Substrate-controlled and highly stereoselective synthesis of 2-aminobut-2-ene-1, 4-diones

Article abstract of DOI:10.1016/j.tet.2012.03.049

2-Methylthio-substituted 1,4-enediones, obtained from readily available aryl methyl ketones, were reacted with primary or secondary amines to afford the desired 1,4-diaryl-2-aminobut-2-ene-1,4-diones in excellent yields with high Z/E-stereoselectivity.

Full text of DOI:10.1016/j.tet.2012.03.049

Tetrahedron 68 (2012) 3828e3834
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Substrate-controlled and highly stereoselective synthesis of 2-aminobut-2-ene-1,
4-diones
,
b
b,
Cong Deng a, Yan Yang a, Meng Gao a, Yan-Ping Zhu a, An-Xin Wu a , Jun-Rui Ma , Guo-Dong Yin
*
*
a Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079, China
b Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, Hubei Normal University, Huangshi 435002, China
a r t i c l e i n f o
a b s t r a c t
Article history:
2-Methylthio-substituted 1,4-enediones, obtained from readily available aryl methyl ketones, were re-
acted with primary or secondary amines to afford the desired 1,4-diaryl-2-aminobut-2-ene-1,4-diones in
excellent yields with high Z/E-stereoselectivity.
Received 5 January 2012
Received in revised form 6 March 2012
Accepted 15 March 2012
Available online 22 March 2012
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Aryl methyl ketones
Amines
2-Aminobut-2-ene-1,4-diones
Substrate-controlled
Z/E-Stereoselectivity
1. Introduction
2-aminobut-2-ene-1,4-diones by the treatment of 2-(methylthio)-
1,4-diaryl-2-butene-1,4-dione with the primary or secondary
The compounds, which have a skeleton consisting of 1,4-diaryl-
2-aminobut-2-ene-1,4-diones constitute an important class of
materials in the manufacture of agrochemicals, pharmaceutical and
other industrial products.1e4 They are also the building blocks of
various heterocyclic compounds in organic synthesis,5 such as hy-
drazine,6 furan7,8 and imidazo[1,2-a]pyridin-3(2H)-ones.9 There-
fore, the development of new methodologies for these compounds
has been the driving force for numerous synthetic efforts.
amines (Scheme 2).
Up until now, a variety of methods have been reported for the
synthesis of 1,4-diaryl-2-aminobut-2-ene-1,4-diones (Scheme 1).
Generally, they could be synthesized by the reaction of aryl methyl
ketones with nitrobenzenes,6 diaroylacetylene with various
amines5,9,10 or aryl azide,11
a
,
b
-unsaturated
pounds with amines12 or sulfilimines,13 using sulfur ylides,14 pyr-
idinium ylides15 or -tosyloxyacetophenones16 as one of substrates,
g-dicarbonyl com-
a
as well as through other pathways.6,17e19 Recently, we established
a simple and attractive reaction for the preparation of substituted
2-butene-1,4-dione skeleton from readily available aryl methyl
ketones in the presence of copper(II) oxide, iodine and dimethyl
sulfoxide.20 As a continuation of our work, we herein report an
efficient and stereoselective method for the synthesis of 1,4-diaryl-
Scheme 1. Various methods for the synthesis of 2-aminobut-2-ene-1,4-diones.
2. Results and discussion
Initially, we investigated the optimum conditions for the for-
mation of (Z)-1,4-diphenyl-2-(phenylamino)but-2-ene-1,4-dione
(3aa) using the Z-isomer of 2-(methylthio)-1,4-diphenylbut-2-
ene-1,4-dione (1a) and aniline (2a) as the model substrates in
ethanol. After careful optimization of the molar ratios and reaction
* Corresponding authors. Tel./fax: þ86 27 67867773 (A.-X. W.); tel./fax: þ86 714
6515602 (G.-D. Y.); e-mail addresses: chwuax@mail.ccnu.edu.cn (A.-X. Wu), gdyin@
hbnu.edu.cn (G.-D. Yin).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.03.049

C. Deng et al. / Tetrahedron 68 (2012) 3828e3834
3829
Table 2
Reaction scope of 2-methylthio-substituted 1,4-enediones 1
Diketonesa
Ar
Products
Yieldsb (%)
(Z)-1a
(E)-1a
1b
1c
1d
1e
1f
1g
1h
Ph
Ph
3aa
3aa
3ba
3ca
3da
3ea
3fa
3ga
3ha
3ia
95
95
97
96
89
90
91
88
92
96
98
4-MeC6H4
4-MeOC6H4
4-ClC6H4
4-BrC6H4
4-O2NC6H4
1-NaPh
2-NaPh
2-Furyl
2-Thienyl
Scheme 2. Synthesis of 1,4-diaryl-2-(arylamino)but-2-ene-1,4-diones from aryl
methyl ketones.
temperature (Table 1, entries 1e9), it was found that the desired
product 3aa was obtained in 95% yield with the ratio of 1:2.5 (1a/2a)
at reflux (78 ꢀC) for 28 h. This transformation was also attempted in
other different solvents, such as THF, acetonitrile, toluene and DMF,
3aa was isolated in 30e85% yields (entries 10e13). No expected
product was observed in DMSO at 100 ꢀC (entry 14). Therefore, the
optimized reaction condition was identified as: 1a reacted with
2.5 equiv of 2a in refluxing ethanol for 28 h.
1i
1j
3ja
a
Compounds 1bej involved a mixture of Z/E-isomers with the ratio of 6:1, see
Ref. 20; reaction conditions: 1 (1.0 mmol), 2a (2.5 mmol) in EtOH (2 mL) at reflux for
28 h.
b
Isolated yields.
Table 1
Optimization of the reaction conditions
Entry
Molar ratio (Z)-1a/2a
Solvents
Temp (ꢀC)
Yieldsa (%)
1
2
3
4
5
6
7
8
1:1
1:1.5
1:2
1:2.5
1:3
1:2.5
1:2.5
1:2.5
1:2.5
1:2.5
1:2.5
1:2.5
1:2.5
1:2.5
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
THF
Reflux
Reflux
Reflux
Reflux
Reflux
60
50
40
20
Reflux
Reflux
Reflux
100
50
62
86
95
95
75
50
42
25
41
80
85
30
0
9
10
11
12
13
14
CH3CN
Toluene
DMF
Fig. 1. X-ray crystal structure of compound 3aa.
