Regio- and chemoselective palladium-catalyzed benzylallylation of activated olefins: The remarkable effect of palladium nanoparticles

Article abstract of DOI:10.1039/c3ob40487k

The palladium-catalyzed three-component reactions of benzyl halides, activated olefins, and allyltributylstannane were successfully conducted to produce the corresponding benzylallylation products in satisfactory to high yields. The benzylallylation reaction proceeded smoothly under mild conditions in the presence of palladium nanoparticles in tetrahydrofuran. The Royal Society of Chemistry 2013.

Full text of DOI:10.1039/c3ob40487k

Organic &
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Regio- and chemoselective palladium-catalyzed
benzylallylation of activated olefins: the remarkable
effect of palladium nanoparticles†
Cite this: Org. Biomol. Chem., 2013, 11,
4016
Xuan Zhang, Xiujuan Feng,* Xiaoqiang Yu, Ren He and Ming Bao*
Received 9th March 2013,
Accepted 16th April 2013
The palladium-catalyzed three-component reactions of benzyl halides, activated olefins, and allyltributyl-
stannane were successfully conducted to produce the corresponding benzylallylation products in satis-
factory to high yields. The benzylallylation reaction proceeded smoothly under mild conditions in the
presence of palladium nanoparticles in tetrahydrofuran.
DOI: 10.1039/c3ob40487k
www.rsc.org/obc
allyltributylstannane.11 These reactions proceeded smoothly
and exclusively via π-benzyl π-allylpalladium intermediates in
1. Introduction
The chemistry of π-allylpalladium complexes has become one the presence of a PPh3 ligand to produce the dearomatization
of the most successful areas of organometallic catalysis.1 products. The π-benzyl π-allylpalladium intermediates possess
Mono-π-allylpalladium complexes react with a wide variety of similar structures to the bis-π-allylpalladium complexes. This
nucleophiles to construct new carbon–carbon or carbon– structural similarity encouraged us to consider whether the
heteroatom bonds (Tsuji–Trost-type reaction).2–7 Yamamoto benzylallylation of activated olefins could similarly occur via
et al.8 demonstrated that the bis-π-allylpalladium complexes π-benzyl π-allylpalladium intermediates (eqn (2)). The main
could react with electrophiles to produce new carbon–carbon problem is that π-benzyl π-allylpalladium intermediates can
bonds. The amphiphilic behavior of a bis-π-allylpalladium easily undergo allylative dearomatization in the presence of
complex was likewise revealed by the same group.9 That is, a the phosphine ligand. A possible solution for this problem is
bis-π-allylpalladium complex generated in situ from the reac- to develop a novel catalytic system without the phosphine
tion of allyl chloride, allyltributylstannane, and a palladium ligand. The results of such a system are reported in this paper.
species can react with activated olefins to produce double ally-
lation products (eqn (1)).9
2. Results and discussion
ð1Þ
The three-component reaction of benzyl chloride (1a),
2-benzylidenemalononitrile (2a), and allyltributylstannane in
the presence of a palladium precatalyst was chosen as a model
in our preliminary studies to optimize the reaction conditions.
The results are shown in Table 1. The precatalysts PdCl2, Pd
ð2Þ
(OAc)2, Pd(acac)2, and Pd2(dba)3 in tetrahydrofuran (THF) were
initially tested at 60 °C in the presence of tetrabutyl-
ammonium bromide (TBAB). A relatively high yield was
obtained using Pd2(dba)3 as a precatalyst (entry 4 vs. entries
The π-benzylpalladium complexes are widely used in
organic synthesis as special π-allylpalladium intermediates.10
1–3). The formation of the Stille coupling and allylative de-
aromatization products was not observed. No reaction
We previously reported the facile palladium-catalyzed
occurred in the absence of TBAB (entry 5). The quaternary
allylative dearomatization reactions of benzyl chlorides with
ammonium salt was a necessary additive to avoid the gene-
ration of palladium black. Thus, the quaternary ammonium
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian
salts were screened using Pd2(dba)3 in THF as the precatalyst
116023, China. E-mail: fengxiujuan@dlut.edu.cn, mingbao@dlut.edu.cn;
(entries 4 and 6–8). Four quaternary ammonium salts, namely
Fax: +86-0411-84986180; Tel: +86-0411-84986181
TBAB, tetrabutylammonium chloride (TBAC), tetrabutyl-
ammonium iodide (TBAI), and tetrabutylammonium acetate
†Electronic supplementary information (ESI) available: Experimental procedures
and spectroscopic data for isolated compounds. See DOI: 10.1039/c3ob40487k
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Table 1 Screening of reaction conditionsa
Table 2 Palladium-catalyzed three-component reaction of 2-benzylidenemalono-
nitrile, allytributylstannane, and various benzyl halidesa,b
Entry
Pd catalyst
Additive
Solvent
Yieldb (%)
1
2
3
PdCl2
TBAB
TBAB
TBAB
TBAB
None
TBAC
TBAI
TBAAc
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
Acetone
DMF
Toluene
THF
71
74
73
81
NRd
62
78
56
50
65
34
80
74
40
64
79
Entry
1
Benzyl halide 1
Product 3
Yieldb (%)
81
Pd(OAc)2
Pd(acac)2
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
1a
1b
3a
3b
4
5c
6
7
8
2
3
4
80
83
79
9e
10f
11
12
13
14g
15h
16i
1c
3c
THF
THF
1d
3d
a Reaction conditions: benzyl chloride (1a, 0.6 mmol, 75.9 mg),
2-benzylidenemalononitrile (2a, 0.5 mmol, 77.0 mg),
allyltributylstannane (0.6 mmol, 198.6 mg), Pd catalyst [10 mol%
PdCl2, Pd(OAc)2, and Pd(acac)2, respectively;
5 mol% Pd2(dba)3],
additive (1.5 equiv.), and solvent (2 mL) at 60 °C for 24 h. b Isolated
yield. c The reaction was performed in the absence of TBAB. d No
reaction (NR). e 1.0 equiv. TBAB was used. f 2.0 equiv. TBAB was used.
g The reaction was performed at room temperature. h The reaction was
performed at 40 °C. i The reaction was performed at 80 °C.
5
6
1e
1f
3e
3f
83
83
(TBAAc), were tested as additives. Among these salts, TBAB
produced the highest yield of the desired benzylallylation
product 3a (entry 4, 81%). The reaction yield was likewise
influenced by the amount of TBAB. The 3a yield was decreased
when 1.0 or 2.0 equivalents of TBAB were employed (entry 9,
50%; entry 10, 65%, respectively). The solvents were subsequently
screened using Pd2(dba)3 and TBAB as the precatalyst and the
additive, respectively. Nonpolar (toluene) and polar [THF,
acetone, and N,N-dimethyl formamide (DMF)] solvents were
examined (entries 4 and 11–13). THF proved to be the best
solvent (entry 4). The suitable reaction temperature was finally
investigated (entries 4 and 14–16). These results suggested that
7
8
9
1g
1h
3g
3h
82
70
1i
1j
3i
3j
62
82
87
60 °C is suitable temperature for the reaction. Therefore, the sub- 10
sequent palladium-catalyzed benzylallylation reactions of acti-
vated olefins were performed in THF at 60 °C for 24 h with
Pd2(dba)3 as the precatalyst and TBAB (1.5 equiv.) as the additive.
