Palladium-catalyzed heck-type reactions of allylic esters with arylboronic acids or potassium aryltrifluoroborates

Article abstract of DOI:10.1002/adsc.201100889

A selective and general route to (E)-1,3-diaryl-prop-1-enes and (E)-3-arylallyl acetates has been developed by palladium-catalyzed Heck-type reactions of allylic esters with arylboronic acids or potassium aryltrifluoroborates. The present method selectively proceeds including β-OAc elimination or β-H elimination on the basis of the boronic acids. Whereas a variety of allylic esters were reacted with arylboronic acids, palladium(II) acetate [Pd(OAc)₂], tetra(n-butyl)ammonium chloride [(n-Bu)₄NCl] and postassium dihydrogen phosphate (KH ₂PO₄) to afford the corresponding diarylation products in moderate to good yields, treatment of allylic esters with potassium aryltrifluoroborates furnished the corresponding monoarylation products. Copyright

Full text of DOI:10.1002/adsc.201100889

FULL PAPERS
DOI: 10.1002/adsc.201100889
Palladium-Catalyzed Heck-Type Reactions of Allylic Esters with
Arylboronic Acids or Potassium Aryltrifluoroborates
Bo Yao,a Yan Liu,a Meng-Ke Wang,a Jin-Heng Li,b,* Ri-Yuan Tang,a
Xing-Guo Zhang,a and Chen-Liang Denga,*
a
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Peopleꢀs Republic of China
Fax : (+86)-577-8668-9372; phone: (+86)-577-8668-9615; e-mail: dengchenliang78@tom.com
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
b
University, Changsha 410082, Peopleꢀs Republic of China
Fax : (+86)-731-8887-2531; phone: (+86)-731-8887-2576; e-mail: jhli@hnu.edu.cn
Received: November 16, 2011; Revised: January 11, 2012; Published online: April 12, 2012
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201100889.
Abstract: A selective and general route to (E)-1,3- tetraACTHNUTRGNEG(NU n-butyl)ammonium chloride [(n-Bu)4NCl] and
diaryl-prop-1-enes and (E)-3-arylallyl acetates has postassium dihydrogen phosphate (KH2PO4) to
been developed by palladium-catalyzed Heck-type afford the corresponding diarylation products in
reactions of allylic esters with arylboronic acids or moderate to good yields, treatment of allylic esters
potassium aryltrifluoroborates. The present method with potassium aryltrifluoroborates furnished the
selectively proceeds including b-OAc elimination or corresponding monoarylation products.
b-H elimination on the basis of the boronic acids.
Whereas a variety of allylic esters were reacted with Keywords: allylic esters; arylboronic acids; Heck re-
arylboronic acids, palladium(II) acetate [PdACTHNUGTRNEUNG(OAc)2], action; palladium; potassium aryltrifluoroborates
Introduction
for the pharmaceutical and material industries.[2] In
the past several decades, the scope of the Heck reac-
The palladium-catalyzed Heck reaction has become tion has been significantly expanded. However, exam-
a powerful tool for constructing carbon-carbon bonds ples of selective Heck reactions of allylic esters are
in organic synthesis[1] and is of growing importance much less abundant.[3] Lautens and co-workers have
Scheme 1. The Heck reactions of allylic esters.
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Table 1. Screening for optimal conditions.[a]
reported an intermolecular Heck reaction of allylic
acetates with aryl iodides to afford the corresponding
monoarylation products in good yields, in which a b-
OAc elimination process takes place (Scheme 1, route
a). Notably, some diarylation side-products were ob-
served in the Lautens procedures, but poor yields and
low selectivity hindered the further exploitation.[4c–e,g]
Recently, Jiao and co-workers found that allylic esters
could selectively undergo the Heck reaction with aryl
halides or arylboronic acids including a b-H elimina-
tion process, offering the monoarylation ester prod-
ucts alone in moderate to good yields (Scheme 1,
route b).[5–6] We also described a selective route for
the synthesis of diarylation products by a palladium-
catalyzed Heck-type diarylation reaction of allylic