DMSO
100
a
Isolated yields.
react with 1a. As can be seen from Table 3, aromatic primary
amines, including 4-chloroaniline (2b), 4-aminophenol (2c), ben-
zene-1,4-diamine (2d), naphthyl amine (2f) and pyridin-3-amine
(2g) did not affect the overall efficiency, affording the corre-
sponding products in excellent yields. However, ethyl 4-
aminobenzoate (2e) gave the expected product 3ae only in 45%
yield after 72 h. To our delight, aliphatic amines, such as ethan-
amine (2h), propan-2-amine (2i), butan-1-amine (2j), cyclo-
hexanamine (2k) and phenylmethanamine (2l) were also suitable
substrates for the reaction, furnishing the expected products
3aheal in 89e95% yields. X-ray single-crystal diffraction analysis22
of 3al showed that the molecule also adopted a Z-configuration
(Fig. 2).
Next, we extended this process to secondary amines including
diethylamine (2m), pyrrolidine (2n), piperidine (2o) and morpho-
line (2p). Much to our satisfaction, the corresponding 2-amino-
substituted 1,4-diones products 3ameap were isolated in 83e92%
yields (Table 4). However, the X-ray diffraction analysis of 3am,23
3ao24 and 3ap25 showed that these molecules adopted an E-con-
figuration, probably due to the higher thermal stability of E-iso-
mers. The crystal structure of 3ap was shown in Fig. 3.
With the optimized condition in hand, we examined the scope
of 2-methylthio-substituted 1,4-enediones (Table 2). It was found
that 3aa was the only product in 95% yield even if the E-isomer of
1a reacted with 2a under the above-mentioned conditions. The
structure of 3aa was confirmed by IR, 1H NMR, 13C NMR and HRMS.
The low-field of NH resonance signal (12.57 ppm) highlighted the
possibility of intramolecular hydrogen bonding, which was further
confirmed by the single-crystal X-ray diffraction analysis.19,21 As
shown in Fig. 1, the molecule adopted a Z-configuration with re-
spect to the carbonecarbon double bond. This was due to intra-
molecular six-membered ring NeH/O hydrogen-bonding, with
ꢀ
the H1/O2 distance of 2.658(1) A. Since both Z- and E-isomers of
1a gave the same Z-configuration product 3aa, substrates 1bek
involved in this reaction were a mixture of Z/E-isomers.20 We were
pleased to find that regardless of the electronic or steric properties
of substituents (Me, OMe, Cl, Br, NO2) on the phenyl ring, the re-
action proceeded smoothly to afford Z-configuration products
3baefa in 89e97% yields. In addition, naphthalene ring and het-
erocyclic substituted substrates 1gej could also work well under
these conditions (88e98%).
Interestingly, the treatment of a mixture of Z/E-isomers of 2-
methylthio-substituted 1,4-enediones (1) with primary amines
provided the desired 2-amino-substituted 1,4-enediones (3) in a Z-
Encouraged by the results obtained with 2-methylthio-
substituted 1,4-enediones, a variety of amines were investigated to

3830
C. Deng et al. / Tetrahedron 68 (2012) 3828e3834
Table 3
Table 4
Reaction scope of primary amine 2a
Reaction scope of secondary amine 2a
Yieldsb (%)
81
Amines
Products
Yieldsb (%)
83
Amines
Products
2m
3am
2b
3ab
2n
2o
3an
3ao
91
83
2c
3ac
3ad
96
90
2d
45c
95
2p
3ap
92
2e
2f
3ae
3af
a
Compound 1a involved a mixture of Z/E-isomers with the ratio of 6:1, see Ref.
20; reaction conditions: 1a (1.0 mmol), 2 (2.5 mmol) in EtOH (2 mL) at reflux for
28 h.
b
Isolated yields.
2g
3ag
92
2h
2i
3ah
3ai
95
90
2j
3aj
92
90
2k
3ak
2l
3al
89
a
Compound 1a involved a mixture of Z/E-isomers with the ratio of 6:1, see Ref.
20; reaction conditions: 1 (1.0 mmol), 2a (2.5 mmol) in EtOH (2 mL) at reflux for
28 h.
b
Isolated yields.
Reflux for 72 h.
c
Fig. 3. X-ray crystal structure of compound 3ap.
Michael addition of aniline (2a) to 1a, and then eliminated the
methanethiol (HSMe) to deliver the same Z-configuration product
3aa, which was thermodynamically more stable for the existence of
intramolecular six-membered hydrogen-bonding. In order to con-
firm this additioneelimination process, (Z)-4-(4-chlorophenyl)-2-
(methylthio)-1-(thiophen-2-yl)but-2-ene-1,4-dione (4) was syn-
thesized according to our reported method.26,27 The treatment of 4
with 2a under the standard condition only gave the Z-configuration
product 5 in 98% yield (Scheme 4), which was unambiguously de-
termined by 1H NOESY NMR Spectra (see Supplementary data) and
X-ray crystallographic analysis (Fig. 4).28 Obviously, the amino
group was close to the thiophene ring, showing that the Michael
addition reaction occurred at the carbon atom attached to the
methylthio group. This experimental result indicated that the for-
mation of intermediate I was possible. In addition, it has been
reported that methylthio group in the aromatic ring could be easily
replaced by the amines.29 Hence we put forward another possible
pathway: (ii) firstly, the methylthio group was replaced by the
primary or secondary amines, respectively. Then, the correspond-
ing thermodynamically more stable product Z-isomer of 3aa or E-
isomer of 3ao was delivered due to the isomerization of the en-
amine into the tautomeric imine III30 or resonance stabilized
zwitterionic intermediate IV.31
Fig. 2. X-ray crystal structure of compound 3al.
configuration, and allowed formation of an E-configuration product
with the secondary amines. Consequently, the plausible mecha-
nisms were further investigated. Two potential pathways were
proposed as follows using 1a as an example (Scheme 3): (i) the
saturated 1,4-diones intermediates I or II were formed by the

C. Deng et al. / Tetrahedron 68 (2012) 3828e3834
3831
given in parts per million relative to tetramethylsilane. Data are
reported as follows: chemical shift, multiplicity (s¼singlet,
d¼doublet, t¼triplet, m¼multiplet), coupling constants (Hz) and
integration. 13C spectra were recorded in CDCl3 or DMSO on 100/
150 MHz spectrometers and resonances (d) are given in ppm. HRMS
were obtained on a Bruker 7-T FT-ICR MS and apex-Ultra MS
equipped with an electrospray source. MS was carried out on
a Finnigan Trace MS spectrometer (EI, 70 eV). Column chromatog-
raphy was performed on silica gel (200e300 mesh). The X-ray
crystal structure determinations of compounds were obtained on
a Bruker SMART APEX CCD system.
4.2. Synthesis of 2-(methylthio)-1,4-diaryl-2-butene-1,4-
dione (1)
Scheme 3. The plausible mechanism of the present reaction.
The preparation and characterization of 2-(methylthio)-1,4-
diaryl-2-butene-1,4-diones (1) have been previously reported.20
4.3. Synthesis of (Z)-4-(4-chlorophenyl)-2-(methylthio)-1-
(thiophen-2-yl)but-2-ene-1,4-dione (4)
The preparation and characterization of (Z)-4-(4-chlorophenyl)-
2-(methylthio)-1-(thiophen-2-yl)but-2-ene-1,4-dione (4) have
been previously reported.20 The crystal structure data see Ref. 25
and Supplementary data.