11
1k
3k
The activated olefin substrate 2a was used as a starting
material to determine the scope of benzyl halide substrates
under the optimized reaction conditions. The results are sum-
marized in Table 2. High yields similar to that of 3a were
observed when 4-fluorobenzyl chloride (1b), 4-chlorobenzyl
chloride (1c), and 4-bromobenzyl chloride (1d) were employed
12
1l
3l
81
85
under optimized reaction conditions (79%–83%). Notably, the
13
1m
3m
Cl and Br atoms linked to the benzene ring were maintained
in the structures of the products 3c and 3d under the opti-
mized conditions. These atoms provided opportunities for the
further functionalization of these compounds. The reactions
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or para position provided high yields of the products 3l–3n
(81%–85%). These results indicate that the reactivities of
benzyl chlorides are not influenced by steric effects of their
substituents. Subsequently, the chloromethyl naphthalene
substrates 1o–1r were utilized in this type of three-component
reaction. The respective products 3o–3r were obtained in
79%–83% yields. Finally, the reactivities of the bromide
substrates were investigated. The reactions of benzyl
bromide (1s) and 1-(bromomethyl)naphthalene (1t) smoothly
proceeded to produce 3a and 3o in high yields (86% and 85%,
respectively).
Table 2 (Contd.)
Entry
14
Benzyl halide 1
Product 3
Yieldb (%)
85
1n
3n
The reactivities of various activated olefins were then inves-
tigated using the chloride substrate 1a as a starting material,
and the results are shown in Table 3. No significant electronic
effects were observed after substituents were added to the
benzene ring of activated olefins. The reactions of the 2-benzyl-
idenemalononitrile substrates 2b–2f with electron-withdrawing
(F, Cl, and Br) or electron-donating (Me and OMe) groups
smoothly proceeded to synthesize the benzylallylation pro-
ducts 4b–4f in high yields (78%–87%). The Cl and Br atoms
were similarly maintained in the structures of these products.
The benzylallylation products 4g and 4h were obtained in high
yields (82% and 80%, respectively) from the reactions of
1-naphthylmethylidenemalononitrile (2g) and 2-naphthyl-
methylidenemalononitrile (2h), respectively. This type of three-
component reaction could be extended to heterocycle-contain-
ing activated olefins. The use of 2-(thiophen-2-ylmethylene)-
malononitrile (2i) as a starting material led to the formation of
the benzylallylation product 4i in 78% yield. The activated
olefin 2j with CN and CO2Et groups could similarly be used in
this type of reaction. The benzylallylation product 4j was
obtained in 76% yield with a 95 : 5 diastereomeric ratio.
However, no reactions were observed while testing the acti-
vated olefins 2k or 2l, which possess two CO2Et or two COMe
groups, respectively. These results indicate that the reactivity
of the activated olefin strongly depends on the electronic effect
of substituents linked to the olefin carbon atom.
15
16
17
18
1o
1p
1q
1r
3o
3p
3q
3r
80
83
79
80
19
20
1s
1t
3a
3o
86
85
a Reaction conditions: benzyl halides (1a to 1t, 0.6 mmol),
2-benzylidenemalononitrile (2a, 0.5 mmol, 77.0 mg),
allyltributylstannane (0.6 mmol, 198.6 mg), Pd2(dba)3 (5 mol%,
22.9 mg), TBAB (1.5 equiv., 241.8 mg), and THF (2 mL) at 60 °C for
24 h. b Isolated yield.
Transmission electron microscopy (TEM) was performed to
investigate the reason for the high activity of the palladium
catalyst system (Pd/TBAB) in this type of three-component reac-
tion. A sample TEM micrograph is shown in Fig. 1. The pres-
ence of (2.4 0.5) nm sized palladium nanoparticles in the
reaction mixture is evident in the TEM image (Fig. 1). These
results revealed that the additive TBAB acts as a stabilizer to
disperse the palladium nanoparticles generated in situ.12
These palladium nanoparticles are known to exhibit higher
catalytic activity, as compared with other related molecular
catalysts.13 Therefore, the high activity of this palladium cata-
lyst system could be ascribed to the formation of palladium
nanoparticles.
of 2-chlorobenzyl chloride (1e), 2,4-dichlorobenzyl chloride
(1f), and 3,4-dichlorobenzyl chloride (1g) proceeded smoothly
to produce the desired benzylallylation products 3e–3g in high
yields (82%–83%). The products 3h and 3i were obtained in
relatively low yields (70% and 62%, respectively) from the reac-
tions of the benzyl chlorides 1h and 1i. These chlorides, 1h
and 1i, contain the strong electron-withdrawing nitro (NO2)
and acetoxy (AcO) groups, respectively, at the para position.
The electron density of the π-benzyl carbon-based ligand was
greatly decreased by the strong electron-withdrawing NO2 and
AcO groups that were linked to the benzene ring. Thus, the
nucleophilic reactivity of the π-allyl group in the π-benzyl
π-allylpalladium intermediate was reduced (eqn (2)). The
benzyl chlorides 1j and 1k had one or two electron-donating
methyl (Me) groups on the benzene ring. As expected, these
reactions provided high yields of the products 3j and 3k (82%
and 87%, respectively). Reactions of the benzyl chlorides 1l–1n
that contained a methoxy (MeO) group at the ortho, meta,
3. Conclusions
In conclusion, we have successfully achieved the benzylallyla-
tion of activated olefins by utilizing palladium nanoparticles
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Table 3 Palladium-catalyzed three-component reaction of benzyl chloride,
allyltributylstannane, and various activated olefinsa,b
Entry
1
Activated olefin 2
Product 4
Yieldb (%)
78
2b
4b
Fig. 1 TEM image (left) and size distribution (right) of palladium nanoparticles.
2
3
4
5
2c
2d
2e
2f
4c
4d
4e
4f
84
87
80
79
substrate scope are the features of the novel and general cata-
lytic method proposed in this paper. These compounds
obtained could be converted to 3-arylpropanoic acid deriva-
tives through hydrolysis of a CN group. On the other hand, the
allyl group should make these compounds useful in organic
synthesis. Further studies focused on extending the scope of
the reaction using other allylmetal reagents and applying the
benzylallylation products in organic synthesis are currently
underway in our laboratory.
4. Experimental section
General information
6
7
2g
2h
4g
4h
82
80
All reactions were carried out under a nitrogen atmosphere
unless otherwise noted. Solvents were purified by standard
techniques without special instructions. 1H and 13C NMR
spectra were recorded on either a Varian Inova-400 spectro-
1
meter (400 MHz for H, 100 MHz for 13C) or a Bruker Avance
1
II-400 spectrometer (400 MHz for H, 100 MHz for 13C); CDCl3
8
2i
2j
2k
2l
4i
4j
4k
4l
78
and TMS were used as a solvent and an internal standard,
respectively. The chemical shifts are reported in ppm down-
field (δ) 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 spectrometer. High resolution
mass spectra were recorded on a GC-TOF mass spectrometer.
