Direct olefination of benzaldehydes into 1,3-diarylpropenes via a copper-catalyzed heterodomino Knoevenagel-decarboxylation-Csp3-H activation sequence

Article abstract of DOI:10.1039/c4ob00155a

Copper-catalyzed direct olefination of benzaldehydes into 1,3-diarylpropenes by a novel domino Knoevenagel-decarboxylation-Csp ³-H activation sequence is reported. This method provides a concise and effective route toward the synthesis of unsymmetrical 1,3-diarylpropene derivatives. the Partner Organisations 2014.

Full text of DOI:10.1039/c4ob00155a

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Direct olefination of benzaldehydes into
1,3-diarylpropenes via a copper-catalyzed
heterodomino Knoevenagel-decarboxylation-
Csp3-H activation sequence†
Cite this: DOI: 10.1039/c4ob00155a
Yaping Zhao, Lu Sun, Tieqiang Zeng, Jiayi Wang, Yanqing Peng and Gonghua Song*
Received 21st January 2014,
Accepted 26th March 2014
Copper-catalyzed direct olefination of benzaldehydes into 1,3-diarylpropenes by a novel domino
Knoevenagel-decarboxylation-Csp3-H activation sequence is reported. This method provides a concise
and effective route toward the synthesis of unsymmetrical 1,3-diarylpropene derivatives.
DOI: 10.1039/c4ob00155a
www.rsc.org/obc
Introduction
In the last two decades, there has been increasing interest in
the development of more efficient and environmentally
friendly methods for chemical syntheses.1 One of the related
research areas is the development of sequential formation of
multiple C–C bonds in one pot.2 In general, these processes
eliminate intermediate recovery steps, thereby considerably
decreasing the amount of waste generated.3 For the past few
years, a number of notable domino sequence reactions invol-
ving decarboxylation have been developed using simpler sub-
strates like benzaldehydes.4 However, to the best of our
knowledge, examples of utilizing benzaldehydes for one pot
methylenation coupling into 1,3-diarylpropenes have not been
explored.
Furthermore, 1,3-diarylpropenes are often known to be pri-
vileged structures or key intermediates in the synthesis of
natural products and the development of biologically active
compounds.5 Traditionally, strategies toward the syntheses
of 1,3-diarylpropenes include allylic arylation/alkenylation
(Scheme 1, route a),6 allylic selective defunctionalization (route
b),7 decarboxylation of cinnamic acids (route c),8 cross-coup-
ling reactions of potassium alkenyltrifluoroborates with benzyl
halides (route d)9 and alkylation of benzene (route e).10
However, most of the above methods have to bear disadvan-
tages such as limited substrates, multistep procedures and
necessary prefunctionalization. Encouraged by the ecological
and economic advantages of domino reactions, we wish to
Scheme 1 Strategies toward syntheses of 1,3-diarylpropenes.
report herein the synthesis of unsymmetrical 1,3-diaryl-
propenes through a domino Knoevenagel-decarboxylation-Csp3-H
activation sequence (Scheme 1).