esters with aryl halides through b-OAc elimination
#
[Pd]
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(PPh3)2Cl2
PdCl2
Additive
Base
Solvent Yield
[%][b]
1
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
N
A
Et3N
MeCN trace
2
E
K2CO3
DMF
41
3
E
Cs2CO3 DMF
NaOMe DMF
NaHCO3 DMF
52
4
R
trace
56
5
ACHTUNGTRENNUNG
(Scheme 1, route c).[7] In the presence of Pd
ACTHNUTRGNEN(UG OAc)2,
6
R
K3PO4
DMF
51
(n-Bu)4NCl and Et3N, allylic esters reacted with vari-
ous aryl halides smoothly to furnish the respective
products in moderate to good yields. Moreover, this
methodology was applied in the synthesis of indoles
and benzofurans. As part of our continuing interest in
applications of allylic esters, we report here the first
diarylation reaction between allylic esters and aryl-
boronic acids to prepare unsymmetrical 1,3-diarylpro-
7
G
K2HPO4 DMF
KH2PO4 DMF
40
8
R
68
9
R
KH2PO4 DMSO 20
KH2PO4 toluene 36
KH2PO4 MeCN 28
KH2PO4 dioxane 48
10
11
ACHTUNGTRENNUNG
penes using the Pd
ACHTUTGNERNNUG(OAc)2/CAHTUNGTREN(NUNG n-Bu)4NCl/KH2PO4 cata-
ACHTUNGTRENNUNG
lytic system (Scheme 1). Interestingly, the monoaryla-
tion reaction of allylic esters with potassium aryltri- 12
fluoroborates also took place, furnishing the corre-
ACHTUNGTRENNUNG
13
A
KH2PO4 DMF
KH2PO4 DMF
KH2PO4 DMF
25
45
32
sponding arylallyl acetates in moderate yields. It is
noteworthy that the products, unsymmetrical 1,3-di-
14
AHCTUNGTRENNUNG
ACHTUNGTRENNUNGarylpropene compounds, represent the skeleton of
colchicine and its derivatives.[8]
15
Pd
2A
ACHTUNGTRENNUNG
16
17
Pd
Pd
N
G
trace
41
Results and Discussion
KH2PO4 DMF
KH2PO4 DMF
KH2PO4 DMF
KH2PO4 DMF
KH2PO4 DMF
KH2PO4 DMF
KH2PO4 DMF
The reaction between allyl acetate (1a) and phenyl- 18
boronic acid (2a) was investigated to optimize the re-
Pd
37
88
65
90
51
83
19[b] Pd
20[b,c] Pd
21[b,d] Pd
22[b,e] Pd
23[b,f] Pd
action conditions, and the results are summarized in
Table 1. Initially, the reaction between allyl acetate
(1a) and phenylboronic acid (2a) was tested under the
reported reaction conditions:[7] a trace of diarylation
product 3 was observed in the presence of PdACTHNUGTRENUNG(OAc)2,
(n-Bu)4NCl and Et3N for 12 h (entry 1). To our de-
light, the yield of the desired product 3 was enhanced
to 41% when K2CO3 combined with DMF was used
to replace the Et3N/MeCN system (entry 2). It is
noteworthy that the configuration of the carbon-
carbon double bond in product 3 was determined ac-
[a]
Reaction conditions: 1a (0.2 mmol), 2a (0.5 mmol), [Pd]
(10 mol%), additive (1.5 equiv.) and base (2 equiv.) in
solvent (2 mL) at 1208C for 12 h under N2 atmosphere.
DMF (anhydrous) as solvent for 6 h.
PdACTHUNTRGENNG(U OAc)2 (5 mol%).
1a (1.0 mmol) and 2a (2.5 mmol) for 6 h.
At 1008C for 12 h.
1
cording to the diagnostic HNMR spectra. Encour-
[b]
[c]
[d]
[e]
[f]
aged by this result, a series of bases, such as Cs2CO3,
NaOMe, NaHCO3, K3PO4, K2HPO4 and KH2PO4, was
examined (entries 3–8). The results demonstrated that
the reaction gave the best yield when using KH2PO4
base (entry 8). Subsequently, a number of other sol-
vents, including DMSO, toluene, CH3CN and dioxane,
Under air atmosphere.
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Palladium-Catalyzed Heck-Type Reactions of Allylic Esters with Arylboronic Acids
Table 2. Palladium-catalyzed diarylation reactions of allylic esters (1) with arylboronic acids (2).[a]
Entry
1
Allylic ester 1
Arylboronic acid 2
Time [h]
8
Yield[b] (Product)
1a
2b
72% (4)
2
3
4
5
6
7
1a
1a
1a
1a
1a
1a
2c
2d
2e
2f
2g
2h
6
6
6
7
7
8
76% (5)
84% (6)
66% (7)
82% (8)
56% (9)
72% (10)
8
9
1a
1a
2i
2j
8
7
62% (11)
72% (12)
10
1a
1a
1a
1a
1a
2k
2l
8
70% (13)
64% (14)
72% (15)
77% (16)
67% (17)
11
11
12
11
16
12
2m
2n
2o
13
14[c]
15
16
17
1b
1c
1d
2d
2d
2d
8
9
6
71% (6)
70% (6)
75% (6)
18
19
1e
1f
2d
2d
7
6
81% (6)
80% (6)
[a]
Reaction conditions: 1 (0.2 mmol), 2 (0.5 mmol), PdACTHUNGRTNEGNU(OAc)2 (10 mol%), (n-Bu)4NCl (1.5 equiv.) and KH2PO4 (2 equiv.) in
DMF (2 mL, anhydrous) at 1208C under N2 atmosphere.
Isolated yield.
At 1008C.