Transmission electron microscopy (TEM) was performed on a
Tecnai G2 microscope operating at 100 kV. After the three-com-
ponent reaction of benzyl chloride, allyltributylstannane, and
2-benzylidenemalononitrile was performed for 6 h under opti-
mized conditions, the reaction mixture was directly used for
TEM determination. TLC was carried out on SiO2 (silica gel 60
9
76 (95/5)c
NRd
10
11
NRd
F
254, Merck), and the spots were located with UV light, iodo-
a Reaction conditions: benzyl chloride (1a, 0.6 mmol, 75.9 mg),
activated olefins (2, 0.5 mmol), allyltributylstannane (0.6 mmol,
198.6 mg), Pd2(dba)3 (5 mol%, 22.9 mg), TBAB (1.5 equiv., 241.8 mg),
and THF (2 mL) at 60 °C for 24 h. b Isolated yield. c Diastereomeric
ratio was determined by proton nuclear magnetic resonance
spectroscopy. d No reaction (NR); starting materials were recovered.
platinate reagent or 1% aqueous KMnO4. Flash chromato-
graphy was carried out on basic alumina (Al2O3 90,
100–200 meth). Melting points were determined using a
micro-melting point apparatus and are uncorrected.
The chlorides (1a–1c, 1e–1h, 1j, 1n–1p, and 1r) and
bromides (1s and 1t) starting materials as well as allyltributyl-
stannane are commercially available. The starting materials
1d,14 1i,15 1l,16 1m,17 1n,18 and 1q10b appeared in the
as the catalyst. The exclusive regio- and chemoselectivity, mild
reaction conditions, experimental simplicity, and broad
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literature. The activated olefins 2 were prepared by Knoevena- 129.3, 129.2, 129.0, 128.9, 118.7, 115.6, 114.4, 52.6, 45.5, 42.5,
gel condensation.
36.5; IR (KBr) ν (cm−1) 3451, 3076, 2945, 2244, 1642, 1497,
1456, 1440, 991, 924, 767, 709; HRMS (EI) Calcd for C20H18N2
286.1470 [M]+, found 286.1465.
General procedure for obtaining products 3 and 4
An oven-dried reaction tube (25 mL), fitted with a magnetic
2-(4-Fluorobenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile (3b).
stirrer, was charged with Pd2(dba)3 (22.9 mg, 0.025 mmol), White solid (121.7 mg, 80% yield); mp: 90–92 °C. 1H NMR
activated olefins (2, 0.5 mmol). The tube was evacuated and (CDCl3, 400 MHz) δ 7.45–7.38 (m, 5H), 7.29–7.24 (m, 2H), 7.04
purged with nitrogen for three times. Then, TBAB (248 mg, (dd, J = 8.5, 8.5 Hz, 2H), 5.56–5.45 (m, 1H), 5.09 (d, J = 17.0 Hz,
0.75 mmol), benzyl chlorides (1, 0.6 mmol), freshly distilled 1H), 4.98 (d, J = 10.1 Hz, 1H), 3.18 (dd, J = 11.2, 4.3 Hz, 1H),
THF (2 mL), and allyltributylstannane (198.6 mg, 0.6 mmol) 3.01–2.89 (m, 3H), 2.77 (d, J = 13.8 Hz, 1H); 13C NMR (CDCl3,
1
were sequentially added. The reaction mixture was heated to 100 MHz) δ 163.1 (d, JC–F = 246.4 Hz), 135.1, 133.4, 132.0 (d,
4
60 °C for 24 h. After the reaction was completed, the resultant 3JC–F = 8.3 Hz), 129.3, 129.2, 128.5, 128.2 (d, JC–F = 2.9 Hz),
2
mixture was evaporated in a vacuum to give the crude product, 118.7, 116.0 (d, JC–F = 21.5 Hz), 115.4, 114.3, 52.4, 45.5, 41.6,
which was then purified via basic Al2O3 chromatography 36.5; IR (KBr) ν (cm−1) 3068, 3032, 2933, 2246, 1603, 1511,
(eluent: ethyl acetate–petroleum ether = 1 : 30 to 1 : 10) to 1455, 1226, 1160, 922, 838, 757, 710; HRMS (EI) Calcd for
afford benzylallylation products 3 and 4.
C20H17N2F 304.1376 [M]+, found 304.1382.
4-Bromobenzyl chloride (1d). To a solution of 4-bromobenz-
2-(4-Chlorobenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile (3c).
aldehyde (3.70 g, 20 mmol) in THF (50 mL) at 0 °C, sodium White solid (133.1 mg, 83% yield); mp: 84–86 °C. 1H NMR
borohydride (NaBH4, 0.38 g, 10 mmol) was added slowly. After (CDCl3, 400 MHz) δ 7.45–7.37 (m, 5H), 7.32 (d, J = 8.4 Hz, 2H),
the resulting mixture was stirred overnight at room temp- 7.23 (d, J = 8.4 Hz, 2H), 5.55–5.45 (m, 1H), 5.09 (dd, J = 17.0,
erature, water (50 mL) was added slowly to quench the reac- 1.1 Hz, 1H), 4.98 (d, J = 10.2 Hz, 1H), 3.17 (dd, J = 11.1, 4.4 Hz,
tion. The product was extracted with ethyl ether (50 mL × 2), 1H), 2.89–3.00 (m, 3H), 2.76 (d, J = 13.7 Hz, 1H); 13C NMR
and the combined organic layers were washed with brine (CDCl3, 100 MHz) δ 135.0, 134.9, 133.4, 131.6, 130.9, 129.4,
(50 mL × 2), dried over Na2SO4. The solvent was removed 129.2, 129.1, 118.7, 115.3, 114.2, 52.5, 45.3, 41.7, 36.5; IR (KBr)
under reduced pressure, and the residue obtained was purified ν (cm−1) 3067, 3032, 2932, 2246, 1642, 1494, 1455, 1096, 1016,
via silica gel chromatography (eluent: petroleum ether–ethyl 922, 842, 731, 718, 700; HRMS (EI) Calcd for C20H17N2Cl
acetate = 5 : 1) to afford 4-bromobenzyl alcohol as a white solid 320.1080 [M]+, found 320.1077.
(3.53 g, 95% yield). Then, the starting material, 4-bromobenzyl
2-(4-Bromobenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile (3d).
chloride (1d), was prepared via chlorination reaction of 4-bro- White solid (144.3 mg, 79% yield); mp: 82–84 °C. 1H NMR
mobenzyl alcohol with SOCl2 (white solid, 3.70 g, 95% yield). (CDCl3, 400 MHz) δ 7.49 (d, J = 8.4 Hz, 2H), 7.46–7.43 (m, 5H),
1H NMR (400 MHz, CDCl3) δ 4.53 (s, 2H), 7.26 (d, J = 8.4 Hz, 7.17 (d, J = 8.3 Hz, 2H), 5.55–5.45 (m, 1H), 5.09 (dd, J = 17.0,
2H), 7.49 (d, J = 8.4 Hz, 2H).
1.2 Hz, 1H), 4.98 (d, J = 9.8 Hz, 1H), 3.17 (dd, J = 11.1, 4.4 Hz,
4-Acetoxybenzyl chloride (1i). This compound was prepared 1H), 3.01–2.89 (m, 3H), 2.74 (d, J = 13.7 Hz, 1H); 13C NMR
according to the abovementioned procedure. Brown oil (2.12 g, (CDCl3, 100 MHz) δ 135.0, 133.4, 132.2, 131.9, 131.4, 129.4,
1
85%). H NMR (400 MHz, CDCl3) δ 2.36 (s, 3H), 4.64 (s, 2H), 129.3, 129.2, 123.2, 118.8, 115.3, 114.2, 52.5, 45.2, 41.8, 36.5;
7.15 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H).
