Regioselective control by a catalyst switch in palladium-catalyzed benzylallylation of arylethylidene malononitriles

Article abstract of DOI:10.1016/j.jorganchem.2013.07.047

Regioselective control by a catalyst switch in palladium-catalyzed benzylallylation of arylethylidene malononitriles (α-benzyl-β- allylation versus α-allyl-β-benzylation) is described. The three-component reaction of 2-(bromomethyl)naphthalenes, arylethyl

Full text of DOI:10.1016/j.jorganchem.2013.07.047

Journal of Organometallic Chemistry 745-746 (2013) 177e185
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Regioselective control by a catalyst switch in palladium-catalyzed
benzylallylation of arylethylidene malononitriles
,
a
b
,
a
Xuan Zhang a, Xiaoqiang Yu a , Xiujuan Feng , Hesong Liu
, Ren He ,
*
**
Yoshinori Yamamoto a c, Ming Bao a
,
a State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, China
b Department of Dermatology & Venereology, The First Hospital of Jilin University, Changchun 130021, China
c WPI-AIMR (WPI-Advanced Institute for Materials Research), Tohoku University, Sendai 980-8577, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Regioselective control by a catalyst switch in palladium-catalyzed benzylallylation of arylethylidene
Received 3 June 2013
Received in revised form
11 July 2013
malononitriles (
reaction of 2-(bromomethyl)naphthalenes, arylethylidene malononitriles, and allyltributylstannane
proceeds smoothly with palladium nanoparticles as a catalyst to provide -benzyl- -allylation products
in good yields. The regioselectivity of the benzylallylation reaction is completely overturned with
a-benzyl-b-allylation versus a-allyl-b-benzylation) is described. The three-component
a
b
Accepted 17 July 2013
Pd(PPh3)4 as the catalyst instead of palladium nanoparticles to obtain
moderate to good yields.
a-allyl-b-benzylation products in
Keywords:
Regioselective control
Catalyst switch
Ó 2013 Elsevier B.V. All rights reserved.
2-(Bromomethyl)naphthalene
Arylethylidene malononitrile
Allyltributylstannane
1. Introduction
catalyst switch. Scheme 1 shows that the three-component reac-
tion of 2-(bromomethyl)naphthalenes 1, arylethylidene malononi-
triles 2, and allyltributylstannane proceeded smoothly in the
presence of palladium nanoparticles generated in situ as a catalyst
The palladium-catalyzed bisfunctionalization of activated ole-
fins as a promising and powerful tool for the construction of two
chemical bonds in one-pot procedures has achieved remarkable
progress [1,2]. Many palladium-catalyzed methods, including
alkynylallylation [3], bisallylation [4e9], propargylallylation [10],
acetoallylation [11], alkoxyallylation [12], cyanoallylation [13],
aminoallylation [14], and hydroallylation [15] have been developed
over the past two decades for the bisfunctionalization of activated
olefins. We have recently reported a new type of palladium-
catalyzed bisfunctionalization reaction of activated olefins,
namely, benzylallylation of activated olefins, which proceeds with
to provide
a-benzyl-b-allylation products 3 in good yields. The
regioselectivity of the three-component reaction was completely
overturned with Pd(PPh3)4 as the catalyst instead of palladium
nanoparticles to obtain a-allyl-b-benzylation products 4 in mod-
erate to good yields. The observations are reported in this paper.
2. Results and discussion
Initially, the
a-benzyl-b-allylation reactions of arylethylidene
chemo- and regioselectivity via
p-benzylep-allylpalladium in-
malononitriles 2 with 2-(bromomethyl)naphthalenes 1 and allyl-
tributylstannane occurred at the conditions similar to those
employed in our previous work [16]. The results are summarized in
Table 1. The three-component reaction of 2-(bromomethyl)naph-
thalene (1a), 2-benzylidenemalononitrile (2a), and allyltributyl-
stannane proceeded smoothly in the presence of palladium
nanoparticles,whichweregeneratedinsitu fromPd2(dba)3 and TBAB,
termediates in the presence of palladium nanoparticles [16].
In the course of our continuous research on palladium-catalyzed
benzylallylation of activated olefins with 2-(bromomethyl)naph-
thalenes as benzylating regents, we found that the regioselectivity
of the benzylallylation reaction can be easily controlled with a
in THF at 60 ꢀC to provide
a-benzyl-b-allylation product 3a in 80%
yield (entry 1). Good yields similar to that of 3a were observed when
2-(4-fluorobenzylidene)malononitrile (2b), 2-(4-chlorobenzylidene)
malononitrile (2c), and 2-(4-bromobenzylidene)malononitrile (2d)
were employed at optimized reaction conditions (entries 2e4 versus
* Corresponding author. Tel.: þ86 411 84986184; fax: þ86 411 84986181.
** Corresponding author. Tel.: þ86 431 88782663; fax: þ86 431 85654528.
E-mail addresses: yuxiaoqiang@dlut.edu.cn (X. Yu), liuhesong126@126.com
(H. Liu).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.07.047

178
X. Zhang et al. / Journal of Organometallic Chemistry 745-746 (2013) 177e185
entry 1; 80%e86%). The Cl and Br atoms linked to the benzene ring
were maintained in the structures of products 3c and 3d at the re-
action conditions. These atoms provide opportunities for further
functionalization of these compounds. Compared with activated
olefin substrates 2aed, activated olefin substrates 2e and 2f, which
bear an electron-donating group (Me or OMe) at the para position of
the benzene ring, exhibited relatively low reactivity to provide target
products 3e and 3f in 78% and 76% yields, respectively (entries 5 and
6). The use of naphthyl- and thienyl-containing activated olefin sub-
Scheme 1. Regioselective control in the three-component reaction of 1, 2, and allyl-
strates 2g and 2h led to the formation of
a-benzyl-b-allylation
tributylstannane with a catalyst switch.
products also in good yields (entries 7 and 8). Other bromide sub-
strates 1bef that contain a halogen atom (Cl or Br) and methoxy
Table 1
Palladium-catalyzed a-benzyl-b
-allylation reaction of arylethylidene malononitriles with 2-(bromomethyl)naphthalenes and allyltributylstannane.a
Entry
1
Bromide 1
Activated olefin 2
Product 3
Yield (%)b
80
1a
2a
3a
2
3
4
5
6
1a
1a
1a
1a
1a
80
82
86
78
76
2b
3b
2c
2d
2e
3c
3d
3e
3f
2f
7
8
1a
1a
80
74
2g
3g
2h
3h

X. Zhang et al. / Journal of Organometallic Chemistry 745-746 (2013) 177e185
179
Table 1 (continued )
Entry
Bromide 1
Activated olefin 2
Product 3
Yield (%)b
9
2a
70
65
72
1b
1c
3i
3j
10
11
2a
2a
1d
3k
12
2a
2a
74
81
1e
3l
13
1f
3m
a
Reaction conditions: 2-(bromomethyl)naphthalene (1, 0.6 mmol), arylethylidene malononitrile (2, 0.5 mmol), allyltributylstanane (0.6 mmol, 198.6 mg), Pd2(dba)3 (5 mol
%, 22.9 mg), and TBAB (1.5 equiv, 241.8 mg) in THF (2 mL) at 60 ꢀC for 24 h.
b
Isolated yield.