[b]
[c]
were investigated, but they were inferior to DMF in three other palladium catalysts, PdCl2, PdCl
2ACHTUNGTRENNUNG(PPh3)2
terms of yields (entries 9–12). Screening revealed that and Pd2A(dba)3, have reactivity to catalyze this reac-
CTHUNGTRENNUNG
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Scheme 2. Diarylation of cinnamyl acetate (1g) with 4-methoxyphenylboronic acid (2d).
tion, but they were less efficient than PdACTHNUTRGENN(UG OAc)2 (en- acid (2d), PdAHCUTNTGERNN(UGN OAc)2, (n-Bu)4NCl, and KH2PO4 (en-
tries 13–15). Notably, the phase-transfer catalysts, tries 15–19). The results indicated that various allylic
quaternary ammonium salts, were found to affect the esters, including allyl benzoate (1b), allyl 2-phenylace-
reaction: The yield was lowered to some extent when tate (1c), allyl ethyl carbonate (1d), allyl 4-methylben-
using (n-Bu)4NF, (n-Bu)4NBr or (n-Bu)4NOAc as the zenesulfonate (1e) and allyl pivalate (1f), were suc-
phase-transfer catalysts (entries 16–18).[9] It was inter- cessfully diarylated with boronic acid 2d in good
esting to find that the yield of the desired product 3 yields (entries 15–19). For example, the reaction of
was increased sharply to 88% when using anhydrous allyl 4-methylbenzenesulfonate (1e) with 4-methoxy-
DMF media (entry 19). However, the yield was re- phenylboronic acid (2d), Pd
duced to 65% when the reaction was carried out at KH2PO4 proceeded smoothly to afford the desired
a loading of 5 mol% Pd(OAc)2 (entry 20). Gratifying- product 6 in 81% yield (entry 18).
ly, a good yield was still achieved from the reaction of Notably, cinnamyl acetate (1g) could also react
ACHTUNGTREN(NUNG OAc)2, (n-Bu)4NCl and
AHCTUNGTRENNUNG
allyl acetate (1a) on a 1-mmol scale: a 90% yield of with 4-methoxyphenylboronic acid (2d) smoothly to
the desired product 3 was obtained in the presence of provide (E)-4,4’-(3-phenylprop-1-ene-1,3-diyl)bis(me-
PdACHTUNGTRENNUNG(OAc)2, (n-Bu)4NCl, KH2PO4 and anhydrous DMF thoxybenzene) (18) in 43% yield (Scheme 2). These
(entry 21). Among the reaction temperatures exam- findings suggest that the reaction proceeds in
ined, it turned out that the reaction at 1208C offered a manner involving an olefin isomerization process.
the best yield (entries 19 and 22). It is noteworthy
To our surprise, the selectivity was shifted towards
that the yield of 3 was decreased slightly under an air the monoarylation products when commercially avail-
atmosphere (entries 19 and 23).
able potassium aryltrifluoroborates 2 was used to
As shown in Table 2, the scope of both allylic esters
1 and arylboronic acids 2 reaction partners for the re-
action was explored under the optimal reaction condi-
Table 3. Palladium-catalyzed monoarylation reaction of allyl
acetate (1a) with potassium aryltrifluoroborates (2).[a]
tions. In the presence of PdACHTUNTRGNEUNG(OAc)2, (n-Bu)4NCl, and
KH2PO4, a variety of arylboronic acids 2b–2n was em-
ployed to react with allyl acetate (1a) (entries 1–13).
The results disclosed that several functional groups,
including MeO, Me, Cl, acetyl, CF3 and CN, on the ar-
omatic ring of boronic acids 2 were tolerated well.
MeO-substituted arylboronic acids 2b–2d, for in-
stance, underwent the diarylation with substrate 1a in
good yields, and the order of their reactivity is: para-
MeO>meta-MeO>ortho-MeO (entries 1–3). We
were pleased to observe that substrates 2e and 2f
bearing a ortho-Me or a para-Me group were consis-
tent with the optimal conditions (entries 4 and 5). Im-
portantly, the chloro substitution in arylboronic acids
2g–2k can be tolerated in this diarylation reaction,
thereby facilitating additional modifications at the
halogenated positions (entries 6–10). Screening also
disclosed that the optimal conditions were compatible
with electron-deficient arylboronic acids 2l–2n (en-
tries 11–13). Notably, heteroarylboronic acid 2o was
also a suitable substrate for the reaction with sub-
strate 1a in moderate yield (entry 14).
Entry ArBF3K 2
Time
[h]
Isolated yield [%]
(Product)
1
2
2o 12
55 (19)
61 (20)
2p 10
3
4
2q 16
2r 13
35 (21)
44 (22)
48 (23)
5
11
2s
[a]
Reaction conditions: 1a (0.2 mmol),
2
(0.5 mmol),
Pd(OAc)2 (10 mol%), (n-Bu)4NCl (1.5 equiv.) and
AHCTUNGTRENNUNG
A series of allylic esters 1b–1f was subsequently in-
vestigated in the presence of 4-methoxyphenylboronic
KH2PO4 (2 equiv.) in DMF (2 mL, anhydrous) at 1208C
under N2 atmosphere.
