1. HRMS (ESI): calcd. for C13H16NaO2 [M
Ethyl 2-(3-Methylbenzyl)acrylate (24a): Colorless oil (0.116 g,
+ Na]+ 227.1048; found 227.1048.
75%). 1H NMR (500 MHz, CDCl3): δ = 7.16–7.19 (m, 1 H, ArH),
6.99–7.03 (m, 3 H, ArH), 6.22 (br. s, 1 H, C=CH2), 5.45 (br. s, 1
H, C=CH2), 4.17 (q, J = 7.1 Hz, 2 H, OCH2CH3), 3.59 (s, 2 H,
Ethyl 2-(4-Methoxybenzyl)acrylate (18a):[16b,19] Colorless liquid
1
(0.135 g, 82%). H NMR (500 MHz, CDCl3): δ = 7.09–7.11 (m, 2
H, ArH), 6.81–6.83 (m, 2 H, ArH), 6.18 (br. s, 1 H, C=CH2), 5.41 CH2), 2.32 (s, 3 H, CH3), 1.27 (t, J = 7.0 Hz, 3 H, OCH2CH3) ppm.
(br. s, 1 H, C=CH2), 4.17 (q, J = 7.0 Hz, 2 H, OCH2CH3), 3.77 (s,
13C NMR (125 MHz, CDCl3): δ = 166.9, 140.4, 138.6, 137.9, 129.8,
3 H, OCH3), 3.55 (s, 2 H, CH2), 1.25 (t, J = 7.0 Hz, 3 H, 128.2, 127.0, 126.0, 125.9, 60.6, 37.9, 21.3, 14.1 ppm. IR (film): ν
˜
OCH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 166.9, 158.0,
= 1718, 1632, 1246, 1194, 1133, 752 cm–1. HRMS (ESI): calcd. for
C13H16NaO2 [M + Na]+ 227.1048; found 227.1045.
140.7, 130.7, 130.0, 125.6, 113.7, 60.6, 55.2, 37.1, 14.1 ppm. IR
(film): ν = 1716, 1615, 1258, 1197, 1134, 949, 783 cm–1. HRMS
˜
Ethyl 2-(4-Ethoxybenzyl)acrylate (25a): Brown oil (0.142 g, 81%).
1H NMR (500 MHz, CDCl3): δ = 7.09 (d, J = 8.8 Hz, 2 H, ArH),
6.82 (d, J = 8.5 Hz, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2), 5.42 (br.
s, 1 H, C=CH2), 4.17 (q, J = 7.1 Hz, 2 H, OCH2CH3), 4.01 (q, J
= 7.0 Hz, 2 H, OCH2CH3), 3.56 (s, 2 H, CH2), 1.40 (t, J = 7.0 Hz,
3 H, OCH2CH3), 1.26 (t, J = 7.2 Hz, 3 H, OCH2CH3) ppm. 13C
NMR (125 MHz, CDCl3): δ = 167.0, 157.4, 140.7, 130.6, 130.0,
(ESI): calcd. for C13H16NaO3 [M + Na]+ 243.0997; found 243.0992.
Ethyl 2-(4-Fluorobenzyl)acrylate (19a): Colorless liquid (0.125 g,
80%). 1H NMR (500 MHz, CDCl3): δ = 7.12–7.15 (m, 2 H, ArH),
6.94–6.97 (m, 2 H, ArH), 6.21 (br. s, 1 H, C=CH2), 5.44 (br. s, 1
H, C=CH2), 4.16 (q, J = 7.2 Hz, 2 H, OCH2CH3), 3.58 (s, 2 H,
CH2), 1.24 (t, J = 7.2 Hz, 3 H, OCH2CH3) ppm. 13C NMR
(125 MHz, CDCl3): δ = 166.7, 161.5 (d, J = 242.0 Hz), 140.2, 134.4,
130.4 (d, J = 8.3 Hz), 125.9, 115.1 (d, J = 21.4 Hz), 60.7, 37.3,
125.5, 114.3, 63.3, 60.6, 37.1, 14.8, 14.1 ppm. IR (film): ν = 1717,
˜
1631, 1612, 1511, 1246, 1116, 1028 cm–1. HRMS (ESI): calcd. for
C14H18O3 [M + H]+ 235.1334; found 235.1338.
14.1 ppm. IR (film): ν = 1716, 1632, 1510, 1223, 1136, 951 cm–1.
˜
HRMS (ESI): [M – H]+ calcd. for C12H13FO2 207.0822; found
207.0826.