(MeO)group atthenaphthalene ring, respectively, were subsequently
examined with 2a as the activated olefin substrate. Corresponding
products 3iem were also obtained in satisfactory to good yields
(entries 9e13; 65%e81%). These results suggest that the reactivity of
bromide substrates is not influenced by the substituent property
(electron withdrawing versus electron donating).
bromide substrate 1b proceeded smoothly to provide desired
product 4i in satisfactory yield (entry 9; 67%). However, desired
products 4j and 4k were obtained in only 47% and 49% yields along
with the byproducts 5 and 6 in 31% and 50% yields from the
-benzylation reaction of 2a with bromide substrates 1c and 1d,
respectively (entries 10 and 11). Bromide substrates 1e and 1f
exhibited good reactivity in the -allyl- -benzylation reaction of
a-allyl-
b
The
a
-allyl-b-benzylation reactions of arylethylidene malono-
a
b
nitriles with 2-(bromomethyl)naphthalenes and allyltributyl-
stannane were observed with Pd(PPh3)4 as the catalyst. The results
2a. Products 4l and 4m were obtained in 75% and 87% yields,
respectively (entries 12 and 13).
are presented in Table 2.
a-Allyl-b-benzylation product 4a was
isolated in 70% yield from the palladium-catalyzed three-compo-
nent reaction of 2-(bromomethyl)naphthalene (1a), 2-
benzylidenemalononitrile (2a), and allyltributylstannane (entry
1). Slightly reduced yields were observed when activated olefin
substrates 2bed were employed in this type of bisfunctionalization
reaction (entries 2e4; 65%e67%). The Cl and Br atoms linked to the
benzene ring were also maintained in the structures of products 4c
and 4d at the reaction conditions. As observed in the aforemen-
A plausible mechanism is presented in Scheme 2. Oxidative
tioned
a
-benzyl-
b-allylation reaction, activated olefin substrates 2e
addition of 1a to Pd(0) followed by transmetalation with allyl-
and 2f also exhibited relatively low reactivity in the
a
-allyl-
b
-
tributylstannane would generate p-benzylep-allylpalladium in-
benzylation reaction. Products 4e and 4f were obtained in 56% and
49% yields, respectively (entries 5 and 6). Naphthyl- and thienyl-
containing activated olefin substrates 2g and 2h proved to be un-
termediate A. Activated olefin 2a coordinated with Pd(II) to
produce intermediate B in the absence of PPh3. The Michael-type
nucleophilic addition of an allyl group to 2a produced intermedi-
ate C, which subsequently underwent reductive elimination to
suitable reaction partners. The desired a-allyl-b-benzylation prod-
ucts (4g and 4h) were obtained in low yields (entries 7 and 8; 55%
and 32%, respectively). Other bromide substrates 1bef were sub-
sequently examined with 2a as the activated olefin substrate. The
provide
species. However, the phosphine ligand PPh3 coordinated with A to
produce intermediate D in which the -allyl group still functioned
as a ligand. The behavior of the -allyl group was considered
a-benzyl-b-allylation product 3a and regenerated the Pd(0)
p
a
-allyl-b-benzylation reaction of 2a with chlorine-containing
p

180
X. Zhang et al. / Journal of Organometallic Chemistry 745-746 (2013) 177e185
Table 2
Palladium-catalyzed
a
-allyl-
b
-benzylation reaction of arylethylidene malononitriles with 2-(bromomethyl)naphthalenes and allyltributylstannane.a
Entry
1
Bromide 1
Activated olefin 2
Product 4
Yield (%)b
70
1a
2a
4a
2
3
1a
1a
66
65
2b
4b
2c
4c
4
5
6
1a
1a
1a
67
2d
2e
4d
4e
56
49c
4f
2f
7
8
1a
1a
55c
2g
4g
32c
2h
4h
9
2a
2a
67
47
1b
1c
4i
10
4j

X. Zhang et al. / Journal of Organometallic Chemistry 745-746 (2013) 177e185
181
Table 2 (continued )
Entry
Bromide 1
Activated olefin 2
Product 4
Yield (%)b
11
12
2a
49
75
1d
4k
2a
1e
4l
13
2a
87
4m
1f
a
Reaction conditions: 2-(bromomethyl)naphthalene (1, 0.6 mmol), arylethylidene malononitrile (2, 0.5 mmol), allyltributylstanane (0.6 mmol, 198.6 mg), and Pd(PPh3)4
(10 mol%, 57.8 mg) in toluene (2 mL) at 70 ꢀC for 24 h.
b
Isolated yield.
Reaction was performed at 90 ꢀC for 36 h.
c
because of its relatively strong stability. The Michael-type nucleo-
philic addition of -benzyl group to 2a produced intermediate E.
Reductive elimination from provided -allyl- -benzylation
techniques without special instructions. 1H and 13C NMR spectra
s
were recorded on either a Varian Inova-400 spectrometer
E
a
b
(400 MHz for 1H, 100 MHz for 13C) or a Bruker Avance II-400
spectrometer (400 MHz for 1H, 100 MHz for 13C); CDCl3 and
TMS were used as a solvent and an internal standard, respectively.
product 4a and regenerated the Pd(0) species.
3. Conclusion
The chemical shifts are reported in ppm downfield (d) from TMS,
the coupling constants J are given in Hz. The peak patterns are
indicated as follows: s, singlet; d, doublet; t, triplet; m, multiplet;
q, quartet. IR spectra were recorded on a NEXUS FT-IR spec-
trometer. High resolution mass spectra were recorded on a GC-
TOF mass spectrometry. TLC was carried out on SiO2 (silica gel
60 F254, Merck), and the spots were located with UV light, iodo-
platinate reagent or 1% aqueous KMnO4. Flash chromatography
was carried out on either SiO2 (silica gel 60, 200e300 mesh) or
basic alumina (Al2O3 90, 100e200 mesh). Melting points were
In conclusion, regioselective control in the three-component re-
action of 2-(bromomethyl)naphthalenes, arylethylidene malononi-
triles, and allyltributylstannane was successfully achieved with a
catalystswitch. The a-benzyl-b-allylation reactionproceeds smoothly
with palladium nanoparticles as a catalyst, whereas the regiose-
lectivity of the three-component reactionwas completely overturned
with Pd(PPh3)4 as the catalyst instead of palladium nanoparticles. The
a-allyl-b-benzylation reaction provides a novel and general method
for the bisfunctionalization of activated olefin compounds.
determined using
uncorrected.
a micro-melting point apparatus and are
The allyltributylstannane is commercially available. The starting
materials 2-(bromomethyl)naphthalene (1a) [17], 2-(bromo-
methyl)-1-chloronaphthalene (1b) [18],1-bromo-2-(bromomethyl)
naphthalene (1c) [19], 2-(bromomethyl)-1-methoxynaphthalene
(1e) [20], and 2-(bromomethyl)-6-methoxynaphthalene (1f) [21]
were prepared according to the literature procedures. The
4. Experimental section
4.1. General information
All reactions were carried out under a nitrogen atmosphere
unless otherwise noted. Solvents were purified by standard
Scheme 2. Proposed mechanism for regioselective palladium-catalyzed benzylallylation of arylethylidene malononitriles.

182
X. Zhang et al. / Journal of Organometallic Chemistry 745-746 (2013) 177e185
arylethylidene malononitriles 2 were prepared by Knoevenagel
condensation.
4.3.3. 2-(1-(4-Chlorophenyl)but-3-en-1-yl)-2-(naphthalen-2-
ylmethyl)malononitrile (3c)
White solid (152.0 mg, 82% yield); mp 92e94 ꢀC. 1H NMR
(400 MHz, CDCl3)
d 7.85e7.81 (m, 3H), 7.77 (s, 1H), 7.50e7.48 (m,
4.2. Preparation of starting material 2-bromo-6-(bromomethyl)
naphthalene (1d)
2H), 7.42e7.40 (m, 3H), 7.34 (d, J ¼ 8.5 Hz, 2H), 5.53e5.43 (m, 1H),
5.08 (dd, J ¼ 17.0, 1.3 Hz, 1H), 5.00 (dd, J ¼ 10.2, 0.8 Hz, 1H), 3.21e
3.16 (m, 2H), 3.03e2.98 (m, 2H), 2.93e2.84 (m, 1H); 13C NMR
To a solution of (6-bromonaphthalen-2-yl)methanol (1.19 g,
5 mmol) in anhydrous Et2O (40 mL) at 0 ꢀC, PBr3 (1.52 g, 22 mmol)
was added dropwise, and the resulting solution was stirred at room
temperature for 3 h. The resultant mixture was neutralized with an
aq. NaHCO3, and the product was extracted with Et2O (40 mL ꢁ 2).
The organic layers were dried over Na2SO4, filtered and concen-
trated. Then, the crude product was purified by flash silica gel
chromatography (eluent: petroleum ether) to afford 1d (1.27 g, 85%
yield) as a white solid.
