Target-oriented synthesis: Miscellaneous synthetic routes to access 1,4-enediones through the coupling of 1,3-dicarbonyl compounds with multiform substrates

Article abstract of DOI:10.1016/j.tet.2013.05.106

Target-oriented synthetic protocol was presented for the synthesis of 1,4-enediones. The approach can efficiently construct 1,4-enediones through different reaction pathways from multiform substrates α-halo aromatic ketones, 2-hydroxy-aromatic ketones and methyl carbinols. In this reaction, CuI was found to be the most efficient catalyst. Multiform substrates were also found to perform well to afford the products in a one-pot fashion.

Full text of DOI:10.1016/j.tet.2013.05.106

Accepted Manuscript
Target-oriented synthesis: miscellaneous synthetic routes to access 1,4-enediones
through the coupling of 1,3-dicarbonyl compounds with multiform substrates
Yan-ping Zhu, Qun Cai, Qing-he Gao, Feng-cheng Jia, Mei-cai Liu, Meng Gao, An-xin
Wu
PII:
S0040-4020(13)00862-4
10.1016/j.tet.2013.05.106
TET 24444
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 23 April 2013
Accepted Date: 23 May 2013
Please cite this article as: Zhu Y-p, Cai Q, Gao Q-h, Jia F-c, Liu M-c, Gao M, Wu A-x, Target-oriented
synthesis: miscellaneous synthetic routes to access 1,4-enediones through the coupling of 1,3-
dicarbonyl compounds with multiform substrates, Tetrahedron (2013), doi: 10.1016/j.tet.2013.05.106.
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Target-oriented synthesis: miscellaneous
synthetic routes to access 1,4-enediones
through the coupling of 1,3-dicarbonyl
compounds with multiform substrates
Leave this area blank for abstract info.
Yan-ping Zhu, Qun Cai, Qing-he Gao, Feng-cheng Jia, Mei-cai Liu, Meng Gao, An-xin Wu
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China
Normal University, Wuhan 430079, China

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1
Tetrahedron
journal homepage: www.elsevier.com
Target-oriented synthesis: miscellaneous synthetic routes to access 1,4-enediones
through the coupling of 1,3-dicarbonyl compounds with multiform substrates
Yan-ping Zhu, Qun Cai, Qing-he Gao, Feng-cheng Jia, Mei-cai Liu, Meng Gao, An-xin Wu
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Target-oriented synthetic protocol was presented for the synthesis of 1,4-enediones. The
approach can efficiently construct 1,4-enediones through different reaction pathways from
multiform substrates α-halo aromatic ketones, 2-hydroxy-aromatic ketones and methyl carbinols.
In this reaction, CuI was found to be the most efficient catalyst. Multiform substrates were also
found to perform well to afford the products in a one-pot fashion.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
1,4-enediones
1,3-dicarbonyl compounds
multiform substrates
α-halogenation ketones
miscellaneous protocols
1. Introduction
In recently years, many novel and versatile synthetic strategies
have been proposed and utilized to obtain miscellaneous and
1-6
sophisticated molecular structures.
In particular, diversity-
oriented synthesis (DOS), which aims to generate a collection of
structurally diverse small molecules from a given synthetic
scheme, has been widely used in drug precursors screening and
drug-discovery programmes.1a-d The process is well-known for
converting simple starting materials into diverse molecules in a
divergent manner (Scheme 1A). As an alternative to the
divergent synthetic method, the target-oriented synthesis is also
very important in synthetic chemistry and pharmaceutical
chemistry (Scheme 1B).1e-f It is highly advantageous for chemists
to have two or more distinct pathways for accessing the same
target product during the process of natural products total
synthesis or target-oriented synthesis. When considering the
demands of actual synthesis, the development of miscellaneous
protocols would be of high value in synthetic chemistry, as it
would allow for changes in substrates and provide flexibility in
synthetic plans.
Scheme
synthesis.
1
Diversity-oriented synthesis and target-oriented
The 1,4-enedione is an important framework that is widely
present in natural products and medicinal compounds.7 By virtue
of their multifunctional composition, 1,4-enediones can also
serve as versatile precursors for the synthesis of furans,
thiophenes, pyrroles and pyridazines.8 In addition, they can
perform many other useful transformations, such as Diels-Alder
cyclization and Michael addition.9 Although there have been
many useful advancements in this area,10 further research into
———
Corresponding author. Tel.: +0-086-027-67867773; fax: +0-086-027-67867773; e-mail: chwuax@mail.ccnu.edu.cn

ACCEPTED MANUSCRIPT
2
Tetrahedron
diverse methods to construct 1,4-enediones from simple and
readily available starting materials remains highly desirable.
The scope of the substrates was examined under the optimized
conditions (Table 2); various substituted α-iodide aryl methyl
ketones were thus employed in the transformation.16 To our
delight, all of the α-iodide aryl methyl ketones 1 proceeded
smoothly to afford the desired products in moderate to high
yields (Table 2, 3a–3v, 58–95%). The electronic and steric
properties of the substrates were seen to have little influence on
the reaction efficiency. Both mono-substituted and multi-
substituted α-iodide aryl methyl ketones 1 were employed in the
reaction to provide the corresponding products in high yields
(Table 2, 86-95%, 3d–3f and 3k). Notably, the substrates with
heterocycle, such as furanyl (1l), thiophenyl (1m) and benzofuryl
(1n) also reacted to furnish the corresponding products 3l-3n in
good yields (78–88%). Meanwhile, the substrates with 2-
naphthyl (1p) and 1-naphthyl (1q) also reacted with 2a to obtain
satisfying results (3p and 3q, 90% and 88% yields). The scope of
substrate 2 was subsequently examined. The reaction was seen to
tolerate substituted dibenzoylmethane 2b to provide the expected
product 3r in 89% yield. Various β-keto esters were also
employed for the reaction. Electron-neutral (H), electron-
deficient (NO2) and heterocycle (furanyl) containing β-keto esters
provided satisfying results (3s, 3u–3v, 62–91% yields). However,
the strong electron-donating groups (3,4,5-OMe3) attached to the
phenyl of β-keto ester produced 58% yield (Table 2, 3t). In these
cases, the reaction afforded a mixture of E/Z isomers. α-Bromo
aryl methyl ketones were also examined for the transformation
(Table 2).17 Regardless of their electronic or steric properties, all
of the α-bromo aryl methyl ketones performed smoothly to afford
their corresponding products 3a–3v in good yields under the
optimized conditions (62–90%; Table 2). The diversity of β-keto
esters was also investigated for the reaction. All of the
corresponding products were obtained in 62–90% yields (Table 2,
3s–3v). Interestingly, the reactivity of α-bromo aryl methyl
ketones was found to be very similar to that of α-iodide aryl
methyl ketones.
Scheme
enediones.
2 Target-oriented synthetic protocol to access 1,4-
We herein report a target-oriented synthetic protocol to
synthesize 1,4-enediones from 1,3-dicarbonyl compounds with α-
halo aromatic ketones, 2-hydroxy-aromatic ketones and methyl
carbinols (Scheme 2). In the process, different substrates α-halo
aromatic ketones, 2-hydroxy-aromatic ketones and methyl
carbinols were converted in situ through different reaction
pathways into the same intermediate arylglyoxal, which was then
utilized by 1,3-dicarbonyl compounds to afford 1,4-enediones.
2. Results and discussion
Initially, the reaction conditions were fully optimized with
phenacyl iodine (1a) and dibenzoylmethane (2a) as model
substrates. The reaction of 1a with 2a performed smoothly to
afford the desired product with 72% yield in the presence of CuO
in DMSO at 80 ꢀ. However, the same reaction in the absence of
CuO provided a moderate yield (Entry 2). Thus, a series of
catalysts, such as Cu(OAc)2, CuI, CuBr, CuCl, CuCl2, CuBr2,
CuSO4 and Cu(acac)2 were screened for the reaction (Table 1,
Entries 3–10). Among them, CuI was found the most efficient
catalyst for the transformation (Table 1, Entry 4). In addition,
CuSO4 and Cu(OAc)2 also provided good results (Entries 3 and
9). The other catalysts provided only low to moderate yields. The
influence of temperature was then investigated, the results shown
that the reaction worked fine in the range of 80–100 ꢀ(Table 1,
Entries 4, 11–12).
Table 2. The scope of α-iodide/α-bromo aromatic ketones and
1,3-dicarbonyl compounds a,b
Table 1 Optimization of the reaction conditions a
O
O
O
O
O
CuI
Ar
R1
R2
X
R1
O
R2
Ar
DMSO, 90 o
C
1, X= I
4, X=Br
2
3
O
OMe
O
O
O
O
O
O
O
O
O
O
Me
Ph MeO
Ph
Ph
Ph
Ph
MeO
Ph
Ph
Ph
O
3a, X= I, 85%
X=Br, 84%
O
3b, X= I, 80%
X=Br, 68%
3c, X= I, 82%
X=Br, 82%
3d, X= I, 95%
X=Br, 83%
Entry
Catalyst /equiv T / ꢀ Time / h
Yield / % b
O
O
O
O
O O
O
O
O
Ph
Ph
Cl
Ph Br
Ph
Ph
O
Ph
Ph
O
Ph
1
2
CuO (0.5)
-
80
80
80
80
80
80
80
80
80
80
90
100
25
12
24
12
6
72
52
80
84
65
68
60
45
78
O
O
O
O
3h, X= I, 88%
3f, X= I, 93%
X=Br, 80%
3g, X= I, 87%
X=Br, 70%
3e, X= I, 95%
X=Br, 68%
X=Br, 74%
O
O
O O
O
O
O
O
O
O
3
Cu(OAc)2 (0.5)
CuI (0.5)
Ph
Ph
Cl
Ph
Ph
Ph
Ph
O2
N
Ph
Ph
O2N
Cl
4
O
O
O
3j, X= I, 80%
3l, X= I, 78%
X=Br, 62%
3k, X= I, 86%
X=Br, 83%
3i, X= I, 85%
X=Br, 80%
5
CuBr (0.5)
CuCl (0.5)
CuCl2 (0.5)
CuBr2 (0.5)
CuSO4 (0.5)
Cu(acac)2 (0.5)
CuI (0.5)
12
12
12
12
12
12
4
X=Br, 78%
O
O
O
O
O
O
O
O
S
O
Ph
Ph
6
Ph
Ph
Ph
Ph
Ph
Ph
Ph
7
O
O
O
O
3p, X= I, 90%
X=Br, 70%
3o, X= I, 85%
X=Br,
3m, X= I, 80%
X=Br, 70%
3n, X= I, 88%
b X=Br, 82%
8
OMe
OMe
OEt OMe
O
O
9
O O
O
O
O
O
Ph
Ph
Ph
OMe
Ph
Ph
10
11
12
13
<10
84
84
0
O
OEt
O
O
O
3s, X= I, 91% (E/Z> 95:5)c
3r, X= I, 89%
X=Br, 70%
3t, X= I, 58% (E/Z = 72:28)c
3q, X= I, 88%
X=Br,
MeO
X=Br, 90% (E/Z> 95:5)
CuI (0.5)
4
X=Br, 62% (E/Z = 62:38)
O
O
O
O
O
Ph
CuI (0.5)
24
Ph
NO2
OEt
OEt
O
3u, X= I, 62% (E/Z = 62:38)c
a Reaction conditions: 1a (0.5 mmol), 2a (0.5 mmol) in DMSO
3v, X= I, 75% (E/Z = 70:30)c
O
X=Br,68% (E/Z = 63:37)
(3–5 mL). b Isolated yield.