IR (KBr) ν (cm−1) 3066, 3032, 2930, 2246, 1642, 1490, 1455,
2-Methoxybenzyl chloride (1l). This compound was pre- 1073, 1012, 922, 839, 726, 716, 700; HRMS (EI) Calcd for
pared according to the abovementioned procedure. Colorless C20H17N2Br 364.0575 and 366.0555 [M]+, found 364.0585 and
oil (2.67 g, 90% yield). 1H NMR (400 MHz, CDCl3) δ 3.85 366.0580.
(s, 3H), 4.65 (s, 2H), 6.87–6.95 (m, 2H), 7.27–7.35 (m, 2H).
2-(2-Chlorobenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile (3e).
3-Methoxybenzyl chloride (1m). This compound was pre- White solid (133.1 mg, 83% yield); mp: 78–80 °C. 1H NMR
pared according to the abovementioned procedure. Colorless (CDCl3, 400 MHz) δ 7.46–7.39 (m, 7H), 7.29–7.23 (m, 2H),
oil (2.83 g, 95% yield). 1H NMR (400 MHz, CDCl3) δ 3.79 5.57–5.47 (m, 1H), 5.09 (dd, J = 17.0, 1.2 Hz, 1H), 4.98 (d, J =
(s, 3H), 4.54 (s, 2H), 6.83–6.86 (m, 1H), 6.92–6.96 (m, 2H), 7.25 10.1 Hz, 1H), 3.29 (d, J = 12.0 Hz, 1H), 3.24 (dd, J = 11.6, 4.1
(dd, J = 8.0, 8.0 Hz, 1H).
Hz, 1H), 3.03–2.91 (m, 3H); 13C NMR (CDCl3, 100 MHz) δ
4-Methoxybenzyl chloride (1n). This compound was pre- 135.2, 135.1, 133.5, 131.7, 130.7, 130.3, 130.1, 129.3, 129.2,
pared according to the abovementioned procedure. Colorless 129.1, 127.4, 118.7, 115.2, 114.2, 52.9, 44.1, 38.5, 36.3; IR (KBr)
oil (2.77 g, 93% yield). 1H NMR (400 MHz, CDCl3) δ 3.82 ν (cm−1) 3362, 3066, 3031, 2924, 2246, 1642, 1495, 1475, 1455,
(s, 3H), 4.59 (s, 2H), 6.91 (d, J = 8.6 Hz, 2H), 7.34 (d, J = 8.6 Hz, 1445, 1057, 991, 922, 762, 737, 716, 700; HRMS (EI) Calcd for
2H).
2-Benzyl-2-(1-phenylbut-3-en-1-yl)malononitrile (3a). White
C20H17N2Cl 320.1080 [M]+, found 320.1079.
2-(2,4-Dichlorobenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile
1
solid (116.0 mg, 81% yield); mp: 105–107 °C. H NMR (CDCl3, (3f). White solid (147.4 mg, 83% yield); mp: 94–96 °C.
400 MHz) δ 7.44–7.29 (m, 10H), 5.55–5.45 (m, 1H), 5.10 (dd, J = 1H NMR (CDCl3, 400 MHz) δ 7.46–7.37 (m, 7H), 7.26–7.24 (m,
17.0, 1.2 Hz, 1H), 4.97 (d, J = 10.2 Hz, 1H), 3.17 (dd, J = 11.3, 1H), 5.57–5.47 (m, 1H), 5.10 (dd, J = 17.0, 1.1 Hz, 1H), 4.99 (d,
4.2 Hz, 1H), 3.03–2.89 (m, 3H), 2.81 (d, J = 13.7 Hz, 1H); J = 10.1 Hz, 1H), 3.26–3.22 (m, 2H), 3.04–2.91 (m, 3H); 13C
13C NMR (CDCl3, 100 MHz) δ 135.3, 133.6, 132.4, 130.3, 129.4, NMR (CDCl3, 100 MHz) δ 135.9, 135.5, 134.9, 133.3, 132.4,
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130.1, 129.4, 129.3, 129.2, 127.8, 118.8, 115.1, 114.0, 52.8, 44.0, 11.5, 4.2 Hz, 1H), 3.02–2.88 (m, 3H), 2.77 (d, J = 13.6 Hz, 1H),
38.0, 36.4; IR (KBr) ν (cm−1) 3066, 3032, 2926, 2246, 1643, 2.25 (s, 6H); 13C NMR (CDCl3, 100 MHz) δ 137.3, 137.2, 135.5,
1588, 1495, 1475, 1455, 1440, 1380, 1104, 1058, 991, 922, 869, 133.7, 131.5, 130.2, 129.8, 129.4, 129.2, 127.7, 118.6, 115.8,
848, 824, 748, 724, 705; HRMS (EI) Calcd for C20H16N2Cl2 114.7, 52.4, 45.6, 42.1, 36.5, 20.0, 19.7; IR (KBr) ν (cm−1) 3012,
354.0691 [M]+, found 354.0696.
2917, 2244, 1641, 1505, 1496, 1444, 1025, 931, 821, 753, 738,
2-(3,4-Dichlorobenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile 708; HRMS (EI) Calcd for C22H22N2 314.1783 [M]+, found
(3g). White solid (145.6 mg, 82% yield); mp: 92–94 °C. 1H 314.1787.
NMR (CDCl3, 400 MHz) δ 7.45–7.37 (m, 7H), 7.16 (dd, J = 8.2,
2-(2-Methoxybenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile
1.8 Hz, 1H), 5.56–5.45 (m, 1H), 5.10 (dd, J = 17.0, 1.0 Hz, 1H), (3l). White solid (128.2 mg, 81% yield); mp: 82–84 °C. 1H
4.99 (d, J = 10.1 Hz, 1H), 3.17 (dd, J = 11.0, 4.4 Hz, 1H), NMR (CDCl3, 400 MHz) δ 7.40–7.23 (m, 7H), 6.94–6.88 (m, 2H),
3.02–2.89 (m, 3H), 2.74 (d, J = 13.8 Hz, 1H); 13C NMR (CDCl3, 5.56–5.46 (m, 1H), 5.07 (d, J = 17.0 Hz, 1H), 4.97 (d, J =
100 MHz) δ 134.8, 133.3, 133.2, 133.0, 132.5, 132.1, 130.9, 10.1 Hz, 1H), 3.78 (s, 3H), 3.21–3.16 (m, 2H), 3.03–2.88
129.5, 129.4, 129.3, 129.1, 118.8, 115.1, 113.9, 55.3, 52.5, 44.9, (m, 3H); 13C NMR (CDCl3, 100 MHz) δ 157.8, 135.6, 133.8,
41.3, 36.5; IR (KBr) ν (cm−1) 3066, 3032, 2932, 2250, 1642, 131.9, 131.5, 131.1, 130.4, 130.1, 129.2, 129.1, 128.9, 127.8,
1473, 1455, 1401, 1135, 1033, 922, 825, 729, 717, 700; HRMS 127.7, 121.2, 120.7, 118.4, 115.7, 114.8, 110.9, 55.3, 52.4, 44.6,
(EI) Calcd for C20H16N2Cl2 354.0691 [M]+, found 354.0697.