(100 MHz, CDCl3)
129.7, 129.6, 128.9, 128.2, 127.9, 127.6, 126.9, 126.8, 119.2, 115.3,
114.4, 51.8, 45.4, 42.5, 36.3; IR (KBr)
(cmꢂ1) 3398, 3055, 2924,
2247, 1642, 1599, 1508, 1493, 1437, 1414, 1095, 1014, 989, 936, 857,
835, 818, 779, 762, 740; HRMS (EI) Calcd for C24H19ClN2 370.1237
[M]þ, found 370.1241.
d 136.3, 135.3, 133.9, 133.4, 133.2, 130.7, 129.9,
n
4.3.4. 2-(1-(4-Bromophenyl)but-3-en-1-yl)-2-(naphthalen-2-
ylmethyl)malononitrile (3d)
Mp 124e125 ꢀC. 1H NMR (400 MHz, CDCl3)
1H), 7.75 (d, J ¼ 8.6 Hz, 1H), 7.69 (d, J ¼ 8.7 Hz, 1H), 7.58e7.52 (m,
2H), 4.64 (s, 2H); 13C NMR (CDCl3, 100 MHz)
135.8, 134.2, 131.7,
130.1, 130.0, 129.7, 128.0, 127.9, 120.8, 33.8; IR (KBr)
(cmꢂ1) 3448,
d 7.99 (s, 1H), 7.80 (s,
White solid (178.5 mg, 86% yield); mp 123e125 ꢀC. 1H NMR
(400 MHz, CDCl3)
d 7.87e7.84 (m, 3H), 7.78 (s, 1H), 7.59 (d,
d
J ¼ 8.4 Hz, 2H), 7.52e7.50 (m, 2H), 7.42 (dd, J ¼ 8.5, 1.7 Hz, 1H), 7.30
(d, J ¼ 8.4 Hz, 2H), 5.53e5.44 (m, 1H), 5.10 (dd, J ¼ 16.8, 0.8 Hz, 1H),
5.02 (dd, J ¼ 10.4, 1.0 Hz, 1H), 3.23e3.16 (m, 2H), 3.06e2.99 (m, 2H),
n
1637, 1587, 1211, 1132, 1061, 898, 887, 824, 736, 668; HRMS (EI)
Calcd for C11H8Br2 297.8993 [M]þ, found 297.9002.
2.94e2.86 (m, 1H); 13C NMR (100 MHz, CDCl3)
d 134.4, 133.3, 133.1,
132.6,131.0,129.5,128.9,128.2,127.9,127.5,126.8,126.7,123.5,119.1,
4.3. Representative procedure for the
of arylethylidene malononitriles
a
-benzyl-
b
-allylation reaction
115.3, 114.3, 51.9, 45.2, 42.5, 36.3; IR (KBr)
n
(cmꢂ1) 3054, 2924,
2246, 1642, 1600, 1508, 1489, 1438, 1410, 1076, 1010, 989, 937, 856,
832, 818, 777, 762, 738; HRMS (EI) Calcd for C24H19BrN2 414.0732
and 416.0711 [M]þ, found 414.0728 and 416.0716.
An oven-dried reaction tube (25 mL) was charged with
Pd2(dba)3 (22.9 mg, 0.025 mmol), arylethylidene malononitrile
(2, 0.5 mmol), and 2-(bromomethyl)naphthalene (1, 0.6 mmol).
The tube was evacuated and purged with nitrogen gas for three
times. Then, TBAB (248 mg, 0.75 mmol), freshly distilled THF
(2 mL), and allyltributylstannane (198.6 mg, 0.6 mmol) were
sequentially added. The reaction mixture was heated to 60 ꢀC for
24 h. After the reaction completed, the resultant mixture was
evaporated in vacuo to give the crude product, which was then
purified via basic Al2O3 chromatography (eluent: ethyl acetate/
4.3.5. 2-(Naphthalen-2-ylmethyl)-2-(1-(p-tolyl)but-3-en-1-yl)
malononitrile (3e)
White solid (136.6 mg, 77% yield); mp 116e118 ꢀC. 1H NMR
(400 MHz, CDCl3)
d 7.85e7.81 (m, 3H), 7.77 (s, 1H), 7.50e7.48 (m,
2H), 7.42 (dd, J ¼ 8.4, 1.3 Hz, 1H), 7.30 (d, J ¼ 8.1 Hz, 2H), 7.24 (d,
J ¼ 8.0 Hz, 2H), 5.58e5.47 (m, 1H), 5.10 (d, J ¼ 17.0 Hz, 1H), 4.99 (d,
J ¼ 9.9 Hz, 1H), 3.20e3.16 (m, 2H), 3.01e2.90 (m, 3H), 2.39 (s, 3H);
13C NMR (100 MHz, CDCl3)
d 133.7, 133.3, 133.2, 132.1, 130.1, 130.0,
petroleum ether ¼ 1:30 to 1:20) to afford
a
-benzyl-
b
-allylation
129.8,129.2,128.8,128.2,127.9,127.7, 126.7, 126.6,118.6, 115.7, 114.6,
products 3.
52.3, 45.5, 42.6, 36.5, 21.4; IR (KBr)
n
(cmꢂ1) 3410, 3055, 2923, 2244,
1642, 1600, 1514, 1437, 1384, 989, 935, 856, 818, 779, 763, 746;
HRMS (EI) Calcd for C25H22N2 350.1783 [M]þ, found 350.1785.
4.3.1. 2-(Naphthalen-2-ylmethyl)-2-(1-phenylbut-3-en-1-yl)
malononitrile (3a)
White solid (134.5 mg, 80% yield); mp 134e136 ꢀC. 1H NMR
4.3.6. 2-(1-(4-Methoxyphenyl)but-3-en-1-yl)-2-(naphthalen-2-
ylmethyl)malononitrile (3f)
(400 MHz, CDCl3)
d 7.85e7.82 (m, 3H), 7.77 (s, 1H), 7.51e7.48 (m,
2H), 7.45e7.41 (m, 6H), 5.57e5.47 (m, 1H), 5.10 (d, J ¼ 17.0 Hz, 1H),
White solid (139.2 mg, 76% yield); mp 126e128 ꢀC. 1H NMR
4.99 (d, J ¼ 10.2 Hz, 1H), 3.23e3.18 (m, 2H), 3.02e2.92 (m, 3H);
(400 MHz, CDCl3)
d 7.85e7.81 (m, 3H), 7.77 (s, 1H), 7.50e7.48 (m,
13C NMR (100 MHz, CDCl3)
d
135.3, 133.6, 133.3, 133.2, 129.83,
2H), 7.42 (d, J ¼ 8.5 Hz, 1H), 7.33 (d, J ¼ 8.6 Hz, 2H), 6.97 (d,
J ¼ 8.7 Hz, 2H), 5.57e5.47 (m, 1H), 5.10 (d, J ¼ 17.0 Hz, 1H), 4.99 (d,
J ¼ 10.2 Hz, 1H), 3.84 (s, 3H), 3.19e3.16 (m, 2H), 3.03e2.88 (m, 3H);
129.79, 129.4, 129.3, 129.2, 128.8, 128.2, 127.9, 127.6, 126.7, 126.6,
118.7, 115.6, 114.5, 52.6, 45.4, 42.6, 36.5; IR (KBr)
(cmꢂ1) 3058,
2925, 2246, 1642, 1600, 1508, 1495, 1455, 989, 936, 856, 820, 751,
n
13C NMR (100 MHz, CDCl3)
d 160.1, 133.7, 133.3, 133.2, 130.4, 130.0,
702; HRMS (EI) Calcd for
336.1630.
C
24H20N2 336.1626 [M]þ, found
129.8, 128.8, 128.2, 127.8, 127.6, 127.0, 126.7, 126.6, 118.5, 115.7, 114.7,
114.6, 55.4, 51.9, 45.7, 42.5, 36.5; IR (KBr)
n
(cmꢂ1) 3057, 2934, 2246,
1642,1610,1514,1441,1302,1254,1181,1032, 991, 915, 835, 821, 751,
734; HRMS (EI) Calcd for C25H22N2O 366.1732 [M]þ, found 366.1741.
