Generally applicable and efficient oxidative Heck reaction of arylboronic acids with olefins catalyzed by cyclopalladated ferrocenylimine under base- and ligand-free conditions

Article abstract of DOI:10.1016/j.tet.2009.12.027

A mild and efficient method for oxidative Heck-type reaction of arylboronic acids with olefins catalyzed by cyclopalladated ferrocenylimine was developed. The results represent the first examples involving the palladacycle as the catalyst for such couplings. Moreover, the catalytic system could tolerate various functional groups, such as F, Cl, Br, NO₂ and CH₃O, and the substrates could be extended to a wide range of olefins from acrylic esters, α,β-unsaturated ketones to alkenes. Furthermore, the olefination could proceed well under base- and ligand-free conditions and employ oxygen as the environmentally benign oxidant.

Full text of DOI:10.1016/j.tet.2009.12.027

Tetrahedron 66 (2010) 1244–1248
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Generally applicable and efficient oxidative Heck reaction of arylboronic
acids with olefins catalyzed by cyclopalladated ferrocenylimine
under base- and ligand-free conditions
*
Yuting Leng, Fan Yang, Kun Wei, Yangjie Wu
Department of Chemistry, Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Key Laboratory of Applied Chemistry of Henan Universities,
Zhengzhou University, Zhengzhou 450052, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A mild and efficient method for oxidative Heck-type reaction of arylboronic acids with olefins catalyzed
by cyclopalladated ferrocenylimine was developed. The results represent the first examples involving the
palladacycle as the catalyst for such couplings. Moreover, the catalytic system could tolerate various
functional groups, such as F, Cl, Br, NO2 and CH3O, and the substrates could be extended to a wide range
Received 30 September 2009
Received in revised form
2 December 2009
Accepted 8 December 2009
Available online 24 December 2009
of olefins from acrylic esters,
a,b-unsaturated ketones to alkenes. Furthermore, the olefination could
proceed well under base- and ligand-free conditions and employ oxygen as the environmentally benign
oxidant.
Keywords:
Ó 2009 Elsevier Ltd. All rights reserved.
Palladium
Olefin
Arylboronic acid
Homogeneous catalysis
Oxidative Heck reaction
1. Introduction
reactions since more than ten years ago.6 We found a novel kind of
palladacyclic catalysts: cyclopalladated ferrocenylimines are often
The palladium-catalyzed carbon–carbon bond forming re-
actions have become one of the most important and reliable tools in
a great number of synthesis during the last ten years.1 After being
firstly discovered by Heck, oxidative Heck reaction has attracted
considerable attention and various systems under palladium ca-
talysis have been developed.2–4 Notably, Larhed and co-workers
firstly reported a Pd(II)/dmphen catalytic version for the olefination
of organoboronic acids with olefins using O2 as the oxidant.3g
Subsequently, Jung and co-workers developed the first base-free
oxidative Heck reaction.4d Very recently, Jiao and co-workers
demonstrated a palladium-catalyzed ligand-free protocol for highly
stable and convenient to be prepared and easy to handle and can be
used as important alternatives to simple palladium species.7 We
have investigated their applications in catalytic reactions, such as
Heck reaction,8,9 Suzuki reaction,10 Sonogashira reaction and cross-
coupling of arylboronic acids/esters with terminal alkynes.11 To the
best of our knowledge, there were no examples of palladacycles as
catalysts for oxidative Heck reaction. Herein we would like to report
a palladacycle-catalyzed general and mild efficient system for oxi-
dative Heck reaction of arylboronic acids with various olefins using
O2 as the oxidant under the base- and ligand-free conditions (Fig. 1).
selective control of b-H elimination in the oxidative Heck-type re-
actions of allyl esters with AgOAc/CuF2 and KHF2 as the oxidants
and additive, respectively.5 However, the reported methods mostly
required a high catalyst loading, higher temperature and relatively
longer reaction time as well as the participation of bases, ligands
and metal salts additives. Therefore, the more mild, convenient and
efficient catalytic system should still be developed.
N
Fe Pd Cl
2
Figure 1. Palladacycle.