1
n-Butyl 2-Benzylacrylate (26a): Colorless liquid (0.144 g, 88%). H
NMR (500 MHz, CDCl3): δ = 7.18–7.29 (m, 5 H, ArH), 6.22 (br.
s, 1 H, C=CH2), 5.44 (br. s, 1 H, C=CH2), 4.11 (t, J = 6.5 Hz, 2
Ethyl 2-(3-Methoxybenzyl)acrylate (20a): Colorless liquid (0.135 g,
1
82%). H NMR (500 MHz, CDCl3): δ = 7.18–7.21 (m, 1 H, ArH), H, OCH2CH2CH2CH3), 3.62 (s, 2 H, CH2), 1.57–1.63 (m, 2 H,
6.74–6.79 (m, 3 H, ArH), 6.22 (br. s, 1 H, C=CH2), 5.46 (br. s, 1
H, C=CH2), 4.18 (q, J = 7.0 Hz, 2 H, OCH2CH3), 3.78 (s, 3 H,
OCH2CH2CH2CH3), 1.31–1.35 (m, 2 H, OCH2CH2CH2CH3), 0.90
(t, 7.3 Hz,
H, OCH2CH2CH2CH3) ppm. 13C NMR
(125 MHz, CDCl3): δ = 167.1, 140.4, 138.8, 129.1, 128.4, 126.3,
J
=
3
OCH3), 3.59 (s,
2 H, CH2), 1.26 (t, J = 7.2 Hz, 3 H,
OCH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 166.8, 159.6,
126.1, 64.7, 38.1, 30.6, 19.2, 13.8 ppm. IR (film): ν = 1718, 1632,
˜
140.3, 140.1, 129.3, 126.0, 121.4, 114.7, 111.6, 60.7, 55.1, 38.0,
1195, 1135, 945, 701 cm–1. HRMS (ESI): calcd. for C14H18NaO2
[M + Na]+ 241.1204; found 241.1200.
14.1 ppm. IR (film): ν = 1716, 1630, 1601, 1455, 1258, 1148, 1049,
˜
784, 754, 699 cm–1. HRMS (ESI): calcd. for C13H16NaO3
[M + Na]+ 243.0997; found 243.0995.
n-Butyl 2-(4-Methylbenzyl)acrylate (27a):[20] Colorless liquid
1
(0.149 g, 85%). H NMR (500 MHz, CDCl3): δ = 7.06–7.10 (m, 4
Ethyl 2-(4-Isopropoxybenzyl)acrylate (21a): Colorless liquid
(0.158 g, 85%). H NMR (500 MHz, CDCl3): δ = 7.07–7.08 (m, 2
H, ArH), 6.20 (br. s, 1 H, C=CH2), 5.43 (br. s, 1 H, C=CH2), 4.11
(t, J = 6.7 Hz, 2 H, OCH2CH2CH2CH3), 3.58 (s, 2 H, CH2), 2.31
1
H, ArH), 6.79–6.81 (m, 2 H, ArH), 6.18 (br. s, 1 H, C=CH2), 5.42 (s, 3 H, CH3), 1.56–1.63 (m, 2 H, OCH2CH2CH2CH3), 1.31–1.36
(br. s, 1 H, C=CH2), 4.47–4.52 (m, 1 H, OCH), 4.17 (q, J = 7.1 Hz, (m, H, OCH2CH2CH2CH3), 0.90 (t, 7.4 Hz, H,
2 H, OCH2CH3), 3.54 (s, 2 H, CH2), 1.31 [d, J = 6.0 Hz, 6 H,
OCH2CH2CH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ =
C(CH3)2], 1.22–1.27 (m,
H, OCH2CH3) ppm. 13C NMR 167.1, 140.6, 135.8, 135.7, 129.1, 128.9, 125.9, 64.7, 37.7, 30.7, 21.1,
2
J
=
3
3
(125 MHz, CDCl3): δ = 167.0, 156.3, 140.7, 130.5, 130.0, 125.5, 19.2, 13.8 ppm. IR (film): ν = 1718, 1633, 1514, 1191, 1135, 947,
˜
115.7, 69.8, 60.6, 37.1, 22.0, 14.1 ppm. IR (film): ν = 1717, 1630, 815 cm–1. HRMS (ESI): calcd. for C15H20O2 [M + H]+ 233.1542;
˜
1611, 1509, 1243, 1135, 955, 861, 844, 816 cm–1. HRMS (ESI):
calcd. for C15H20O3 [M + H]+ 249.1491; found 249.1498.
found 233.1545.