Results and discussion
We started our research by using benzaldehyde (1a) as the
standard substrate. The combination of malonic acid, CuO,
di-t-butyl peroxide (DTBP) and piperidine in toluene at 115 °C
(oil bath temperature, unless otherwise noted) gave the desired
product 1,3-diarylpropenes (2a) in 68% GC yield within 12 h
(Table 1, entry 1). Other copper catalysts (entries 2 and 3), oxi-
dants (entry 6), bases (entry 7), or solvents (entry 8) decreased
the yield.11 Employment of Fe3O4 or ferrocene resulted in a
dramatic decrease in yield (entries 4 and 5). Modifying the
quantity of oxidant, base, catalyst and time did not afford
better results (entries 9–11 and 15).11 Higher yields were
obtained when the reaction was carried out at an elevated
temperature. Particularly, trace amounts of the target product
were detected below the boiling point of toluene (entry 12)
and a good result in 77% GC yield was achieved at 125 °C
Shanghai Key Laboratory of Chemical Biology, Institute of Pesticides and
Pharmaceuticals, East China University of Science and Technology, Shanghai
200237, P.R. China. E-mail: ghsong@ecust.edu.cn
†Electronic supplementary information (ESI) available: Detailed experimental
procedures, characterization data, copies of 1H-NMR and 13C-NMR spectra. See
DOI: 10.1039/c4ob00155a
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Table 1 Optimization of the conditions for copper catalyzed domino
olefination of benzaldehydes into 1,3-diarylpropenesa
Table 2 Substrate scope of the copper-catalyzed domino reaction of
different benzaldehydes 1 with 2aa,b
Entry
Catalyst
Oxidant
Base
Solvent
Yieldb (%)
1
2
3
4
5
6
7
8
CuO
CuBr2
CuI
DTBP
DTBP
DTBP
DTBP
DTBP
TBHP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
DBU
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
DMSO
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
68
53
50
30
Trace
42
24
11
69
8
33
NR
77
49
55
11
Fe3O4
Ferrocene
CuO
CuO
CuO
CuO
CuO
CuO
CuO
CuO
CuO
CuO
—
9c
10d
11e
12f
13g
14h
15i
16
a Catalytic conditions: benzaldehyde (0.3 mmol), malonic acid
(0.5 mmol), toluene (0.5 mmol), solvent (2 mL), base (0.2 mmol),
catalyst (20 mol%), oxidant (4 equiv.), 115 °C, 12 h, N2 atmosphere.
b GC yields were given using dodecane as the internal standard. c The
reaction was conducted within 24 h. d 0.1 mmol of piperidine was
used. e 2 equiv. of DTBP was used. f The reaction was conducted at
105 °C under a N2 atmosphere. g The reaction was conducted at 125 °C
under a N2 atmosphere. h The reaction was conducted at 125 °C under
an air atmosphere. i 10 mol% of CuO was used.
a Catalytic conditions: benzaldehydes (1) (0.3 mmol), malonic acid
(0.5 mmol), toluene (2a) (2 mL), piperidine (0.2 mmol), CuO (20 mol
%), DTBP (4 equiv.), 125 °C, 12 h, N2 atmosphere. b Isolated yields
based on benzaldehyde.
Table 3 Substrate scope of the copper-catalyzed domino reaction of
4-methoxybenzaldehyde (1b) with 2a,b
(entry 13). However, when the reaction was conducted under
an air atmosphere, the yield decreased to 49% (entry 14). A
control experiment showed that the domino reaction was
poorly efficient when the reaction was carried out in the
absence of a copper catalyst (entry 16).
Under the optimized reaction conditions, the allylation of a
variety of benzaldehyde derivatives was examined. As shown in
Table 2, benzaldehydes bearing a variety of substituents were
found to afford exclusively 1,3-diarylpropenes in moderate to
good yields (3-1a–3-1h). Obviously, an electron-donating group
at the para-position, such as the methoxy substituent in 3-1b,
afforded a higher yield compared with an electron-withdraw-
ing group, such as a cyano group substituent in 3-1g. para-Sub-
stituted benzaldehydes (3-1b) gave a superior product yield
compared to that of ortho- or meta-substituted benzaldehydes
(3-1i and 3-1j). The domino reaction with 4-nitrobenzaldehyde
(3-1h) was also successful. OH-, Cl- and Br-substituted com-
pounds (3-1d, 3-1e and 3-1f) were also well tolerated. It turned
out that multiple substituent groups (3-1k, 3-1l and 3-1m)
would decrease the reaction efficiency.
a Catalytic conditions: 4-methoxybenzaldehyde (1b) (0.3 mmol), malonic
acid (0.5 mmol), benzylic hydrocarbons (2) (2 mL), piperidine
(0.2 mmol), CuO (20 mol%), DTBP (4 equiv.), 125 °C, 12 h, N2
atmosphere. b Isolated yields based on benzaldehyde.
Subsequently, we surveyed the substrate scope of benzylic
Considering the effects of electronic parameters on the
hydrocarbons (Table 3). All kinds of xylenes and mesitylene reaction, it was found that the yield roughly decreased with the
(3-2b–3-2e) offered the mono-coupling products in moderate increase of Hammett constant (σ) values of the substituents on
yields. The toluenes substituted by electron-withdrawing benzaldehyde. For example, the yield of 3-1b (p-CH3O, σp
=
groups (3-2f, 3-2g and 3-2h) were less reactive than xylenes −0.27) is 78%, and the yield of 3-1g (p-CN, σp = 0.66) is 53% as
(3-2b and 3-2d).
shown in Table 4. The exceptional substrates are p-hydroxyl
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Table 4 Relationship between Hammett constant values (σ) of the sub-
stituents on benzaldehyde and domino reaction yields
Experimental
General information
Substituents on benzaldehyde
σ
Yield
All reactions were carried out under an N2 atmosphere. CuO
was purchased from Aladdin-reagent with high purity (99.5%).