36.3, 35.7; IR (KBr) ν (cm−1) 3066, 3031, 2940, 2245, 1642,
2-(4-Nitrobenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile (3h). 1602, 1495, 1465, 1455, 1439, 1252, 1123, 1049, 1028, 921, 756,
Yellowish solid (116.0 mg, 70% yield); mp: 102–104 °C. 1H 714, 700; HRMS (EI) Calcd for C21H20N2O 316.1576 [M]+,
NMR (CDCl3, 400 MHz) δ 8.23 (d, J = 8.6 Hz, 2H), 7.50 (d, J = found 316.1580.
8.6 Hz, 2H), 7.48–7.40 (m, 5H), 5.58–5.48 (m, 1H), 5.12 (d, J =
2-(3-Methoxybenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile
17.0 Hz, 1H), 5.01 (d, J = 10.1 Hz, 1H), 3.25 (dd, J = 10.9, (3m). White solid (134.5 mg, 85% yield); mp: 96–98 °C. 1H
4.6 Hz, 1H), 3.14 (d, J = 13.6 Hz, 1H), 3.03–2.95 (m, 2H), 2.89 NMR (CDCl3, 400 MHz) δ 7.42–7.38 (m, 5H), 7.28–7.24 (m, 1H),
(d, J = 13.6 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 148.2, 139.6, 6.89–6.85 (m, 3H), 5.55–5.45 (m, 1H), 5.08 (d, J = 17.0 Hz, 1H),
134.6, 133.1, 132.0, 131.3, 129.4, 129.3, 129.1, 124.0, 118.9, 4.97 (d, J = 10.1 Hz, 1H), 3.78 (s, 3H), 3.16 (dd, J = 11.3, 4.0 Hz,
114.9, 113.8, 52.6, 44.8, 41.8, 36.5; IR (KBr) ν (cm−1) 3082, 1H), 3.01–2.89 (m, 3H), 2.79 (d, J = 13.6 Hz, 1H); 13C NMR
3032, 2924, 2246, 1642, 1607, 1523, 1495, 1455, 1348, 1121, (CDCl3, 100 MHz) δ 159.8, 135.2, 133.7, 133.5, 129.9, 129.3,
922, 856, 757, 706; HRMS (EI) Calcd for C20H17N3O2 331.1321 129.2, 129.1, 122.5, 118.6, 115.7, 115.5, 114.4, 55.3, 52.4, 45.2,
[M]+, found 331.1316.
42.4, 36.4; IR (KBr) ν (cm−1) 3065, 3032, 2938, 2246, 1642,
4-(2,2-Dicyano-3-phenylhex-5-en-1-yl)phenyl acetate (3i). 1602, 1586, 1492, 1466, 1455, 1439, 1266, 1171, 1157, 1041,
Colorless oil (106.8 mg, 62% yield). 1H NMR (CDCl3, 400 MHz) 994, 922, 786, 742, 709; HRMS (EI) Calcd for C21H20N2O
δ 7.44–7.37 (m, 5H), 7.31 (d, J = 8.5 Hz, 2H), 7.09 (d, J = 8.5 Hz, 316.1576 [M]+, found 316.1581.
2H), 5.55–5.45 (m, 1H), 5.08 (dd, J = 17.0, 1.2 Hz, 1H), 4.98 (d,
2-(4-Methoxybenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile
J = 10.2 Hz, 1H), 3.17 (dd, J = 11.2, 4.3 Hz, 1H), 3.02 (d, J = 13.8 (3n). White solid (134.5 mg, 85% yield); mp: 96–98 °C. 1H
Hz, 1H), 2.98–2.89 (m, 2H), 2.80 (d, J = 13.8 Hz, 1H), 2.28 (s, NMR (CDCl3, 400 MHz) δ 7.44–7.38 (m, 5H), 7.22 (d, J = 8.6 Hz,
3H); 13C NMR (CDCl3, 100 MHz) δ 169.4, 151.2, 135.2, 133.6, 2H), 6.88 (d, J = 8.6 Hz, 2H), 5.55–5.45 (m, 1H), 5.08 (dd, J =
131.5, 130.0, 129.4, 129.3, 122.2, 118.8, 115.5, 114.4, 52.5, 45.4, 17.0, 1.0 Hz, 1H), 4.97 (d, J = 10.1 Hz, 1H), 3.78 (s, 3H), 3.15
41.8, 36.5, 21.3; IR (neat) ν (cm−1) 3067, 3034, 2932, 2246, (dd, J = 11.3, 4.2 Hz, 1H), 3.00–2.88 (m, 3H), 2.77 (d, J =
1765, 1642, 1604, 1509, 1523, 1455, 1369, 1199, 1168, 1018, 13.8 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 159.9, 135.3, 133.6,
914, 851, 763, 714, 700; HRMS (EI) Calcd for C22H20N2O2 131.4, 129.3, 129.2, 129.1, 124.3, 118.6, 115.6, 114.5, 114.3,
344.1525 [M]+, found 344.1531.
55.3, 52.2, 45.8, 41.7, 36.4; IR (KBr) ν (cm−1) 3066, 3034, 2934,
2-(4-Methylbenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile (3j). 2245, 1642, 1612, 1514, 1455, 1305, 1253, 1180, 1032, 922, 835,
White solid (123.2 mg, 82% yield); mp: 82–84 °C. 1H NMR 752, 729, 709; HRMS (EI) Calcd for C21H20N2O 316.1576 [M]+,
(CDCl3, 400 MHz) δ 7.44–7.38 (m, 5H), 7.23–7.14 (m, 4H), found 316.1585.
5.55–5.45 (m, 1H), 5.08 (dd, J = 17.0, 0.7 Hz, 1H), 4.97 (d, J =
2-(Naphthalen-1-ylmethyl)-2-(1-phenylbut-3-en-1-yl)malono-
10.1 Hz, 1H), 3.16 (dd, J = 11.5, 4.2 Hz, 1H), 3.00–2.88 (m, 3H), nitrile (3o). White solid (143.0 mg, 85% yield); mp:
2.78 (d, J = 13.7 Hz, 1H), 2.33 (s, 3H); 13C NMR (CDCl3, 121–123 °C. 1H NMR (CDCl3, 400 MHz) δ 7.87–7.84 (m, 2H),
100 MHz) δ 138.5, 135.3, 133.5, 130.1, 129.6, 129.3, 129.2, 7.70–7.68 (m, 1H), 7.57 (d, J = 6.8 Hz, 1H), 7.50–7.45 (m, 8H),
129.1, 129.0, 118.5, 115.6, 114.4, 52.3, 45.5, 42.0, 36.4, 21.2; IR 5.61–5.51 (m, 1H), 5.12 (dd, J = 17.0, 1.4 Hz, 1H), 5.01 (d, J =
(KBr) ν (cm−1) 3030, 2980, 2925, 2245, 1643, 1516, 1495, 1455, 10.2 Hz, 1H), 3.50 (d, J = 14.4 Hz, 1H), 3.38 (d, J = 14.5 Hz, 1H),
1118, 992, 921, 816, 751, 723, 709; HRMS (EI) Calcd for 3.35–3.32 (m, 1H), 3.09–2.96 (m, 2H); 13C NMR (CDCl3,
C21H20N2 300.1626 [M]+, found 300.1635.