X=Br, 84% (E/Z = 82:18)
a The reaction was carried out with 1.0 equiv of 1 or 4, 1.0

ACCEPTED MANUSCRIPT
3
b
and 3i). Nucleophiles 1,3-bis(4-methoxyphenyl)propane-1,3-
equiv of 2, 50 mol% CuI in DMSO at 90 ꢀ for 2–10 h.
dione 2b and ethyl benzoylacetate 2c also reacted with 2-
hydroxy-aromatic ketones to obtain the corresponding products
in 60% and 68% yields, respectively (Table 4, 3r and 3s).
Isolated yields. c E:Z ratio of compounds 3s–3v determined
by 1H NMR.
In addition to α-iodide and α-bromo aryl methyl ketones, more
challenging α-chloro aryl methyl ketones 5 were also examined
(Table 3). To our delight, both electron-donating and electron-
withdrawing groups attached to the phenyl rings of 5 could
smoothly react with 2a and 2b to afford the corresponding
products in moderate to good yields (Table 3, 56–93%). It was
therefore determined that the overall reaction efficiency was not
influenced by the electronic or steric properties of 5. Yet, when
the substrates ethyl benzoylacetate 2c and ethyl 4-
nitrobenzoylacetate 2f were used as nucleophiles, only very low
yields were obtained (3s and 3v). Subsequently, some additives
were added. The reaction efficiency showed no improvement
with the addition of NaI, KI and TBAI. However, the yields were
greatly improved when 1 equivalent of I2 was added to the
reaction system (Table 4, 3s and 3v).
Table 4 The scope of 2-hydroxy-aromatic ketones and 1,3-
dicarbonyl compounds a
Yield /
%
Entry
Ar
2
3
b
1
2
C6H5 (6a)
4-Me-C6H4
(6b)
4-OMe-C6H4
(6c)
4-Cl-C6H4
(6g)
3a
3b
72
65
73
74
75
3
4
5
3c
3g
3h
2a
Table 3 The scope of α-chloro aromatic ketones and 1,3-
dicarbonyl compounds a
4-Br-C6H4
(6h)
6
7
C6H4 (6a)
3r
3s
60
2b
2c
68 (E/Z
Yield /
%
C6H5 (6a)
Entry
Ar
2
3
b
> 95:5) c
a The reaction was carried out with 1.0 equiv of 6, 1.0 equiv of 2,
1
2
3
4
5
6
7
C6H5 (5a)
3a
3b
3g
3h
3i
85
88
78
93
90
92
90
b
4-Me-C6H4 (5b)
4-Cl-C6H4 (5g)
4-Br-C6H4 (5h)
4-NO2-C6H4 (5i)
3-NO2-C6H4 (5j)
2-naphthyl (5p)
0.8 equiv of IBX, 50 mol% CuI in DMSO at 90 ꢀ. Isolated
yields. c E:Z ratio of compounds 3s determined by 1H NMR.
Methyl carbinols 7 are widely known for their ability to
oxidize into methyl ketones 8 in the presence of oxidant (Scheme
3a).12 In our previous studies, we found that methyl ketones could
easily react with 1,3-diketones to afford the desired 1,4-
enediones (Scheme 3b).11 We therefore wanted to examine the
possibility of affording 1,4-enediones from methyl carbinols and
1,3-diketones (Scheme 3c). After many optimized processes, it
was found that methyl carbinols 8 could react with 1,3-diketones
2 to obtain the desired 1,4-enediones 3 in the presence of IBX
(0.75 equiv), I2 (1.0 equiv) and CuI (0.5 equiv) in DMSO at 90 ꢀ.
With the optimized conditions in hand, the generality, electronic
and steric properties of the substrates 7 were evaluated. Both the
electron-donating and electron-withdrawing groups attached to
the phenyl rings of 7 could obtain the corresponding products 3a-
3h (Table 5, 58-85% yields). The steric influence was not
obvious in the reaction. The substrates 1,3-bis(4-
methoxyphenyl)propane-1,3-dione 2b and ethyl benzoylacetate
2c were also found suitable for the transformation, obtaining the
corresponding products in 48% and 63% yields, respectively
(Table 5, 3r and 3s).
2a
3j
3p
8
C6H5 (5a)
C6H5 (5a)
3r
3s
63
2b
2c
15 (85)c
E/Z >
95:5 d
9b
<10
(56)c
10b
C6H5 (5a)
3v
E/Z =
65:35 d
2f
a The reaction was carried out with 1.0 equiv of 5, 1.0 equiv
of 2, 50 mol% CuI in DMSO at 90 ꢀ. b Isolated yields. The
c
reaction was carried out with 1.0 equiv of 5, 1.0 equiv of 2,
d
1.0 equiv of I2, and 50 mol% CuI in DMSO at 90 ꢀ. E:Z
ratio of compounds 3s and 3v determined by 1H NMR.
The substrates were subsequently extended to 2-hydroxy-
aromatic ketones 6 (Table 4). On the basis of previous reports,
we found that 2-hydroxy-aromatic ketones in the presence of
IBX were easily transformed into 2-aryl-2-oxoacetaldehyde,
which was then captured by dibenzoylmethane 2a to afford the
desired products in good yields. In addition, the scope of 2-
hydroxy-aromatic ketones and 1,3-diketones was examined in the
presence of IBX (0.8 equiv) and CuI (0.5 equiv). Electron-neutral
(H, Me), electron-donating (OMe) and electron-withdrawing (Br,
NO2) groups attached to the phenyl ring of 6 were found tolerable
in the reaction to produce yields of 60–75% (Table 4, 3a–3c, 3h

ACCEPTED MANUSCRIPT
4
Tetrahedron
Scheme 3 Synthesis of 1,4-enediones from methyl carbinols and
1,3-dicarbonyl compounds in one-pot
Table 5 The scope of methyl carbinols and 1,3-dicarbonyl
compounds a
Scheme 4 Control experiments.
Based on the above results, we proposed
a possible
mechanism for the present reactions (Scheme 5). Initially,
carbinol 7a was oxidized by IBX to afford acetophenone 8a,
which was followed by iodination and Kornblum oxidation to
provide phenylglyoxal (A). α-Halo aryl methyl ketones (1a, 4a
and 5a) and 2-hydroxy-1-phenylethanone (6a) were oxidized by
either IBX or DMSO to afford phenylglyoxal (A). Meanwhile,
dibenzoylmethane (2a) was activated by CuI to form
intermediate 11a.15 Activated intermediate 11a subsequently
reacted with phenylglyoxal (A) to obtain intermediate C. Finally,
intermediate C underwent dehydration to afford the desired
product 1,4-enedione 3a.
Yield /
%
Entry
Ar
2
3
b
1
2
C6H5 (7a)
4-Me-C6H4
(7b)
4-OMe-C6H4
(7c)
2-OMe-C6H4
(7w)
3a
3b
84
85
3
4
5
3c
3w
3h
65
60
58
2a
4-Br-C6H4
(7h)
6
7
C6H4 (7a)
3r
3s
48
2b
2c
63 (E/Z
= 90:10)
C6H5 (7a)
c
a
The reaction was carried out with 7 (1.0 equiv), 2 (1.0
equiv), IBX (0.75 equiv), I2 (1.0 equiv) and 50 mol% CuI in
b
DMSO at 90 ꢀ. Isolated yields. c E:Z ratio of compounds
3s determined by 1H NMR.
Scheme 3 The proposed mechanism for the transformation.
As shown in Scheme 4, various control experiments were
performed. It was found that α-halo methyl ketones (1a, 4a, 5a)
could be converted to the same product phenylglyoxal (A) with
excellent conversion in DMSO at 90 ꢀ (Scheme 4a). 2-
Hydroxy-1-phenylethanone 6a was also oxidized to afford
phenylglyoxal (A) by IBX in DMSO (Scheme 4b).13 IBX was
shown to efficiently oxidize 1-phenylethanol 7a to furnish
acetophenone 8a in a quantitative 94% yield (Scheme 4c). With
the addition of IBX and I2 to 1-phenylethanol 7a, the product
phenylglyoxal A was produced (Scheme 4d).13 Moreover, I2 and
DMSO oxidized acetophenone 8a to produce phenylglyoxal A in
quantitative conversion at 100 ꢀ (Scheme 4e).14 The reaction of
With the aforementioned successful results in hand, we
attempted to integrate the miscellaneous reactions (Table 2–5)
into one pot, thus providing a successful novel model of domino
reaction. To our delight, the reaction could efficiently perform in
the conditions of IBX (1.5 equiv), I2 (0.8 equiv), CuI (2.5 equiv)
in DMSO at 90 ꢀ . The scope of the substrates was also
examined (Table 6); it was found that both the electron-donating
and electron-withdrawing groups attached to the phenyl rings of
substrates 1, 4, 5, 6 and 7 could afford the corresponding 1,4-
enediones (Table 6, 3a–3b, 3h). Nucleophiles 1,3-diketones 2b–
2c were also tolerated in the reaction to obtain the corresponding
products in 53% and 84% yields, respectively (3r and 3s). The
results demonstrate that an efficient integrated domino synthetic
strategy is feasible under suitable conditions.
hydrated phenylglyoxal
B with dibenzoylmethane 2a also
performed efficiently with a good yield of 82% (Scheme 4f).
Table 6 Multiform substrates performed in a one-pot fashion. a,b

ACCEPTED MANUSCRIPT
5
chromatography on silica gel to yield the desired product 3a as
a yellow solid.