4.3.2. 2-(1-(4-Fluorophenyl)but-3-en-1-yl)-2-(naphthalen-2-
ylmethyl)malononitrile (3b)
White solid (141.7 mg, 80% yield); mp 124e126 ꢀC. 1H NMR
4.3.7. 2-(1-(Naphthalen-2-yl)but-3-en-1-yl)-2-(naphthalen-2-
ylmethyl)malononitrile (3g)
(400 MHz, CDCl3)
d 7.87e7.82 (m, 3H), 7.78 (s, 1H), 7.52e7.49 (m,
2H), 7.43e7.38 (m, 3H), 7.15 (dd, J ¼ 8.4, 8.4 Hz, 2H), 5.55e5.45 (m,
1H), 5.09 (d, J ¼ 17.0 Hz, 1H), 5.01 (d, J ¼ 10.1 Hz, 1H), 3.24e3.19 (m,
2H), 3.05e2.99 (m, 2H), 2.94e2.86 (m, 1H); 13C NMR (100 MHz,
White solid (154.6 mg, 80% yield); mp 94e96 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
7.93 (d, J ¼ 8.6 Hz, 1H), 7.89e7.78 (m, 6H), 7.74
(s, 1H), 7.58e7.52 (m, 3H), 7.48e7.45 (m, 2H), 7.40 (dd, J ¼ 8.4,
1.1 Hz, 1H), 5.57e5.47 (m, 1H), 5.11 (d, J ¼ 16.9 Hz, 1H), 4.95 (d,
J ¼ 10.1 Hz, 1H), 3.40e3.36 (m, 1H), 3.22 (d, J ¼ 13.7 Hz, 1H), 3.11e
3.07 (m, 2H), 3.00 (d, J ¼ 13.7 Hz, 1H); 13C NMR (100 MHz, CDCl3)
1
4
CDCl3)
d
163.1 (d, JCeF ¼ 247.5 Hz), 133.4, 133.3, 131.2 (d, JCe
¼ 3.1 Hz), 131.1, 131.0, 129.8, 129.6, 128.9, 128.2, 127.9, 127.6, 126.8
F
(d, 3JCeF ¼ 9.1 Hz), 119.0, 116.47 (d, 2JCeF ¼ 21.4 Hz), 115.4, 114.4, 51.7,
45.5, 42.6, 36.5; IR (KBr)
n
(cmꢂ1) 3428, 3058, 2927, 2244, 1643,
d 133.5, 133.4, 133.3, 133.2, 132.7, 129.8, 129.4, 129.3, 128.8, 128.1,
1603, 1511, 1442, 1229, 1162, 991, 922, 840, 822, 751; HRMS (EI)
127.9, 127.8, 127.6, 127.0, 126.9, 126.7, 126.6, 125.9, 118.8, 115.7, 114.5,
Calcd for C24H19FN2 354.1532 [M]þ, found 354.1542.
52.7, 45.4, 42.6, 36.6; IR (KBr)
n
(cmꢂ1) 3434, 3056, 2976, 2244,

X. Zhang et al. / Journal of Organometallic Chemistry 745-746 (2013) 177e185
183
1642, 1618, 1600, 1509, 1439, 1272, 1127, 991, 922, 859, 820, 779,
752, 477; HRMS (EI) Calcd for C28H22N2 386.1783 [M]þ, found
386.1788.
(s, 3H), 3.31 (d, J ¼ 13.7 Hz,1H), 3.23 (dd, J ¼ 11.7, 3.7 Hz,1H), 3.18 (d,
J ¼ 13.8 Hz, 1H), 3.08e3.02 (m, 1H), 2.99e2.91 (m, 1H); 13C NMR
(100 MHz, CDCl3)
d 155.5, 135.6, 135.2, 133.7, 129.3, 129.2, 129.1,
128.4, 127.7, 127.5, 126.8, 126.5, 124.8, 122.7, 121.4, 118.5, 115.9, 114.7,
4.3.8. 2-(Naphthalen-2-ylmethyl)-2-(1-(thiophen-2-yl)but-3-en-1-
yl)malononitrile (3h)
62.6, 52.4, 44.4, 36.2, 35.8; IR (KBr)
n
(cmꢂ1) 3065, 3032, 2939,
2249, 1642, 1598, 1573, 1508, 1455, 1372, 1261, 1089, 987, 912, 820,
754, 734, 714; HRMS (EI) Calcd for C25H22N2O 366.1732 [M]þ, found
366.1743.
White solid (126.6 mg, 70% yield); mp 156e158 ꢀC. 1H NMR
(400 MHz, CDCl3)
d 7.87e7.84 (m, 3H), 7.81 (s, 1H), 7.52e7.50 (m,
2H), 7.45 (dd, J ¼ 8.5, 1.3 Hz, 1H), 7.40 (d, J ¼ 5.1 Hz, 1H), 7.19 (d,
J ¼ 3.2 Hz, 1H), 7.12e7.10 (m, 1H), 5.65e5.55 (m, 1H), 5.15 (d,
J ¼ 17.2 Hz, 1H), 5.06 (d, J ¼ 10.2 Hz, 1H), 3.54 (dd, J ¼ 11.7, 3.5 Hz,
1H), 3.25 (d, J ¼ 13.7 Hz, 1H), 3.14 (d, J ¼ 13.7 Hz, 1H), 3.08e3.02 (m,
4.3.13. 2-((6-Methoxynaphthalen-2-yl)methyl)-2-(1-phenylbut-3-
en-1-yl)malononitrile (3m)
White solid (148.4 mg, 81% yield) mp 133e135 ꢀC. 1H NMR
1H), 2.91e2.83 (m, 1H); 13C NMR (100 MHz, CDCl3)
d
137.7, 137.6,
(400 MHz, CDCl3) d 7.74e7.71 (m, 2H), 7.69 (s, 1H), 7.45e7.41 (m,
133.4, 133.1, 129.9, 129.8, 128.9, 128.2, 127.9, 127.6, 126.8, 126.7,
5H), 7.38 (dd, J ¼ 8.5, 1.8 Hz,1H), 7.16 (dd, J ¼ 8.8, 2.4 Hz, 1H), 7.13 (d,
J ¼ 2.1 Hz, 1H), 5.57e5.47 (m, 1H), 5.10 (dd, J ¼ 17.0, 1.5 Hz, 1H), 4.99
(dd, J ¼ 10.2, 1.5 Hz, 1H), 3.92 (s, 3H), 3.22e3.15 (m, 2H), 3.02e2.95
126.6,126.5,119.2, 119.1,115.3, 114.3, 48.3, 45.8, 42.4, 38.4; IR (KBr)
n
(cmꢂ1) 3411, 3057, 2927, 2245, 1642, 1600, 1509, 1438, 1370, 1247,
991, 924, 820, 750, 707; HRMS (EI) Calcd for C22H18N2S 342.1191
[M]þ, found 342.1198.
(m, 3H); 13C NMR (100 MHz, CDCl3)
d 158.3, 135.4, 134.5, 133.6,
129.7, 129.6, 129.4, 129.3, 129.2, 128.8, 128.2, 127.6, 127.4, 119.6,
118.7,115.7,114.6,105.7, 55.5, 52.5, 45.5, 42.5, 36.5; IR (KBr)
n
(cmꢂ1
)
4.3.9. 2-((1-Chloronaphthalen-2-yl)methyl)-2-(1-phenylbut-3-en-
1-yl)malononitrile (3i)
3061, 3030, 2936, 2245, 1634, 1607, 1484, 1393, 1267, 1176, 1030,
992, 917, 719, 700; HRMS (EI) Calcd for C25H22N2O 366.1732 [M]þ,
found 366.1737.
White solid (129.8 mg, 70% yield); mp 126e128 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
8.31 (d, J ¼ 8.5 Hz, 1H), 7.85 (d, J ¼ 8.3 Hz, 1H),
7.78 (d, J ¼ 8.5 Hz, 1H), 7.63e7.54 (m, 2H), 7.52 (d, J ¼ 8.5 Hz, 1H),
7.47e7.42 (m, 5H), 5.60e5.50 (m, 1H), 5.12 (d, J ¼ 17.0 Hz, 1H), 5.01
(d, J ¼ 10.1 Hz,1H), 3.55 (d, J ¼ 14.0 Hz,1H), 3.30 (dd, J ¼ 11.6, 4.0 Hz,
1H), 3.26 (d, J ¼ 14.0 Hz, 1H), 3.08e2.95 (m, 2H); 13C NMR
4.4. Representative procedure for the
of arylethylidene malononitriles
a-allyl-b-benzylation reaction
An oven-dried reaction tube (25 mL) was charged with
Pd(PPh3)4 (57.8 mg, 0.05 mmol), arylethylidene malononitrile (2,
0.5 mmol), and 2-(bromomethyl)naphthalene (1, 0.6 mmol). The
tube was evacuated and purged with nitrogen gas for three times.