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Palladium-Catalyzed Heck-Type Reactions of Allylic Esters with Arylboronic Acids
Conclusions
In summary, we have described a new protocol for
the selective synthesis of polysubstituted olefins by
palladium-catalyzed Heck-type reactions of allylic
esters with boronic acids and their salts. The present
method selectively proceeds involving b-OAc elimina-
tion or b-H elimination in dependence on the boronic
acids and their salts, which provides a simple and se-
lective approach to polysubstituted olefins synthesis.
Experimental Section
Scheme 3. Possible mechanism.
Typical Experimental Procedure for the Palladium-
Catalyzed Diarylation Reactions of Allylic Esters (1)
with Arylboronic Acids (2)
react with allyl acetate (1a) under the optimal condi-
tions (Table 3).[10] For example, treatment of allyl ace-
tate (1a) with potassium phenyltrifluoroborate (2o),
To a Schlenk tube were added allylic ester 1 (0.2 mmol), ar-
ylboronic acid 2 (0.5 mmol), PdACTHNUTRGNENUG(OAc)2 (10 mol%), (n-
Pd
ACHTUNGTRENNUNG
Bu)4NCl (1.5 equiv.), KH2PO4 (2.0 equiv.) and anhydrous
DMF (2 mL). Then the content of the tube was stirred at
1208C (oil bath temperature) under an N2 atmosphere for
the indicated time until complete consumption of starting
material as monitored by TLC and GC-MS analysis. After
the reaction was finished, the reaction mixture was cooled
to room temperature, diluted in diethyl ether, and washed
with brine, extracted with EtOAc, dried over anhydrous
Na2SO4, and evaporated under vacuum. The residue was pu-
rified by flash column chromatography on silica gel (EtOAc/
petroleum ether) to afford the desired products.
a monoACHTUNGTRENNUNG
Substrate 2p with a five-membered oxygen-containing
ring was also suitable for the reaction under the same
conditions (entry 2). Gratifyingly, several functional
groups, NO2, CN and Cl, on the aryl rings of the po-
tassium aryltrifluoroborates 2 were perfectly tolerated
(entries 3–5).
The results disclosed that the presence of air low-
ered the activity of the Pd catalytic system to some
extent (Table 1), implying that the present reaction
may not proceed via an oxidative Heck-type process.
Moreover, the monoarylation products were obtained
from the reaction between potassium aryltrifluorobo-
rates 2 and allyl acetate (1a) under the present opti-
mal conditions. Therefore, a possible mechanism was
proposed as outlined in Scheme 3. Oxidative addition
of PdLn with ArB(OH)2 takes place to afford inter-
mediate A.[3a–c] Subsequently, complexation of inter-
mediate A with allyl acetate furnishes intermediate B,
followed by addition to give intermediate C. Inter-
mediate C can participate in two pathways: (i) the
generation of allyl-Pd intermediate D involving de-
composition of OAc group using arylboronic acids,
and (ii) the ocurrence of reductive elimination to
yield 3-arylallyl acetates in the presence of potassium
aryltrifluoroborates. The reason is that the potassium
(E)-Prop-1-ene-1,3-diyldibenzene (3):[7] Colorless liquid;
1H NMR (300 MHz, CDCl3): d=7.38–7.17 (m, 10H), 6.46
(d, J=15.9 Hz, 1H), 6.40–6.31 (m, 1H), 3.55 (d, J=6.3 Hz,
2H); 13C NMR (125 MHz, CDCl3): d=140.2, 137.5, 131.1,
129.3, 128.7, 128.5, 128.3, 127.1, 126.2, 126.1, 39.4; MS (EI
70 eV): m/z (%)=194 (M+, 100), 179 (44), 116 (57), 115
(93), 93 (54).
(E)-2,2’-(Prop-1-ene-1,3-diyl)bis(methoxybenzene) (4):[7]
Colorless liquid; 1H NMR (300 MHz, CDCl3): d=7.42 (d,
J=7.5 Hz, 1H), 7.32–7.14 (m, 3H), 6.92–6.82 (m, 4H), 6.77–
6.65 (m, 1H), 6.42–6.32 (m, 1H), 3.83 (s, 3H), 3.82 (s, 3H),
3.56 (d, J=6.9 Hz, 2H); 13C NMR (125 MHz, CDCl3): d=
157.3, 156.4, 129.8, 129.5, 129.1, 127.9, 127.2, 126.8, 126.5,
125.4, 120.6, 120.5, 110.8, 110.3, 55.4 (2C), 33.8; MS (EI,
70 eV): m/z (%)=254 (M+, 100), 223 (59), 145 (34), 115
(34), 91 (50).