4.2.2 General procedure for preparation of 3 from 2-
hydroxy-aromatic ketones 6 (3a as an example):
A sealed tube was charged with 2-hydroxy aromatic ketone
6a (136 mg, 1.0 mmol), dibenzoylmethane 2a (224 mg, 1.0
mmol), IBX (224 mg) and CuI (95 mg, 0.5 mmol) at room
temperature, and then solvent DMSO (3 mL) was added. The
resulting mixture was stirred at 90 ꢀ, after disappearance of the
reactant (monitored by TLC), then added 50mL water to the
mixture, extracted with EtOAc 3 times (3 × 50 mL). The extract
was washed with 10% NaCl solution, dried over anhydrous
Na2SO4 and concentrated under reduced pressure. The residue
was purified by column chromatography on silica gel to yield the
desired product 3a in 72% yield.
a
The reaction was carried out with 1 (1.0 equiv), 4 (1.0
4.2.3 General procedure for preparation of 3 from Methyl
carbinols 7 (3a as an example):
equiv), 5 (1.0 equiv), 6 (1.0 equiv), 7 (1.0 equiv), 2 (5.0
equiv), CuI (2.5 equiv), I2 (0.8 equiv) and IBX (1.5 equiv) in
A sealed tube was charged with methyl carbinol 7a (122 mg,
1.0 mmol), dibenzoylmethane 2a (224 mg, 1.0 mmol), IBX (210
mg, 0.75 mmol) and CuI (95 mg, 0.5 mmol) at room temperature,
and then solvent DMSO (3 mL) was added. The resulting
mixture was stirred at 90 ꢀ, after disappearance of the reactant
(monitored by TLC), then added 50mL water to the mixture,
extracted with EtOAc 3 times (3 × 50 mL). The extract was
washed with 10% NaCl solution, dried over anhydrous Na2SO4
and concentrated under reduced pressure. The residue was
purified by column chromatography on silica gel to yield the
desired product 3a in 84% yield.
b
c
DMSO at 90 ꢀ. Isolated yields. E:Z ratio of compounds
3s determined by 1H NMR.
3. Conculsion
In conclusion, a target-oriented synthetic protocol has been
developed for the construction of 1,4-enediones. In this reaction,
multiform substrates α-halo aromatic ketones, 2-hydroxy-
aromatic ketones and methyl carbinols could react with 1,3-
dicarbonyl compounds to afford 1,4-enediones through different
pathways. CuI was identified as a powerful catalyst for the
reaction. The reaction was advantageous due to its simple and
readily available starting materials, inexpensive catalyst and wide
substrate scope; it should therefore prove highly valuable in
organic chemistry.
4.3. Spectroscopic data
4.3.1 2-Benzoyl-1,4-diphenylbut-2-ene-1,4-dione (3a): yellow
solid, mp 101–103 ꢀ (lit11 mp 101–102 ꢀ); IR (KBr): 3443,
1
3056, 1685, 1641, 1594, 1444, 1360, 1266, 1212, 1006 cm-1; H
4. Experimental
NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 7.6 Hz, 2H), 7.99 (d, J
= 7.6 Hz, 2H), 7.88 (d, J = 7.6 Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H),
7.58 (t, J = 7.2 Hz, 4H), 7.42-7.54 (m, 5H); 13C NMR (100 MHz,
CDCl3): δ =193.9, 193.8, 188.6, 152.7, 136.2, 135.8, 135.6, 134.1,
133.7, 130.9, 130.2, 129.1, 128.9, 128.8, 128.74, 128.68; HRMS
(ESI): m/z [M+Na]+ calcd for C23H16NaO3: 363.0992; found:
363.0987.
4.1. General method
Unless otherwise noted, all reagents were obtained from
commercial suppliers and used without further purification. TLC
analysis was performed using pre-coated glass plates. Column
chromatography was performed using silica gel (200-300 mesh).
IR spectra were recorded on a Perkin-Elmer PE-983 infrared
spectrometer as KBr pellets with absorption in cm–1. NMR
spectra were recorded on a Varian Mercury 400 or 600 MHz
spectrometer Chemical shifts are reported in ppm (CDCl3 δ 7.26
for 1H NMR and 77.0 for 13C NMR, ppm), relative to the internal
standard of tetramethylsilane (TMS), multiplicities are indicated
s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet);
coupling constants (J) are given in Hertz (Hz). HRMS were
obtained on a Bruker Apex-Ultra 7.0T FTMS equipped with an
electrospray source (ESI) or Atmospheric-pressure chemical
ionization (APCI).
4.3.2 2-Benzoyl-1-phenyl-4-(p-tolyl)but-2-ene-1,4-dione (3b):
yellow solid, mp 109–111 ꢀ; IR (KBr): 3459, 3059, 1666, 1646,
1597, 1448, 1377, 1317, 1268, 1232, 1209, 1180, 1125, 1103,
1019 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 7.6 Hz,
2H), 8.00 (d, J = 8.0 Hz, 2H), 7.79 (d, J = 8.4 Hz, 2H), 7.64 (t, J
= 7.2 Hz, 1H), 7.50-7.58 (m, 5H), 7.42-7.48 (m, 2H), 7.24 (d, J =
7.6 Hz, 1H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3): δ =
194.0, 192.9, 188.0, 152.3, 145.3, 135.7, 135.5, 134.0, 133.7,
133.6, 131.0, 130.2, 129.6, 129.0, 128.9, 128.8, 128.7, 21.7;
HRMS (APCI): m/z [M + H]+ calcd for C24H19O3: 355.1329;
found: 355.1329.
4.2.1 General procedure for preparation of 3 from 1, 4 and 5
(3a as an example):
4.3.3
2-Benzoyl-4-(4-methoxyphenyl)-1-phenylbut-2-ene-1,4-
dione (3c): yellow solid, mp 125–127 ꢀ; IR (KBr): 3058, 2938,
A sealed tube was charged with α-iodide aromatic ketone 1a
(123 mg, 0.5 mmol), dibenzoylmethane 2a (112 mg, 0.5 mmol),
and CuI (47.6 mg, 0.25 mmol) at room temperature, and then
solvent DMSO (3 mL) was added. The resulting mixture was
stirred at 90 ꢀ, after disappearance of the reactant (monitored by
TLC), then added 50mL water to the mixture, extracted with
EtOAc 3 times (3 × 50 mL). The extract was washed with 10%
NaCl solution, dried over anhydrous Na2SO4 and concentrated
under reduced pressure. The residue was purified by column
1662, 1643, 1594, 1569, 1512, 1447, 1426, 1372, 1318, 1275,
1
1228, 1172, 1123, 1009 cm-1; H NMR (400 MHz, CDCl3): δ =
8.05 (d, J = 5.2 Hz, 2H), 7.99 (d, J = 5.2 Hz, 2H), 7.88 (d, J = 6.0
Hz, 2H), 7.64 (t, J = 4.8 Hz, 1H), 7.51-70.54 (m, 4H), 7.44 (t, J =
5.2 Hz, 2H), 6.91 (d, J = 6.0 Hz, 1H), 3.86 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ = 194.1, 193.0, 186.8, 164.3, 151.9, 134.0,
133.5, 131.3, 130.2, 129.3, 129.0, 128.8, 128.6, 114.1, 55.5;
HRMS (APCI): m/z [M + H]+ calcd for C24H19O4: 371.1278;

ACCEPTED MANUSCRIPT
6
Tetrahedron
found: 371.1278.
1318, 1247, 1218, 1178, 1110, 1098, 1073, 1032, 1024, 1007 cm-
1
1; H NMR (400 MHz, CDCl3): δ = 8.27 (d, J = 8.4 Hz, 2H),
4.3.4 2-Benzoyl-4-(2,4-dimethoxyphenyl)-1-phenylbut-2-ene-1,4-
dione (3d): yellow solid, mp 121–123 ꢀ; IR (KBr): 3097, 1683,
1667, 1642, 1612, 1596, 1597, 1529, 1520, 1482, 1445, 1352,
8.03-8.05 (br, 4H), 7.97 (d, J = 8.4 Hz, 2H), 7.63 (t, J = 7.6 Hz,
1H), 7.50-7.57 (m, 3H), 7.48 (s, 1H), 7.45 (t, J = 7.6 Hz, 2H); 13
C
NMR (100 MHz, CDCl3): δ = 193.2, 192.1, 187.5, 154.4, 150.5,
140.4, 135.3, 135.0, 134.4, 134.0, 130.2, 129.7, 129.6, 129.1,
128.9, 128.8, 124.0; HRMS (APCI): m/z [M + H]+ calcd for
C23H16O5N: 386.1023; found: 386.1024.
1315, 1293, 1276, 1225, 1168, 1100, 1019, 1000 cm-1; H NMR
1
(400 MHz, CDCl3): δ = 8.01 (t, J = 8.0 Hz, 4H), 7.63 (d, J = 15.2
HZ, 1H), 7.60 (s, 2H), 7.48-7.52 (m, 3H), 7.42 (t, J = 8.0 Hz, 2H),
6.45 (dd, J1 = 8.8 Hz, J2 = 2.0 Hz, 1H), 6.39 (t, J = 2.4 Hz, 1H),
3.79 (s, 6H); 13C NMR (100 MHz, CDCl3): δ = 194.5, 193.8,
187.6, 165.6, 161.1, 147.7, 133.4, 133.2, 129.9, 128.9, 128.4,
119.8, 105.9, 98.0, 55.6, 55.5; HRMS (APCI): m/z [M + H]+
calcd for C25H21O5: 401.1384; found: 401.1383.
4.3.10 2-Benzoyl-4-(3-nitrophenyl)-1-phenylbut-2-ene-1,4-dione
(3j): yellow solid, mp 125–127 ꢀ; IR (KBr): 3448, 3095, 1682,
1641, 1597, 1525, 1481, 1444, 1352, 1265, 1225, 1100, 1020 cm-
1; 1H NMR (400 MHz, CDCl3): δ = 8.69 (s, 1H), 8.42 (d, J = 8.0
Hz, 1H), 8.21 (d, J = 6.8 Hz, 1H), 8.06 (d, J = 7.2 Hz, 2H), 7.98
(d, J = 7.2 Hz, 2H), 7.51-7.67 (m, 2H), 7.45-7.49 (m, 6H); 13C
NMR (100 MHz, CDCl3): δ = 193.2, 192.1, 186.9, 154.6, 148.4,
137.3, 135.4, 135.1, 134.4, 134.1, 134.0, 130.2, 129.5, 129.1,
128.9, 128.8, 128.4, 128.1, 123.4; HRMS (APCI): m/z [M + H]+
calcd for C23H16O5N: 386.1023; found: 386.1022.