Scheme 4. The controlled experiment to prove the mechanism.
4.4. General procedure for synthesis of 3 (3aa as an example)
The mixture of (Z)-2-(methylthio)-1,4-diphenyl-2-butene-1,4-
dione (0.28 g, 1.0 mmol) and aniline (0.23 g, 2.5 mmol) was stir-
red at reflux in ethanol for 28 h. After the reactant disappeared
(monitored by TLC), the mixture was cooled to room temperature,
and the collected organic phase was evaporated to dryness and the
resulting crude mixture was purified by column chromatography
on silica gel (eluent: petroleum ether/EtOAc) to afford the desired
product
(3aa)6 as a yellow solid (0.31 g, 95%). Mp 114e115 ꢀC; 1H NMR
(CDCl3, 600 MHz):
(Z)-1,4-diphenyl-2-(phenylamino)but-2-ene-1,4-dione
d
(ppm) 12.57 (s, 1H), 7.97 (d, J¼7.8 Hz, 2H), 7.93
(d, J¼7.2 Hz, 2H), 7.54e7.49 (m, 2H), 7.44 (t, J¼7.5 Hz, 2H), 7.40 (t,
J¼7.8 Hz, 2H), 7.14 (t, J¼7.8 Hz, 2H), 6.98 (d, J¼8.4 Hz, 3H), 6.12 (s,
1H); 13C NMR (CDCl3, 150 MHz):
d (ppm) 191.9, 190.7, 156.5, 138.7,
138.4, 134.4, 134.2, 131.8, 129.5, 129.2, 129.1, 128.7, 128.6, 128.4,
128.3, 127.2, 124.9, 121.5, 94.8; IR (KBr, cmꢁ1): 3059, 1664, 1578,
1550, 1503, 1446, 1320, 1280, 1238, 1173, 1056, 1023, 979, 914, 801,
758, 696, 552; HRMS (ESI): m/z [MþH]þ calcd for C22H17NO2:
328.1332; found: 328.1327.
Fig. 4. X-ray crystal structure of compound 5.
3. Conclusion
Compound 3aa was also obtained in 95% yield starting from (E)-
1a under the same reaction conditions.
In conclusion, we have developed a convenient protocol for
substrate-controlled and highly stereoselective synthesis of 1,4-
diaryl-2-aminobut-2-ene-1,4-diones from readily available aryl
methyl ketones. The high efficiency and wide substrate scope of
this new methodology encourages and facilitates further utilization
of 2-amino-substituted 1,4-enediones for the construction of more
complicated molecules. Further investigations on the applications
of this transformation are currently underway in our laboratory.
4.5. Characterization data
4.5.1. (Z)-2-(Phenylamino)-1,4-di-p-tolylbut-2-ene-1,4-dione
(3ba).6 Yield 97%, yellow solid, mp 129e131 ꢀC; 1H NMR (CDCl3,
400 MHz):
J¼8.0 Hz, 2H), 7.25e7.12 (m, 6H), 6.97 (d, J¼6.4 Hz, 3H), 6.07 (s, 1H),
2.39 (s, 3H), 2.37 (s, 3H); 13C NMR (CDCl3, 100 MHz):
(ppm) 191.5,
d
(ppm) 12.56 (s, 1H), 7.89 (d, J¼8.0 Hz, 2H), 7.83 (d,
d
4. Experimental
190.5, 156.5, 145.4, 142.4, 138.6, 136.2, 132.1, 129.7, 129.3, 129.0,
127.3, 124.6, 121.3, 94.7, 21.6, 21.4; IR (KBr, cmꢁ1): 3029, 2917, 1662,
1602, 1570, 1503, 1446, 1407, 1282, 1242, 1170, 1060, 1014, 980, 914,
838, 790, 751, 696, 621, 549; HRMS (ESI): m/z [MþH]þ calcd for
C24H21NO2: 356.1645; found: 356.1641.
4.1. General method
All reagents were purchased from commercial suppliers and
used without further purification. All solvents were of analytical
grade and dried according to published methods and distilled be-
fore use. IR spectra were recorded on an infrared spectrometer as
4.5.2. (Z)-1,4-Bis(4-methoxyphenyl)-2-(phenylamino)but-2-ene-1,4-
dione (3ca).16 Yield 97%, yellow solid, mp 132e133 ꢀC; 1H NMR
KBr pellets with absorption in cmꢁ1
.
1H spectra were recorded in
) are
(CDCl3, 400 MHz):
(d, J¼8.8 Hz, 2H), 7.15 (t, J¼7.8 Hz, 2H), 6.98 (d, J¼8.4 Hz, 3H), 6.93
d
(ppm) 12.54 (s, 1H), 7.98 (d, J¼8.8 Hz, 2H), 7.92
CDCl3 on 400/600 MHz NMR spectrometers and resonances (
d

3832
C. Deng et al. / Tetrahedron 68 (2012) 3828e3834
(d, J¼8.8 Hz, 2H), 6.88 (d, J¼9.2 Hz, 2H), 6.05 (s, 1H), 3.86 (s, 3H),
3.85 (s, 3H); 13C NMR (CDCl3, 100 MHz):
(ppm) 190.4, 189.5, 164.3,
911, 862, 755, 692, 554; HRMS (ESI): m/z [MþH]þ calcd for
d
C30H21NO2: 428.1645; found: 428.1636.
162.5, 156.3, 138.7, 132.0, 131.5, 129.2, 129.0,127.4, 124.4,121.1,113.9,
113.5, 94.4, 55.3, 55.1; IR (KBr, cmꢁ1): 2927, 2835, 1657, 1594, 1510,
1456, 1420, 1314, 1247, 1169, 1060, 1030, 912, 847, 793, 758, 696,
626, 554; HRMS (ESI): m/z [MþH]þ calcd for C24H21NO4: 388.1543;
found: 388.1549.