n-Butyl 2-(4-Methoxybenzyl)acrylate (28a): Colorless liquid
1
Ethyl 2-(Thiophen-2-ylmethyl)acrylate (22a): Brown liquid (0.111 g,
75%). 1H NMR (500 MHz, CDCl3): δ = 7.13–7.14 (m, 1 H, ArH),
6.82–6.93 (m, 2 H, ArH), 6.24 (br. s, 1 H, C=CH2), 5.57 (br. s, 1
H, C=CH2), 4.20 (q, J = 7.1 Hz, 2 H, OCH2CH3), 3.82 (s, 2 H,
CH2), 1.28 (t, J = 7.1 Hz, 3 H, OCH2CH3) ppm. 13C NMR
(125 MHz, CDCl3): δ = 166.5, 141.1, 139.7, 126.8, 126.1, 125.7, (t,
(0.149 g, 80%). H NMR (500 MHz, CDCl3): δ = 7.09–7.11 (m, 2
H, ArH), 6.81–6.83 (m, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2), 5.41
(br. s, 1 H, C=CH2), 4.11 (t, J = 6.7 Hz, 2 H, OCH2CH2CH2CH3),
3.77 (s, 3 H, OCH3), 3.55 (s, 2 H, CH2), 1.57–1.63 (m, 2 H,
OCH2CH2CH2CH3), 1.32–1.36 (m, 2 H, OCH2CH2CH2CH3), 0.91
J
=
7.4 Hz,
3
H, OCH2CH2CH2CH3) ppm. 13C NMR
124.0, 60.8, 32.0, 14.1 ppm. IR (film): ν = 1718, 1633, 1199, 1157,
(125 MHz, CDCl3): δ = 167.1, 158.1, 140.8, 130.8, 130.0, 125.8,
˜
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7

Job/Unit: O20543
/KAP1
Date: 05-07-12 16:22:42
Pages: 11
M. L. N. Rao, S. Giri
FULL PAPER
113.8, 64.7, 55.3, 37.3, 30.7, 19.2, 13.8 ppm. IR (film): ν = 1717,
n-Butyl 2-(4-Chlorobenzyl)acrylate (34a): Colorless oil (0.116 g,
61%). 1H NMR (500 MHz, CDCl3): δ = 7.23–7.25 (m, 2 H, ArH),
7.12 (d, J = 8.2 Hz, 2 H, ArH), 6.22 (br. s, 1 H, C=CH2), 5.46 (br.
˜
1631, 1512, 1248, 1133, 1036, 948, 817 cm–1. HRMS (ESI): calcd.
for C15H20O3 [M + H]+ 249.1491; found 249.1491.
s,
1 H, C=CH2), 4.09–4.13 (m, 2 H, OCH2CH2CH2CH3),
n-Butyl 2-(4-Isopropoxybenzyl)acrylate (29a): Colorless liquid
(0.167 g, 81%). 1H NMR (500 MHz, CDCl3): δ = 7.07 (d, J =
8.4 Hz, 2 H, ArH), 6.80 (d, J = 8.7 Hz, 2 H, ArH), 6.19 (br. s, 1
H, C=CH2), 5.42 (br. s, 1 H, C=CH2), 4.47–4.52 (m, 1 H, OCH),
4.11 (t, J = 6.7 Hz, 2 H, OCH2CH2CH2CH3), 3.54 (s, 2 H, CH2),
1.55–1.63 (m, 2 H, OCH2CH2CH2CH3), 1.30–1.36 {m, 8 H,
3.58 (s, 2 H, CH2), 1.56–1.66 (m, 2 H, OCH2CH2CH2CH3),
1.24–1.35 (m, 2 H, OCH2CH2CH2CH3), 0.89–0.92 (m, 3 H,
OCH2CH2CH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ =
166.7, 139.8, 137.2, 132.0, 130.2, 128.4, 126.2, 64.7, 37.5, 30.5, 19.1,
13.6 ppm. IR (film): ν = 1717, 1632, 1491, 1250, 1195, 815 cm–1.
˜
HRMS (ESI): calcd. for C14H17ClO2 [M + H]+ 253.0995; found
253.0993.
[OCH2CH2CH2CH3,
C(CH3)2]},
0.89–0.92
(m,
3
H,
OCH2CH2CH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ =
n-Butyl 2-(4-Fluorobenzyl)acrylate (35a): Colorless oil (0.113 g,
64%). 1H NMR (500 MHz, CDCl3): δ = 7.13–7.16 (m, 2 H, ArH),
6.95–6.98 (m, 2 H, ArH), 6.22 (br. s, 1 H, C=CH2), 5.45 (br. s, 1
H, C=CH2), 4.12 (t, J = 6.7 Hz, 2 H, OCH2CH2CH2CH3), 3.59 (s,
2 H, CH2), 1.57–1.63 (m, 2 H, OCH2CH2CH2CH3), 1.30–1.37 (m,
167.1, 156.3, 140.7, 130.6, 129.9, 125.6, 115.8, 69.8, 64.5, 37.2, 30.6,
22.0, 19.1, 13.6 ppm. IR (film): ν = 1718, 1631, 1509, 1243, 1135,
˜
955, 843 cm–1. HRMS (ESI): calcd. for C17H24O3 [M + H]+
277.1804; found 277.1800.