(E)-3,3’-(Prop-1-ene-1,3-diyl)bis(methoxybenzene)
(5):
Colorless liquid; 1H NMR (300 MHz, CDCl3): d=7.20 (t,
aryltrifluoroborate salts are more stable than the bor- J=7.5 Hz, 2H), 6.97–6.89 (m, 2H), 6.83–6.75 (m, 4H), 6.44
(d, J=15.6 Hz, 1H), 6.39–6.29 (m, 1H), 3.80 (s, 6H), 3.52
(d, J=6.3 Hz, 2H); 13C NMR (125 MHz, CDCl3): d=159.8
(2C), 141.7, 138.9, 131.1, 129.4, 129.3, 121.1, 119.7, 118.8,
114.4, 112.9, 111.5, 111.4, 55.2 (2C), 39.3; MS (EI, 70 eV):
m/z (%)=254 (M+, 100), 223 (59), 145 (34), 115 (34), 91
(50); HR-MS (EI): m/z=254.1305, for C17H18O2 (M+): calcd.
254.1307.
onic acids resulting in the ocurrence of reductive
elimination prior to the generation of allylPd inter-
mediate D. AllylPd intermediate D subsequently un-
dergoes the second addition leading to intermediate
E. Finally, reductive elimination of intermediate E
takes place to furnish diarylallyl acetates and regener-
ate the active PdLn species.
(E)-4,4’-(Prop-1-ene-1,3-diyl)bis(methoxybenzene) (6):[7]
1
Colorless liquid; H NMR (300 MHz, CDCl3): d=7.30–7.25
(m, 2H), 7.16 (d, J=8.7 Hz, 2H), 6.37 (d, J=15.9 Hz, 1H),
6.24–6.14 (m, 1H), 3.79 (s, 6H), 3.46 (d, J=6.9 Hz, 2H);
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Bo Yao et al.
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13C NMR (125 MHz, CDCl3): d=158.8, 158.0, 132.5, 130.4,
130.1, 129.6, 127.5, 127.1, 113.9 (2C), 55.3 (2C), 38.4; MS
(EI, 70 eV): m/z (%)=254 (M+,100), 223 (49), 145 (38), 115
(32), 121 (23).
10), 192 (100), 115 (43), 271 (25), 273 (25); HR-MS (EI):
m/z=349.9306, calcd. for C15H1279Br2 (M+): 349.9310.
(E)-4,4’-(Prop-1-ene-1,3-diyl)bis(acetophenone)
(14):[7]
1
Colorless liquid; H NMR (500 MHz, CDCl3): d=7.86–7.82
(m, 2H), 7.35 (d, J=8.7 Hz, 2H), 7.25 (d, J=8.7 Hz, 2H),
6.45–6.37 (m, 2H), 3.50 (d, J=2.7 Hz, 2H), 2.53 (s, 3H),
2.51 (s, 3H); 13C NMR (125 MHz, CDCl3): d=197.8, 197.6,
145.2, 141.8, 135.6, 131.1, 130.9, 128.9, 128.8, 128.7, 128.5,
126.2, 39.3, 26.6 (2C); MS (EI, 70 eV): m/z (%)=278 (M+,
100), 263 (97), 235 (41), 207 (26), 124 (32).
(E)-2,2’-(Prop-1-ene-1,3-diyl)bis(methylbenzene)
(7):[7]
1
Colorless liquid; H NMR (300 MHz, CDCl3): d=7.43–7.39
(m, 1H), 7.21–7.12 (m, 7H), 6.58 (d, J=15.6 Hz, 1H), 6.24–
6.14 (m, 1H), 3.54 (m, 2H), 2.35 (s, 3H), 2.30 (s, 3H);
13C NMR (125 MHz, CDCl3): d=138.4, 136.7, 136.4, 135.0,
130.2, 130.1, 129.9, 129.1, 128.9, 127.0, 126.4, 126.0, 125.6,
126.1, 37.2, 19.8, 19.4; MS (EI, 70 eV): m/z (%)=222 (M+,
100), 207 (98), 115 (78), 91 (21).
(E)-4,4’-(Prop-1-ene-1,3-diyl)bis((trifluoromethyl)ben-
zene) (15): Colorless liquid; 1H NMR (500 MHz, CDCl3):
d=7.51–7.46 (m, 4H), 7.36 (d, J=8.0 Hz, 2H), 7.27 (d, J=
8.0 Hz, 2H), 6.41 (d, J=16.0 Hz, 1H), 6.38–6.32 (m, 1H),
3.50 (d, J=6.0 Hz , 2H); 13C NMR (125 MHz, CDCl3): d=
143.6, 140.6, 130.8, 130.6, 129.0, 128.7, 126.4 (d, J=9.4 Hz,
1C), 125.6 (2C), 125.5 (2C), 124.3 (q, J=270.3 Hz, 1C), 39.1;
MS (EI, 70 eV): m/z (%)=330 (M+, 72), 261 (100), 246 (17),
183 (36), 115 (45); HR-MS (ESI): m/z=330.0841, calcd. for
C17H12F6 (M+): 330.0843.