All reagents were used as supplied without further purification
and drying. Flash column chromatography was performed over
silica gel (48–75 μm) and reactions were monitored by thin
p-OH
p-OCH3
p-CH3
m,m,p-tri-OCH3
p-H
o-OCH3
m-OCH3
p-Cl
−0.37
−0.27
−0.17
−0.03
0
0.04
0.12
0.23
0.23
0.24
0.63
0.66
0.78
41%
78%
75%
55%
72%
65%
66%
65%
61%
61%
60%
53%
34%
1
layer chromatography (TLC) using UV light (254 nm). H NMR
(400 MHz) and 13C NMR (100 MHz) spectra were recorded on a
Bruker Avance 400 MHz NMR spectrometer using d6-DMSO as
a solvent and tetramethylsilane as an internal standard (s =
singlet, d = doublet, t = triplet, m = multiplet). MS analyses
were performed on an Agilent 5975 GC-MS instrument (EI).
HRMS analyses were performed on a Waters Micromass GCT
instrument (EI).
p-Br
m,m-di-OCH3
o,p-di-Cl
p-CN
p-NO2
General procedures for copper-catalyzed allylation of
benzaldehydes
Malonic acid (52 mg, 0.5 mmol) and CuO (4.8 mg, 0.06 mol)
were added into a 10 mL Schlenk flask. Then toluene (2 mL),
benzaldehyde (31 µl, 0.3 mmol), DTBP (120 µl, 1.2 mmol), and
piperidine (20 µl, 0.2 mmol) were added at room temperature.
The reaction vessel was purged with N2 three times. The
mixture was stirred at 125 °C for 12 h. After cooling to room
temperature, the mixture was diluted with CH2Cl2 and water.
The organic phase was washed with brine, dried with MgSO4,
and concentrated under reduced pressure. The residue was
purified by silica gel chromatography (petroleum ether–ethyl
acetate = 100 : 1) to afford the corresponding product.
(E)-1-1,3-Diphenylpropene (3-1a). Prepared according to the
general procedure. A faint yellow liquid. 1H NMR (400 MHz,
d6-DMSO) δ 7.38–7.41 (m, 2H), 7.24–7.33 (m, 6H), 7.18–7.22
(m, 2H), 6.48 (d, J = 15.9 Hz, 1H), 6.46–6.38 (m, 1H), 3.52 (d,
J = 5.8 Hz, 2H). 13C NMR (100 MHz, d6-DMSO) δ 140.52,
137.50, 130.99, 129.88, 129.02, 128.96, 128.92, 127.58, 126.53,
126.44, 39.06. GC/MS (m/z): [M]+ calcd for C15H14, 194.1;
found, 194.1. HRMS (EI+) calcd for C15H14 [M+]: 194.1095.
Found: 194.1096.
(E)-1-(4-Methoxyphenyl)-3-phenylpropene (3-1b). Prepared
according to the general procedure. A faint yellow liquid.
1H NMR (400 MHz, d6-DMSO) δ 7.35–7.18 (m, 7H), 6.87 (d, J =
8.8 Hz, 2H), 6.42 (d, J = 15.8 Hz, 1H), 6.30–6.22 (m, 1H), 3.73
(s, 3H), 3.49 (d, J = 6.9 Hz, 2H). 13C NMR (100 MHz, d6-DMSO)
δ 158.97, 140.80, 130.46, 130.17, 128.91, 128.89, 127.63,
127.43, 126.46, 114.43, 55.51, 39.05. GC/MS (m/z): [M]+ calcd
for C16H16O, 224.1; found, 224.1. HRMS (EI+) calcd for
C16H16O [M+]: 224.1201. Found: 224.1202.