2. Results and discussion
Palladacycles have emerged as a new family of palladium cata-
lysts in carbon–carbon and carbon–heteroatom bonds forming
We initially screened the reaction conditions using phenyl-
boronic acid and styrene as starting substrates. The results for the
oxidative Heck reaction were summarized in Table 1. After various
solvents were examined, the polar solvent DMF indeed gave the
* Corresponding author. Tel.: þ86 371 65213966; fax: þ86 371 67979408
E-mail address: wyj@zzu.edu.cn (Y. Wu).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.12.027

Y. Leng et al. / Tetrahedron 66 (2010) 1244–1248
1245
Table 1
Table 2
Effect of the solvents and oxidants on the oxidative Heck reaction of phenylboronic
acid with styrenea
Oxidative Heck reaction of phenylboronic acid with the olefinsa
R1
R2
B(OH)2
R2
Catalyst (0.5 mol%)
R1
+
R3
B(OH)2
R3
Catalyst( 0.5 mol %)
O
2, DMF, 50 °C
+
Solvent, oxidant
1a
3
2
3a
2a
1a
Entry
1
Olefin
Product
Yieldb (%)
76
Entry
Solvent
Temp (ꢀC)
Time (h)
Oxidant
Yieldb (%)
1
2
3
4
5
6
7
8
DCE
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
23
50
12
12
12
12
12
12
12
6
6
6
6
6
6
6
3
3
3
6
air
air
air
air
air
air
air
CuCl2
Cu(OAc)2
Cu(OTf)2
K2S2O8
Ag2O
BQ
oxone
O2
O2
trace
5
23
CH3NO2
DMA
THF
2b
2c
3b
3c
7
Toluene
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
trace
60
43c
trace
trace
33
2
3
4
99
87
73
9
10
11
12
13
14
15
16
17
18
trace
trace
44
2d
trace
91
3d
40d
38
O2
N2
trace
a
Reaction conditions: styrene 0.25 mmol, phenylboronic acid 0.5 mmol, oxidants
0.25 mmol (entries 8–14) and 0.5 mol % of catalyst in 1.5 mL solvent.
H3CO
2e
3e
H3CO
b
Yields are given for isolated products.
With the addition of Na2CO3 (1 mmol).
0.25 mol % of the catalyst.
c
d
5
99
2f
Cl
best value for the reaction (entries 1–6, Table 1). However, the
addition of base would lead to a lower yield of the desired product
and homo-coupling of phenylboronic acid (entry 7, Table 1). Among
the oxidants screened, O2 was the best choice and the desired
product was obtained with a yield of 91%, while the other oxidants
were relatively ineffective for this reaction (entries 8–15, Table 1).
Under a lower loading of the catalyst and temperature, the yields
dropped sharply (entries 16–17, Table 1). When the reaction was
performed under oxidant-free conditions, only trace amount of the
product was obtained (entries 18, Table 1).
With the optimized conditions in hand, the reactions of phe-
nylboronic acid with various olefins were investigated (Table 2).
Generally, the reactionproceeded well toaffordthe desired products
in high yields. Either electronic effect or steric effect has no signifi-
cant influence on the reactions. For the aryl olefins bearing electron-
donating groups, desired products were also isolated in moderate to
excellent yields (entries 1–4, Table 2). For the olefins containing
electron-withdrawing groups, the reactions proceeded smoothly
generating the products in high yields (entries 5–9, Table 2). On the
other hand, the olefin with a sterically hindered group (2b) also
underwent the olefination and led to a moderate yield of 76% (entry
1, Table 2). Moreover, for other kinds of electron-poor olefins, the
similar yields werealsoobtained with those of the olefins containing
electron-withdrawing groups and (E)/(Z) stereoselectivity would be
higher than 99:1. For example, the reaction of acrylonitrile afforded
exclusively the (E) coupling product in good isolated yield (entry 14,
Table 2); the reaction of ethyl vinyl ketone provided desired prod-
ucts in moderate yield (entry 15, Table 2), and trace amount of
byproduct of homo-coupling of phenylboronic acid was observed
(entries 10–16, Table 2). However, only low yields were isolated for
the reaction of allyl acetate (2r) and allyl alcohol (2s) (entries 17–18,
Table 2), and reaction did not occur for vinylcyclohexane and
vinylcyclopentane (entries 19–20, Table 2).