(E)-4,4’-(Prop-1-ene-1,3-diyl)bis(methylbenzene)
(8):[7]
1
Colorless liquid; H NMR (300 MHz, CDCl3): d=7.25–7.23
(m, 3H), 7.12–7.08 (m, 5H), 6.41 (d, J=15.6 Hz , 1H), 6.33–
6.23 (m, 1H), 3.49 (d, J=6.6 Hz, 2H), 2.33 (s, 3H), 2.32 (s,
3H); 13C NMR (125 MHz, CDCl3): d=137.2, 136.7, 135.6,
134.7, 130.7, 129.2, 129.1, 128.5, 128.4, 125.9, 38.9, 21.0 (2C);
MS (EI, 70 eV): m/z (%)=222 (M+, 100), 207 (98), 115 (78),
91 (21).
(E)-2,2’-(Prop-1-ene-1,3-diyl)bis(chlorobenzene) (9): Col-
(E)-4,4’-(Prop-1-ene-1,3-diyl)dibenzonitrile (16): Colorless
1
orless liquid; H NMR (300 MHz, CDCl3): d=7.53–7.47 (m,
1
liquid; H NMR (500 MHz, CDCl3): d=7.71 (d, J=8.5 Hz,
1H), 7.40–7.12 (m, 8H), 6.87 (d, J=15.6 Hz, 1H), 6.37–6.27
(m, 1H), 3.71 (d, J=6.6 Hz, 2H); 13C NMR (125 MHz,
CDCl3): d=138.4, 136.8, 136.4, 135.0, 130.2 (2C), 129.9,
129.1, 129.0, 127.0, 126.4, 126.1, 126.0, 125.6, 37.2; MS (EI,
70 eV): m/z (%)=264 (M+ +2, 27), 262 (M+, 41), 227 (100),
192 (58), 115 (78); HR-MS (EI): m/z=262.0313, calcd. for
C15H1235Cl2 (M+): 262.0316.
2H), 7.63 (d, J=8.5 Hz, 2H), 7.54 (d, J=8.5 Hz, 2H), 7.40
(d, J=8.5 Hz, 2H), 6.58 (d, J=16.0 Hz, 1H), 6.36–6.32 (m,
1H), 4.69 (dd, J=5.0 Hz, 1.0 Hz, 2H); 13C NMR (125 MHz,
CDCl3): d=143.5, 140.7, 132.9, 132.4, 131.8, 127.9, 127.4,
127.1, 118.8, 118.4, 112.4, 111.3, 30.9; MS (EI, 70 eV): m/z
(%)=244 (M+, 85), 243 (100), 140 (27), 89 (18), 228 (16);
HR-MS (EI): m/z=244.0998, calcd. for C17H12N2 (M)+:
244.1001.
(E)-4,4’-(Prop-1-ene-1,3-diyl)bis(chlorobenzene) (10):[11]
1
Colorless liquid; H NMR (300 MHz, CDCl3): d=7.29–7.25
(E)-2,2’-(Prop-1-ene-1,3-diyl)dithiophene (17):[7] Colorless
(m, 6H), 7.16 (d, J=4.8 Hz, 2H), 6.40–6.36 (m, 1H), 6.31–
6.26 (m, 1H), 3.50 (d, J=3.9 Hz, 2H); 13C NMR (125 MHz,
CDCl3): d=138.2, 135.7, 132.8, 132.1, 130.2, 130.0, 129.3,
128.7, 128.6, 127.3, 38.6 (2C); MS (EI, 70 eV): m/z (%)=
264 (M+ +2, 29), 262 (M+, 45), 227 (100), 192 (35), 115 (56).
(E)-2,2’-(Prop-1-ene-1,3-diyl)bis(4-chloro-1-methoxyben-
zene) (11): Colorless liquid; 1H NMR (300 MHz, CDCl3):
d=7.38–7.36 (m, 1H), 7.14–7.10 (m, 3H), 6.79–6.74 (m,
2H), 6.68–6.54 (m, 1H), 6.36–6.26 (m, 1H), 3.83 (s, 3H),
3.82 (s, 3H), 3.50 (d, J=7.2 Hz, 2H); 13C NMR (125 MHz,
CDCl3): d=155.8, 154.9, 130.5, 129.7, 129.6, 128.1, 127.5,
126.9, 126.2, 125.6, 125.3, 124.9, 111.9, 111.4, 55.7 (2C),
33.62; MS (EI, 70 eV): m/z (%)=324 (M+ +2, 30), 322 (M+,
58), 286 (74), 178 (49), 165 (23), 145 (100); HR-MS (EI): m/
z=322.0525, calcd. for C17H1635Cl2O2 (M+): 322.0527.