Scheme 2 Proposed mechanism.
benzaldehyde and m,m,p-tri-methoxyl benzaldehyde, which
might be dominated by other factors such as hydrogen bonds
and steric hindrance. However, a similar approach for benzylic
hydrocarbons is not applicable.
Based on previous observations and literature reports,4h,8
we proposed a plausible catalytic cycle (Scheme 2). The reac-
tion involves a domino anionic-metal catalyzed pathway,2a,4h
wherein an incipient cinnamic acid (formed in situ from the
K-D reaction) continuously undergoes copper catalyzed cross
coupling and decarboxylation, leading to 1,3-diarylpropenes in
one pot.8
Conclusions
(E)-1-(4-Methyl)-3-phenylpropene (3-1c). Prepared according
In summary, we have developed the first copper-catalyzed one to the general procedure. A faint green solid. 1H NMR
step direct olefination of benzaldehydes into 1,3-diarylpro- (400 MHz, d6-DMSO) δ 7.33–7.18 (m, 7H), 7.11 (d, J = 7.9 Hz,
penes via a novel domino Knoevenagel-decarboxylation-Csp3-H 2H), 6.44 (d, J = 15.9 Hz, 1H), 6.39–6.32 (m, 1H), 3.50 (d, J =
activation sequence. The unsymmetrical 1,3-diarylpropenes 6.4 Hz, 2H), 2.27 (s, 3H). 13C NMR (100 MHz, d6-DMSO)
were obtained in moderate to good yields. All of the substrates δ 140.65, 136.79, 134.73, 130.84, 129.59, 128.93, 128.90,
were economical, simple and readily available.
128.77, 126.49, 126.36, 39.06, 21.19. GC/MS (m/z): [M]+ calcd
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for C16H16, 208.1; found, 208.1. HRMS (EI+) calcd for C16H16 126.47, 125.96, 125.57, 120.96, 111.70, 55.81, 39.37. GC/MS
[M+]: 208.1252. Found: 208.1251. (m/z): [M]+ calcd for C16H16O, 224.1; found, 224.1. HRMS (EI+)
(E)-4-(3-Phenylprop-1-enyl)phenol (3-1d). Prepared accord- calcd for C16H16O [M+]: 224.1201. Found: 224.1202.
ing to the general procedure. A faint yellow solid. 1H NMR
(E)-1-(3-Methoxyphenyl)-3-phenylpropene (3-1j). Prepared
(400 MHz, d6-DMSO) δ 9.48 (s, 1H), 7.38 (s, 1H), 7.20 (d, J = according to the general procedure. A faint yellow liquid.
8.5 Hz, 3H), 6.75 (d, J = 8.5 Hz, 3H), 6.66 (dd, J = 17.7, 11.0 Hz, 1H NMR (400 MHz, d6-DMSO) δ 7.34–7.29 (m, 2H), 7.27–7.19
1H), 5.78–5.55 (m, 2H), 5.07 (d, J = 11.2 Hz, 1H), 3.56 (dd, J = (m, 4H), 6.98 (d, J = 8.3 Hz, 2H), 6.78 (dd, J = 9.4, 2.1 Hz, 1H),
15.9, 9.3 Hz, 1H), 3.11 (dd, J = 15.9, 8.1 Hz, 1H). 13C NMR 6.46 (d, J = 4.2 Hz, 1H), 6.45–6.40 (m, 1H), 3.74 (s, 3H), 3.52 (d,
(100 MHz, d6-DMSO) δ 164.36, 162.50, 141.74, 136.89, 135.27, J = 4.6 Hz, 2H). 13C NMR (100 MHz, d6-DMSO) δ 159.99,
132.84, 132.02, 127.58, 120.43, 116.28, 113.90, 89.25, 42.20. 140.48, 138.99, 130.93, 130.22, 130.01, 128.97, 128.92, 126.53,
GC/MS (m/z): [M]+ calcd for C15H14O, 210.1; found, 210.1. 118.99, 118.99, 113.46, 111.51, 55.44, 39.04. GC/MS (m/z): [M]+
HRMS (EI+) calcd for C15H14O [M+]: 210.1045. Found: calcd for C16H16O, 224.1; found, 224.1. HRMS (EI+) calcd for
210.1046.