3f
Cl
6
7
91
99
2g
Cl
3g
Cl
2h
Cl
Br
3h
Cl
Br
8
99
99
82
83
2i
3i
9
2j
NO2
3j
NO2
OCH2CH3
OCH2CH3
10
11
O
2k
O
O
3k
O(n-C4H9)
O(n-C4H9)
O
2l
3l
Subsequently, we explored the scope and the utility of this
method for the olefination of various arylboronic acids with styrene
(continued on next page)

1246
Table 2 (continued)
Y. Leng et al. / Tetrahedron 66 (2010) 1244–1248
Table 3
Oxidative Heck reaction of styrene with various arylboronic acidsa
Entry
Olefin
Product
Yieldb (%)
79
C2H5
(n-C4H9)
2m
C2H5
(n-C4H9)
3m
B(OH)2
Catalyst (0.5 mol%)
O2, DMF, 50 °C
O
O
O
12
R4
+
R4
O
2a
1
3
OCH3
Entry
Arylboronic acid
Product
Yieldb (%)
OCH3
13
14
15
80
78
62
2n
O
3n
O
B(OH)2
1
95
1b
3b
CN
2o
CN
3o
B(OH)2
1c
2
3
4
80
62
66
2p
O
3p
3c
O
B(OH)2
1d
O
O
16
17
47
3d
2q
3q
B(OH)2
1e
H3CO
3e
OAc
OH
H3CO
18
15
2r
OAc
3r
B(OH)2
1f
5
6
62
74
18
19
2s
OH
F
3s
3t
F
No
Reaction
B(OH)2
1g
d
2t
Cl
3h
Cl
No
Reaction
20
d
2u
a
B(OH)2
1h
Reaction conditions: olefin 0.25 mmol, phenylboronic acid 0.5 mmol and
0.5 mol % of catalyst in 1.5 mL DMF at 50 ꢀC with a O2 balloon for 3 h.
7
8
73
b
Yields are given for isolated products.
Br
3i
Br
B(OH)2
Br
(Table 3). In general, both of steric effect and electronic effect have
no critical influence on the oxidative Heck reaction (entries 1–9,
Table 3). For example, the reaction of arylboronic acid bearing an
ortho-substituted steric group (CH3) afforded the product with
a yield of 95% (entry 1, Table 3). The reactions of arylboronic acids
with either electron-donating groups (OCH3 and CH3) or electron-
withdrawing groups (F, Cl and Br) gave the desired products in
moderate to excellent yields.
57
83
1i
3u
Br
B(OH)2
9
1j
3v
On the basis of the mechanism of previous reports3i,3n and our
results, A possible catalytic cycle for this palladium-catalyzed the
reaction of arylboronic acids with olefins was proposed in
Scheme 1. An immediate Pd(II) 4 was formed firstly and sub-
sequently the replacement of immediate Pd(II) 4 with arylbor-
onic acid 1 afforded an organopalladium intermediate 5. Then,
the intermediate 5 could easily react with olefin 2 to give in-
a
Reaction conditions: styrene 0.25 mmol, arylboronic acid 0.5 mmol and
0.5 mol % of catalyst in 1.5 mL DMF at 50 ꢀC with a O2 balloon for 3 h.
b
Yields are given for isolated products.
3. Conclusions
termediate 6.
b
-H elimination of the intermediate 6 occurred to
In summary, we have described a mild, simple and generally
efficient catalytic system for the olefination of arylboronic acids
with olefins by using cyclopalladated ferrocenylimine as the cata-
lyst. The reactions proceeded smoothly to afford the products in
moderate to excellent yields under a low catalyst loading of
0.5 mol %. Further studies on extending the application of this re-
action in organic synthesis are ongoing in our laboratory.
give the desired products 3 and Pd (0) species 7. Finally, Pd(0)
species 7 could be oxidized to the active intermediate Pd(II) 4 in
the presence of O2 thereby avoiding the appearance of palladium
black to finish the catalytic cycle. While oxidative Heck reaction
could not proceed in the absence of an oxidant under such ca-
talysis (entry 18, Table 1).