Then, freshly distilled toluene (2 mL) and allyltributylstannane
(198.6 mg, 0.6 mmol) were sequentially added. The reaction
mixture was heated to 70 ꢀC for 24 h. After the reaction completed,
the resultant mixture was evaporated in a vacuum to give the crude
product, which was then purified via basic Al2O3 chromatography
(100 MHz, CDCl3)
d 135.2, 134.3, 133.6, 133.1, 131.2, 129.4, 129.3,
129.2, 128.3, 128.1, 127.8, 127.7, 127.6, 127.4, 125.4, 118.8, 115.4, 114.4,
53.2, 44.0, 39.6, 36.4; IR (KBr)
n
(cmꢂ1) 3065, 3033, 2927, 2247,
1642, 1495, 1455, 1440, 1336, 991, 913, 819, 753, 735, 710, 702;
HRMS (EI) Calcd for C24H19ClN2 370.1237 [M]þ, found 370.1238.
4.3.10. 2-((1-Bromonaphthalen-2-yl)methyl)-2-(1-phenylbut-3-
en-1-yl)malononitrile (3j)
White solid (135.0 mg, 65% yield); mp 142e144 ꢀC. 1H NMR
(eluent: ethyl acetate/petroleum ether ¼ 1:30 to 1:20) to afford
a-
(400 MHz, CDCl3)
d
8.32 (d, J ¼ 8.6 Hz,1H), 7.85e7.82 (m, 2H), 7.63e
allyl- -benzylation products 4.
b
7.60 (m, 1H), 7.57e7.54 (m, 2H), 7.48e7.44 (m, 5H), 5.61e5.51 (m,
1H), 5.13 (dd, J ¼ 17.1, 1.2 Hz, 1H), 5.02 (dd, J ¼ 9.9, 1.0 Hz, 1H), 3.60
(d, J ¼ 14.0 Hz, 1H), 3.35e3.30 (m, 2H), 3.07e2.95 (m, 2H); 13C NMR
4.4.1. 2-Allyl-2-(2-(naphthalen-2-yl)-1-phenylethyl)malononitrile
(4a)
(100 MHz, CDCl3)
d
135.1, 134.3, 133.5, 132.6, 130.5, 129.4, 129.3,
White solid (117.7 mg, 70% yield); mp 110e112 ꢀC. 1H NMR
128.4, 128.3, 128.0, 127.6, 127.3, 126.6, 118.7, 115.4, 114.3, 53.2, 44.0,
(400 MHz, CDCl3) d 7.74e7.71 (m, 1H), 7.66e7.62 (m, 2H), 7.42e7.37
42.3, 36.4; IR (KBr)
n
(cmꢂ1) 3441, 3030, 2928, 2248, 1640, 1495,
(m, 3H), 7.29 (s, 5H), 7.06 (d, J ¼ 12.4 Hz, 1H), 5.97e5.86 (m, 1H),
5.41 (d, J ¼ 10.1 Hz, 1H), 5.32 (d, J ¼ 16.9 Hz, 1H), 3.69 (dd, J ¼ 13.4,
2.9 Hz, 1H), 3.52 (dd, J ¼ 13.0, 12.0 Hz, 1H), 3.35 (dd, J ¼ 11.6, 3.0 Hz,
1455, 1384, 991, 925, 823, 757, 697; HRMS (EI) Calcd for C24H19BrN2
414.0732 and 416.0711 [M]þ, found 414.0734 and 416.0719.
1H), 2.53 (dd, J ¼ 14.0, 7.3 Hz, 1H), 2.43 (dd, J ¼ 14.0, 7.2 Hz, 1H); 13
C
4.3.11. 2-((6-Bromonaphthalen-2-yl)methyl)-2-(1-phenylbut-3-en-
1-yl)malononitrile (3k)
NMR (100 MHz, CDCl3) d 134.8, 134.7, 133.3, 132.2, 129.1, 129.0,
128.9, 128.7, 128.1, 127.8, 127.6, 127.5, 127.0, 126.1, 125.7, 123.2, 115.7,
White solid (149.5 mg, 72% yield); mp 129e131 ꢀC. 1H NMR
114.6, 53.6, 43.3, 40.6, 38.9; IR (KBr)
n
(cmꢂ1) 3449, 3084, 3030,
(400 MHz, CDCl3)
d
8.00 (s, 1H), 7.79e7.69 (m, 3H), 7.57 (dd, J ¼ 8.7,
2926, 2248, 1643, 1601, 1508, 1494, 1455, 989, 934, 858, 834, 821,
748, 699; HRMS (EI) Calcd for C24H20N2 336.1626 [M]þ, found
336.1630.
1.8 Hz, 1H), 7.45e7.41 (m, 6H), 5.57e5.47 (m, 1H), 5.11 (dd, J ¼ 17.0,
1.2 Hz, 1H), 5.00 (dd, J ¼ 10.1, 1.0 Hz, 1H), 3.24e3.16 (m, 2H), 3.02e
2.95 (m, 3H); 13C NMR (100 MHz, CDCl3)
d 135.2, 134.3, 133.5, 131.7,
130.4, 130.1, 129.9, 129.8, 129.7, 129.5, 129.3, 128.7, 127.9, 120.8,
4.4.2. 2-Allyl-2-(1-(4-fluorophenyl)-2-(naphthalen-2-yl)ethyl)
malononitrile (4b)
118.8, 115.5, 114.4, 52.7, 45.3, 42.6, 36.6; IR (KBr)
n
(cmꢂ1) 3442,
3069, 2927, 2252, 1639, 1590, 1494, 1455, 1399, 1063, 917, 891, 810,
761, 702; HRMS (EI) Calcd for C24H19BrN2 414.0732 and 416.0711
[M]þ, found 414.0738 and 416.0720.
White solid (116.9 mg, 66% yield); mp 92e94 ꢀC. 1H NMR
(400 MHz, CDCl3) d 7.72e7.69 (m, 1H), 7.65e7.61 (m, 2H), 7.41e7.36
(m, 3H), 7.26e7.22 (m, 2H), 7.03 (d, J ¼ 8.4 Hz, 1H), 6.95 (dd, J ¼ 8.5,
8.5 Hz, 2H), 5.95e5.84 (m, 1H), 5.39 (d, J ¼ 10.2 Hz, 1H), 5.30 (d,
J ¼ 16.9 Hz, 1H), 3.65 (dd, J ¼ 12.8, 2.2 Hz, 1H), 3.41 (dd, J ¼ 12.7,
11.9 Hz, 1H), 3.34 (dd, J ¼ 11.8, 2.4 Hz, 1H), 2.52 (dd, J ¼ 14.0, 7.3 Hz,
4.3.12. 2-((1-Methoxynaphthalen-2-yl)methyl)-2-(1-phenylbut-3-
en-1-yl)malononitrile (3l)
White solid (135.6 mg, 74% yield); mp 70e72 ꢀC. 1H NMR
1H), 2.42 (dd, J ¼ 14.0, 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3)
4
(400 MHz, CDCl3)
d
8.09e8.07 (m, 1H), 7.85e7.82 (m, 1H), 7.63 (d,
d
163.0 (d, 1JCeF ¼ 247.3 Hz), 133.2, 133.1, 131.0 (d, JCeF ¼ 3.4 Hz),
3
J ¼ 8.5 Hz, 1H), 7.53e7.49 (m, 3H), 7.44e7.39 (m, 5H), 5.58e5.48 (m,
130.9, 130.8, 129.7, 129.5, 128.8, 128.0, 127.7, 127.4, 126.6 (d, JCe
¼ 9.1 Hz), 118.8, 116.3 (d, JCeF ¼ 21.4 Hz), 115.2, 114.2, 51.6, 45.3,
2
1H), 5.09 (dd, J ¼ 17.0, 1.4 Hz, 1H), 4.98 (dd, J ¼ 10.2, 1.3 Hz, 1H), 3.78
F

184
X. Zhang et al. / Journal of Organometallic Chemistry 745-746 (2013) 177e185
42.4, 36.3; IR (KBr)
n
(cmꢂ1) 3055, 2959, 2927, 2246, 1604, 1511,
4.4.7. 2-Allyl-2-(1,2-di(naphthalen-2-yl)ethyl)malononitrile (4g)
White solid (106.3 mg, 55% yield); mp 121e123 ꢀC. 1H NMR
(400 MHz, CDCl3) d 7.84e7.79 (m, 2H), 7.76e7.74 (m, 1H), 7.70e7.67
1448, 1371, 1230, 1162, 1015, 988, 960, 857, 841, 819, 784, 764, 747;
HRMS (EI) Calcd for C24H19FN2 354.1532 [M]þ, found 354.1542.