C16H16O [M+]: 224.1201. Found: 224.1202.
(E)-1-(4-Chlorophenyl)-3-phenylpropene
(3-1e). Prepared
(E)-1-(3,5-Dimethoxyphenyl)-3-phenylpropene
(3-1k). Pre-
according to the general procedure. A faint yellow liquid. pared according to the general procedure. A brown liquid.
1H NMR (400 MHz, d6-DMSO) δ 7.43 (d, J = 8.6 Hz, 2H), 1H NMR (400 MHz, d6-DMSO) δ 7.34–7.29 (m, 2H), 7.26–7.19
7.35–7.29 (m, 4H), 7.26–7.19 (m, 3H), 6.48–6.46 (m, 2H), 3.52 (m, 3H), 6.58 (d, J = 2.1 Hz, 2H), 6.50–6.43 (m, 1H), 6.40 (d, J =
(d, J = 4.5 Hz, 2H). 13C NMR (100 MHz, d6-DMSO) δ 140.31, 15.9 Hz, 1H), 6.37 (t, J = 2.1 Hz, 1H), 3.73 (s, 6H), 3.51 (d, J =
136.46, 131.91, 130.97, 129.71, 128.96, 128.93, 128.14, 126.57, 6.2 Hz, 2H). 13C NMR (100 MHz, d6-DMSO) δ 161.07, 140.44,
39.01. GC/MS (m/z): [M]+ calcd for C15H13Cl, 228.1; found, 139.59, 131.03, 130.46, 128.99, 128.91, 128.82, 126.54, 104.42,
228.1. HRMS (EI+) calcd for C15H13Cl [M+]: 228.0706. Found: 99.92, 55.58, 39.03. GC/MS (m/z): [M]+ calcd for C17H18O2,
228.0706.
254.1; found, 254.1. HRMS (EI+) calcd for C17H18O2 [M+]:
(3-1f). Prepared 254.1307. Found: 254.1308.
colorless liquid. (E)-1-(3,4,5-Trimethoxyphenyl)-3-phenylpropene (3-1l). Pre-
(E)-1-(4-Bromophenyl)-3-phenylpropene
according to the general procedure.
A
1H NMR (400 MHz, d6-DMSO) δ 7.48 (d, J = 8.5 Hz, 2H), pared according to the general procedure. A faint yellow
7.38–7.19 (m, 7H), 6.49–6.42 (m, 2H), 3.51 (d, J = 5.3 Hz, 2H). liquid. 1H NMR (400 MHz, d6-DMSO) δ 7.33–7.19 (m, 5H), 6.71
13C NMR (100 MHz, d6-DMSO) δ 140.27, 136.81, 131.88, (s, 2H), 6.42–6.36 (m, 2H), 3.77 (s, 6H), 3.64 (s, 3H), 3.50 (d, J =
131.08, 129.78, 128.97, 128.93, 128.49, 126.58, 120.44, 39.03. 4.9 Hz, 2H). 13C NMR (100 MHz, d6-DMSO) δ 153.45, 140.58,
GC/MS (m/z): [M]+ calcd for C15H13Br, 272.0; found, 272.0. 137.34, 133.28, 131.04, 129.30, 129.01, 128.91, 126.52, 103.80,
HRMS (EI+) calcd for C15H13Br [M+]: 272.0201. Found: 60.47, 56.25, 39.06. GC/MS (m/z): [M]+ calcd for C18H20O2,
272.0200.
284.1; found, 284.1. HRMS (EI+) calcd for C18H20O2 [M+]:
(E)-4-(3-Phenylprop-1-enyl)benzonitrile
(3-1g). Prepared 284.1412. Found: 284.1413.
according to the general procedure. A faint yellow liquid. 1H
(E)-1-(2,4-Chlorophenyl)-3-phenylpropene (3-1m). Prepared
NMR (400 MHz, d6-DMSO) δ 7.75 (d, J = 8.3 Hz, 2H), 7.60 (d, according to the general procedure.
A colorless liquid.