4.5.8. (Z)-1,4-Di(furan-2-yl)-2-(phenylamino)but-2-ene-1,4-dione
(3ia). Yield 96%, red solid, mp 53e55 ꢀC; 1H NMR (CDCl3,
400 MHz): d (ppm) 12.05 (s, 1H), 7.61 (s, 1H), 7.55 (s, 1H), 7.30e7.16
(m, 4H), 7.04 (t, J¼7.2 Hz, 1H), 6,98 (d, J¼8.0 Hz, 2H), 6.51 (d,
J¼7.8 Hz, 2H), 6.13 (s, 1H); 13C NMR (CDCl3, 100 MHz):
d (ppm)
4.5.3. (Z)-1,4-Bis(4-chlorophenyl)-2-(phenylamino)but-2-ene-1,4-
179.7, 178.4, 155.0, 153.3, 150.5, 148.5, 145.5, 138.7, 129.2, 124.8,
122.1, 121.3, 115.0, 112.6, 112.3, 95.7; IR (KBr, cmꢁ1): 3123, 1659,
1575, 1460, 1389, 1272, 1229, 1156, 1070, 1026, 917, 881, 757, 693,
590, 557; HRMS (ESI): m/z [MþH]þ calcd for C18H13NO4: 308.0917;
found: 308.0922.
dione (3da).6 Yield 89%, yellow solid, mp 162e164 ꢀC; 1H NMR
(CDCl3, 400 MHz):
d
(ppm) 12.51 (s, 1H), 7.88 (q, J¼8.4 Hz, 4H), 7.41
(d, J¼8.4 Hz, 2H), 7.35 (d, J¼8.4 Hz, 2H), 7.16 (t, J¼7.6 Hz, 2H), 7.01 (t,
J¼7.4 Hz, 1H), 6.96 (d, J¼8.0 Hz, 2H), 6.06 (s, 1H); 13C NMR (CDCl3,
100 MHz):
d (ppm) 190.9, 189.6, 156.6, 140.9, 138.3, 137.1, 132.8,
130.8, 129.3, 129.1, 128.7, 125.4, 121.8, 94.6; IR (KBr, cmꢁ1): 1667,
1575, 1505, 1398, 1279, 1235, 1170, 1085, 1011, 913, 845, 757, 692,
536; HRMS (ESI): m/z [MþH]þ calcd for C22H15Cl2NO2: 396.0553;
found: 396.0560.
4.5.9. (Z)-2-(Phenylamino)-1,4-di(thiophen-2-yl)but-2-ene-1,4-
dione (3ja). Yield 98%, tan solid, mp 127e128 ꢀC; 1H NMR (CDCl3,
400 MHz):
d
(ppm) 12.12 (s, 1H), 7.81 (d, J¼3.6 Hz, 1H), 7.71 (d,
J¼4.8 Hz, 1H), 7.66 (d, J¼3.6 Hz, 1H), 7.59 (d, J¼5.2 Hz, 1H), 7.20 (t,
J¼7.6 Hz, 2H), 7.12 (t, J¼8.0 Hz, 1H), 7.08 (t, J¼4.2 Hz, 1H), 7.04e6.99
4.5.4. (Z)-1,4-Bis(4-bromophenyl)-2-(phenylamino)but-2-ene-1,4-
(m, 3H), 6.08 (s, 1H); 13C NMR (CDCl3, 100 MHz):
d (ppm) 183.6,
dione (3ea).16 Yield 90%; light yellow solid; mp 163e164 ꢀC; 1H
183.5, 155.3, 145.7, 141.4, 138.6, 136.3, 135.6, 132.3, 129.6, 129.2,
129.0, 128.4, 128.0, 124.8, 121.1, 118.1, 114.8, 95.6; IR (KBr, cmꢁ1):
3092, 1646, 1581, 1506, 1410, 1349, 1295, 1249, 1059, 1005, 854, 792,
738, 692, 538; HRMS (ESI): m/z [MþH]þ calcd for C18H13NO2S2:
340.0460; found: 340.0457.
NMR (CDCl3, 400 MHz):
d
(ppm) 12.49 (s,1H), 7.80 (d, J¼8.0 Hz, 4H),
7.59 (d, J¼7.6 Hz, 2H), 7.54 (d, J¼7.6 Hz, 2H), 7.17 (t, J¼7.6 Hz, 2H),
7.03 (t, J¼7.2 Hz, 1H), 6.96 (d, J¼8.0 Hz, 2H), 6.04 (s, 1H); 13C NMR
(CDCl3, 100 MHz):
d (ppm) 191.1, 189.7, 156.6, 138.3, 137.6, 133.3,
132.2, 131.8,130.9, 130.0,129.9,129.4,129.0,127.0,125.5, 121.9, 94.6;
IR (KBr, cmꢁ1): 1671, 1574, 1504, 1395, 1278, 1236, 1172, 1069, 1008,
790, 756, 692; HRMS (ESI): m/z [MþH]þ calcd for C22H15Br2NO2:
483.9542; found: 485.9514.
4.5.10. (Z)-2-((4-Chlorophenyl)amino)-1,4-diphenylbut-2-ene-1,4-
dione (3ab).6 Yield 81%, yellow solid, mp 153e155 ꢀC; 1H NMR
(CDCl3, 600 MHz):
(d, J¼7.2 Hz, 2H), 7.58 (t, J¼7.2 Hz, 1H), 7.52 (t, J¼7.5 Hz, 1H), 7.44 (q,
J¼7.8 Hz, 4H), 7.12 (d, J¼9.0 Hz, 2H), 6.91 (d, J¼9.0 Hz, 2H), 6.14 (s,
d
(ppm) 12.51 (s, 1H), 7.97 (d, J¼7.2 Hz, 2H), 7.93
4.5.5. (Z)-1,4-Bis(4-nitrophenyl)-2-(phenylamino)but-2-ene-1,4-
dione (3fa). Yield 91%, yellow solid, mp 224.6e225 ꢀC; 1H NMR
1H); 13C NMR (CDCl3, 150 MHz):
d (ppm) 191.8, 191.0, 156.1, 138.6,
(CDCl3, 400 MHz):
d
(ppm) 12.52 (s, 1H), 8.32 (d, J¼8.4 Hz, 2H), 8.20
137.3, 134.5, 134.4, 132.1, 130.3, 129.6, 129.3, 128.8, 128.4, 127.3,
122.8, 95.51, 95.48; IR (KBr, cmꢁ1): 3060, 1668, 1598, 1581, 1556,
1501, 1447, 1320, 1282, 1238, 1171, 1080, 1060, 1024, 1008, 980, 909,
852, 819, 763, 725, 703, 686, 653, 557, 540, 496; HRMS (ESI): m/z
[MþH]þ calcd for C22H16ClNO2: 362.0942; found: 362.0937.
(d, J¼8.0 Hz, 2H), 8.10 (d, J¼8.4 Hz, 2H), 8.03 (d, J¼8.4 Hz, 2H), 7.18
(t, J¼7.4 Hz, 2H), 7.05 (t, J¼7.2 Hz, 1H), 6.98 (d, J¼8.0 Hz, 2H), 6.18 (s,
1H); 13C NMR (DMSO-d6, 100 MHz):
d (ppm) 190.9, 185.1, 150.0,
149.2, 143.0, 139.8, 138.4, 130.9, 130.0, 129.9, 129.8, 129.7, 129.5,
129.3, 129.2, 129.0, 128.8, 125.9, 124.3, 124.2, 123.81, 123.76, 123.0,
122.96, 122.92; IR (KBr, cmꢁ1): 1675, 1587, 1558, 1522, 1348, 1281,
1230, 1175, 1109, 1067, 1012, 857, 800, 757, 718; HRMS (ESI): m/z
[MþH]þ calcd for C22H15N3O6: 418.1034; found: 418.1039.