n-Butyl 2-(4-sec-Butoxybenzyl)acrylate (30a): Colorless liquid
2
H, OCH2CH2CH2CH3), 0.91 (t,
J
=
7.3 Hz,
3
H,
1
(0.198 g, 91%). H NMR (500 MHz, CDCl3): δ = 7.06–7.08 (m, 2
OCH2CH2CH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ =
166.8, 161.5 (d, J = 242.0 Hz), 140.2, 134.3, 130.3 (d, J = 8.3 Hz),
126.0, 115.1 (d, J = 20.2 Hz), 64.6, 37.3, 30.5, 19.1, 13.6 ppm. IR
H, ArH), 6.79–6.81 (m, 2 H, ArH), 6.18 (br. s, 1 H, C=CH2), 5.42
(br. s, 1 H, C=CH2), 4.21–4.26 (m, 1 H, OCH), 4.11 (t, J = 6.5 Hz,
2 H, OCH2CH2CH2CH3), 3.54 (s, 2 H, CH2), 1.55–1.76 [m, 5 H,
(CH2, CH3)], 1.26–1.41 [m, 4 H, (CH2, CH2)], 0.89–0.98 [m, 6 H,
(CH3, CH3)] ppm. 13C NMR (125 MHz, CDCl3): δ = 167.1, 156.7,
140.7, 130.5, 129.9, 125.6, 115.8, 75.0, 64.5, 37.2, 30.6, 29.1, 19.2,
(film): ν = 1718, 1632, 1510, 1222, 1136, 776 cm–1. HRMS (ESI):
˜
calcd. for C14H17FO2 [M + H]+ 237.1291; found 237.1299.
n-Butyl 2-(3-Methylbenzyl)acrylate (36a): Colorless oil (0.146 g,
84%). 1H NMR (500 MHz, CDCl3): δ = 7.16–7.19 (m, 1 H, ArH),
6.98–7.02 (m, 3 H, ArH), 6.22 (br. s, 1 H, C=CH2), 5.45 (br. s, 1
H, C=CH2), 4.12 (t, J = 6.5 Hz, 2 H, OCH2CH2CH2CH3), 3.59 (s,
19.1, 13.6, 9.8 ppm. IR (film): ν = 1718, 1631, 1509, 1243, 1132,
˜
947, 817 cm–1. HRMS (ESI): calcd. for C18H26O3 [M + H]+
291.1960; found 291.1963.
2
H, CH2), 2.32 (s,
OCH2CH2CH2CH3), 1.31–1.38 (m, 2 H, OCH2CH2CH2CH3),
0.89–0.96 (m,
H, OCH2CH2CH2CH3) ppm. 13C NMR
3 H, CH3), 1.58–1.64 (m, 2 H,
n-Butyl 2-(4-Isobutoxybenzyl)acrylate (31a): Brown oil (0.171 g,
1
78%). H NMR (500 MHz, CDCl3): δ = 7.09 (d, J = 8.5 Hz, 2 H,
3
ArH), 6.82 (d, J = 8.5 Hz, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2),
(125 MHz, CDCl3): δ = 167.0, 140.3, 138.6, 137.9, 129.7, 128.2,
5.42 (br. s,
1 H, C=CH2), 4.12 (t, J = 6.5 Hz, 2 H,
127.2, 126.9, 125.9, 64.6, 37.9, 30.5, 21.3, 19.1, 13.6 ppm. IR (film):
ν = 1719, 1632, 1462, 1193, 1135, 948 cm–1. HRMS (ESI): calcd.
OCH2CH2CH2CH3), 3.68 [d, J = 6.7 Hz, 2 H, OCH2C(CH3)2], 3.56
(s, 2 H, CH2), 2.03–2.09 (m, 1 H, CH), 1.59–1.64 (m, 2 H,
OCH2CH2CH2CH3), 1.31–1.39 (m, 2 H, OCH2CH2CH2CH3), 1.01
[d, J = 6.7 Hz, 6 H, C(CH3)2], 0.91 (t, J = 7.4 Hz, 3 H,
OCH2CH2CH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ =
167.0, 157.7, 140.7, 130.5, 129.9, 125.6, 114.4, 64.5, 37.2, 30.6, 28.2,
˜
for C15H20O2 [M + H]+ 233.1542; found 233.1545.
Benzyl 2-Benzylacrylate (37a): Brown liquid (0.158 g, 83%). 1H
NMR (500 MHz, CDCl3): δ = 7.18–7.35 (m, 10 H, ArH), 6.29 (br.
s, 1 H, C=CH2), 5.48–5.49 (m, 1 H, C=CH2), 5.16 (s, 2 H, OCH2),
3.65 (s, 2 H, CH2) ppm. 13C NMR (125 MHz, CDCl3): δ = 166.6,
139.9, 138.5, 135.8, 129.0, 128.5, 128.4, 128.1, 128.0, 126.6, 126.3,
19.2, 19.1, 13.7 ppm. IR (film): ν = 1718, 1631, 1512, 1245, 1006,
˜
817 cm–1. HRMS (ESI): calcd. for C18H26O3 [M + H]+ 291.1960;
found 291.1964.