(E)-4,4’-(Prop-1-ene-1,3-diyl)bis(1,2-dichlorobenzene)
(12):[11] Colorless liquid; 1H NMR (300 MHz, CDCl3): d=
7.43–7.39 (m, 1H), 7.37–7.35 (m, 2H), 7.31–7.30 (m, 1H),
7.16 (d, J=8.4 Hz, 1H), 7.05 (d, J=8.4 Hz, 1H), 6.34 (d, J=
15.9 Hz, 1H), 6.30–6.23 (m, 1H), 3.49 (d, J=5.1 Hz, 2H);
13C NMR (125 MHz, CDCl3): d=139.7, 137.1, 132.7, 132.5,
131.1, 130.6, 130.5(2C), 129.9(2C), 129.7, 128.1, 127.9, 125.4,
38.2; MS (EI, 70 eV): m/z (%)=332 (M+, 63), 294 (89), 189
(37),149 (100), 94 (46).
1
liquid; H NMR (300 MHz, CDCl3): d=7.17–7.11 (m, 2H),
6.96–6.91 (m, 3H), 6.86–6.85 (m, 1H), 6.51 (d, J=15.6 Hz,
1H), 6.25–6.16 (m, 1H), 3.70 (d, J=6.9 Hz, 2H); 13C NMR
(125 MHz, CDCl3): d=142.7, 142.3, 128.0, 127.3, 127.0,
125.1, 124.9, 124.6, 123.9, 123.8, 33.1; MS (EI, 70 eV): m/z
(%)=206 (M+, 100), 205 (32), 173 (26), 97 (34).
(E)-4,4’-(3-Phenylprop-1-ene-1,3-diyl)bis(methoxyben-
1
zene) (18):[7] Colorless liquid; H NMR (300 MHz, CDCl3):
d=7.33–7.26 (m, 4H), 7.24–7.19 (m, 3H), 7.16–7.13 (m,
2H), 6.86–6.82 (m, 4H), 6.55–6.47 (m, 1H), 6.26 (d, J=
14.4 Hz, 1H), 4.82 (d, J=7.2 Hz, 1H), 3.80 (s, 3H), 3.79 (s,
3H); 13C (NMR 125 MHz): d=159.0, 158.1, 144.1, 135.9,
130.8, 130.6, 130.2, 129.6, 128.6, 128.4, 127.4, 126.6, 126.3,
113.9, 113.8, 55.3 (2C), 53.4; MS (EI, 70 eV): m/z (%)=330
(M+, 100), 299 (56), 222 (90), 221 (33), 121 (41).
(E)-Cinnamyl acetate (19):[5b] Colorless liquid; 1H NMR
(500 MHz, CDCl3): d=7.32–7.30 (m, 2H), 7.26–7.23 (m,
2H), 7.19–7.16 (m, 1H), 6.58 (d, J=16.0 Hz, 1H), 6.24–6.18
(m, 1H), 4.66–4.64 (m, 2H), 2.02 (s, 3H); 13C NMR
(125 MHz, CDCl3): d=170.8, 136.2, 134.2, 128.6, 128.1,
126.6, 123.2, 65.1, 21.0; IR (KBr): n=1741 cmÀ1; MS (EI,
70 eV): m/z (%)=176 (M+, 1), 133 (48), 115 (100), 92 (40),
77 (22).
(E)-3-(Benzo[d]ACTHNUTRGNEUNG
[1,3]dioxol-5-yl)allyl acetate (20):[12] Col-
(E)-4,4’-(prop-1-ene-1,3-diyl)bis(bromobenzene)
(13):
1
1
orless liquid; H NMR (500 MHz, CDCl3): d=6.87–6.86 (m,
1H), 6.75–6.74 (m, 1H), 6.70–6.68 (m, 1H), 6.49 (d, J=
15.1 Hz, 1H), 6.08–6.03 (m, 1H), 6.02–5.89 (m, 2H), 4.62 (d,
J=4.5 Hz, 2H), 2.03 (s, 3H); 13C NMR (125 MHz, CDCl3):
d=170.9, 148.1, 147.7, 134.1, 130.7, 121.5, 121.3, 108.3, 105.8,
101.2, 65.2, 21.0; IR (KBr): n=1732 cmÀ1; MS (EI, 70 eV):
White solid; mp 65.9–67.58C; H NMR (500 MHz, CDCl3):
d=7.48–7.44 (m, 4H), 7.25 (d, J=8.5 Hz, 2H), 7.14 (d, J=
8.0 Hz, 2H), 6.42–6.32 (m, 2H), 3.52 (d, J=6.0 Hz, 2H);
13C NMR (125 MHz, CDCl3): d=138.8, 136.2, 131.7, 131.6,
130.45, 130.4, 129.4, 127.7, 121.0, 120.2, 38.7; LR-MS (EI, 70
eV): m/z (%)=354 (M+ +2, 10), 352 (M+, 20), 350 (M+À2,
1074
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ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 1069 – 1076

Palladium-Catalyzed Heck-Type Reactions of Allylic Esters with Arylboronic Acids
m/z (%)=220 (M+, 98), 103 (100), 131 (96), 177 (45), 91
(46).