Y. Leng et al. / Tetrahedron 66 (2010) 1244–1248
1247
palladacycle
(400 MHz, CDCl3)
d
20.4, 123.7, 126.4, 127.1, 127.5, 128.4, 128.5,
128.6, 128.7, 137.2, 137.4, 138.2.
ArB(OH)2
1
4.2.4. (E)-4-Methylstilbene(3d)15. White solid, mp 120–121 ꢀC (lit.
Pd(II)
119–120 ꢀC); 1H NMR (400 MHz, CDCl3)
d 2.36 (s, 3H), 7.05 (d,
O2
4
J¼16.4 Hz, 1H), 7.10 (d, J¼16.5 Hz, 1H), 7.17 (d, J¼7.96 Hz, 2H), 7.22–
7.26 (m, 1H), 7.33–7.37 (m, 2H), 7.41 (d, J¼8.13 Hz, 2H), 7.49–7.52
(m, 2H); 13C NMR (400 MHz, CDCl3)
127.7, 128.6, 129.4, 134.5, 137.5.
d 21.2, 126.37, 126.4, 127.4,
4.2.5. (E)-4-Methoxystilbene(3e)16. White solid, mp 133 ꢀC (lit.
134–136 ꢀC); 1H NMR (400 MHz, CDCl3)
3.84 (s, 3H), 6.89 (d,
Pd(0)
Pd(II)Ar
7
5
d
J¼9.0 Hz, 2H), 6.98 (d, J¼16.3 Hz, 1H), 7.07 (d, J¼16.3 Hz, 1H), 7.24–
7.26 (m, 1H), 7.35 (t, J¼7.4 Hz, 2H), 7.45–7.51 (m, 4H); 13C NMR
(400 MHz, CDCl3)
d 55.3, 114.1,126.2,126.6, 127.2, 127.7,128.2, 128.6,
130.1, 137.6, 159.3.
R
2
R
4.2.6. (E)-2-Chlorostilbene(3f)17. White solid, mp 38–39 ꢀC (lit. 39–
40 ꢀC); 1H NMR (400 MHz, CDCl3)
H
R
Ar
3
Ar
d
7.07 (d, J¼16.3 Hz, 1H), 7.18 (td,
Pd(II)
J¼7.7, 1.6 Hz, 1H), 7.23–7.30 (m, 2H), 7.35–7.39 (m, 3H), 7.49–7.56
6
(m, 3H), 7.68 (dd, J¼7.8, 0.5 Hz, 1H); 13C NMR (400 MHz, CDCl3)
Scheme 1. Proposed mechanism for the oxidative Heck reaction of arylboronic acids
d
124, 126.4, 126.8, 126.9, 128, 128.5, 128.7, 129.8, 131.2, 133.4, 135.4,
with olefins.
137.0.
4.2.7. (E)-3-Chlorostilbene(3g)18. White solid, mp 72–73 ꢀC (lit. 71–
4. Experimental
72 ꢀC); 1H NMR (400 MHz, CDCl3)
d
7.02 (d, J¼16.3 Hz, 1H), 7.11 (d,
J¼16.3 Hz, 1H), 7.21–7.30 (m, 3H), 7.35–7.39 (m, 3H), 7.50–7.51 (m,
3H); 13C NMR (400 MHz, CDCl3)
124.7, 126.3, 126.6, 127.2, 127.5,
4.1. General methods
d
128, 128.7, 129.9, 130, 134.6, 136.8, 139.2.
1H NMR and 13C NMR spectra were recorded on a Bruker DPX-
400 spectrometer with CDCl3 as the solvent and TMS as an internal
standard. Melting points were measured using a WC-1 microscopic
apparatus and are uncorrected. GC analysis was performed on
Agilent 4890D gas chromatograph. The other chemicals were re-
agent grade and used without further purification. All of the
products were known and the purified products were identified by
comparison of melting points, 1H NMR or 13C NMR spectra with the
literatures.
4.2.8. (E)-4-Chlorostilbene(3h)15. White solid, mp 129 ꢀC (lit.