4.5.11. (Z)-2-((4-Hydroxyphenyl)amino)-1,4-diphenylbut-2-ene-1,4-
dione (3ac). Yield 96%, red solid, mp 177e179 ꢀC; 1H NMR (CDCl3,
400 MHz):
2H), 7.45e7.38 (m, 4H), 6.80 (d, J¼8.4 Hz, 2H), 6.62 (d, J¼8.8 Hz, 2H),
6.41(s, 1H), 6.05(s, 1H); 13C NMR (CDCl3, 100 MHz):
(ppm) 192.5,
d (ppm) 12.38 (s, 1H), 7.94e7.89 (m, 4H), 7.57e7.48 (m,
4.5.6. (Z)-1,4-Di(naphthalen-1-yl)-2-(phenylamino)but-2-ene-1,4-
d
dione (3ga). Yield 88%, yellow solid, mp 160e162 ꢀC; 1H NMR
191.0,158.0,153.9,138.8,134.5,134.4,131.9,131.1,129.7,128.8,128.5,
127.3, 124.2, 116.2, 93.8; IR (KBr, cmꢁ1): 3458, 3436, 2974, 2927,
2372, 1666, 1598, 1571, 1513, 1446, 1405, 1386, 1323, 1302, 1278,
1236, 1167, 1065, 984, 913, 759, 711, 554; MS (EI): m/z 343.17.
(CDCl3, 600 MHz):
d
(ppm) 12.56 (s, 1H), 8.88 (d, J¼9.0 Hz, 1H), 8.61
(d, J¼8.4 Hz, 1H), 8.19 (d, J¼7.2 Hz, 1H), 7.99 (d, J¼8.4 Hz, 1H), 7.91
(d, J¼8.4 Hz, 1H), 7.86 (d, J¼7.8 Hz, 1H), 7.83 (d, J¼8.4 Hz, 1H), 7.77
(d, J¼7.2 Hz, 1H), 7.64 (t, J¼7.8 Hz, 1H), 7.57 (t, J¼7.8 Hz,
1H),7.55e7.50 (m, 2H), 7.46 (q, J¼7.5 Hz, 2H), 7.10e7.06 (m, 4H),
6.89 (t, J¼6.6 Hz, 1H), 6.06 (s, 1H); 13C NMR (CDCl3, 150 MHz):
4.5.12. (Z)-2-((4-Aminophenyl)amino)-1,4-diphenylbut-2-ene-1,4-
dione (3ad). Yield 90%, red solid, mp 148e150 ꢀC; 1H NMR (CDCl3,
d
(ppm) 195.1, 193.4, 157.4, 138.6, 138.4, 133.8, 133.7, 132.7, 131.3,
400 MHz):
2H), 7.44e7.36 (m, 4H), 6.78 (d, J¼8.4 Hz, 2H), 6.42 (d, J¼8.4 Hz, 2H),
6.02 (s, 1H), 3.59 (br s, 2H); 13C NMR (CDCl3, 100 MHz):
(ppm)
d (ppm) 12.47(s, 1H), 7.94e7.91 (m, 4H), 7.51e7.46 (m,
130.8, 130.1, 129.1, 128.8, 127.1, 126.8, 126.6, 126.5, 126.2, 125.8,
125.7, 125.4, 125.0, 124.6, 124.2, 124.1, 121.8, 100.5; IR (KBr, cmꢁ1):
3045, 1658, 1584, 1556, 1502, 1339, 1278, 1249, 1115, 984, 910, 786,
749, 697, 569; HRMS (ESI): m/z [MþH]þ calcd for C30H21NO2:
428.1645; found: 428.1637.
d
192.5, 191.3, 157.8, 153.9, 144.3, 139.0, 134.5, 134.2, 131.6, 129.5,
128.6, 128.3, 127.2, 123.9, 115.4, 93.1; IR (KBr, cmꢁ1): 3466, 3439,
3366, 3346, 3057, 1672, 1593, 1571, 1517, 1447, 1385, 1323, 1279,
1237, 1173, 1061, 1025, 984, 911, 825, 760, 713, 690, 551, 506; MS
(EI): m/z 342.22.
4.5.7. (Z)-1,4-Di(naphthalen-2-yl)-2-(phenylamino)but-2-ene-1,4-
dione (3ha). Yield 92%, red oil, 1H NMR (CDCl3, 400 MHz):
d (ppm)
12.74 (s, 1H), 8.57 (s, 1H), 8.50 (s, 1H), 8.07e8.04 (m, 2H), 7.93e7.82
(m, 5H), 7.61e7.48 (m, 3H), 7.12 (t, J¼7.8 Hz, 2H), 7.05 (d, J¼7.6 Hz,
2H), 6.94 (t, J¼7.2 Hz, 1H), 6.35 (s, 1H); 13C NMR (CDCl3, 100 MHz):
4.5.13. (Z)-Ethyl
4-((1,4-dioxo-1,4-diphenylbut-2-en-2-yl)amino)
benzoate (3ae). Yield 45%, yellow oil, 1H NMR (CDCl3, 400 MHz):
d
(ppm) 12.63(s, 1H), 8.01(d, J¼7.6 Hz, 2H), 7.94 (d, J¼7.6 Hz, 2H),
d
(ppm) 191.9, 190.5, 156.7, 138.5, 136.0, 135.8, 134.8, 132.5, 132.0,
7.84 (d, J¼8.0 Hz, 2H), 7.59e7.51 (m, 3H), 7.47e7.42 (m, 3H), 6.99 (d,
J¼8.4 Hz, 2H), 6.21(s, 1H), 4.29 (d, J¼6.8 Hz, 2H), 1.32 (t, J¼7.0 Hz,
131.8, 129.6, 129.3, 129.2, 129.1, 128.7, 128.3, 128.1, 127.7, 127.6, 127.5,
126.8, 126.3, 124.8, 123.9, 123.6, 121.4, 95.2; IR (KBr, cmꢁ1): 3054,
1732, 1667, 1569, 1501, 1465, 1355, 1285, 1238, 1185, 1122, 1047, 950,
3H); 13C NMR (CDCl3, 100 MHz):
d (ppm) 191.8, 191.3, 165.7, 155.1,
142.6, 138.5, 134.9, 134.8, 134.6, 134.3, 132.3, 131.2, 130.9, 129.7,

C. Deng et al. / Tetrahedron 68 (2012) 3828e3834
3833
128.9, 128.5, 127.7, 127.5, 126.1,120.1, 96.8, 60.8, 14.2; IR (KBr, cmꢁ1):
3423, 3110, 3061, 2979, 1713, 1675, 1594, 1517, 1448, 1366, 1318,
1276, 1233, 1176, 1106, 1055, 1020, 977, 914, 854, 766, 723, 694, 639,
570; MS (EI): m/z 399.21.