66.4, 38.0 ppm. IR (film): ν = 1718, 1631, 1495, 1453, 1248, 1193,
˜
949, 746, 699 cm–1. HRMS (EI): calcd. for C17H16O2 [M]+
252.1150; found 252.1151.
n-Butyl 2-(Thiophen-2-ylmethyl)acrylate (32a): Brown liquid
1
(0.141 g, 84%). H NMR (500 MHz, CDCl3): δ = 7.13–7.14 (m, 1
Benzyl 2-(4-Methylbenzyl)acrylate (38a): Brown liquid (0.162 g,
81%). 1H NMR (500 MHz, CDCl3): δ = 7.25–7.34 (m, 5 H, ArH),
7.06–7.10 (m, 4 H, ArH), 6.27 (br. s, 1 H, C=CH2), 5.48–5.49 (m,
1 H, C=CH2), 5.17 (s, 2 H, OCH2), 3.61 (s, 2 H, CH2), 2.32 (s, 3
H, CH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 166.7, 140.1,
135.9, 135.8, 135.5, 129.0, 128.9, 128.4, 128.1, 128.0, 126.4, 66.4,
H, ArH), 6.91–6.92 (m, 1 H, ArH), 6.81–6.82 (m, 1 H, ArH), 6.24
(br. s, 1 H, C=CH2), 5.57 (br. s, 1 H, C=CH2), 4.13–4.17 (m, 2
H, OCH2CH2CH2CH3), 3.81 (s, 2 H, CH2), 1.59–1.69 (m, 2 H,
OCH2CH2CH2CH3), 1.33–1.43 (m, 2 H, OCH2CH2CH2CH3),
0.90–0.96 (m,
3
H, OCH2CH2CH2CH3) ppm. 13C NMR
(125 MHz, CDCl3): δ = 166.6, 141.1, 139.6, 126.8, 126.1, 125.6,
37.6, 21.0 ppm. IR (film): ν = 1718, 1631, 1189, 1130, 1025,
˜
123.9, 64.7, 32.1, 30.5, 19.1, 13.6 ppm. IR (film): ν = 1719, 1632,
˜
697 cm–1. HRMS (EI): calcd. for C18H18O2 [M]+ 266.1307; found
266.1307.
1198, 1156, 949, 850, 694 cm–1. HRMS (ESI): calcd. for C12H16O2S
[M + H]+ 225.0949; found 225.0947.
Benzyl 2-(4-Methoxybenzyl)acrylate (39a): Brown liquid (0.145 g,
68%). 1H NMR (500 MHz, CDCl3): δ = 7.25–7.34 (m, 5 H, ArH),
7.08–7.10 (m, 2 H, ArH), 6.81–6.83 (m, 2 H, ArH), 6.25 (br. s, 1
H, C=CH2), 5.46–5.47 (m, 1 H, C=CH2), 5.16 (s, 2 H, OCH2), 3.78
(s, 3 H, OCH3), 3.58 (s, 2 H, CH2) ppm. 13C NMR (125 MHz,
CDCl3): δ = 166.7, 158.0, 140.3, 135.8, 130.5, 130.0, 128.4, 128.1,
n-Butyl 2-(4-Ethoxybenzyl)acrylate (33a): Colorless oil (0.161 g,
82%). H NMR (500 MHz, CDCl3): δ = 7.08–7.10 (m, 2 H, ArH),
1
6.80–6.83 (m, 2 H, ArH), 6.19 (br. s, 1 H, C=CH2), 5.42 (br. s, 1
H, C=CH2), 4.12 (t, J = 6.5 Hz, 2 H, OCH2CH2CH2CH3), 3.98–
4.02 (m, 2 H, OCH2CH3), 3.55 (s, 2 H, CH2), 1.58–1.64 (m, 2 H,
OCH2 CH2CH2CH3), 1.31–1.41 [m, 5 H, (CH2, CH3)], 0.91 (t, J =
7.3 Hz, 3 H, OCH2CH2CH2CH3) ppm. 13C NMR (125 MHz,
CDCl3): δ = 167.0, 156.4, 140.7, 130.6, 129.9, 125.6, 114.3, 64.5,
128.0, 126.3, 113.7, 66.4, 55.2, 37.2 ppm. IR (film): ν = 1717, 1610,
˜
1511, 1247, 1129, 950, 697 cm–1. HRMS (EI): calcd. for C18H18O3
[M]+ 282.1256; found 282.1253.