4.3.5 4-(Benzo[d][1,3]dioxol-5-yl)-2-benzoyl-1-phenylbut-2-ene-
1,4-dione (3e): yellow solid, mp 125–127 ꢀ; IR (KBr): 3066,
1683, 1660, 1640, 1592, 1515, 1488, 1330, 1290, 1270, 1176,
1119, 1105 cm-1; H NMR (400 MHz, CDCl3): δ = 8.04 (d, J =
1
8.0 Hz, 2H), 7.98 (d, J = 8.0 Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H),
7.53 (d, J = 7.6 Hz, 2H), 7.49 (d, J = 7.6 Hz, 2H), 7.44 (t, J = 7.2
Hz, 3H), 7.33 (s, 1H), 6.82 (d, J = 8.0 Hz, 1H), 6.03 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ = 194.0, 192.9, 186.4, 152.8, 152.0,
148.5, 134.0, 133.6, 131.2, 130.2, 129.0, 128.8, 128.7, 125.8,
108.1, 108.0; HRMS (APCI): m/z [M + H]+ calcd for C24H17O5:
385.1071; found: 385.1071.
4.3.11 2-Benzoyl-4-(3,4-dichlorophenyl)-1-phenylbut-2-ene-1,4-
dione (3k): yellow solid, mp 123–125 ꢀ; IR (KBr): 3091, 3062,
1656, 1595, 1579, 1449, 1392, 1338, 1248, 1213, 1177, 1073,
1045, 1027 cm-1; H NMR (400 MHz, CDCl3): δ = 8.04 (d, J =
1
7.6 Hz, 2H), 7.97 (d, J = 7.6 Hz, 2H), 7.93 (d, J = 2.0 Hz, 1H),
7.69 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 1H), 7.63 (t, J = 7.6 Hz, 1H),
7.49-7.57 (m, 4H), 7.43 (t, J = 7.6 Hz, 2H), 7.41 (s, 1H); 13C
NMR (100 MHz, CDCl3): δ = 193.3, 192.3, 186.6, 153.9, 138.7,
135.6, 135.4, 135.2, 134.3, 133.8, 133.6, 130.9, 130.5, 130.2,
129.6, 129.0, 128.8, 128.7, 127.6; HRMS (APCI): m/z [M + H]+
calcd for C23H15Cl2O3: 409.0393; found: 409.0393.
4.3.6
2-Benzoyl-4-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-1-
phenylbut-2-ene-1,4-dione (3f): yellow solid, mp 131–133 ꢀ; IR
(KBr): 3444, 3063, 2991, 1683, 1658, 1641, 1591, 1510, 1446,
1434, 1330, 1291, 1264, 1238, 1176, 1143, 1103, 1064, 1031,
1002 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.03 (d, J = 8.4 Hz,
2H), 7.98 (d, J = 8.4 Hz, 2H), 7.61-7.63 (m, 2H), 7.52 (d, J = 8.0
Hz, 2H), 7.47 (t, J = 8.4 Hz, 2H), 7.43 (s, 1H), 7.41 (s, 2H), 7.88
(t, J = 9.6 Hz, 1H), 4.20-4.30 (m, 4H); 13C NMR (100 MHz,
CDCl3): δ = 194.1, 193.0, 186.6, 151.9, 149.0, 143.6, 135.8,
135.6, 134.0, 133.5, 131.1, 130.0, 129.0, 128.8, 128.6, 123.1,
121.7, 118.2, 117.5, 64.7, 63.9; HRMS (APCI): m/z [M + H]+
calcd for C25H19O5: 371.1278; found: 371.1278.
4.3.12 2-Benzoyl-4-(furan-2-yl)-1-phenylbut-2-ene-1,4-dione (3l):
yellow solid, mp 106–107 ꢀ; IR (KBr): 3451, 3153, 3124, 3095,
3062, 2924, 1675, 1650, 1602, 1578, 1557, 1460, 1449, 1398,
1366, 1316, 1292, 1261, 1229, 1173, 1157, 1106, 1080, 1052,
1014 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 8.4 Hz,
2H), 8.01 (d, J = 8.4 Hz, 2H), 7.64 (t, J = 7.6 Hz, 1H), 7.59 (s,
1H), 7.52-7.56 (m, 3H), 7.45 (t, J = 7.2 Hz, 2H), 7.38 (s, 1H),
7.25 (t, J = 4.0 Hz, 1H), 7.54-7.55 (dd, J1 = 1.6 Hz, J2 = 3.6 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ = 193.7, 192.7, 175.7, 152.7,
152.4, 147.7, 134.0, 130.2, 128.9, 128.7, 128.6, 119.3, 113.2;
HRMS (APCI): m/z [M + H]+ calcd for C21H15O4: 331.0965;
found: 331.0965.
4.3.7 2-Benzoyl-4-(4-chlorophenyl)-1-phenylbut-2-ene-1,4-dione
(3g): yellow solid, mp 96–98 ꢀ; IR (KBr): 3059, 1665, 1645,
1586, 1490, 1448, 1406, 1317, 1305, 1264, 1228, 1175, 1119,
1093, 1025, 1013 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.05 (d,
J = 8.4 Hz, 2H), 7.99 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 8.8 Hz,
2H), 7.63 (d, J = 7.6 Hz, 1H), 7.52-7.57 (m, 3H), 7.40-7.48 (m,
5H); 13C NMR (100 MHz, CDCl3): δ = 193.6, 192.5, 187.4, 153.2,
140.7, 135.6, 135.3, 134.4, 134.2, 133.8, 130.2, 130.1, 129.2,
129.1, 128.8, 128.7, 128.4; HRMS (APCI): m/z [M + H]+ calcd
for C23H16O3Cl: 375.0782; found: 375.0784.
4.3.13 2-Benzoyl-1-phenyl-4-(thiophen-2-yl)but-2-ene-1,4-dione
(3m): yellow solid, mp 104–106 ꢀ; IR (KBr): 3451, 3115, 1652,
1594, 1517, 1451, 1413, 1358, 1319, 1273, 1243, 1223, 1176,
1090, 1072, 1022 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.05 (d,
J = 7.6 Hz, 2H), 8.01 (d, J = 8.4 Hz, 2H), 7.73 (d, J = 4.0 Hz,
1H), 7.69 (d, J = 4.0 Hz, 1H), 7.63 (t, J = 7.6 Hz, 1H), 7.49-7.51
(m, 3H), 7.46 (t, J = 7.6 Hz, 2H),7.36 (s, 1H), 7.11 (t, J = 4.0 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ = 193.5, 192.5, 180.1, 152.7,
143.7, 136.2, 135.6, 135.3, 134.1, 133.6, 133.5, 130.2, 129.6,
129.0, 128.7, 128.6; HRMS (APCI): m/z [M + H]+ calcd for
C21H15O3S: 347.0736; found: 347.0737.
4.3.8 2-Benzoyl-4-(4-bromophenyl)-1-phenylbut-2-ene-1,4-dione
(3h): yellow solid, mp 108–110 ꢀ; IR (KBr): 3058, 1665, 1645,
1595, 1518, 1487, 1448, 1403, 1374, 1317, 1263, 1227, 1175,
1118, 1102, 1072, 1025, 1010 cm-1; 1H NMR (400 MHz, CDCl3):
δ = 8.05 (d, J = 8.4 Hz, 2H), 7.98 (d, J = 8.0 Hz, 2H), 7.75 (d, J =
8.0 Hz, 2H), 7.66 (t, J = 7.6 Hz, 1H), 7.58 (d, J = 8.4 Hz, 2H),
7.51-7.56 (m, 3H), 7.43-7.47 (m, 3H); 13C NMR (100 MHz,
CDCl3): δ = 193.7, 192.5, 187.7, 153.3, 135.6, 135.3, 134.8,
134.2, 133.8, 132.2, 130.2, 129.6, 129.0, 128.8, 128.7; HRMS
(APCI): m/z [M + H]+ calcd for C23H16O3Br: 419.0277; found:
419.0278.
4.3.14
4-(Benzofuran-2-yl)-2-benzoyl-1-phenylbut-2-ene-1,4-
dione (3n): yellow solid, mp 105–107 ꢀ; IR (KBr): 3457, 3057,
1653, 1595, 1550, 1450, 1375, 1340, 1278, 1255, 1227, 1166,
1138, 1093 cm-1; H NMR (400 MHz, CDCl3): δ = 8.08 (d, J =
1
8.4 Hz, 2H), 8.03 (d, J = 8.0 Hz, 2H), 7.67 (d, J = 7.6 Hz, 1H),
7.63 (d, J = 7.2 Hz, 1H), 7.42-7.55 (m, 9H), 7.29 (t, J = 7.2 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ = 193.5, 192.5, 177.8, 155.9,
153.4, 152.2, 135.6, 135.3, 134.1, 133.6, 130.3, 129.1, 129.0,
4.3.9 2-Benzoyl-4-(4-nitrophenyl)-1-phenylbut-2-ene-1,4-dione
(3i): yellow solid, mp 90–93 ꢀ; IR (KBr): 3106, 3060, 2926,
2853, 1812, 1670, 1656, 1596, 1578, 1523, 1449, 1407, 1343,

ACCEPTED MANUSCRIPT
7
128.8, 128.7, 128.6, 124.2, 123.5, 115.1, 112.4; HRMS (APCI):
m/z [M + H]+ calcd for C25H17O4: 381.1121; found: 381.1122.
CDCl3) (E/Z): δ = 191.9, 191.1, 190.1, 188.5, 164.1, 163.7,
153.2, 144.2, 140.4, 136.1, 135.7, 134.2, 130.9, 130.7, 128.9,
128.7, 107.1, 107.0, 106.0, 105.8, 62.4, 56.2, 56.1, 56.0, 14.0,
13.8; HRMS (APCI): m/z [M + H]+ calcd for C22H23O7: 399.1438;
found: 399.1439.
4.3.15 4-([1,1'-Biphenyl]-4-yl)-2-benzoyl-1-phenylbut-2-ene-1,4-
dione (3o): yellow solid, mp 111–113 ꢀ; IR (KBr): 3453, 1657,
1597, 1556, 1448, 1407, 1367, 1314, 1264, 1225, 1185, 1118,
1
1028, 1004 cm-1; H NMR (400 MHz, CDCl3): δ = 8.06 (d, J =
4.3.21 Ethyl 2-(furan-2-carbonyl)-4-oxo-4-phenylbut-2-enoate
1
8.4 Hz, 2H), 8.01 (d, J = 8.4 Hz, 2H), 7.95 (d, J = 8.4 Hz, 2H),
7.63-7.66 (m, 3H), 7.55-7.61 (m, 3H), 7.49-7.53 (m, 3H), 7.38-
7.46 (m, 5H); 13C NMR (100 MHz, CDCl3): δ = 193.9, 192.8,
188.0, 152.5, 146.7, 139.3, 135.8, 135.6, 134.9, 134.0, 133.6,
130.9, 130.2, 129.3, 129.0, 128.9, 128.8, 128.6, 128.5, 127.4,
127.2; HRMS (APCI): m/z [M + H]+ calcd for C29H21O3:
417.1485; found: 417.1485.