(CDCl3, 400 MHz):
d
(ppm) 11.01 (s, 1H), 8.07 (d, J¼7.6 Hz, 2H),
7.84 (d, J¼7.6 Hz, 2H), 7.67 (t, J¼7.2 Hz, 1H), 7.53 (t, J¼7.6 Hz, 2H),
7.44e7.36 (m, 3H), 5.69 (s, 1H), 3.21e3.19 (br s, 1H), 1.88e1.85 (m,
2H), 1.72e1.70 (m, 2H), 1.51(s, 1H), 1.41e1.37 (m, 2H), 1.26e1.20
(m, 3H); 13C NMR (CDCl3, 100 MHz):
d (ppm) 191.7, 189.5, 160.1,
4.5.14. (Z)-2-(Naphthalene-2-ylamino)-1,4-diphenylbut-2-ene-1,4-
139.4, 134.7, 134.5, 131.1, 130.0, 128.9, 128.2, 127.0, 89.8, 53.7, 34.1,
25.0, 24.2; IR (KBr, cmꢁ1): 3061, 2928, 2851, 1679, 1576, 1447,
1328, 1294, 1237, 1148, 1055, 1024, 954, 775, 733, 597; HRMS
(ESI): m/z [MþH]þ calcd for C22H23NO2: 334.1802; found:
334.1787.
dione (3af). Yield 95%, orange solid, mp 131e132 ꢀC; 1H NMR
(CDCl3, 400 MHz):
d (ppm) 12.75 (s, 1H), 8.00e7.95 (m, 4H),
7.66e7.58 (m, 4H), 7.52e7.42 (m, 4H), 7.38e7.30 (m, 4H), 7.14 (d,
J¼8.8 Hz, 1H), 6.18 (s, 1H); 13C NMR (CDCl3, 100 MHz):
d (ppm)
192.3, 190.9, 156.6, 138.8, 136.1, 134.5, 134.3, 133.4, 131.9, 130.7,
129.5, 129.3, 128.7, 128.4, 127.5, 127.3, 127.2, 126.6, 125.3, 121.0,
118.5, 95.3; IR (KBr, cmꢁ1): 3053, 1667, 1599, 1577, 1557, 1513, 1448,
1321, 1282, 1238, 1213, 1176, 1122, 1061, 1024, 964, 857, 807, 757,
726, 702; HRMS (ESI): m/z [MþH]þ calcd for C26H19NO2: 378.1489;
found: 378.1482.
4.5.20. (Z)-2-(Benzylamino)-1,4-diphenylbut-2-ene-1,4-dione
(3al). Yield 89%, light yellow solid, mp 91e93 ꢀC; 1H NMR (CDCl3,
600 MHz):
d
(ppm) 11.12 (s, 1H), 8.02 (d, J¼7.6 Hz, 2H), 7.85 (d,
J¼7.6 Hz, 2H), 7.64 (t, J¼7.2 Hz, 1H), 7.50e7.43 (m, 3H), 7.38 (t,
J¼7.4 Hz, 2H), 7.30e7.21 (m, 4H), 5.82 (s, 1H), 4.39 (d, J¼6.4 Hz,
2H); 13C NMR (CDCl3, 150 MHz):
d (ppm) 191.5, 189.9, 160.3, 139.1,
4.5.15. (Z)-1,4-Diphenyl-2-(pyridin-3-ylamino)but-2-ene-1,4-dione
137.1, 134.6, 134.3, 131.3, 130.0, 128.8, 128.6, 128.2, 127.7, 127.5,
127.1, 127.0, 91.1, 48.7; IR (KBr, cmꢁ1): 3061, 2939, 1671, 1580, 1450,
1324, 1297, 1240, 1176, 1054, 1024, 996, 924, 773, 736, 574; HRMS
(ESI): m/z [MþH]þ calcd for C23H19NO2: 342.1489; found:
342.1482.
(3ag). Yield 92%, yellow solid, mp 120e121 ꢀC; 1H NMR (CDCl3,
600 MHz):
d
(ppm) 12.50 (s, 1H), 8.34 (br s, 1H), 8.24 (d, J¼4.2 Hz,
1H), 7.99 (d, J¼7.8 Hz, 2H), 7.94 (d, J¼7.8 Hz, 2H), 7.59 (t, J¼7.2 Hz,
1H), 7.53 (t, J¼7.5 Hz, 1H), 7.45 (q, J¼6.6 Hz, 4H), 7.27 (d, J¼6.6 Hz,
1H), 7.09 (q, J¼4.2 Hz, 1H), 6.22 (s, 1H); 13C NMR (CDCl3, 150 MHz):
d
(ppm) 191.3, 191.2, 155.7, 145.6, 143.0, 138.3, 135.3, 134.6, 134.3,
4.5.21. (E)-2-(Diethylamino)-1,4-diphenylbut-2-ene-1,4-dione
132.2, 129.6, 128.8, 128.4, 128.3, 127.3, 123.4, 96.42, 96.37; IR (KBr,
cmꢁ1): 3055, 1671, 1593, 1572, 1482, 1447, 1321, 1277, 1234, 1180,
1057, 1021, 979, 907, 803, 765, 722, 703, 613; HRMS (ESI): m/z
[MþH]þ calcd for C21H16N2O2: 329.1285; found: 329.1279.
(3am). Yield 83%, light yellow solid, mp 159e162 ꢀC; 1H NMR
(CDCl3, 400 MHz):
d
(ppm) 8.01 (d, J¼7.2 Hz, 2H), 7.84 (d,
J¼6.8 Hz, 2H), 7.53 (t, J¼7.4 Hz, 1H), 7.47e7.33 (m, 5H), 6.00 (s,
1H), 3.46 (br s, 2H), 3.14 (br s, 2H), 1.39 (br s, 3H), 1.08 (br s, 3H);
13C NMR (CDCl3, 100 MHz):
d (ppm) 193.6, 186.3, 160.4, 139.3,
4.5.16. (Z)-2-(Ethylamino)-1,4-diphenylbut-2-ene-1,4-dione
135.8, 133.2, 131.1, 128.8, 128.0, 127.9, 127.7, 127.6, 91.4, 46.2, 44.3,
14.3, 11.3, 11.2; IR (KBr, cmꢁ1): 3060, 2977, 1672, 1605, 1573, 1512,
1463, 1388, 1354, 1224, 1151, 1067, 1006, 965, 895, 779, 708, 596;
HRMS (ESI): m/z [MþH]þ calcd for C20H21NO2: 308.1645; found:
308.1639.