63.3, 37.2, 30.6, 19.1, 14.8, 13.6 ppm. IR (film): ν = 1717, 1631,
˜
1511, 1246, 1134, 1049, 817 cm–1. HRMS (ESI): calcd. for
C16H22O3 [M + H]+ 263.1647; found 263.1647.
Benzyl 2-(3-Chlorobenzyl)acrylate (40a): Brown liquid (0.168 g,
78%). 1H NMR (500 MHz, CDCl3): δ = 7.17–7.34 (m, 9 H, ArH),
8
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20543
/KAP1
Date: 05-07-12 16:22:42
Pages: 11
Arylation of Baylis–Hillman Bromides and Acetates
6.31 (br. s, 1 H, C=CH2), 5.53 (br. s, 1 H, C=CH2), 5.15 (s, 2 H, 19.2 ppm. IR (film): ν = 2223, 1612, 1512, 1470, 1246, 1175,
˜
OCH2), 3.61 (s, 2 H, CH2) ppm. 13C NMR (125 MHz, CDCl3): δ 1033 cm–1. HRMS (ESI): calcd. for C14H17NO [M + H]+ 216.1388;
= 166.3, 140.6, 139.2, 135.7, 134.1, 129.6, 129.0, 128.5, 128.1, 128.0,
found 216.1381.
127.2, 127.1, 126.5, 66.6, 37.7 ppm. IR (film): ν = 1718, 1632, 1431,
˜
2-(4-n-Butoxybenzyl)acrylonitrile (48a): Colorless oil (0.116 g,
72%). 1H NMR (500 MHz, CDCl3): δ = 7.09–7.11 (m, 2 H, ArH),
6.85–6.87 (m, 2 H, ArH), 5.88 (br. s, 1 H, C=CH2), 5.66–5.67 (m,
1 H, C=CH2), 3.94 (t, J = 6.4 Hz, 2 H, OCH2CH2CH2CH3), 3.48
1192, 1133, 952, 729, 696 cm–1. HRMS (EI): calcd. for C17H15ClO2
[M]+ 286.0761; found 286.0760.
2-Benzylacrylonitrile (41a):[17] Colorless oil (0.0781 g, 73%). 1H
NMR (500 MHz, CDCl3): δ = 7.20–7.36 (m, 5 H, ArH), 5.91 (br. (s, 2 H, CH2), 1.73–1.79 (m, 2 H, OCH2CH2CH2CH3), 1.46–1.51
s, 1 H, C=CH2), 5.69 (br. s, 1 H, C=CH2), 3.55 (s, 2 H, CH2) ppm.
(m, H, OCH2CH2CH2CH3), 0.97 (t, 7.4 Hz, H,
13C NMR (125 MHz, CDCl3): δ = 135.5, 131.0, 128.8, 127.3, 122.6, OCH2CH2CH2CH3) ppm. 13C NMR (125 MHz, CDCl3): δ =
2
J
=
3
118.4, 40.7 ppm. IR (film): ν = 2223, 1621, 1495, 1454, 943, 727,
158.4, 130.5, 129.9, 127.2, 123.1, 118.5, 114.8, 67.6, 39.9, 31.3, 19.2,
˜
699 cm–1. HRMS (ESI): calcd. for C10H9N [M + H]+ 144.0813;
found 144.0819.
13.8 ppm. IR (film): ν = 2223, 1612, 1512, 1247, 1177 cm–1. HRMS
˜
(ESI): calcd. for C14H17NO [M + H]+ 216.1388; found 216.1382.
2-(4-Methylbenzyl)acrylonitrile (42a):[17] Colorless oil (0.0812 g,
69%). 1H NMR (500 MHz, CDCl3): δ = 7.09–7.16 (m, 4 H, ArH),
5.90 (br. s, 1 H, C=CH2), 5.68–5.69 (m, 1 H, C=CH2), 3.51 (s, 2
H, CH2), 2.34 (s, 3 H, CH3) ppm. 13C NMR (125 MHz, CDCl3): δ
= 137.0, 132.4, 130.7, 129.5, 128.7, 122.8, 118.5, 40.2, 21.0 ppm.
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the 1H NMR and 13C NMR spectra of all important
intermediates and final products.
Acknowledgments
IR (film): ν = 2223, 1621, 1514, 1433, 942, 819, 760 cm–1. HRMS
˜
(ESI): calcd. for C11H11N [M + H]+ 158.0970; found 158.0979.
Financial support from the Department of Science and Technology
(DST), New Delhi under the Green Chemistry programme (DST
No. SR/S5/GC-11/2008) is gratefully acknowledged. S. G. also ac-
knowledges the Council of Scientific and Industrial Research
(CSIR), New Delhi for a research fellowship.