(3u): lit11 yellow oil, H NMR (600 MHz, CDCl3): δ = 8.07 (s,
1H), 7.95 (d, J = 7.8 Hz, 2H), 7.61 (t, J = 7.2 Hz, 1H), 7.55 (s,
1H), 7.49 (q, J = 7.8 Hz, 2H), 7.20 (d, J = 3.0 Hz, 1H), 6.55 (s,
1H), 4.31 (q, J = 7.2 Hz, 2H), 1.27 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) (E/Z): δ = 188.7, 180.6, 163.3, 152.0, 147.9,
142.5, 136.1, 134.7, 134.2, 128.8, 118.2, 112.9, 112.5, 62.4, 13.9;
HRMS (APCI): m/z [M + H]+ calcd for C17H15O5: 299.0914;
found: 299.0914.
4.3.16
2-Benzoyl-4-(naphthalen-2-yl)-1-phenylbut-2-ene-1,4-
dione (3p): yellow solid, mp 51–53 ꢀ; IR (KBr): 3455, 3058,
1652, 1626, 1595, 1578, 1468, 1448, 1359, 1343, 1317, 1279,
1219, 1178, 1125, 1073, 1001 cm-1; 1H NMR (400 MHz, CDCl3):
δ = 8.39(s, 1H), 8.08 (d, J = 8.4 Hz, 2H), 8.03 (d, J = 7.2 Hz, 2H),
7.85-7.90 (m, 2H), 7.79-7.82 (m, 2H), 7.68 (s, 1H), 7.54-7.61 (m,
2H), 7.50 (br, 4H), 7.40 (t, J = 7.2 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ = 193.9, 192.8, 188.2, 152.5, 135.7, 135.8, 135.4,
134.0, 133.6, 132.1, 130.1, 129.6, 129.1, 129.0, 128.7, 128.6,
127.7, 127.0, 123.6; HRMS (APCI): m/z [M + H]+ calcd for
C27H19O3: 391.1329; found: 391.1328.
4.3.22 Ethyl 2-(4-nitrobenzoyl)-4-oxo-4-phenylbut-2-enoate (3v):
1
yellow solid, mp 96–97 ꢀ (lit4 mp 97-98 ꢀ); H NMR (600
MHz, CDCl3): δ = 8.32 (d, J = 8.4 Hz, 2H), 8.21 (s, 1H), 8.07 (d,
J = 8.4 Hz, 2H), 7.97 (d, J = 7.2 Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H),
7.51 (t, J = 7.2 Hz, 2H), 4.31 (q, J = 7.8 Hz, 2H), 1.24 (t, J = 7.8
Hz, 3H); 13C NMR (150 MHz, CDCl3) (E/Z): δ = 192.0, 188.1,
163.0, 144.1, 140.2, 135.7, 134.6, 133.9, 129.4, 129.2, 128.8,
124.0, 123.9, 62.7, 13.9, 13.8; HRMS (ESI): m/z [M+Na]+ calcd
for C19H15NNaO6: 376.0792; found: 376.0801.
4.3.23
2-Benzoyl-4-(2-methoxyphenyl)-1-phenylbut-2-ene-1,4-
dione (3w): White solid, mp 95–98 ꢀ; IR (KBr): 3445, 3055,
2940, 1662, 1645, 1594, 1569, 1515, 1447, 1426, 1375, 1318,
1275, 1228, 1172, 1123, 1010 cm-1; 1H NMR (400 MHz, CDCl3):
δ =8.05 (d, J = 7.2 Hz, 2H), 8.00 (d, J = 7.2 Hz, 2H), 7.58-7.63
(m, 2H), 7.52 (t, J = 7.6 Hz, 4H), 7.45 (q, J = 7.2 Hz, 3H), 6.94
(q, J = 7.2 Hz, 3H), 3.86 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
= 194.3, 193.6, 189.9, 159.1, 148.4, 136.3, 136.1, 136.0, 135.0,
133.7, 133.4, 131.1, 130.1, 129.1, 128.6, 121.0, 111.6, 55.7;
HRMS (APCI): m/z [M + H]+ calcd for C24H19O4: 371.1278;
found: 371.1278.
4.3.17
2-Benzoyl-4-(naphthalen-1-yl)-1-phenylbut-2-ene-1,4-
dione (3q): yellow solid, mp 97–99 ꢀ; IR (KBr): 3452, 3045,
1672, 1641, 1594, 1576, 1506, 1449, 1355, 1277, 1260, 1240,
1223, 1181, 1116, 1099 cm-1; H NMR (400 MHz, CDCl3): δ =
1
8.51 (d, J = 7.2 Hz, 1H), 8.08 (d, J = 7.2 Hz, 2H), 8.00 (t, J = 8.0
Hz, 3H), 7.92 (d, J = 7.2 Hz, 1H), 7.82-7.85 (m, 1H), 7.63 (t, J =
7.2 Hz, 1H), 7.51-7.54 (m, 5H), 7.40-7.50 (m, 4H); 13C NMR
(100 MHz, CDCl3): δ = 193.9, 193.0, 191.5, 151.4, 135.9, 135.6,
134.7, 134.2, 134.0, 133.8, 133.7, 133.6, 130.1, 129.9, 129.0,
128.8, 128.4; HRMS (APCI): m/z [M + H]+ calcd for C27H19O3:
391.1329; found: 391.1329.
Acknowledgments
4.3.18 2-(4-Methoxybenzoyl)-1-(4-methoxyphenyl)-4-phenylbut-
We thank the National Natural Science Foundation of China
(Grant 21032001 and 21272085). We also thank Dr. Chuanqi
Zhou, Hebei University, for analytical support.
2-ene-1,4-dione (3r): yellow oil, IR (KBr): 3443, 3056, 1685,
1
1641, 1594, 1529, 1520, 1444, 1360, 1266, 1212, 1006 cm-1; H
NMR (600 MHz, CDCl3): δ = 8.08 (d, J = 8.4 Hz, 2H), 7.99 (t, J
= 8.4 Hz, 2H),7.90 (d, J = 8.4 Hz, 2H), 7.57 (t, J = 7.2 Hz, 1H),
7.44 (t, J = 7.2 Hz, 2H), 7.41 (s, 1H), 6.97 (d, J = 9.0 Hz, 2H),
6.90 (d, J = 9.0 Hz, 2H), 3.86 (s, 3H), 3.82 (s, 3H); 13C NMR
(150 MHz, CDCl3): δ = 192.2, 191.1, 188.6, 164.5, 164.0, 154.3,
136.4, 133.8, 133.0, 132.8, 131.7, 131.5, 128.9, 128.7, 128.6,
128.3, 114.1, 114.0, 113.9, 113.9, 55.5, 55.3; HRMS (APCI): m/z
[M + H]+ calcd for C25H21O5: 401.1384; found: 401.1384.
References and notes
1. Selective examples for diversity-oriented synthesis: (a) Burke, M. D.;
Schreiber, S. L. Angew. Chem. Int. Ed. 2003, 43, 46–58. (b) Kumagai,
N.; Muncipinto, G.; Schreiber, S. L. Angew. Chem. Int. Ed. 2006, 46,
3635–3638; (c) Galloway, W. R. J. D.; Isidro-Llobet, A.; Spring, D. R.
Nat. Commun., 2010, 1, 80; (d) O' Connor, C. J.; Beckmann, H. S. G.
Spring, D. R. Chem. Soc. Rev., 2012, 41, 4444–4456; (e) Schreiber, S. L.
Science, 2000, 287, 1964–1969; (f) Burke1, M. D.; Lalic, G. Chemistry
& Biology, 2002, 9, 535-541.
4.3.19 Ethyl 2-benzoyl-4-oxo-4-phenylbut-2-enoate (3s):lit11
yellow oil, 1H NMR (600 MHz, CDCl3): δ = 8.15 (s, 1H), 7.95 (d,
J = 7.8 Hz, 2H), 7.90 (d, J = 7.2 Hz, 2H), 7.55-7.60 (m, 2H), 7.46
(q, J = 11.4 Hz, 4H), 4.27 (q, J = 10.8 Hz, 2H), 1.21 (t, J = 10.8
Hz, 3H); 13C NMR (150 MHz, CDCl3) (E/Z): δ = 193.3, 188.3,
163.6, 144.8, 136.1, 135.8, 134.2, 133.5, 128.9, 128.8, 128.7,
128.5, 128.4, 62.4, 31.9; HRMS (APCI): m/z [M + H]+ calcd for
C19H17O4: 309.1121; found: 309.1121.
2. Selective examples for synergistic catalysis: (a) Strater, N.; Lipscomb,
W. N.; Klabunde, T., Krebs, B. Angew. Chem. Int. Ed. 1996, 35, 2024–
2055; (b) Sawamura, M.; Sudoh, M.; Ito, Y. J. Am. Chem. Soc. 1996,
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Santos, E. N. Coord. Chem. Rev. 2004, 248, 2365–2379; (b) Wasilke, J.
C.; Obrey, S. J.; Baker, R. T.; Bazan, G. C. Chem. Rev. 2005, 105,
1001–1020; (c) Shindoh, N.; Takemoto, Y.; Takasu, K. Chem.-Eur. J.
2009, 15, 12168–12179.
4.3.20 Ethyl 4-oxo-4-phenyl-2-(3,4,5-trimethoxybenzoyl)but-2-
enoate (3t): lit11 yellow oil,1H NMR (600 MHz, CDCl3): δ = 8.14
(s, 1H), 7.97 (d, J = 12.0 Hz, 2H), 7.62 (t, J = 10.8 Hz, 1H), 7.49
(t, J = 11.4 Hz, 2H), 7.15 (s, 2H), 4.31 (q, J = 10.8 Hz, 2H), 3.85-
3.91 (m, 9H), 1.26 (t, J = 10.8 Hz, 3H); 13C NMR (150 MHz,

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8
Tetrahedron
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A. X. Chem. Commun. 2012, 48, 9086–9088.
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3116.
17. General procedure for preparation of 4 and 5 see: Lee, J. C.; Bae, Y. H.;
Chang, S.-K. Bull. Korean. Chem. Soc. 2003, 24, 407–408.