(m, 1H), 7.64e7.57 (m, 2H), 7.51e7.45 (m, 5H), 7.38e7.36 (m, 2H),
7.07 (dd, J ¼ 8.4, 1.3 Hz, 1H), 5.98e5.87 (m, 1H), 5.41 (dd, J ¼ 10.1,
0.4 Hz, 1H), 5.30 (dd, J ¼ 16.9, 0.9 Hz, 1H), 3.78 (dd, J ¼ 13.4, 3.0 Hz,
1H), 3.67 (dd, J ¼ 13.4, 11.5 Hz, 1H), 3.54 (dd, J ¼ 11.3, 3.0 Hz, 1H),
2.56 (dd, J ¼ 14.2, 7.3 Hz,1H), 2.42 (dd, J ¼ 13.9, 7.0 Hz,1H); 13C NMR
4.4.3. 2-Allyl-2-(1-(4-chlorophenyl)-2-(naphthalen-2-yl)ethyl)
malononitrile (4c)
White solid (120.5 mg, 65% yield); mp 87e89 ꢀC. 1H NMR
(400 MHz, CDCl3) d 7.75e7.73 (m, 1H), 7.69e7.65 (m, 2H), 7.45e7.40
(m, 3H), 7.29e7.23 (m, 4H), 7.06 (dd, J ¼ 8.4, 1.6 Hz, 1H), 5.97e5.87
(m, 1H), 5.44 (d, J ¼ 14.0 Hz, 1H), 5.34 (d, J ¼ 17.0 Hz, 1H), 3.69 (dd,
J ¼ 13.2, 2.6 Hz, 1H), 3.45 (dd, J ¼ 13.0, 11.9 Hz,1H), 3.36 (dd, J ¼ 11.8,
2.8 Hz, 1H), 2.55 (dd, J ¼ 13.9, 7.3 Hz, 1H), 2.47 (dd, J ¼ 14.0, 7.1 Hz,
(100 MHz, CDCl3) d 134.9, 133.4, 133.2, 132.3, 129.2, 129.1, 128.8,
128.3, 128.2, 127.9, 127.8, 127.7, 127.1, 126.9, 126.8, 126.2, 125.8,
123.4, 115.9, 114.7, 114.6, 54.0, 43.6, 40.8, 39.1; IR (KBr)
n
(cmꢂ1
)
3450, 3053, 2923, 2250, 1642, 1600, 1508, 1440, 1375, 990, 936, 861,
830, 813, 782, 750, 743, 478; HRMS (EI) Calcd for C28H22N2 386.1783
[M]þ, found 386.1784.
1H); 13C NMR (100 MHz, CDCl3)
d 135.0, 134.3, 133.4, 133.3, 132.2,
130.3, 129.4, 128.4, 128.3, 127.8, 127.6, 127.5, 126.8, 126.3, 125.9,
123.5, 115.3, 114.4, 52.5, 43.2, 40.5, 38.7; IR (KBr)
n
(cmꢂ1) 3055,
2958, 2928, 2246, 1701, 1643, 1599, 1508, 1493, 1438, 1414, 1370,
1095, 1014, 989, 960, 939, 892, 857, 836, 818, 780, 762, 743; HRMS
(EI) Calcd for C24H19ClN2 370.1237 [M]þ, found 370.1241.
4.4.8. 2-Allyl-2-(2-(naphthalen-2-yl)-1-(thiophen-2-yl)ethyl)
malononitrile (4h)
White solid (54.8 mg, 32% yield); mp 110e112 ꢀC. 1H NMR
(400 MHz, CDCl3)
d 7.76e7.74 (m, 1H), 7.70e7.67 (m, 2H), 7.48 (s,
4.4.4. 2-Allyl-2-(1-(4-bromophenyl)-2-(naphthalen-2-yl)ethyl)
malononitrile (4d)
1H), 7.45e7.40 (m, 2H), 7.24 (d, J ¼ 7.0 Hz, 1H), 7.12 (d, J ¼ 8.4 Hz,
1H), 6.99 (d, J ¼ 3.2 Hz, 1H), 6.93 (dd, J ¼ 4.9, 3.7 Hz, 1H), 5.99e5.88
(m, 1H), 5.44 (d, J ¼ 10.1 Hz, 1H), 5.38 (d, J ¼ 16.8 Hz, 1H), 3.73 (dd,
J ¼ 13.0, 2.7 Hz, 1H), 3.68 (dd, J ¼ 11.5, 2.8 Hz, 1H), 3.42 (dd, J ¼ 12.7,
White solid (139.1 mg, 67% yield); mp 81e83 ꢀC. 1H NMR
(400 MHz, CDCl3) d 7.74e7.72 (m, 1H), 7.68e7.64 (m, 2H), 7.43e7.39
(m, 5H), 7.17 (d, J ¼ 8.1 Hz, 2H), 7.05 (dd, J ¼ 8.4, 1.2 Hz, 1H), 5.96e
5.85 (m, 1H), 5.43 (d, J ¼ 10.1 Hz, 1H), 5.33 (d, J ¼ 16.9 Hz, 1H), 3.68
(dd, J ¼ 13.2, 2.8 Hz, 1H), 3.43 (dd, J ¼ 13.0, 11.9 Hz, 1H), 3.34 (dd,
J ¼ 11.8, 2.8 Hz, 1H), 2.54 (dd, J ¼ 14.0, 7.3 Hz, 1H), 2.45 (dd, J ¼ 13.9,
11.8 Hz, 1H), 2.63e2.53 (m, 2H); 13C NMR (100 MHz, CDCl3)
d 137.0,
134.5, 133.5, 132.4, 128.7, 128.3, 128.2, 128.0, 127.7, 127.4, 126.9,
126.4, 126.3, 125.9, 123.7, 115.4, 114.5, 49.4, 43.9, 40.8, 40.5; IR (KBr)
n
(cmꢂ1) 3447, 2957, 2923, 2853, 2252, 1636, 1508, 1458, 1442, 1295,
7.1 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d
134.4, 134.0, 133.4, 132.4,
1076, 992, 935, 859, 833, 785, 746, 702; HRMS (EI) Calcd for
C
22H18N2S 342.1191 [M]þ, found 342.1199.
130.8, 128.6, 128.5, 128.0, 127.8, 127.7, 126.9, 126.4, 126.0, 123.7,
123.3, 115.5, 114.5, 53.0, 43.2, 40.7, 38.8; IR (KBr)
n
(cmꢂ1) 3054,
2955, 2925, 2246, 1698, 1643, 1600, 1590, 1508, 1489, 1438, 1410,
1371, 1272, 1076, 1010, 989, 960, 937, 857, 832, 818, 777, 762, 743,
720; HRMS (EI) Calcd for C24H19BrN2 414.0732 and 416.0711 [M]þ,
found 414.0731 and 416.0718.