100 MHz) δ 135.3, 134.0, 133.5, 131.9, 129.5, 129.4, 129.3,
2-(3,4-Dimethylbenzyl)-2-(1-phenylbut-3-en-1-yl)malononitrile 129.2, 129.0, 128.9, 128.6, 126.3, 126.1, 125.2, 123.2, 118.6,
(3k). White solid (136.8 mg, 87% yield); mp: 130–132 °C. 1H 115.8, 114.4, 53.2, 44.7, 37.9, 36.5; IR (KBr) ν (cm−1) 3436,
NMR (CDCl3, 400 MHz) δ 7.45–7.38 (m, 5H), 7.11 (d, J = 7.4 Hz, 3066, 2924, 2244, 1639, 1607, 1497, 1457, 1442, 988, 923, 802,
1H), 7.05 (s, 1H), 7.04 (d, J = 7.3 Hz, 1H), 5.55–5.45 (m, 1H), 777, 725, 705; HRMS (EI) Calcd for C24H20N2 336.1626 [M]+,
5.08 (d, J = 17.1 Hz, 1H), 4.98 (d, J = 10.1 Hz, 1H), 3.15 (dd, J = found 336.1628.
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2-((2-Methylnaphthalen-1-yl)methyl)-2-(1-phenylbut-3-en-1- 11.8, 3.7 Hz, 1H), 3.06–2.96 (m, 2H), 2.91–2.83 (m, 2H); 13C
yl)malononitrile (3p). White solid (145.4 mg, 83% yield); mp: NMR (CDCl3, 100 MHz) δ 135.2, 133.9, 133.2, 132.2, 130.6,
127–129 °C. 1H NMR (CDCl3, 400 MHz) δ 7.80–7.72 (m, 3H), 130.3, 129.6, 129.1, 129.0, 119.1, 115.2, 114.3, 51.7, 45.4, 42.4,
7.56–7.42 (m, 7H), 7.31 (d, J = 8.4 Hz, 1H), 5.61–5.51 (m, 1H), 36.3; IR (KBr) ν (cm−1) 3067, 3033, 2932, 2246, 1643, 1596,
5.13 (dd, J = 17.0, 1.0 Hz, 1H), 5.01 (d, J = 10.3 Hz, 1H), 3.66 1494, 1455, 1442, 1413, 1093, 1014, 923, 838, 822, 765, 702;
(d, J = 14.9 Hz, 1H), 3.46 (d, J = 14.9 Hz, 1H), 3.36 (dd, J = 11.6, HRMS (EI) Calcd for
3.9 Hz, 1H), 3.11–2.97 (m, 2H); 13C NMR (CDCl3, 100 MHz) 320.1089.
C
20H17N2Cl 320.1080 [M]+, found
δ 136.6, 135.4, 133.7, 132.7, 132.6, 129.6, 129.5, 129.1,
2-Benzyl-2-(1-(4-bromophenyl)but-3-en-1-yl)malononitrile
128.8, 126.2, 125.4, 124.0, 118.7, 116.2, 114.8, 54.0, 43.6, (4d). White solid (158.9 mg, 87% yield); mp: 104–106 °C.
36.4, 33.8, 21.3; IR (KBr) ν (cm−1) 3441, 3064, 2978, 2248, 1H NMR (CDCl3, 400 MHz) δ 7.56 (d, J = 8.4 Hz, 2H), 7.40–7.24
1644, 1600, 1513, 1494, 1455, 1439, 917, 812, 783, 744, 732, (m, 7H), 5.52–5.42 (m, 1H), 5.08 (d, J = 16.8 Hz, 1H), 5.00 (d,
717, 705; HRMS (EI) Calcd for C25H22N2 350.1783 [M]+, found J = 10.0 Hz, 1H), 3.15 (dd, J = 10.8, 3.5 Hz, 1H), 3.06–2.97 (m,
350.1786.
2H), 2.91–2.83 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ 134.3,
2-((2-Methoxynaphthalen-1-yl)methyl)-2-(1-phenylbut-3-en-1- 133.1, 132.5, 132.1, 130.9, 130.2, 129.0, 128.9, 123.3, 119.0,
yl)malononitrile (3q). White solid (144.7 mg, 79% yield); mp: 115.2, 114.2, 51.7, 45.2, 42.3, 36.1; IR (KBr) ν (cm−1) 3066,
1
119–121 °C. H NMR (CDCl3, 400 MHz) δ 7.82 (d, J = 9.0 Hz, 3032, 2931, 2246, 1643, 1491, 1455, 1076, 1010, 922, 837, 765,
1H), 7.75 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 8.6 Hz, 1H), 7.52–7.39 702; HRMS (EI) Calcd for C20H17N2Br 364.0575 and 366.0555
(m, 6H), 7.30 (dd, J = 7.4, 7.4 Hz, 1H), 7.22 (d, J = 6.2 Hz, 1H), [M]+, found 364.0585 and 366.0571.
5.60–5.50 (m, 1H), 5.10 (d, J = 17.0 Hz, 1H), 4.99 (d, J =
2-Benzyl-2-(1-(p-tolyl)but-3-en-1-yl)malononitrile (4e). White
1
10.2 Hz, 1H), 3.89 (s, 3H), 3.66 (d, J = 14.2 Hz, 1H), 3.39 (d, J = solid (120.2 mg, 80% yield); mp: 119–121 °C. H NMR (CDCl3,
14.2 Hz, 1H), 3.33 (dd, J = 11.8, 3.6 Hz, 1H), 3.01–2.94 (m, 2H); 400 MHz) δ 7.33–7.20 (m, 9H), 5.56–5.46 (m, 1H), 5.08 (d, J =
13C NMR (CDCl3, 100 MHz) δ 156.1, 135.9, 134.0, 133.2, 130.9, 17.0 Hz, 1H), 4.97 (d, J = 10.1 Hz, 1H), 3.14 (dd, J = 11.3,
129.6, 129.3, 129.2, 129.1, 128.9, 127.1, 123.8, 123.0, 118.5, 3.9 Hz, 1H), 3.02–2.87 (m, 3H), 2.81 (d, J = 13.6 Hz, 1H), 2.36
116.4, 115.3, 114.1, 112.5, 56.0, 53.6, 43.6, 36.5, 31.3; IR (KBr) (s, 3H); 13C NMR (CDCl3, 100 MHz) δ 138.9, 133.6, 132.5,
ν (cm−1) 3066, 3007, 2938, 2245, 1642, 1625, 1597, 1515, 1473, 132.0, 130.2, 129.9, 129.0, 128.8, 128.6, 118.4, 115.5, 114.4,
1455, 1267, 1255, 1148, 1100, 918, 810, 747, 733, 711, 701; 52.0, 45.5, 42.2, 36.3, 21.2; IR (KBr) ν (cm−1) 3081, 3065, 3032,
HRMS (EI) Calcd for C25H22N2O 366.1732 [M]+, found 2921, 2246, 1643, 1515, 1497, 1455, 1442, 991, 923, 819, 767,
366.1733.
2-((4-Methylnaphthalen-1-yl)methyl)-2-(1-phenylbut-3-en-1- 300.1637.