Alonso, I. P. Beletskeya, M. Yus, Tetrahedron 2005, 61,
11771; e) J. D. Crowley, K. D. Hꢂnni, A. L. Lee, D. A.
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nenberg, T. Schulz, H. J. Jiao, M. Beller, J. Am. Chem.
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m) G. A. Molander, R. Figueroa, Aldrichimica Acta
2005, 38, 49–56.
(E)-3-(3-Nitrophenyl)allyl acetate (21): Colorless liquid;
1H NMR (500 MHz, CDCl3): d=8.18 (s, 1H), 8.05–8.03 (m,
1H), 7.64–7.61 (m, 1H), 7.45–7.42 (m, 1H), 6.63 (d, J=
16.0 Hz, 1H), 6.39–6.33 (m, 1H), 4.71–4.69 (m, 2H), 2.06 (s,
3H); 13C NMR (125 MHz, CDCl3): d=170.8, 148.6, 138.0,
132.4, 131.2, 129.6, 126.7, 122.6, 121.2, 64.3, 20.9; IR (KBr):
n=1726 cmÀ1; MS (EI, 70 eV): m/z (%)=221 (M+, 17), 162
(13), 161 (29), 115 (100), 77 (13); HR-MS (EI): m/z=
221.0686, calcd. for C11H11NO4 (M)+: 221.0688.
(E)-3-(4-Cyanophenyl)allyl acetate (22):[5b] Colorless
1
liquid; H NMR (500 MHz, CDCl3): d=7.54 (d, J=8.5 Hz,
2H), 7.40 (d, J=8.5 Hz, 2H), 6.58 (d, J=17.0 Hz, 1H),
6.39–6.30 (m, 1H), 4.69–4.68 (m, 2H), 2.05 (s, 3H);
13C NMR (125 MHz, CDCl3): d=170.7, 140.7, 132.9, 132.5,
131.8, 127.9, 127.4, 127.1, 118.8, 111.3, 64.4, 20.9; IR (KBr):
n=1738 cmÀ1; MS (EI, 70 eV): m/z (%)=201 (M+, 34), 159
(100), 140 (86), 130 (94), 89 (16).
[4] a) P. Gomes, C. Gosmini, J. Pꢃrichon, Org. Lett. 2003,
5, 1043–1045; b) L. Botella, C. Nꢄjera, J. Organomet.
Chem. 2002, 663, 46–57; c) M. Lautens, E. Tayama, C.
Herse, J. Am. Chem. Soc. 2005, 127, 72–73; d) B. Ma-
riampillai, C. Herse, M. Lautens, Org. Lett. 2005, 7,
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dorff, M. Lautens, Org. Lett. 2006, 8, 4569–4572; f) S. E.
Denmark, S. T. Nguyen, Org. Lett. 2009, 11, 781–784;
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h) H. Ohmiya, Y. Makida, T. Tanaka, M. Sawamura, J.
Am. Chem. Soc. 2008, 130, 17276–17277; i) H. Ohmiya,
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Ohmiya, M. Sawamura, Chem. Asian J. 2011, 6, 410–
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(E)-3-(4-Chlorophenyl)allyl acetate (23):[5b] Colorless
1
liquid; H NMR (500 MHz, CDCl3): d=7.25–7.19 (m, 4H),
6.52 (J=16.0 Hz, 1H), 6.21–6.16 (m, 1H), 4.65–4.64 (m,
2H), 2.03 (m, 3H); 13C NMR (125 MHz, CDCl3): d=170.8,
134.7, 133.8, 132.8, 128.8, 127.8, 123.9, 64.8, 20.9; IR (KBr):
n=1749 cmÀ1; MS (EI, 70 eV): m/z (%)=212 (M+ +2, 7.5),
210 (M+, 22.5), 168 (30), 116 (33), 115 (100).
Acknowledgements
We thank the Natural Science Foundation of China (Nos.
21102104 and 21172060), Zhejiang Provincial Natural Sci-
ence Foundation of China (Nos. Y4100307 and Y4080169),
and Zhejiang Province Department of Education fund (No.
201120337) for financial support. Mr Yao also thank the
Emerging Talent Program of Zhejiang Province (No.
2011R424051).
[5] a) D. Pan, A. Chen, Y. Su, W. Zhou, S. Li, W. Jia, J.
Xiao, Q. Liu, L. Zhang, N. Jiao, Angew. Chem. 2008,
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Chem. Asian J. 2010, 5, 1090–1093.
[6] For other diarylation processes in Heck reactions, see:
a) F. Naso, O. Sciacovelli, Tetrahedron Lett. 1983, 24,
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