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Supporting Information available
Target-oriented synthesis: miscellaneous synthetic routes to access
1,4-enediones through the coupling of 1,3-dicarbonyl compounds with
multiform substrates
Yan-ping Zhu, Qun Cai, Qing-he Gao, Feng-cheng Jia, Mei-cai Liu, Meng Gao,
An-xin Wu*
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Central China
Normal University, Wuhan 430079, P. R. China
E-mail: chwuax@mail.ccnu.edu.cn
General.………………………………………………........…............... S2
General procedure for preparation of 3a-3w, 1, 4, and 5.......................S2-S3
Spectral data of compound 3a-3w…………………………….............S3-S8
Reference……………………………………………………………..…S8
Appendix: spectral copies of 1H NMR, and 13C NMR …....................S8-S31
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1. General
Unless otherwise noted, all 1,3-dicarbonyl compounds (2a-f), 2-hydroxy-aromatic ketones 6,
methyl carbinols 7, and other reagents were obtained from commercial suppliers and used without
further purification. TLC analysis was performed using pre-coated glass plates. Column
chromatography was performed using silica gel (200-300 mesh).
IR spectra were recorded on a Perkin-Elmer PE-983 infrared spectrometer as KBr pellets with
absorption in cm–1. NMR spectra were recorded on a Varian Mercury 400 or 600 MHz
1
spectrometer Chemical shifts are reported in ppm (CDCl3: δ 7.26 ppm for H NMR and 77.0 ppm
for 13C NMR), relative to the internal standard of tetramethylsilane (TMS), multiplicities are
indicated s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet); coupling constants (J) are
given in Hertz (Hz). HRMS were obtained on a Bruker Apex-Ultra 7.0T FTMS equipped with an
electro-spray source (ESI) or Atmospheric-pressure chemical ionization (APCI). Melting points
were determined using XT-4 apparatus and not corrected.
2. Synthesis of 3a-3w
2.1 General procedure for preparation of 3 from 1, 4 and 5 (3a as an example):
General procedure: A sealed tube was charged with α-iodide aromatic ketone 1a (123 mg, 0.5
mmol), dibenzoylmethane 2a (112 mg, 0.5 mmol), and CuI (47.6 mg, 0.25 mmol) at room
temperature, and then dried solvent DMSO (3 mL) was added. The resulting mixture was stirred at
90 ꢀ, after disappearance of the reactant (monitored by TLC), then added 50mL water to the
mixture, extracted with EtOAc 3 times (3 × 50 mL). The extract was washed with 10% NaCl
solution, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was
purified by column chromatography on silica gel (petroleum ether/EtOAc = 8:1) to yield the desired
product 3a as a yellow solid (85% yield).
2.2 General procedure for preparation of from 2-hydroxy-aromatic ketones 6 (3a as an
example):
General procedure: A sealed tube was charged with 2-hydroxy aromatic ketone 6a (136 mg,
1.0 mmol), dibenzoylmethane 2a (224 mg, 1.0 mmol), IBX (224 mg) and CuI (95 mg, 0.5
mmol) at room temperature, and then solvent DMSO (3 mL) was added. The resulting mixture
was stirred at 90 ꢀ, after disappearance of the reactant (monitored by TLC), then added
50mL water to the mixture, extracted with EtOAc 3 times (3 × 50 mL). The extract was
washed with 10% NaCl solution, dried over anhydrous Na2SO4 and concentrated under
reduced pressure. The residue was purified by column chromatography on silica gel to yield
the desired product 3a in 72% yield.
2.3 General procedure for preparation of 3 from Methyl carbinols 7 (3a as an example):
General procedure: A sealed tube was charged with methyl carbinol 7a (122 mg, 1.0 mmol),
dibenzoylmethane 2a (224 mg, 1.0 mmol), IBX (210 mg, 0.75 mmol) and CuI (95 mg, 0.5
mmol) at room temperature, and then solvent DMSO (3 mL) was added. The resulting mixture
-S2-

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was stirred at 90 ꢀ, after disappearance of the reactant (monitored by TLC), then added
50mL water to the mixture, extracted with EtOAc 3 times (3 × 50 mL). The extract was
washed with 10% NaCl solution, dried over anhydrous Na2SO4 and concentrated under
reduced pressure. The residue was purified by column chromatography on silica gel to yield
the desired product 3a in 84% yield.
2.4 Synthesis of starting material 1(1a as an example):1 Finely powdered CuO (0.8 g, 10.0
mmol) and I2 (2.53 g, 10.0 mmol) were added to a solution of aryl methyl ketone 9a (1.2 g,
10.0 mmol) in anhydrous MeOH (20 mL). The mixture was refluxed for 1-2.5 h. After
disappearance of aryl methyl ketone 9a (monitored by TLC), the mixture was filtered and the
solvent was removed under reduced pressure. The residue was poured into 10% Na2S2O3
solution (50 mL), the mixture was extracted with EtOAc (3 × 50 mL), and the organic layer
was dried (Na2SO4). Removal of the solvent and purification of the residue by column
chromatography gave the desired product 1a in 96% yield.
2.5 Synthesis of starting material 4 (4a as an example):2 N-Bromobutanimide (NBS, 356 mg,
2.0 mmol) and 4-Methylbenzenesulfonic acid (PTSA, 344 mg, 2.0 mmol) were added to a
well-stirred solution of aryl methyl ketone 8a (240 mg, 2.0 mmol) in anhydrous MeCN (15 mL).
The mixture was stirred at room temperature for 1 h, and then refluxed for another 1-2.5 h. After
disappearance of aryl methyl ketone 8a (monitored by TLC), the solvent was removed under
reduced pressure, then added 50mL water to the mixture, extracted with EtOAc 3 times (3 × 50
mL). The extract was washed with 10% NaCl solution, dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The residue was purified by column chromatography on silica
gel to yield the desired product 4a as a white solid in 90% yield.
2.6 Synthesis of starting material 5 (5a as an example):2 : N-Chlorosuccinimide (NCS, 266 mg,
2.0 mmol) and 4-Methylbenzenesulfonic acid (PTSA, 344 mg, 2.0 mmol) were added to a
well-stirred solution of aryl methyl ketone 8a (240 mg, 2.0 mmol) in anhydrous MeCN (15 mL).
The mixture was stirred at room temperature for 1 h, and then refluxed for another 1-2.5 h. After
disappearance of aryl methyl ketone 8a (monitored by TLC), the solvent was removed under
reduced pressure, then added 50mL water to the mixture, extracted with EtOAc 3 times (3 × 50
mL). The extract was washed with 10% NaCl solution, dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The residue was purified by column chromatography on silica
gel to yield the desired product 5a as a white solid in 85% yield.
3. Spectral data of compound 3a-3w.
2-benzoyl-1,4-diphenylbut-2-ene-1,4-dione (3a): yellow solid, mp 101–103ꢀ (lit3
mp 101–102 ꢀ); IR (KBr): 3443, 3056, 1685, 1641, 1594, 1444, 1360, 1266, 1212, 1006 cm-1; 1H
NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 7.6 Hz, 2H), 7.99 (d, J = 7.6 Hz, 2H), 7.88 (d, J = 7.6
Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H), 7.58 (t, J = 7.2 Hz, 4H), 7.42-7.54 (m, 5H); 13C NMR (100 MHz,
CDCl3): δ =193.9, 193.8, 188.6, 152.7, 136.2, 135.8, 135.6, 134.1, 133.7, 130.9, 130.2, 129.1,
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128.9, 128.8, 128.74, 128.68; HRMS (ESI): m/z [M+Na]+ calcd for C23H16NaO3: 363.0992; found:
363.0987.
2-benzoyl-1-phenyl-4-(p-tolyl)but-2-ene-1,4-dione (3b): yellow solid, mp
109–111ꢀ; IR (KBr): 3459, 3059, 1666, 1646, 1597, 1448, 1377, 1317, 1268, 1232, 1209, 1180,
1125, 1103, 1019 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 7.6 Hz, 2H), 8.00 (d, J = 8.0
Hz, 2H), 7.79 (d, J = 8.4 Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H), 7.50-7.58 (m, 5H), 7.42-7.48 (m, 2H),
7.24 (d, J = 7.6 Hz, 1H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3): δ = 194.0, 192.9, 188.0, 152.3,
145.3, 135.7, 135.5, 134.0, 133.7, 133.6, 131.0, 130.2, 129.6, 129.0, 128.9, 128.8, 128.7, 21.7;
HRMS (APCI): m/z [M + H]+ calcd for C24H19O3: 355.1329; found: 355.1329.
2-benzoyl-4-(4-methoxyphenyl)-1-phenylbut-2-ene-1,4-dione (3c): yellow
solid, mp 125–127 ꢀ; IR (KBr): 3058, 2938, 1662, 1643, 1594, 1569, 1512, 1447, 1426, 1372,
1
1318, 1275, 1228, 1172, 1123, 1009 cm-1; H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 5.2 Hz,
2H), 7.99 (d, J = 5.2 Hz, 2H), 7.88 (d, J = 6.0 Hz, 2H), 7.64 (t, J = 4.8 Hz, 1H), 7.51-70.54 (m, 4H),
7.44 (t, J = 5.2 Hz, 2H), 6.91 (d, J = 6.0 Hz, 1H), 3.86 (s, 3H); 13C NMR (100 MHz, CDCl3): δ =
194.1, 193.0, 186.8, 164.3, 151.9, 134.0, 133.5, 131.3, 130.2, 129.3, 129.0, 128.8, 128.6, 114.1,
55.5; HRMS (APCI): m/z [M + H]+ calcd for C24H19O4: 371.1278; found: 371.1278.
2-benzoyl-4-(2,4-dimethoxyphenyl)-1-phenylbut-2-ene-1,4-dione
(3d):
yellow solid, mp 121–123 ꢀ; IR (KBr): 3097, 1683, 1667, 1642, 1612, 1596, 1597, 1529, 1520,
1
1482, 1445, 1352, 1315, 1293, 1276, 1225, 1168, 1100, 1019, 1000 cm-1; H NMR (400 MHz,
CDCl3): δ = 8.01 (t, J = 8.0 Hz, 4H), 7.63 (d, J = 15.2 HZ, 1H), 7.60 (s, 2H), 7.48-7.52 (m, 3H),
7.42 (t, J = 8.0 Hz, 2H), 6.45 (dd, J1 = 8.8 Hz, J2 = 2.0 Hz, 1H), 6.39 (t, J = 2.4 Hz, 1H), 3.79 (s,
6H); 13C NMR (100 MHz, CDCl3): δ = 194.5, 193.8, 187.6, 165.6, 161.1, 147.7, 133.4, 133.2,
129.9, 128.9, 128.4, 119.8, 105.9, 98.0, 55.6, 55.5; HRMS (APCI): m/z [M + H]+ calcd for
C25H21O5: 401.1384; found: 401.1383.