J = 8.3 Hz, 2H), 7.34–7.19 (m, 5H), 6.72–6.64 (m, 1H), 6.56 (d, 1H NMR (400 MHz, d6-DMSO) δ 7.67 (t, J = 7.0 Hz, 1H), 7.55 (d,
J = 15.9 Hz, 1H), 3.56 (d, J = 6.9 Hz, 2H). 13C NMR (100 MHz, J = 2.0 Hz, 1H), 7.37–7.29 (m, 3H), 7.28–7.19 (m, 3H), 6.77–6.67
d6-DMSO) δ 142.26, 139.92, 134.38, 132.98, 129.70, 129.02, (m, 1H), 6.59–6.47 (m, 1H), 3.57 (d, J = 6.9 Hz, 2H). 13C NMR
129.00, 128.98, 127.23, 126.68, 119.45, 109.73, 39.09. GC/MS (100 MHz, d6-DMSO)
δ 139.85, 134.46, 134.25, 132.62,
(m/z): [M]+ calcd for C16H13N, 219.1; found, 219.1. HRMS (EI+) 129.28, 129.01, 128.96, 128.58, 128.01, 126.66, 125.48, 39.15.
calcd for C16H13N [M+]: 219.1048. Found: 219.1047.
(E)-4-(3-Phenylprop-1-enyl)nitrobenzene
GC/MS (m/z): [M]+ calcd for C15H12Cl2, 262.0; found, 262.0.
(3-1h). Prepared HRMS (EI+) calcd for C15H12Cl2 [M+]: 262.0316. Found:
1
according to the general procedure. A yellow liquid. H NMR 262.0320.
(400 MHz, d6-DMSO) δ 8.13 (d, J = 8.8 Hz, 2H), 7.65 (d, J =
(E)-3-(2-Methylphenyl)-1-(4-methoxyphenyl)-propene (3-2b).
8.8 Hz, 2H), 7.37–7.15 (m, 6H), 6.73 (m, 1H), 6.60 (d, J = 15.9 Prepared according to the general procedure. A faint yellow
Hz, 1H), 3.57 (d, J = 6.8 Hz, 2H). 13C NMR (100 MHz, liquid. 1H NMR (400 MHz, d6-DMSO) δ 7.31 (d, J = 6.8 Hz, 2H),
d6-DMSO) δ 151.26, 149.11, 144.52, 140.28, 134.03, 133.78, 7.19–7.10 (m, 4H), 6.85 (d, J = 9.7 Hz, 2H), 6.33 (d, J = 15.9 Hz,
133.73, 132.11, 131.45, 129.06, 43.92. GC/MS (m/z): [M]+ calcd 1H), 6.26–6.18 (m, 1H), 3.72 (s, 3H), 3.46 (d, J = 6.4 Hz, 2H),
for C15H13NO2, 239.1; found, 239.1. HRMS (EI+) calcd for 2.28 (s, 3H). 13C NMR (100 MHz, d6-DMSO) δ 163.70, 143.58,
C15H13NO2 [M+]: 239.0946. Found: 239.0949.
141.08, 135.20, 135.07, 134.96, 134.16, 132.33, 131.38, 131.35,
(E)-1-(2-Methoxyphenyl)-3-phenylpropene
(3-1i). Prepared 131.21, 119.17, 60.25, 41.41, 24.21. GC/MS (m/z): [M]+ calcd for
according to the general procedure. A faint yellow solid. C17H18O, 238.1; found, 238.1. HRMS (EI+) calcd for C17H18O
1H NMR (400 MHz, d6-DMSO) δ 7.44 (dd, J = 7.6, 1.6 Hz, 1H), [M+]: 238.1358. Found: 238.1359.
7.32–7.18(m, 6H), 6.97 (d, J = 7.6 Hz, 1H), 6.89 (t, J = 7.5 Hz,
(E)-3-(3-Methylphenyl)-1-(4-methoxyphenyl)-propene (3-2c).