128–129 ꢀC); 1H NMR (400 MHz, CDCl3)
d
7.04 (d, J¼16.3 Hz,
1H), 7.09 (d, J¼16.4 Hz, 1H), 7.26–7.30 (m, 1H), 7.31–7.38 (m,
4H), 7.43–7.46 (m, 2H), 7.50–7.52 (m, 2H); 13C NMR (400 MHz,
CDCl3)
d 126.5, 127.3, 127.6, 127.9, 128.7, 128.8, 129.3, 133.1,
135.8, 137.0.
4.2.9. (E)-4-Bromostilbene(3i)17. Yellow solid, mp 137–138 ꢀC (lit.
136–137 ꢀC); 1H NMR (400 MHz, CDCl3)
d
7.02 (d, J¼16.3 Hz, 1H),
4.2. Typical experimental procedure for the oxidative Heck
reaction of arylboronic acids with olefins
7.09 (d, J¼16.3 Hz, 1H), 7.25–7.30 (m, 1H), 7.34–7.38 (m, 4H), 7.46–
7.51 (m, 4H); 13C NMR (400 MHz, CDCl3)
128.0, 128.7, 129.4, 131.7, 136.3, 137.0.
d 121.3, 126.5, 127.4, 127.9,
Under oxygen atmosphere,
(0.25 mmol), arylboronic acid
a
mixture of the olefin
(0.5 mmol), palladacycle
4.2.10. (E)-3-Nitrostilbene(3j)15. Yellow solid, mp 106–107 ꢀC (lit.
105–106 ꢀC); 1H NMR (400 MHz, CDCl3)
7.11 (d, J¼16.3 Hz, 1H),
(0.5 mol %), and DMF (1.5 mL) was stirred at 50 ꢀC and the re-
action was followed by TLC or GC. After the reaction was com-
plete, the mixture was diluted with ethyl acetate (10 ml), and
washed with saturated aqueous NaHCO3, water and saturated
brine. The combined organic layer was dried over anhydrous
Na2SO4 and filtered. After removal of the solvent in vacuum, the
residue was purified by column chromatography to give the de-
sired products.
d
7.22 (d, J¼15.7 Hz,1H), 7.26–7.56 (m, 6H), 7.80 (d, J¼8.0 Hz,1H), 8.10
(d, J¼8.2 Hz, 1H), 8.37 (s, 1H); 13C NMR (400 MHz, CDCl3)
d 120.8,
121.93, 125.99, 126.77, 127.60, 128.46, 128.78, 129.48, 129.98, 131.64,
132.17, 136.17, 139.05, 148.62.
4.2.11. Ethyl(E)-cinnamate(3k)19. Colourless liquid; 1H NMR
(400 MHz, CDCl3)
d
1.35 (t, J¼7.2 Hz, 3H), 4.27–4.31 (m, 2H), 6.44 (d,
J¼16.0 Hz, 1H), 7.28–7.41 (m, 3H), 7.52–7.55 (m, 2H), 7.67 (d,
4.2.1. (E)-Stilbene (3a)12. Whitesolid,mp123–124 ꢀC (lit.124 ꢀC);1H
J¼16.0 Hz, 1H); 13C NMR (400 MHz, CDCl3)
d 14.29, 60.47, 118.2,
NMR (300 MHz, CDCl3)
d
7.15 (s, 2H), 7.30 (m, 2H), 7.39 (m, 4H), 7.56
126.5, 127.6, 128.6, 128.7, 137.3.
128.01, 128.84, 130.19, 134.39, 144.55, 166.97.
(m, 4H); 13C NMR (400 MHz, CDCl3)
d
4.2.12. Butyl(E)-cinnamate(3l)20. Yellow liquid; 1H NMR (400 MHz,
CDCl3)
4.2.2. (E)-2-Methylstilbene (3b)13. White solid, mp 30 ꢀC (lit. 31–
32 ꢀC); 1H NMR (400 MHz, CDCl3)
2.42 (s, 3H), 7.01 (d, J¼16.1 Hz,
1H), 7.16–7.37 (m, 7H), 7.52 (d, J¼7.8 Hz, 2H), 7.59 (d, J¼7.3 Hz, 1H);
13C NMR (400 MHz, CDCl3)
19.8, 125.3, 126.2, 126.5, 127.5, 127.5,
d
0.95 (t, J¼7.2 Hz, 3H), 1.39–1.49 (m, 2H), 1.65–1.73 (m, 2H),
d
4.20 (t, J¼7.2 Hz, 2H), 6.42 (d, J¼16.1 Hz, 1H), 7.36–7.38 (m, 3H),
7.50–7.53 (m, 2H), 7.66 (d, J¼16.0 Hz, 1H); 13C NMR (400 MHz,
d
CDCl3)
167.0.