747, 702; HRMS (EI) Calcd for C21H20N2 300.1626 [M]+, found
yl)malononitrile (3r). White solid (140.0 mg, 80% yield); mp:
2-Benzyl-2-(1-(4-methoxyphenyl)but-3-en-1-yl)malononitrile
1
118–120 °C. H NMR (CDCl3, 400 MHz) δ 8.02 (d, J = 8.1 Hz, (4f). Colorless oil (125.0 mg, 79% yield). 1H NMR (CDCl3,
1H), 7.71 (d, J = 8.6 Hz, 1H), 7.54–7.45 (m, 8H), 7.31 (d, J = 400 MHz) δ 7.35–7.29 (m, 7H), 6.94 (d, J = 8.4 Hz, 2H),
7.2 Hz, 1H), 5.60–5.50 (m, 1H), 5.12 (dd, J = 17.0, 1.2 Hz, 1H), 5.56–5.46 (m, 1H), 5.08 (d, J = 17.0 Hz, 1H), 4.98 (d, J =
5.01 (dd, J = 9.9, 1.2 Hz, 1H), 3.48 (d, J = 14.5 Hz, 1H), 10.2 Hz, 1H), 3.81 (s, 3H), 3.14 (dd, J = 11.6, 3.7 Hz, 1H), 3.01
3.37–3.31 (m, 2H), 3.06–2.96 (m, 2H), 2.69 (s, 3H); 13C NMR (d, J = 13.6 Hz, 1H), 2.97–2.86 (m, 2H), 2.83 (d, J = 13.6 Hz,
(CDCl3, 100 MHz) δ 136.0, 135.4, 133.7, 133.2, 132.0, 129.5, 1H); 13C NMR (CDCl3, 100 MHz) δ 160.0, 133.7, 132.5, 130.4,
129.4, 129.3, 128.9, 126.8, 126.3, 126.0, 125.9, 125.2, 123.9, 130.3, 128.9, 128.7, 127.0, 118.5, 115.6, 114.6, 114.5, 55.4, 51.8,
118.7, 116.0, 114.6, 53.3, 45.0, 38.0, 36.6, 19.9; IR (KBr) 45.7, 42.3, 36.4; IR (neat) ν (cm−1) 3066, 3033, 2934, 2245,
ν (cm−1) 3433, 3068, 2977, 2245, 1642, 1597, 1517, 1496, 1455, 1642, 1611, 1514, 1456, 1310, 1254, 1181, 1032, 921, 838, 766,
1440, 923, 834, 779, 759, 711; HRMS (EI) Calcd for C25H22N2 702; HRMS (EI) Calcd for C21H20N2O 316.1576 [M]+, found
350.1783 [M]+, found 350.1793.
316.1585.
2-Benzyl-2-(1-(4-fluorophenyl)but-3-en-1-yl)malononitrile (4b).
2-Benzyl-2-(1-(naphthalen-1-yl)but-3-en-1-yl)malononitrile
White solid (118.7 mg, 78% yield); mp: 92–94 °C. 1H NMR (4g). White solid (138.0 mg, 82% yield); mp: 163–165 °C. 1H
(CDCl3, 400 MHz) δ 7.39–7.31 (m, 7H), 7.12 (dd, J = 8.4, 8.4 Hz, NMR (CDCl3, 400 MHz) δ 7.98 (d, J = 8.3 Hz, 1H), 7.94–7.89 (m,
2H), 5.53–5.43 (m, 1H), 5.08 (d, J = 17.0 Hz, 1H), 4.99 (d, J = 3H), 7.63–7.50 (m, 3H), 7.31–7.23 (m, 5H), 5.51–5.41 (m, 1H),
10.1 Hz, 1H), 3.18 (dd, J = 11.8, 3.5 Hz, 1H), 3.06–2.97 (m, 2H), 5.09 (d, J = 17.0 Hz, 1H), 4.88 (d, J = 10.4 Hz, 1H), 4.28 (dd, J =
2.91–2.82 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ 163.0 (d, 1JC–F
=
10.8, 3.8 Hz, 1H), 3.19–3.06 (m, 3H), 2.62 (d, J = 13.7, 1H); 13C
3
247.0 Hz), 133.2, 132.2, 131.1 (d, JC–F = 2.9 Hz), 131.0, 130.9, NMR (CDCl3, 100 MHz) δ 134.1, 133.3, 133.0, 132.3, 131.8,
2
130.2, 129.0, 128.9, 118.9, 116.3 (d, JC–F = 21.3 Hz), 115.3, 130.3, 129.6, 129.5, 128.9, 128.8, 127.2, 126.2, 125.8, 125.1,
114.3, 51.5, 45.5, 42.3, 36.3; IR (KBr) ν (cm−1) 3068, 3034, 2927, 122.1, 118.7, 116.0, 114.3, 46.2, 44.2, 42.0, 37.6; IR (KBr)
2246, 1605, 1511, 1455, 1230, 1163, 923, 842, 767, 702; HRMS ν (cm−1) 3064, 3033, 2932, 2246, 1642, 1598, 1513, 1497, 1455,
(EI) Calcd for C20H17N2F 304.1376 [M]+, found 304.1381.
1440, 921, 801, 782, 765, 701; HRMS (EI) Calcd for C24H20N2
2-Benzyl-2-(1-(4-chlorophenyl)but-3-en-1-yl)malononitrile (4c). 336.1626 [M]+, found 336.1625.
1
White solid (134.7 mg, 84% yield); mp: 107–109 °C. H NMR
2-Benzyl-2-(1-(naphthalen-2-yl)but-3-en-1-yl)malononitrile
(CDCl3, 400 MHz) δ 7.42–7.30 (m, 9H), 5.53–5.43 (m, 1H), 5.08 (4h). Colorless oil (134.6 mg, 80% yield). 1H NMR (CDCl3,
(dd, J = 17.0, 0.8 Hz, 1H), 5.00 (d, J = 10.1 Hz, 1H), 3.16 (dd, J = 400 MHz) δ 7.93–7.83 (m, 4H), 7.55–7.52 (m, 3H), 7.33–7.29
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(m, 5H), 5.56–5.46 (m, 1H), 5.10 (d, J = 17.0 Hz, 1H), 4.94 (d,
J = 10.1 Hz, 1H), 3.35 (t, J = 7.8 Hz, 1H), 3.08–3.04 (m, 3H),
2.82 (d, J = 13.7 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 133.5,
133.3, 132.6, 132.3, 130.3, 129.3, 129.2, 128.9, 128.8, 128.2,
127.9, 126.9, 126.8, 125.9, 118.7, 115.6, 114.4, 52.7, 45.4, 42.5,
36.5; IR (neat) ν (cm−1) 3062, 3032, 2931, 2245, 1641, 1600,
1497, 1455, 1441, 991, 920, 860, 819, 756, 701; HRMS (EI)
Calcd for C24H20N2 336.1626 [M]+, found 336.1631.
3 For selected examples of C–C bond formation via the
Tsuji–Trost-type reaction, see: (a) R. Jana, J. J. Partridge and
J. A. Tunge, Angew. Chem., Int. Ed., 2011, 50, 5157;
(b) P. Zhang, L. A. Brozek and J. P. Morken, J. Am. Chem.
Soc., 2010, 132, 10686; (c) M. Braun and T. Meier, Angew.