4-(benzo[d][1,3]dioxol-5-yl)-2-benzoyl-1-phenylbut-2-ene-1,4-dione (3e): yellow
solid, mp 125–127 ꢀ; IR (KBr): 3066, 1683, 1660, 1640, 1592, 1515, 1488, 1330, 1290, 1270,
1176, 1119, 1105 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.04 (d, J = 8.0 Hz, 2H), 7.98 (d, J = 8.0
Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H), 7.53 (d, J = 7.6 Hz, 2H), 7.49 (d, J = 7.6 Hz, 2H), 7.44 (t, J = 7.2
Hz, 3H), 7.33 (s, 1H), 6.82 (d, J = 8.0 Hz, 1H), 6.03 (s, 3H); 13C NMR (100 MHz, CDCl3): δ =
194.0, 192.9, 186.4, 152.8, 152.0, 148.5, 134.0, 133.6, 131.2, 130.2, 129.0, 128.8, 128.7, 125.8,
108.1, 108.0; HRMS (APCI): m/z [M + H]+ calcd for C24H17O5: 385.1071; found: 385.1071.
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2-benzoyl-4-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-1-phenylbut-2-ene-1,4-dione
(3f): yellow solid, mp 131–133 ꢀ; IR (KBr): 3444, 3063, 2991, 1683, 1658, 1641, 1591, 1510,
1
1446, 1434, 1330, 1291, 1264, 1238, 1176, 1143, 1103, 1064, 1031, 1002 cm-1; H NMR (400
MHz, CDCl3): δ = 8.03 (d, J = 8.4 Hz, 2H), 7.98 (d, J = 8.4 Hz, 2H), 7.61-7.63 (m, 2H), 7.52 (d, J
= 8.0 Hz, 2H), 7.47 (t, J = 8.4 Hz, 2H), 7.43 (s, 1H), 7.41 (s, 2H), 7.88 (t, J = 9.6 Hz, 1H),
4.20-4.30 (m, 4H); 13C NMR (100 MHz, CDCl3): δ = 194.1, 193.0, 186.6, 151.9, 149.0, 143.6,
135.8, 135.6, 134.0, 133.5, 131.1, 130.0, 129.0, 128.8, 128.6, 123.1, 121.7, 118.2, 117.5, 64.7,
63.9; HRMS (APCI): m/z [M + H]+ calcd for C25H19O5: 371.1278; found: 371.1278.
2-benzoyl-4-(4-chlorophenyl)-1-phenylbut-2-ene-1,4-dione (3g): yellow solid, mp
96–98 ꢀ; IR (KBr): 3059, 1665, 1645, 1586, 1490, 1448, 1406, 1317, 1305, 1264, 1228, 1175,
1119, 1093, 1025, 1013 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 8.4 Hz, 2H), 7.99 (d, J
= 8.0 Hz, 2H), 7.82 (d, J = 8.8 Hz, 2H), 7.63 (d, J = 7.6 Hz, 1H), 7.52-7.57 (m, 3H), 7.40-7.48 (m,
5H); 13C NMR (100 MHz, CDCl3): δ = 193.6, 192.5, 187.4, 153.2, 140.7, 135.6, 135.3, 134.4,
134.2, 133.8, 130.2, 130.1, 129.2, 129.1, 128.8, 128.7, 128.4; HRMS (APCI): m/z [M + H]+ calcd
for C23H16O3Cl: 375.0782; found: 375.0784.
2-benzoyl-4-(4-bromophenyl)-1-phenylbut-2-ene-1,4-dione (3h): yellow solid,
mp 108–110ꢀ; IR (KBr): 3058, 1665, 1645, 1595, 1518, 1487, 1448, 1403, 1374, 1317, 1263,
1
1227, 1175, 1118, 1102, 1072, 1025, 1010 cm-1; H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 8.4
Hz, 2H), 7.98 (d, J = 8.0 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H), 7.66 (t, J = 7.6 Hz, 1H), 7.58 (d, J = 8.4
Hz, 2H), 7.51-7.56 (m, 3H), 7.43-7.47 (m, 3H); 13C NMR (100 MHz, CDCl3): δ = 193.7, 192.5,
187.7, 153.3, 135.6, 135.3, 134.8, 134.2, 133.8, 132.2, 130.2, 129.6, 129.0, 128.8, 128.7; HRMS
(APCI): m/z [M + H]+ calcd for C23H16O3Br: 419.0277; found: 419.0278.
2-benzoyl-4-(4-nitrophenyl)-1-phenylbut-2-ene-1,4-dione (3i): yellow solid,
mp 90–93 ꢀ; IR (KBr): 3106, 3060, 2926, 2853, 1812, 1670, 1656, 1596, 1578, 1523, 1449, 1407,
1
1343, 1318, 1247, 1218, 1178, 1110, 1098, 1073, 1032, 1024, 1007 cm-1; H NMR (400 MHz,
CDCl3): δ = 8.27 (d, J = 8.4 Hz, 2H), 8.03-8.05 (br, 4H), 7.97 (d, J = 8.4 Hz, 2H), 7.63 (t, J = 7.6
Hz, 1H), 7.50-7.57 (m, 3H), 7.48 (s, 1H), 7.45 (t, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ
= 193.2, 192.1, 187.5, 154.4, 150.5, 140.4, 135.3, 135.0, 134.4, 134.0, 130.2, 129.7, 129.6, 129.1,
128.9, 128.8, 124.0; HRMS (APCI): m/z [M + H]+ calcd for C23H16O5N: 386.1023; found:
386.1024.
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2-benzoyl-4-(3-nitrophenyl)-1-phenylbut-2-ene-1,4-dione (3j): yellow solid, mp
125–127 ꢀ; IR (KBr): 3448, 3095, 1682, 1641, 1597, 1525, 1481, 1444, 1352, 1265, 1225, 1100,
1020 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.69 (s, 1H), 8.42 (d, J = 8.0 Hz, 1H), 8.21 (d, J = 6.8
Hz, 1H), 8.06 (d, J = 7.2 Hz, 2H), 7.98 (d, J = 7.2 Hz, 2H), 7.51-7.67 (m, 2H), 7.45-7.49 (m, 6H);
13C NMR (100 MHz, CDCl3): δ = 193.2, 192.1, 186.9, 154.6, 148.4, 137.3, 135.4, 135.1, 134.4,
134.1, 134.0, 130.2, 129.5, 129.1, 128.9, 128.8, 128.4, 128.1, 123.4; HRMS (APCI): m/z [M + H]+
calcd for C23H16O5N: 386.1023; found: 386.1022.
2-benzoyl-4-(3,4-dichlorophenyl)-1-phenylbut-2-ene-1,4-dione (3k): yellow
solid, mp 123–125 ꢀ; IR (KBr): 3091, 3062, 1656, 1595, 1579, 1449, 1392, 1338, 1248, 1213,
1177, 1073, 1045, 1027 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.04 (d, J = 7.6 Hz, 2H), 7.97 (d, J
= 7.6 Hz, 2H), 7.93 (d, J = 2.0 Hz, 1H), 7.69 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 1H), 7.63 (t, J = 7.6 Hz,
1H), 7.49-7.57 (m, 4H), 7.43 (t, J = 7.6 Hz, 2H), 7.41 (s, 1H); 13C NMR (100 MHz, CDCl3): δ =
193.3, 192.3, 186.6, 153.9, 138.7, 135.6, 135.4, 135.2, 134.3, 133.8, 133.6, 130.9, 130.5, 130.2,
129.6, 129.0, 128.8, 128.7, 127.6; HRMS (APCI): m/z [M + H]+ calcd for C23H15Cl2O3: 409.0393;
found: 409.0393.
2-benzoyl-4-(furan-2-yl)-1-phenylbut-2-ene-1,4-dione (3l): yellow solid, mp 106–107
ꢀ; IR (KBr): 3451, 3153, 3124, 3095, 3062, 2924, 1675, 1650, 1602, 1578, 1557, 1460, 1449,
1
1398, 1366, 1316, 1292, 1261, 1229, 1173, 1157, 1106, 1080, 1052, 1014 cm-1; H NMR (400
MHz, CDCl3): δ = 8.05 (d, J = 8.4 Hz, 2H), 8.01 (d, J = 8.4 Hz, 2H), 7.64 (t, J = 7.6 Hz, 1H), 7.59
(s, 1H), 7.52-7.56 (m, 3H), 7.45 (t, J = 7.2 Hz, 2H), 7.38 (s, 1H), 7.25 (t, J = 4.0 Hz, 1H), 7.54-7.55
(dd, J1 = 1.6 Hz, J2 = 3.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ = 193.7, 192.7, 175.7, 152.7,
152.4, 147.7, 134.0, 130.2, 128.9, 128.7, 128.6, 119.3, 113.2; HRMS (APCI): m/z [M + H]+ calcd
for C21H15O4: 331.0965; found: 331.0965.
2-benzoyl-1-phenyl-4-(thiophen-2-yl)but-2-ene-1,4-dione (3m): yellow solid, mp
104–106 ꢀ; IR (KBr): 3451, 3115, 1652, 1594, 1517, 1451, 1413, 1358, 1319, 1273, 1243, 1223,
1176, 1090, 1072, 1022 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 7.6 Hz, 2H), 8.01 (d, J
= 8.4 Hz, 2H), 7.73 (d, J = 4.0 Hz, 1H), 7.69 (d, J = 4.0 Hz, 1H), 7.63 (t, J = 7.6 Hz, 1H), 7.49-7.51
(m, 3H), 7.46 (t, J = 7.6 Hz, 2H),7.36 (s, 1H), 7.11 (t, J = 4.0 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ = 193.5, 192.5, 180.1, 152.7, 143.7, 136.2, 135.6, 135.3, 134.1, 133.6, 133.5, 130.2,
129.6, 129.0, 128.7, 128.6; HRMS (APCI): m/z [M + H]+ calcd for C21H15O3S: 347.0736; found:
347.0737.
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4-(benzofuran-2-yl)-2-benzoyl-1-phenylbut-2-ene-1,4-dione (3n): yellow solid,
mp 105–107 ꢀ; IR (KBr): 3457, 3057, 1653, 1595, 1550, 1450, 1375, 1340, 1278, 1255, 1227,
1166, 1138, 1093 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.08 (d, J = 8.4 Hz, 2H), 8.03 (d, J = 8.0
Hz, 2H), 7.67 (d, J = 7.6 Hz, 1H), 7.63 (d, J = 7.2 Hz, 1H), 7.42-7.55 (m, 9H), 7.29 (t, J = 7.2 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ = 193.5, 192.5, 177.8, 155.9, 153.4, 152.2, 135.6, 135.3,
134.1, 133.6, 130.3, 129.1, 129.0, 128.8, 128.7, 128.6, 124.2, 123.5, 115.1, 112.4; HRMS (APCI):
m/z [M + H]+ calcd for C25H17O4: 381.1121; found: 381.1122.