d 13.7, 19.1, 30.7, 64.4, 118.2, 128.0, 128.8, 130.1, 134.4, 144.5,
128.6, 129.9, 130.3, 135.7, 136.3, 137.6.
4.2.3. (E)-3-Methylstilbene(3c)14. White solid, mp 49 ꢀC (lit. 48.6–
4.2.13. 2-Ethylhexyl(E)-cinnamate(3m)21. Colourless liquid; 1H
NMR (400 MHz, CDCl3) 0.89–0.95 (m, 6H), 1.25–1.44 (m, 8H),
1.64–1.66 (m, 1H), 4.09–4.16 (m, 2H), 6.45 (d, J¼16.0 Hz, 1H), 7.26–
49.2 ꢀC); 1H NMR (400 MHz, CDCl3)
d
2.48 (s, 3H), 7.17–7.19 (m, 3H),
d
7.33–7.37 (m, 2H), 7.41–7.47 (m, 4H), 7.61 (d, J¼7.4 Hz, 2H); 13C NMR

1248
Y. Leng et al. / Tetrahedron 66 (2010) 1244–1248
7.39 (m, 3H), 7.52–7.54 (m, 2H), 7.68 (d, J¼16.0 Hz, 1H); 13C NMR
References and notes
(400 MHz, CDCl3) d 11.0, 14.0, 22.9, 23.8, 28.9, 30.4, 38.8, 67.0, 118.3,
1. For selected reviews, see: (a) Farina, V. Adv. Synth. Catal. 2004, 346, 1553; (b)
Blaser, H.-U.; Indolese, A.; Naud, F.; Nettekoven, U.; Schnyder, A. Adv. Synth.
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128.0, 128.8, 130.1, 134.5, 144.4, 167.2.
4.2.14. Methyl(E)-
(400 MHz, CDCl3)
a
-methylcinnamate(3n)22. Orange oil; 1H NMR
2.12 (d, J¼1.5 Hz, 3H), 3.82 (s, 3H), 7.29–7.40 (m,
d
5H), 7.69 (d, J¼1.5 Hz, 1H); 13C NMR (400 MHz, CDCl3)
d 14.3, 52.3,
128.3, 128.4, 128.4, 129.7, 135.9, 139.0, 169.2.
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4.2.15. (E)-Cinnamonitrile(3o)23. Colourless liquid; 1H NMR
(400 MHz, CDCl3)
d
5.87 (d, J¼16.7 Hz, 1H), 7.41 (d, J¼16.7 Hz, 1H),
7.38–7.46 (m, 5H); 13C NMR (400 MHz, CDCl3)
129.1, 131.2, 133.5, 150.6.
d 94.3, 118.1, 127.3,
4.2.16. (E)-1-Phenylpent-1-en-3-one(3p)24. Light orange oil; 1H
NMR (400 MHz, CDCl3)
1.17 (t, J¼7.3 Hz, 3H), 2.70 (q, J¼7.3 Hz,
d
2H), 6.74 (d, J¼16.2 Hz, 1H), 7.38–7.39 (m, 3H), 7.53–7.57 (m, 3H);
13C NMR (400 MHz, CDCl3)
142.2, 200.9.
d 8.2, 34, 126.0, 128.2, 128.9, 130.3, 134.6,
4.2.17. 3-Phenyl-2-cyclohexene-l-one(3q)25. Light yellow solid, mp
64 ꢀC (lit. 64–65 ꢀC); 1H NMR (400 MHz, CDCl3)
2.04–2.20 (m,
d
2H), 2.47–2.51 (m, 2H), 2.76–2.79 (m, 2H), 6.42 (s, 1H), 7.27–7.55
(m, 5H); 13C NMR (400 MHz, CDCl3)
128.7, 129.9, 138.7, 159.8, 199.9.
d 22.8, 28.1, 37.2, 125.4, 126.0,
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4.2.18. (E)-Cinnamyl acetate(3r)26. Colourless liquid; 1H NMR
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Sinica 2003, 61, 959.