Chem., Int. Ed., 2006, 45, 6952; (d) U. Kazmaier and
F. L. Zumpe, Angew. Chem., Int. Ed., 1999, 38, 1468.
4 For selected examples of C–N bond formation via the
Tsuji–Trost-type reaction, see: (a) A. M. Johns, Z. Liu and
J. F. Hartwig, Angew. Chem., Int. Ed., 2007, 46, 7259;
(b) Y. Imada, M. Nishida, K. Kutsuwa, S.-I. Murahashi and
T. Naota, Org. Lett., 2005, 7, 5837; (c) T. Nemoto,
T. Masuda, Y. Akimoto, T. Fukuyama and H. Hamada, Org.
Lett., 2005, 7, 4447.
5 For selected examples of C–O bond formation via the
Tsuji–Trost-type reaction, see: (a) B. M. Trost, D. A. Bringley
and S. M. Silverman, J. Am. Chem. Soc., 2011, 133, 7664;
(b) H. Miyabe, K. Yoshida, M. Yamauchi and Y. Takemoto,
J. Org. Chem., 2005, 70, 2148; (c) B. M. Trost and
F. D. Toste, J. Am. Chem. Soc., 1998, 120, 9074.
6 For selected examples of C–S bond formation via the Tsuji–
Trost-type reaction, see: (a) B. M. Trost, M. L. Crawley and
C. B. Lee, Chem.–Eur. J., 2006, 12, 2171; (b) H.-J. Gais and
A. Böhme, J. Org. Chem., 2002, 67, 1153.
2-Benzyl-2-(1-(thiophen-2-yl)but-3-en-1-yl)malononitrile
(4i).
1
White solid (114.0 mg, 78% yield); mp: 120–122 °C. H NMR
(CDCl3, 400 MHz) δ 7.37–7.34 (m, 6H), 7.16 (d, J = 2.9 Hz, 1H),
7.08 (dd, J = 4.0, 4.0 Hz, 1H), 5.64–5.54 (m, 1H), 5.13 (d, J =
17.0 Hz, 1H), 5.04 (d, J = 10.1 Hz, 1H), 3.49 (dd, J = 11.7,
3.1 Hz, 1H), 3.08–2.93 (m, 3H), 2.88–2.80 (m, 1H); 13C NMR
(CDCl3, 100 MHz) δ 137.5, 133.1, 132.3, 130.3, 129.0, 128.9,
128.4, 128.1, 127.5, 126.4, 119.1, 115.2, 114.2, 48.2, 45.8, 42.2,
38.3; IR (KBr) ν (cm−1) 3067, 3033, 2928, 2246, 1642, 1604,
1497, 1455, 1440, 991, 923, 851, 766, 701; HRMS (EI) Calcd for
C18H16N2S 292.1034 [M]+, found 292.1040.
Ethyl 2-benzyl-2-cyano-3-phenylhex-5-enoate (4j). Colorless
oil (126.7 mg, 76% yield), dr = 95/5. 1H NMR (CDCl3, 400 MHz)
δ 7.35–7.23 (m, 10.5H), 5.58–5.48 (m, 1H), 5.06 (d, J = 17.1 Hz,
1H), 4.99–4.89 (m, 1.1H), 4.05 (q, J = 7.2 Hz, 0.1H), 3.66 (q, J =
7.2 Hz, 2H), 3.39 (d, J = 13.2 Hz, 1H), 3.30 (d, J = 13.2 Hz,
1.1H), 3.22 (t, J = 7.7 Hz, 1H), 2.94 (d, J = 13.2 Hz, 0.05H), 2.86
(t, J = 7.1 Hz, 2H), 2.53–2.43 (m, 0.1H), 1.04 (t, J = 7.2 Hz,
0.15H), 0.71 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz)
δ 167.4, 137.9, 134.8, 134.4, 130.2, 129.2, 128.7, 128.5, 128.0,
127.9, 118.3, 117.7, 62.2, 57.8, 52.2, 42.4, 35.2, 13.5; IR (neat)
ν (cm−1) 3064, 3032, 2980, 2936, 2242, 1737, 1642, 1496, 1455,
1368, 1303, 1279, 1245, 1221, 1094, 1014, 994, 918, 858, 748,
701; HRMS (EI) Calcd for C22H23NO2 333.1729 [M]+, found
333.1717.
7 For selected examples of C–P bond formation via the Tsuji–
Trost-type reaction, see: A. Duraud, O. Jacquet, J.-C. Fiaud,
R. Guillot and M. Toffano, ChemCatChem, 2011, 3, 883 and
references cited therein.
8 (a) H. Nakamura, M. Bao and Y. Yamamoto, Angew. Chem.,
Int. Ed., 2001, 40, 3208 and references cited therein;
(b) M. Bao, H. Nakamura and Y. Yamamoto, Tetrahedron
Lett., 2000, 41, 131; (c) K. Nakamura, H. Nakamura and
Y. Yamamoto, J. Org. Chem., 1999, 64, 2614.
9 H. Nakamura, J. G. Shim and Y. Yamamoto, J. Am. Chem.
Soc., 1997, 119, 8113.
10 For a selected review, see: (a) B. Liégault, J.-L. Renaud and
C. Bruneau, Chem. Soc. Rev., 2008, 37, 290; For selected
examples, see: (b) S. Zhang, Y. Wang, X. Feng and M. Bao,
J. Am. Chem. Soc., 2012, 134, 5492; (c) B. Peng, X. Feng,
X. Zhang, S. Zhang and M. Bao, Org. Lett., 2011, 13, 5402;
(d) Y. Dai, X. Feng, H. Liu, H. Jiang and M. Bao, J. Org.
Chem., 2011, 76, 10068 and references cited therein;
(e) W. H. Fields and J. J. Chruma, Org. Lett., 2010, 12, 316
Acknowledgements
We are grateful to the National Natural Science Foundation of
China (Nos. 21073025 and 21072023) for their financial
support.
Notes and references
and references cited therein;
(f) R. Kuwano and
1 For selected books, see: (a) J. Tsuji, Palladium Reagents and
Catalysts, John Wiley and Sons, Chichester, 2004;
(b) S. A. Codleski, Comprehensive Organic Synthesis, ed.
M. F. Semmelhack, Pergamon Press, Oxford, 1991; For
H. Kusano, Org. Lett., 2008, 10, 1979 and references
cited therein; (g) A. M. Johns, J. W. Tye and J. F. Hartwig,
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selected reviews, see: ; (c) B. M. Trost and M. L. Crawley, 11 (a) S. Lu, Z. Xu, M. Bao and Y. Yamamoto, Angew. Chem.,
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Acc. Chem. Res., 2000, 33, 336.
Int. Ed., 2008, 47, 4366; (b) M. Bao, H. Nakamura and
Y. Yamamoto, J. Am. Chem. Soc., 2001, 123, 759.
2 For selected reviews, see: (a) B. M. Trost, M. R. Machacek 12 For a selected review, see: (a) D. Astruc, F. Lu and
and A. Aponick, Acc. Chem. Res., 2006, 39, 747;
(b) B. M. Trost and D. L. Van Vranken, Chem. Rev., 1996, 96,
355; (c) J. Tsuji and I. Minami, Acc. Chem. Res., 1987, 20,
140.
J. R. Aranzaes, Angew. Chem., Int. Ed., 2005, 44, 7852; For a
selected example, see: (b) L. Adak, K. Chattopadhyay and
B. C. Ranu, J. Org. Chem., 2009, 74, 3982.
13 See: ref. 12a.
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