2-(4-Methoxybenzyl)acrylonitrile (43a): Colorless oil (0.0969 g,
75%). 1H NMR (500 MHz, CDCl3): δ = 7.11–7.13 (m, 2 H, ArH),
6.87–6.89 (m, 2 H, ArH), 5.88 (br. s, 1 H, C=CH2), 5.67 (br. s, 1
H, C=CH2), 3.80 (s, 3 H, CH3), 3.49 (s, 2 H, CH2) ppm. 13C NMR
(125 MHz, CDCl3): δ = 158.8, 130.5, 129.9, 127.4, 123.1, 118.5,
114.2, 55.2, 39.9 ppm. IR (film): ν = 2223, 1611, 1512, 1248, 1178,
˜
[1] a) D. Basavaiah, G. Veeraraghavaiah, Chem. Soc. Rev. 2012,
41, 68–78; b) D. Basavaiah, B. S. Reddy, S. S. Badsara, Chem.
Rev. 2010, 110, 5447–5674; c) D. Basavaiah, K. V. Rao, R. J.
Reddy, Chem. Soc. Rev. 2007, 36, 1581–1588; d) D. Basavaiah,
A. J. Rao, T. Satyanarayana, Chem. Rev. 2003, 103, 811–891.
[2] S. Gowrisankar, H. S. Lee, S. H. Kim, K. Y. Lee, J. N. Kim,
Tetrahedron 2009, 65, 8769–8780.
[3] Selected references: a) D. Basavaiah, S. Roy, Org. Lett. 2008,
10, 1819–1822; b) Q.-Q. Min, C.-Y. He, H. Zhou, X. Zhang,
Chem. Commun. 2010, 46, 8029–8031; c) S. Zimdars, X. M.
Jourdin, F. Crestey, T. Carell, P. Knochel, Org. Lett. 2011, 13,
792–795; d) M. P. Sibi, K. Patil, Tetrahedron: Asymmetry 2006,
17, 516–519; e) Y. J. Lee, A. Kubota, A. Ishiwata, Y. Ito, Tetra-
hedron Lett. 2011, 52, 418–421; f) H. Guthmann, D. Conole,
E. Wright, K. Körber, D. Barker, M. A. Brimble, Eur. J. Org.
Chem. 2009, 1944–1960; g) Z.-H. Chen, Y.-Q. Zhang, Z.-M.
Chen, Y.-Q. Tu, F.-M. Zhang, Chem. Commun. 2011, 47, 1836–
1838.
1033, 942 cm–1. HRMS (ESI): calcd. for C11H11NO [M + H]+
174.0919; found 174.0914.
2-(4-Chlorobenzyl)acrylonitrile (44a):[17] Colorless oil (0.0814 g,
1
61%). H NMR (500 MHz, CDCl3): δ = 7.32 (d, J = 8.6 Hz, 2 H,
ArH), 7.15 (d, J = 8.0 Hz, 2 H, ArH), 5.93 (br. s, 1 H, C=CH2),
5.71 (br. s, 1 H, C=CH2), 3.52 (s, 2 H, CH2) ppm. 13C NMR
(125 MHz, CDCl3): δ = 133.9, 133.3, 131.2, 130.2, 129.0, 122.2,
118.1, 40.0 ppm. IR (film): ν = 2224, 1622, 1491, 1406, 1089, 1016,
˜
943 cm–1. HRMS (EI): calcd. for C10H8ClN [M]+ 177.0345; found
177.0347.
2-(4-Ethoxybenzyl)acrylonitrile (45a): Brown oil (0.112 g, 80%). 1H
NMR (500 MHz, CDCl3): δ = 7.10–7.11 (m, 2 H, ArH), 6.85–6.88
(m, 2 H, ArH), 5.88 (br. s, 1 H, C=CH2), 5.67 (br. s, 1 H, C=CH2),
4.02 (q, J = 7.0 Hz, 2 H, OCH2CH3), 3.48 (s, 2 H, CH2), 1.41 (t,
J = 7.0 Hz, 3 H, OCH2CH3) ppm. 13C NMR (125 MHz, CDCl3):
δ = 158.2, 130.5, 129.9, 127.3, 123.1, 118.5, 114.8, 63.4, 39.9,
[4] a) D. Basavaiah, M. Krishnamacharyulu, A. J. Rao, Synth.
Commun. 2000, 30, 2061–2069; b) S. Brass, N.-S. Chan, C. Ger-
lach, T. Luksch, J. Böttcher, W. E. Diederich, J. Organomet.
Chem. 2006, 691, 5406–5422.
14.8 ppm. IR (film): ν = 2223, 1612, 1512, 1247, 1178, 1115, 1047,
˜
942 cm–1. HRMS (ESI): calcd. for C12H13NNaO [M + Na]+
210.0895; found 210.0890.
[5] Selected references: a) A. Zakarian, A. Batch, R. A. Holton, J.