4.4.9. 2-Allyl-2-(2-(1-chloronaphthalen-2-yl)-1-phenylethyl)
malononitrile (4i)
White solid (124.2 mg, 67% yield); mp 94e96 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
8.26 (d, J ¼ 8.5 Hz, 1H), 7.69 (d, J ¼ 8.1 Hz, 1H),
7.57e7.53 (m,1H), 7.47e7.40 (m, 2H), 7.27 (s, 5H), 6.83 (d, J ¼ 8.4 Hz,
1H), 5.98e5.88 (m, 1H), 5.40 (d, J ¼ 10.1 Hz, 1H), 5.32 (d, J ¼ 16.9 Hz,
1H), 3.95 (dd, J ¼ 20.0, 10.5 Hz, 1H), 3.58e3.51 (m, 2H), 2.59 (dd,
J ¼ 13.9, 7.4 Hz, 1H), 2.47 (dd, J ¼ 14.0, 7.0 Hz, 1H); 13C NMR
4.4.5. 2-Allyl-2-(2-(naphthalen-2-yl)-1-(p-tolyl)ethyl)
malononitrile (4e)
White solid (98.1 mg, 56% yield); mp 104e106 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
7.74e7.72 (m, 1H), 7.67e7.62 (m, 2H), 7.44e7.39
(100 MHz, CDCl3) d 135.0, 133.5, 132.5, 131.3, 131.1, 129.1, 129.0,
(m, 3H), 7.18 (d, J ¼ 7.6 Hz, 2H), 7.10e7.06 (m, 3H), 5.96e5.86 (m,
1H), 5.41 (d, J ¼ 9.8 Hz, 1H), 5.32 (d, J ¼ 17.0 Hz, 1H), 3.67 (dd,
J ¼ 13.8, 3.0 Hz,1H), 3.50 (dd, J ¼ 13.5, 11.7 Hz,1H), 3.33 (dd, J ¼ 11.5,
3.2 Hz, 1H), 2.52 (dd, J ¼ 14.2, 7.4 Hz, 1H), 2.43 (dd, J ¼ 14.0, 7.2 Hz,
128.8, 128.5, 128.1, 127.3, 126.6, 126.5, 124.5, 123.4, 115.3, 114.7, 51.0,
43.2, 40.8, 37.6; IR (KBr)
(cmꢂ1) 3061, 3035, 2929, 2248, 1643,
1598, 1560, 1496, 1455, 1334, 1227, 992, 935, 910, 818, 771, 753, 733,
705; HRMS (EI) Calcd for
370.1242.
n
C
24H19ClN2 370.1237 [M]þ, found
1H), 2.29 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 138.9, 135.1, 133.5,
132.3, 131.8, 129.9, 129.0, 128.9, 128.2, 127.9, 127.7, 127.2, 126.2,
125.8, 123.3, 115.9, 114.8, 53.4, 43.6, 40.7, 39.0, 21.3; IR (KBr)
n
4.4.10. 2-Allyl-2-(2-(1-bromonaphthalen-2-yl)-1-phenylethyl)
malononitrile (4j)
(cmꢂ1) 3450, 3057, 3025, 2926, 2248, 1644, 1632, 1516, 1444, 989,
935, 856, 834, 823, 779, 765, 742; HRMS (EI) Calcd for C25H22N2
350.1783 [M]þ, found 350.1787.
White solid (97.6 mg, 47% yield); mp 104e106 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
8.28 (d, J ¼ 8.6 Hz, 1H), 7.68 (d, J ¼ 8.1 Hz, 1H),
7.58e7.54 (m, 1H), 7.48e7.43 (m, 2H), 7.28 (s, 5H), 6.81 (d,
J ¼ 8.4 Hz, 1H), 5.99e5.89 (m, 1H), 5.41 (d, J ¼ 10.2 Hz, 1H), 5.33 (d,
J ¼ 16.8 Hz, 1H), 3.98 (dd, J ¼ 24.1, 14.0 Hz, 1H), 3.64e3.55 (m, 2H),
2.61 (dd, J ¼ 13.9, 7.4 Hz, 1H), 2.48 (dd, J ¼ 14.0, 7.1 Hz,1H); 13C NMR
4.4.6. 2-Allyl-2-(1-(4-methoxyphenyl)-2-(naphthalen-2-yl)ethyl)
malononitrile (4f)
White solid (95.3 mg, 49% yield); mp 120e122 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
7.74e7.71 (m, 1H), 7.68e7.62 (m, 2H), 7.44e7.39
(100 MHz, CDCl3) d 134.9, 134.7, 133.5, 132.4, 129.2, 129.1, 129.0,
(m, 3H), 7.26e7.20 (m, 2H), 7.07 (d, J ¼ 8.3 Hz, 1H), 6.81 (d,
J ¼ 8.1 Hz, 2H), 5.96e5.86 (m, 1H), 5.41 (d, J ¼ 10.2 Hz, 1H), 5.32 (dd,
J ¼ 16.9, 10.2 Hz, 1H), 3.74 (s, 3H), 3.66 (dd, J ¼ 13.4, 2.9 Hz, 1H), 3.47
(dd, J ¼ 13.2, 11.9 Hz, 1H), 3.32 (dd, J ¼ 11.7, 2.9 Hz, 1H), 2.52 (dd,
J ¼ 14.0, 7.4 Hz, 1H), 2.43 (dd, J ¼ 14.0, 7.2 Hz, 1H); 13C NMR
128.9,128.8,128.1,127.6,127.4,127.3,126.5,124.5,123.4,115.3,114.7,
50.8, 43.1, 40.8, 40.3; IR (KBr)
n
(cmꢂ1) 3061, 3034, 2930, 2248,1643,
1597,1557,1497,1455,1330,1257,1224, 978, 936, 908, 819, 769, 753,
733, 704; HRMS (EI) Calcd for C24H19BrN2 414.0732 and 416.0711
[M]þ, found 414.0721 and 416.0720.
(100 MHz, CDCl3)
d 135.1, 133.5, 132.3, 130.3, 128.9, 128.2, 127.9,
127.7, 127.2, 126.7, 126.2, 125.8, 123.3, 115.9, 114.8, 114.5, 55.4, 53.0,
4.4.11. 2-Allyl-2-(2-(6-bromonaphthalen-2-yl)-1-phenylethyl)
malononitrile (4k)
43.7, 40.7, 39.0; IR (KBr)
n
(cmꢂ1) 3448, 3054, 3012, 2933, 2246,
1611, 1514, 1463, 1440, 1305, 1254, 1181, 1033, 989, 936, 857, 836,
812, 783, 745; HRMS (EI) Calcd for C25H22N2O 366.1732 [M]þ, found
366.1741.
White solid (101.7 mg, 49% yield); mp 94e96 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
7.88 (s, 1H), 7.55e7.51 (m, 2H), 7.47 (dd, J ¼ 8.8,
1.8 Hz, 1H), 7.38 (s, 1H), 7.29 (s, 5H), 7.08 (dd, J ¼ 8.6, 1.6 Hz, 1H),

X. Zhang et al. / Journal of Organometallic Chemistry 745-746 (2013) 177e185
185
5.96e5.86 (m, 1H), 5.42 (d, J ¼ 10.5 Hz, 1H), 5.32 (d, J ¼ 17.0 Hz, 1H),
3.67 (dd, J ¼ 13.4, 3.0 Hz, 1H), 3.50 (dd, J ¼ 11.6, 11.6 Hz, 1H), 3.32
(dd, J ¼ 11.5, 3.2 Hz, 1H), 2.52 (dd, J ¼ 13.7, 7.3 Hz, 1H), 2.43 (dd,
4.4.15. ((6-Bromonaphthalen-2-yl)methyl)tributylstannane (6)
Colorless oil (153.0 mg, 50% yield). 1H NMR (400 MHz, CDCl3)
d
7.88 (s,1H), 7.56 (d, J ¼ 8.4 Hz,1H), 7.52 (d, J ¼ 8.6 Hz,1H), 7.44 (dd,
J ¼ 13.5, 7.1 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d
135.4, 134.8, 133.4,
J ¼ 8.4, 2.0 Hz, 1H), 7.35 (s, 1H), 7.16 (dd, J ¼ 8.4, 1.6 Hz, 1H), 2.45 (s,
131.8, 129.7, 129.6, 129.32, 129.27, 129.2, 129.1, 128.8, 128.2, 127.9,
2H), 1.46e1.38 (m, 6H), 1.29e1.20 (m, 6H), 0.86e0.79 (m, 15H); 13
NMR (100 MHz, CDCl3) 142.5, 132.6, 131.7, 129.7, 129.2, 128.5,
128.4, 127.0, 123.5, 29.2, 27.5, 19.0, 13.9, 9.7; IR (neat)
(cmꢂ1) 3049,
C
127.3, 123.5, 119.8, 115.7, 114.6, 53.6, 43.4, 40.7, 39.1; IR (KBr)
n
d
(cmꢂ1) 3032, 2924, 2246, 1590, 1498, 1455, 1062, 989, 936, 879, 807,
731, 706; HRMS (EI) Calcd for C24H19BrN2 414.0732 and 416.0711
[M]þ, found 414.0721 and 416.0722.
n
2955, 2923, 2869, 2851, 1586, 1495, 1462, 1194, 1064, 896, 875, 810,
799.