1H), 6.72 (d, J = 15.9 Hz, 1H), 6.42–6.34 (m, 1H), 3.78 (s, 3H), Prepared according to the general procedure. A faint yellow
3.52 (d, J = 7.0 Hz, 2H). 13C NMR (100 MHz, d6-DMSO) liquid. 1H NMR (400 MHz, d6-DMSO) δ 7.33 (d, J = 8.7 Hz, 2H),
δ 156.47, 140.73, 130.22, 128.93, 128.90, 128.79, 126.67, 7.19 (t, J = 7.5 Hz, 1H), 7.05–7.00 (m, 3H), 6.89–6.50 (m, 2H),
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6.41 (d, J = 15.8 Hz, 1H), 6.28–6.20 (m, 1H), 3.73 (s, 3H), 3.45
(d, J = 6.9 Hz, 2H), 2.28 (s, 3H). 13C NMR (100 MHz, d6-DMSO)
Notes and references
δ
158.97, 140.69, 137.92, 130.37, 130.19, 129.55,
1 P. T. Anastas and J. C. Warner, in Green Chemistry: Theory
and Practice, Oxford University Press, Oxford, 1998.
128.77, 127.63, 127.49, 127.10, 125.99, 114.43, 55.51, 39.04,
21.45. GC/MS (m/z): [M]+ calcd for C17H18O, 238.1; found,
238.1. HRMS (EI+) calcd for C17H18O [M+]: 238.1358. Found:
238.1360.
2 For
a
seminal review on domino reactions, see:
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(E)-3-(4-Methylphenyl)-1-(4-methoxyphenyl)-propene (3-2d).
Prepared according to the general procedure. A faint yellow
liquid. 1H NMR (400 MHz, d6-DMSO) δ 7.33 (d, J = 8.7 Hz, 2H),
7.12 (s, 4H), 6.86 (d, J = 8.7 Hz, 2H), 6.39 (d, J = 15.8 Hz, 1H),
6.31–6.17 (m, 1H), 3.73 (s, 3H), 3.44 (d, J = 6.9 Hz, 2H), 2.27 (s,
3H). 13C NMR (100 MHz, d6-DMSO) δ 158.94, 137.65, 135.37,
130.24, 130.21, 129.45, 128.80, 127.67, 127.59, 114.43, 55.51,
38.63, 21.07. GC/MS (m/z): [M]+ calcd for C17H18O, 238.1;
found, 238.1. HRMS (EI+) calcd for C17H18O [M+]: 238.1358.
Found: 238.1359.
(E)-1-(4-Methoxyphenyl)-3-(3,5-dimethylphenyl)-propene
(3-2e). Prepared according to the general procedure. A faint
yellow liquid. 1H NMR (400 MHz, d6-DMSO) δ 7.32 (d, J =
11.6 Hz, 2H), 6.85–6.82 (m, 5H), 6.40 (d, J = 15.8 Hz, 1H),
6.26–6.18 (m, 1H), 3.73 (s, 3H), 3.40 (d, J = 6.9 Hz, 2H), 2.23 (s,
6H). 13C NMR (100 MHz, d6-DMSO) δ 163.70, 145.34, 142.51,
135.01, 134.96, 132.63, 132.37, 132.31, 131.43, 119.18, 60.27,
43.77, 26.10. GC/MS (m/z): [M]+ calcd for C18H20O, 252.1;
found, 252.1. HRMS (EI+) calcd for C18H20O [M+]: 252.1514.
Found: 252.1513.
(E)-1-(4-Methoxyphenyl)-3-(4-chlorophenyl)-propene (3-2f).
Prepared according to the general procedure. A faint green
liquid. 1H NMR (400 MHz, d6-DMSO) δ 7.37–7.32 (m, 4H), 7.27
(d, J = 8.5 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 6.41 (d, J = 15.8 Hz,
1H), 6.28–6.20 (m, 1H), 3.74 (s, 3H), 3.48 (d, J = 6.9 Hz, 2H).
13C NMR (100 MHz, d6-DMSO) δ 159.03, 139.86, 131.09,
130.83, 130.78, 130.06, 128.80, 127.68, 126.88, 114.44, 55.53,
38.21. GC/MS (m/z): [M]+ calcd for C16H15ClO, 258.1; found,
258.1. HRMS (EI+) calcd for C16H15ClO [M+]: 258.0811. Found:
258.0813.
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1
7.34 (d, J = 8.7 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 6.87 (d, J =
8.8 Hz, 2H), 6.41 (d, J = 15.8 Hz, 1H), 6.28–6.20 (m, 1H), 3.74
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Acknowledgements
The financial support for this study from the National
Basic Research Program of China (973 Program) (grant
2010CB126101) is gratefully acknowledged.
This journal is © The Royal Society of Chemistry 2014
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