Am. Chem. Soc. 2003, 125, 7822–7824; b) Y. Nakao, J. Satoh,
E. Shirakawa, T. Hiyama, Angew. Chem. 2006, 118, 2329; An-
gew. Chem. Int. Ed. 2006, 45, 2271–2274; c) B. Leroy, Tetrahe-
dron Lett. 2005, 46, 7563–7566; d) A. Metzger, M. A. Schade,
P. Knochel, Org. Lett. 2008, 10, 1107–1110; e) C.-Y. Liu, P.
Knochel, Synlett 2007, 2081–2085; f) T. Stüdemann, P. Kno-
chel, Angew. Chem. 1997, 109, 132; Angew. Chem. Int. Ed. Engl.
1997, 36, 93–95; g) M. Szlosek-Pinaud, P. Diaz, J. Martinez, F.
Lamaty, Tetrahedron Lett. 2003, 44, 8657–8659; h) A. Krasov-
skiy, V. Malakhov, A. Gavryushin, P. Knochel, Angew. Chem.
2006, 118, 6186; Angew. Chem. Int. Ed. 2006, 45, 6040–6044; i)
T. Stüdemann, M. Ibrahim-Ouali, P. Knochel, Tetrahedron
1998, 54, 1299–1316; j) O. Baron, P. Knochel, Angew. Chem.
2005, 117, 3193; Angew. Chem. Int. Ed. 2005, 44, 3133–3155.
[6] a) P.-A. R. Breuil, F. W. Patureau, J. N. H. Reek, Angew. Chem.
2009, 121, 2196; Angew. Chem. Int. Ed. 2009, 48, 2162–2165;
b) O. Roy, A. Riahi, F. Hénin, J. Muzart, Tetrahedron 2000, 56,
8133–8140; c) S. Ma, S. Yu, Z. Peng, H. Guo, J. Org. Chem.
2-(4-Isopropoxybenzyl)acrylonitrile (46a): Colorless oil (0.117 g,
77%). 1H NMR (500 MHz, CDCl3): δ = 7.02–7.04 (m, 2 H, ArH),
6.78–6.80 (m, 2 H, ArH), 5.82 (br. s, 1 H, C=CH2), 5.61 (br. s, 1
H, C=CH2), 4.44–4.49 (m, 1 H, OCH), 3.42 (s, 2 H, CH2), 1.27 [d,
J = 6.3 Hz, 6 H, OCH(CH3)2] ppm. 13C NMR (125 MHz, CDCl3):
δ = 157.1, 130.5, 129.9, 127.2, 123.1, 118.6, 116.1, 69.8, 39.9,
22.0 ppm. IR (film): ν = 2223, 1612, 1509, 1245, 1183, 1119,
˜
953 cm–1. HRMS (ESI): calcd. for C13H15NNaO [M + Na]+
224.1051; found 224.1055.
2-(4-Isobutoxybenzyl)acrylonitrile (47a): Colorless oil (0.113 g,
71%). 1H NMR (500 MHz, CDCl3): δ = 7.09–7.12 (m, 2 H, ArH),
6.85–6.88 (m, 2 H, ArH), 5.88 (br. s, 1 H, C=CH2), 5.66–5.67 (m,
1 H, C=CH2), 3.70 [d, J = 6.6 Hz, 2 H, OCH2CH(CH3)2], 3.47 (s,
2 H, CH2), 2.01–2.12 [m, 1 H, OCH2CH(CH3)2], 1.02 [d, J =
6.8 Hz, 6 H, OCH2CH(CH3)2] ppm. 13C NMR (125 MHz, CDCl3):
δ = 158.5, 130.5, 129.9, 127.2, 123.1, 118.6, 114.8, 74.4, 39.9, 28.2,
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
9

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/KAP1
Date: 05-07-12 16:22:42
Pages: 11
M. L. N. Rao, S. Giri
FULL PAPER
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Lett. 2004, 45, 8419–8422; f) M. Takagi, K. Yamamoto, Chem.
Lett. 1989, 2123–2124.
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Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20543
/KAP1
Date: 05-07-12 16:22:42
Pages: 11
Arylation of Baylis–Hillman Bromides and Acetates
Cross-Coupling
M. L. N. Rao,* S. Giri .................... 1–11
Pd-Catalyzed Threefold Arylation of
Baylis–Hillman Bromides and Acetates
with Triarylbismuth Reagents
Functionalized alkyl 2-benzylacrylates and
2-benzylacrylonitriles were synthesized by
cross-coupling of Baylis–Hillman bromides
or acetates with BiAr3 under palladium-
catalyzed conditions. These reactions in-
volve threefold aryl couplings using BiAr3
reagents with bromides and acetates, are
fast, and provide high product yields.
Keywords: Bismuth / Palladium / Alkenes /
Synthetic methods / C–C coupling
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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