4.4.12. 2-Allyl-2-(2-(1-methoxynaphthalen-2-yl)-1-phenylethyl)
malononitrile (4l)
Acknowledgments
White solid (137.4 mg, 75% yield); mp 110e112 ꢀC. 1H NMR
We are grateful to the National Natural Science Foundation of
China (Nos. 21002010 and 21072023) for financial support. This
work was partly supported by the Fundamental Research Funds for
the Central Universities (DUT12LK44).
(400 MHz, CDCl3)
d
8.05 (d, J ¼ 8.4 Hz, 1H), 7.72 (d, J ¼ 8.3 Hz, 1H),
7.50e7.47 (m, 1H), 7.44e7.40 (m, 1H), 7.33e7.26 (m, 6H), 6.84 (d,
J ¼ 8.4 Hz, 1H), 5.98e5.88 (m, 1H), 5.40 (d, J ¼ 10.0 Hz, 1H), 5.31 (d,
J ¼ 16.8 Hz, 1H), 3.99 (s, 3H), 3.79 (dd, J ¼ 13.0, 2.8 Hz, 1H), 3.58 (dd,
J ¼ 13.0, 2.8 Hz,1H), 3.41 (dd, J ¼ 12.7,12.7 Hz,1H), 2.53 (dd, J ¼ 13.9,
7.3 Hz,1H), 2.41 (dd, J ¼ 14.0, 7.0 Hz,1H); 13C NMR (100 MHz, CDCl3)
Appendix A. Supplementary data
d
154.3, 135.3, 134.4, 129.1, 129.0, 128.9, 128.5, 128.2, 128.0, 126.1,
This material can be found in the online version, at http://dx.doi.
org/10.1016/j.jorganchem.2013.07.047.
126.0, 124.0, 123.3, 122.1, 115.9, 114.8, 62.3, 52.1, 43.6, 40.7, 34.3; IR
(KBr)
n
(cmꢂ1) 3063, 2937, 2247, 1643, 1597, 1573, 1507, 1495, 1455,
1371, 1260, 1246, 1080, 990, 935, 911, 820, 754, 732, 702; HRMS (EI)
Calcd for C25H22N2O 366.1732 [M]þ, found 366.1732.
References
[1] I. Nakamura, Y. Yamamoto, Chem. Rev. 104 (2004) 2127e2198.
[2] N.T. Patil, Y. Yamamoto, Synlett 13 (2007) 1994e2005.
[3] B.M. Trost, C.-J. Li, Tetrahedron Lett. 34 (1993) 2271e2274.
[4] H. Nakamura, J.G. Shim, Y. Yamamoto, J. Am. Chem. Soc. 119 (1997) 8113e
8114.
[5] N. Solin, S. Narayan, K.J. Szabó, J. Org. Chem. 66 (2001) 1686e1693.
[6] S.C. George, J. John, S. Anas, J. John, Y. Yamamoto, E. Suresh,
K.V. Radhakrishnan, Eur. J. Org. Chem. (2010) 5489e5497.
[7] H. Nakamura, K. Shimizu, Tetrahedron Lett. 52 (2011) 426e429.
[8] S.C. George, S. Thulasi, K.V. Radhakrishnan, Y. Yamamoto, Org. Lett. 13 (2011)
4984e4987.
[9] L. Adak, S. Bhadra, K. Chattopadhyay, B.C. Ranu, New J. Chem. 35 (2011) 430e
437.
[10] M. Jeganmohan, M. Shanmugasundaram, C.-H. Cheng, J. Org. Chem. 69 (2004)
4053e4062 (and references therein).
[11] J.G. Shim, H. Nakamura, Y. Yamamoto, J. Org. Chem. 120 (1998) 8470e8474.
[12] H. Nakamura, M. Sekido, M. Ito, Y. Yamamoto, J. Am. Chem. Soc. 120 (1998)
6838e6839.
[13] H. Nakamura, H. Shibata, Y. Yamamoto, Tetrahedron Lett. 41 (2000) 2911e
2914.
4.4.13. 2-Allyl-2-(2-(6-methoxynaphthalen-2-yl)-1-phenylethyl)
malononitrile (4m)
White solid (159.4 mg, 87% yield); mp 110e112 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
7.54 (dd, J ¼ 9.5, 9.5 Hz, 2H), 7.34 (s, 1H), 7.29 (s,
5H), 7.08 (dd, J ¼ 8.8, 2.5 Hz, 1H), 7.00e7.03 (m, 2H), 5.86e5.96 (m,
1H), 5.41 (d, J ¼ 10.2 Hz, 1H), 5.31 (d, J ¼ 17.0 Hz, 1H), 3.87 (s, 3H),
3.65 (dd, J ¼ 13.6, 3.3 Hz, 1H), 3.48 (dd, J ¼ 13.3, 11.6 Hz, 1H), 3.32
(dd, J ¼ 11.5, 3.2 Hz, 1H), 2.52 (dd, J ¼ 14.1, 7.5 Hz, 1H), 2.42 (dd,
J ¼ 14.0, 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 157.6, 135.1, 133.4,
132.5,129.2,129.0,128.9,128.8,127.8, 127.7, 127.0, 123.4,119.1,115.8,
114.7, 105.6, 55.4, 53.8, 43.4, 40.8, 38.9; IR (KBr)
n
(cmꢂ1) 3060,
3032, 3006, 2956, 2246, 1635, 1606, 1484, 1392, 1266, 1232, 1197,
1031, 989, 936, 852, 724, 701; HRMS (EI) Calcd for C25H22N2O
366.1732 [M]þ, found 366.1738.
[14] K. Aoyagi, H. Nakamura, Y. Yamamoto, J. Org. Chem. 67 (2002) 5977e5980.
[15] J.-G. Shim, J.C. Park, C.S. Cho, S.C. Shim, Y. Yamamoto, J. Chem. Soc. Chem.
Commun. (2002) 852e853.
4.4.14. ((1-Bromonaphthalen-2-yl)methyl)tributylstannane (5)
Colorless oil (94.8 mg, 31% yield). 1H NMR (400 MHz, CDCl3)
[16] X. Zhang, X. Feng, X. Yu, R. He, M. Bao, Org. Biomol. Chem. 11 (2013) 4016e
4024.
d
8.19 (d, J ¼ 8.4 Hz, 1H), 7.73 (d, J ¼ 8.0 Hz, 1H), 7.62 (d, J ¼ 8.0 Hz,
1H), 7.52 (dd, J ¼ 7.6, 7.2 Hz,1H), 7.37 (dd, J ¼ 7.6, 6.8 Hz,1H), 7.20 (d,
J ¼ 8.4 Hz, 1H), 2.69 (s, 2H), 1.46e1.38 (m, 6H), 1.25e1.20 (m, 6H),
[17] C. Bazzini, S. Brovelli, T. Caronna, Eur. J. Org. Chem. (2005) 1247e1257.
[18] C.T. Goralski, J.R. McCarthy, W.R. Kracht, J. Lab. Com Rad. (1987) 852e858.
[19] G. Chouhan, H. Alper, J. Org. Chem. 74 (2009) 6181e6189.
[20] N. Kongkathip, B. Kongkathip, P. Siripong, Bioorg. Med. Chem. 11 (2003)
3179e3191.
0.87e0.79 (m, 15H); 13C NMR (100 MHz, CDCl3)
d 142.5,133.0, 131.8,
128.1, 127.6, 127.4, 127.3, 126.5, 124.6, 29.2, 27.5, 22.3, 13.8, 10.5; IR
(neat)
(cmꢂ1) 3049, 2955, 2921, 2869, 2849, 1620, 1595, 1498,
1462, 1374, 1329, 1257, 1220, 1078, 968, 812, 744.
n
[21] R.W. Hartmann, A. Palusczak, F. Lacan, G. Ricci, R. Ruzziconi, J. Enzym. Inhib.
19 (2004) 145e155.