(3ah). Yield 95%, orange solid, mp 120e122 ꢀC; 1H NMR (CDCl3,
400 MHz):
d
(ppm) 10.81 (s, 1H), 8.06 (d, J¼8.4 Hz, 2H), 7.85 (d,
J¼8.0 Hz, 2H), 7.67 (t, J¼7.6 Hz, 1H), 7.53 (t, J¼7.6 Hz, 2H), 7.47e7.37
(m, 3H), 5.73 (s, 1H), 3.22 (q, J¼6.8 Hz, 2H), 1.23 (t, J¼7.2 Hz, 3H); 13C
NMR (CDCl3, 100 MHz):
d (ppm) 191.6, 189.7, 160.9, 139.3, 134.8,
134.3, 131.4, 131.2, 130.0, 129.2, 129.0, 128.6, 128.3, 128.2, 127.0, 89.9,
40.0, 15.99, 15.92; IR (KBr, cmꢁ1): 3240, 3055, 2976, 1678, 1581,
1485, 1423, 1332, 1286, 1219, 1148, 1059, 970, 918, 857, 792, 714,
580; HRMS (ESI): m/z [MþH]þ calcd for C18H17NO2: 280.1332;
found: 280.1325.
4.5.22. (E)-1,4-Diphenyl-2-(pyrrolidin-1-yl)but-2-ene-1,4-dione
(3an). Yield 91%, light yellow solid, mp 171e172 ꢀC; 1H NMR
(CDCl3, 400 MHz):
d
(ppm) 8.02 (d, J¼7.6 Hz, 2H), 7.87 (d, J¼7.6 Hz,
2H), 7.54 (t, J¼7.4 Hz 1H), 7.47e7.40 (m, 3H), 7.35 (t, J¼7.4 Hz 2H),
5.92 (s, 1H), 3.52e3.42 (m, 3H), 3.09e3.06 (br s, 1H), 2.02 (t,
J¼6.6 Hz, 2H), 1.92e1.79 (m, 2H); 13C NMR (CDCl3, 100 MHz):
4.5.17. (Z)-2-(Isopropylamino)-1,4-diphenylbut-2-ene-1,4-dione
d (ppm) 193.6, 186.1, 159.2, 138.9, 134.9, 133.1, 131.0, 128.7, 128.0,
(3ai). Yield 90%, light yellow solid, mp 102e104 ꢀC; 1H NMR (CDCl3,
127.9, 127.4, 92.7, 48.7, 48.2, 25.4, 24.3; IR (KBr, cmꢁ1): 2965, 2870,
1678, 1613, 1574, 1515, 1450, 1395, 1340, 1220, 1176, 1058, 995, 915,
760, 717, 623, 552; HRMS (ESI): m/z [MþH]þ calcd for C20H19NO2:
306.1489; found: 306.1487.
400 MHz):
d
(ppm) 10.83 (s, 1H), 8.07 (d, J¼7.6 Hz, 2H), 7.84 (d,
J¼7.2 Hz, 2H), 7.68 (t, J¼7.4 Hz, 1H), 7.54 (t, J¼7.8 Hz, 2H), 7.45e7.37
(m, 3H), 5.69 (s, 1H), 3.56e3.51 (m, 1H), 1.25 (d, J¼6.4 Hz, 6H); 13C
NMR (CDCl3, 100 MHz):
d (ppm) 191.5, 189.4, 160.0, 139.2, 134.7,
134.3, 131.1, 129.9, 128.8, 128.1, 126.9, 126.8, 89.5, 47.1, 24.0; IR (KBr,
cmꢁ1): 3062, 2976, 2931, 1676, 1578, 1550, 1447, 1325, 1297, 1238,
1207, 1158, 1066, 1024, 939, 763, 724, 694, 581; HRMS (ESI): m/z
[MþH]þ calcd for C19H19NO2: 294.1489; found: 294.1485.
4.5.23. (E)-1,4-Diphenyl-2-(piperidin-1-yl)but-2-ene-1,4-dione
(3ao).31 Yield 83%, light yellow solid, mp 169e171 ꢀC; 1H NMR
(CDCl3, 400 MHz):
2H), 7.55 (t, J¼7.0 Hz, 1H), 7.48e7.41 (m, 3H), 7.36 (t, J¼7.4 Hz, 2H),
d
(ppm) 8.04 (d, J¼8.0 Hz, 2H), 7.85 (d, J¼8.0 Hz,
6.11 (s, 1H), 3.38 (br s, 4H), 1.66 (br s, 6H); 13C NMR (CDCl3,
4.5.18. (Z)-2-(Butylamino)-1,4-diphenylbut-2-ene-1,4-dione
100 MHz): d (ppm) 193.9, 186.5, 160.8, 139.0, 135.6, 133.0, 131.0,
(3aj). Yield 92%, yellow solid, mp 45e47 ꢀC; 1H NMR (CDCl3,
128.6, 127.8, 127.7, 127.4, 91.6, 23.6; IR (KBr, cmꢁ1): 3059, 2938,
2856, 1668, 1616, 1575, 1518, 1450, 1362, 1284, 1220, 1131, 1061,
1026, 968, 905, 852, 766, 730, 696, 606; HRMS (ESI): m/z [MþH]þ
calcd for C21H21NO2: 320.1645; found: 320.1640.
600 MHz):
d
(ppm) 10.89 (s, 1H), 8.06 (d, J¼7.2 Hz, 2H), 7.85 (d,
J¼7.8 Hz, 2H), 7.67 (t, J¼7.2 Hz, 1H), 7.53 (t, J¼7.5 Hz, 2H), 7.45 (t,
J¼7.2 Hz, 1H), 7.39 (t, J¼7.5 Hz, 2H), 5.74 (s, 1H), 3.17 (q, J¼6.6 Hz,
2H), 1.59e1.55(m, 2H), 1.37 (q, J¼7.5 Hz, 2H), 0.87 (t, J¼7.2 Hz, 3H);
13C NMR (CDCl3, 150 MHz):
d
(ppm) 191.6, 189.7, 161.1, 139.3, 134.7,
4.5.24. (E)-2-Morpholino-1,4-diphenylbut-2-ene-1,4-dione
134.3, 131.2, 130.0, 129.0, 128.4, 128.2, 127.0, 89.9, 44.8, 32.4, 19.6,
13.5; IR (KBr, cmꢁ1): 2956, 2869, 1677, 1582, 1451, 1325, 1293, 1236,
1177, 1058, 932, 717, 689, 578; HRMS (ESI): m/z [MþH]þ calcd for
C20H21NO2: 308.1645; found: 308.1641.