4-([1,1'-biphenyl]-4-yl)-2-benzoyl-1-phenylbut-2-ene-1,4-dione (3o): yellow
solid, mp 111–113 ꢀ; IR (KBr): 3453, 1657, 1597, 1556, 1448, 1407, 1367, 1314, 1264, 1225,
1185, 1118, 1028, 1004 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.06 (d, J = 8.4 Hz, 2H), 8.01 (d, J
= 8.4 Hz, 2H), 7.95 (d, J = 8.4 Hz, 2H), 7.63-7.66 (m, 3H), 7.55-7.61 (m, 3H), 7.49-7.53 (m, 3H),
7.38-7.46 (m, 5H); 13C NMR (100 MHz, CDCl3): δ = 193.9, 192.8, 188.0, 152.5, 146.7, 139.3,
135.8, 135.6, 134.9, 134.0, 133.6, 130.9, 130.2, 129.3, 129.0, 128.9, 128.8, 128.6, 128.5, 127.4,
127.2; HRMS (APCI): m/z [M + H]+ calcd for C29H21O3: 417.1485; found: 417.1485.
2-benzoyl-4-(naphthalen-2-yl)-1-phenylbut-2-ene-1,4-dione (3p): yellow solid,
mp 51–53 ; IR (KBr): 3455, 3058, 1652, 1626, 1595, 1578, 1468, 1448, 1359, 1343, 1317, 1279,
1219, 1178, 1125, 1073, 1001 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.39(s, 1H), 8.08 (d, J = 8.4
Hz, 2H), 8.03 (d, J = 7.2 Hz, 2H), 7.85-7.90 (m, 2H), 7.79-7.82 (m, 2H), 7.68 (s, 1H), 7.54-7.61 (m,
2H), 7.50 (br, 4H), 7.40 (t, J = 7.2 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ = 193.9, 192.8, 188.2,
152.5, 135.7, 135.8, 135.4, 134.0, 133.6, 132.1, 130.1, 129.6, 129.1, 129.0, 128.7, 128.6, 127.7,
127.0, 123.6; HRMS (APCI): m/z [M + H]+ calcd for C27H19O3: 391.1329; found: 391.1328.
2-benzoyl-4-(naphthalen-1-yl)-1-phenylbut-2-ene-1,4-dione (3q): yellow solid, mp
97–99 ꢀ; IR (KBr): 3452, 3045, 1672, 1641, 1594, 1576, 1506, 1449, 1355, 1277, 1260, 1240,
1223, 1181, 1116, 1099 cm-1; 1H NMR (400 MHz, CDCl3): δ = 8.51 (d, J = 7.2 Hz, 1H), 8.08 (d, J
= 7.2 Hz, 2H), 8.00 (t, J = 8.0 Hz, 3H), 7.92 (d, J = 7.2 Hz, 1H), 7.82-7.85 (m, 1H), 7.63 (t, J = 7.2
Hz, 1H), 7.51-7.54 (m, 5H), 7.40-7.50 (m, 4H); 13C NMR (100 MHz, CDCl3): δ = 193.9, 193.0,
191.5, 151.4, 135.9, 135.6, 134.7, 134.2, 134.0, 133.8, 133.7, 133.6, 130.1, 129.9, 129.0, 128.8,
128.4; HRMS (APCI): m/z [M + H]+ calcd for C27H19O3: 391.1329; found: 391.1329.
2-(4-methoxybenzoyl)-1-(4-methoxyphenyl)-4-phenylbut-2-ene-1,4-dione
(3r): yellow oil, IR (KBr): 3443, 3056, 1685, 1641, 1594, 1529, 1520, 1444, 1360, 1266, 1212,
1006 cm-1; 1H NMR (600 MHz, CDCl3): δ = 8.08 (d, J = 8.4 Hz, 2H), 7.99 (t, J = 8.4 Hz, 2H),7.90
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(d, J = 8.4 Hz, 2H), 7.57 (t, J = 7.2 Hz, 1H), 7.44 (t, J = 7.2 Hz, 2H), 7.41 (s, 1H), 6.97 (d, J = 9.0
Hz, 2H), 6.90 (d, J = 9.0 Hz, 2H), 3.86 (s, 3H), 3.82 (s, 3H); 13C NMR (150 MHz, CDCl3): δ =
192.2, 191.1, 188.6, 164.5, 164.0, 154.3, 136.4, 133.8, 133.0, 132.8, 131.7, 131.5, 128.9, 128.7,
128.6, 128.3, 114.1, 114.0, 113.9, 113.9, 55.5, 55.3; HRMS (APCI): m/z [M + H]+ calcd for
C25H21O5: 401.1384; found: 401.1384.
ethyl 2-benzoyl-4-oxo-4-phenylbut-2-enoate (3s):lit4 yellow oil, 1H NMR (600
MHz, CDCl3): δ = 8.15 (s, 1H), 7.95 (d, J = 7.8 Hz, 2H), 7.90 (d, J = 7.2 Hz, 2H), 7.55-7.60 (m,
2H), 7.46 (q, J = 11.4 Hz, 4H), 4.27 (q, J = 10.8 Hz, 2H), 1.21 (t, J = 10.8 Hz, 3H); 13C NMR (150
MHz, CDCl3) (E/Z): δ = 193.3, 188.3, 163.6, 144.8, 136.1, 135.8, 134.2, 133.5, 128.9, 128.8, 128.7,
128.5, 128.4, 62.4, 31.9; HRMS (APCI): m/z [M + H]+ calcd for C19H17O4: 309.1121; found:
309.1121.
OMe
O
O
OMe
OEt OMe
ethyl 4-oxo-4-phenyl-2-(3,4,5-trimethoxybenzoyl)but-2-enoate (3t): lit4
O
1
yellow oil, H NMR (600 MHz, CDCl3): δ = 8.14 (s, 1H), 7.97 (d, J = 12.0 Hz, 2H), 7.62 (t, J =
10.8 Hz, 1H), 7.49 (t, J = 11.4 Hz, 2H), 7.15 (s, 2H), 4.31 (q, J = 10.8 Hz, 2H), 3.85-3.91 (m, 9H),
1.26 (t, J = 10.8 Hz, 3H); 13C NMR (150 MHz, CDCl3) (E/Z): δ = 191.9, 191.1, 190.1, 188.5, 164.1,
163.7, 153.2, 144.2, 140.4, 136.1, 135.7, 134.2, 130.9, 130.7, 128.9, 128.7, 107.1, 107.0, 106.0,
105.8, 62.4, 56.2, 56.1, 56.0, 14.0, 13.8; HRMS (APCI): m/z [M + H]+ calcd for C22H23O7:
399.1438; found: 399.1439.
1
ethyl 2-(furan-2-carbonyl)-4-oxo-4-phenylbut-2-enoate (3u): lit4 yellow oil, H
NMR (600 MHz, CDCl3): δ = 8.07 (s, 1H), 7.95 (d, J = 7.8 Hz, 2H), 7.61 (t, J = 7.2 Hz, 1H), 7.55
(s, 1H), 7.49 (q, J = 7.8 Hz, 2H), 7.20 (d, J = 3.0 Hz, 1H), 6.55 (s, 1H), 4.31 (q, J = 7.2 Hz, 2H),
1.27 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) (E/Z): δ = 188.7, 180.6, 163.3, 152.0, 147.9,
142.5, 136.1, 134.7, 134.2, 128.8, 118.2, 112.9, 112.5, 62.4, 13.9; HRMS (APCI): m/z [M + H]+
calcd for C17H15O5: 299.0914; found: 299.0914.
ethyl 2-(4-nitrobenzoyl)-4-oxo-4-phenylbut-2-enoate (3v): yellow solid, mp
1
96–97 ꢀ (lit4 mp 97-98 ꢀ); H NMR (600 MHz, CDCl3): δ = 8.32 (d, J = 8.4 Hz, 2H), 8.21 (s,
1H), 8.07 (d, J = 8.4 Hz, 2H), 7.97 (d, J = 7.2 Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H), 7.51 (t, J = 7.2 Hz,
2H), 4.31 (q, J = 7.8 Hz, 2H), 1.24 (t, J = 7.8 Hz, 3H); 13C NMR (150 MHz, CDCl3) (E/Z): δ =
192.0, 188.1, 163.0, 144.1, 140.2, 135.7, 134.6, 133.9, 129.4, 129.2, 128.8, 124.0, 123.9, 62.7, 13.9,
13.8; HRMS (ESI): m/z [M+Na]+ calcd for C19H15NNaO6: 376.0792; found: 376.0801.
2-benzoyl-4-(2-methoxyphenyl)-1-phenylbut-2-ene-1,4-dione (3w): White solid, mp
95–98 ; IR (KBr): 3445, 3055, 2940, 1662, 1645, 1594, 1569, 1515, 1447, 1426, 1375, 1318,
1275, 1228, 1172, 1123, 1010 cm-1; 1H NMR (400 MHz, CDCl3): δ =8.05 (d, J = 7.2 Hz, 2H), 8.00
(d, J = 7.2 Hz, 2H), 7.58-7.63 (m, 2H), 7.52 (t, J = 7.6 Hz, 4H), 7.45 (q, J = 7.2 Hz, 3H), 6.94 (q, J
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= 7.2 Hz, 3H), 3.86 (s, 3H); 13C NMR (100 MHz, CDCl3): δ = 194.3, 193.6, 189.9, 159.1, 148.4,
136.3, 136.1, 136.0, 135.0, 133.7, 133.4, 131.1, 130.1, 129.1, 128.6, 121.0, 111.6, 55.7; HRMS
(APCI): m/z [M + H]+ calcd for C24H19O4: 371.1278; found: 371.1278.
4. Reference
(1) Yin, G. D.; Gao, M.; She, N. F.; Hu, S. L.; Wu, A. X.; Pan, Y. J. Synthesis 2007, 3113.
(2) Lee. J. C.; Bae, Y. H.; Chang, S.-K. Bull. Korean. Chem. Soc. 2003, 24, 407.
(3) Dien, C.-K.; Lutz, R. E. J. Am. Chem. Soc. 1956, 78, 1987.
(4) Gao, M.; Yang, Y.; Wu, Y. D.; Deng, C.; Cao, L. P.; Meng, X. G.; Wu, A. X. Org. Lett. 2010,
12, 1856.
5. Appendix: spectral copies of 1H NMR, and 13C NMR
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