(400 MHz, CDCl3)
d
2.10 (s, 3H), 4.73 (d, J¼6.2 Hz, 2H), 6.25–6.32
(m, 1H), 6.65 (d, J¼15.9 Hz, 1H), 7.24–7.40 (m, 5H); 13C NMR
(400 MHz, CDCl3)
170.8.
d 21.0, 65.1, 123.1, 126.6, 128.1, 128.6, 134.2, 136.2,
4.2.19. (E)-Cinnamyl alcohol(3s)27. Colourless liquid; 1H NMR
(400 MHz, CDCl3)
d 1.77 (s, 1H), 4.30–4.32 (m, 2H), 6.32–6.40 (m,
1H), 6.60 (d, J¼16.0 Hz, 1H), 7.22–7.40 (m, 5H); 13C NMR (300 MHz,
CDCl3)
d 63.6, 126.5, 127.7, 128.6, 128.6, 131.0, 136.7.
9. (a) Wu, Y.-J.; Yang, L.-R.; Zhang, J.-L.; Wang, M.; Zhao, L.; Song, M.-P.; Gong, J.-F.
ARKIVOC 2004, ix, 111; (b) Gong, J.-F.; Liu, G.-Y.; Du, C.-X.; Zhu, Y.; Wu, Y.-J.
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63, 1963.
4.2.20. (E)-4-fluorostilbene(3t)28. White solid, mp 123–124 ꢀC (lit.
122 ꢀC); 1H NMR (400 MHz, CDCl3)
7.00–7.10 (m, 4H), 7.25–7.28
(m, 1H), 7.34–7.38 (m, 2H), 7.47–7.52 (m, 4H); 13C NMR
d
(400 MHz, CDCl3)
128.5, 128.7.
d 115.5, 115.7, 126.4, 127.5, 127.7, 127.9, 128.0,
11. Yang, F.; Wu, Y.-J. Eur. J. Org. Chem. 2007, 3476.
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4.2.21. (E)-2-Bromostilbene(3u)29. Colourless liquid; 1H NMR
(400 MHz, CDCl3)
7.04 (d, J¼16.2 Hz, 1H), 7.11 (dt, J¼7.6, 1.7 Hz,
d
1H), 7.25–7.40 (m, 4H), 7.45 (d, J¼16.2 Hz, 1H), 7.56 (m, 3H), 7.67
(dd, J¼1.1, 1.5 Hz, 1H); 13C NMR (400 MHz, CDCl3)
d 124.1, 126.6,
126.7, 127.3, 127.4, 128.0, 128.6, 131.3, 133.0, 137.0, 137.1.
17. Wood, C. S.; Mallory, F. B. J. Org. Chem. 1964, 29, 3373.
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4.2.22. (E)-1-Styrylnaphthalene(3v)30. White solid, mp 68–69 ꢀC
(lit. 71–72 ꢀC); 1H NMR (400 MHz, CDCl3)
d
7.13 (d, J¼16.0 Hz,
1H), 7.28–7.60 (m, 8H), 7.72–7.89 (m, 4H), 8.21 (d, J¼8.0 Hz, 1H);
13C NMR (400 MHz, CDCl3)
123.6, 123.8, 125.7, 125.8, 125.8,
d
126.1, 126.7, 127.8, 128.0, 128.6, 128.7, 131.4, 131.7, 133.7, 135.0,
137.6.
24. McConville, M.; Saidi, O.; Blacker, J.; Xiao, J.-L. J. Org. Chem. 2009, 74, 2692.
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Acknowledgements
We are grateful to the National Natural Science Foundation of
China (No. 20772114) and the Innovation Fund for Outstanding
Scholar of Henan Province (No. 0621001100) for financial support of
this research.
}
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