(3ap).8 Yield 98%, light yellow solid, mp 171e172 ꢀC; 1H NMR
(CDCl3, 400 MHz):
d
(ppm) 8.03 (d, J¼8.0 Hz, 2H), 7.84 (d, J¼7.6 Hz,
2H), 7.57 (t, J¼7.0 Hz, 1H), 7.50e7.43 (m, 3H), 7.37 (t, J¼7.4 Hz, 2H),
6.15 (s, 1H), 3.74 (s, 4H), 3.42 (s, 2H), 3.32 (s, 2H); 13C NMR (CDCl3,
100 MHz):
d (ppm) 193.5, 186.6, 160.5, 138.4, 135.3, 133.1, 131.2,
4.5.19. (Z)-2-(Cyclohexylamino)-1,4-diphenylbut-2-ene-1,4-dione
128.6, 127.8, 127.6, 127.3, 92.9, 65.7, 47.2; IR (KBr, cmꢁ1): 2968, 2918,
2858, 1668, 1614, 1574, 1519, 1448, 1357, 1271, 1221, 1115, 1065, 973,
(3ak). Yield 90%, light yellow solid; mp 104e106 ꢀC; 1H NMR

3834
C. Deng et al. / Tetrahedron 68 (2012) 3828e3834
908, 764, 696, 618, 583; HRMS (ESI): m/z [MþH]þ calcd for
18. Roussel, C.; Fihi, R.; Ciamala, K.; Vebrel, J.; Zair, T.; Riche, C. Org. Biomol. Chem.
2003, 1, 2689e2698.
19. Zhou, Y.; Angelici, R. J.; Woo, L. K. Catal. Lett. 2010, 137, 8e15.
20. Yin, G. D.; Zhou, B. H.; Meng, X. G.; Wu, A. X.; Pan, Y. J. Org. Lett. 2006, 8,
2245e2248.
C20H19NO3: 322.1438; found: 322.1439.
4.5.25. (Z)-4-(4-Chlorophenyl)-2-(phenylamino)-1-(thiophen-2-yl)
but-2-ene-1,4-dione (5). Yield 98%, yellow solid, mp 136e138 ꢀC; 1H
21. Crystal structure data for compound 3aa: CCDC number 854744, C22H17NO2,
ꢀ
monoclinic, space group P2(1)/n, a¼5.8740(6), b¼13.4335(13), c¼21.203(2) A,
3
NMR (CDCl3, 600 MHz):
d
(ppm) 12.44 (s, 1H), 7.87 (d, J¼8.4 Hz, 2H),
ꢀ
a
¼90ꢀ,
b
¼94.1700(10)ꢀ,
g
,
¼90ꢀ, V¼1668.6(3) A , T¼100(2) K, Z¼4, DC¼1.
410 mg/m3,
m
¼0.083 mmꢁ1
l
¼0.71073 A, F(000) 688, crystal size 0.20ꢂ0.10ꢂ0.
ꢀ
7.80 (d, J¼3.6 Hz, 1H), 7.69 (d, J¼4.8 Hz, 1H), 7.22 (d, J¼8.4 Hz, 2H),
10 mm3, 4851 independent reflections [R(int)¼0.0993], reflections collected
7.19 (t, J¼7.8 Hz, 2H), 7.07e7.01 (m, 4H), 6.15 (s, 1H); 13C NMR
17035, refinement method: full-matrix least-squares on F2: goodness-of-fit on
(CDCl3, 150 MHz):
d (ppm) 189.5, 183.6, 156.3, 141.5, 138.5, 138.2,
F
2 1.086, final R indices [I>2
s
(I)], R1¼0.0464, wR2¼0.1268, largest diff. peak and
ꢀꢁ3
137.1, 136.4, 135.7, 129.3, 128.72, 128.67, 128.5, 125.1, 121.5, 94.94,
94.92; IR (KBr, cmꢁ1): 3090, 2922,1641,1590,1571,1553,1504,1447,
1411, 1353, 1308, 1286, 1243, 1178, 1089, 1060, 1012, 910, 885, 851,
790, 754, 724, 698, 655, 545; HRMS (ESI): m/z [MþH]þ calcd for
C20H14ClNO2S: 368.0507; found: 368.0501.
hole 0.464 and ꢁ0.285 e A
.
22. Crystal structure data for compound 3al: CCDC number 854743, C23H19NO2,
Orthorhombic, space group P2(1)2(1)2(1), a¼5.9779(11), b¼8.2434(16), c¼37.
3
ꢀ
ꢀ
ꢀ
358(7) A,
232 mg/m3,
a
¼90ꢀ,
b
¼90ꢀ,
g
¼90 , V¼1840.9(6) A , T¼296(2) K, Z¼4, DC¼1.
m
¼0.078 mmꢁ1
¼0.71073 A, F(000) 720, crystal size 0.16ꢂ0.12ꢂ0.
,
l
ꢀ
10 mm3, 5304 independent reflections [R(int)¼0.0211], reflections collected
10367, refinement method: full-matrix least-squares on F2: goodness-of-fit on
F
2 1.035, final R indices [I>2
hole 0.182 and ꢁ0.180 e A
s
(I)], R1¼0.0510, wR2¼0.1339, largest diff. peak and
Acknowledgements
ꢀꢁ3
.
23. Crystal structure data for compound 3am: CCDC number 854742, C20H21NO2,
orthorhombic, space group Pna2(1), a¼11.3970(15), b¼16.715(2), c¼9.
Prof. A.-X.W. thanks the National Natural Science Foundation of
China (Grants 20872042 and 201032001). Dr. G.-D.Y. thanks the
National Natural Science Foundation of China (Grants 20902035
and 21102042). We are also grateful to Dr. Xianggao Meng for his
help with X-ray diffraction analysis.
3
ꢀ
ꢀ
¼90ꢀ,
b
¼90ꢀ,
g
¼90 , V¼1736.8(4) A , T¼296(2) K, Z¼4, DC¼1.
ꢀ
1167(12) A,
a
176 mg/m3,
m
¼0.075 mmꢁ1
¼0.71073 A, F(000) 656, crystal size 0.16ꢂ0.12ꢂ0.
,
l
ꢀ
10 mm3, 2863 independent reflections [R(int)¼0.0246], reflections collected
10875, refinement method: full-matrix least-squares on F2: goodness-of-fit on
F
2 1.064, final R indices [I>2
s
.
(I)], R1¼0.0312, wR2¼0.0861, largest diff. peak and
ꢀꢁ3
hole 0.155 and ꢁ0.091 e A
24. Crystal structure data for compound 3ao: CCDC number 852470, C21H21NO2,
ꢀ
triclinic, space group Pꢁ1, a¼6.707(2), b¼10.031(4), c¼13.162(5) A,
a¼89.
Supplementary data
3
ꢀ
847(6)ꢀ,
b
¼77.706(6)ꢀ,
g
¼87.938(6) , V¼864.7(5) A , T¼298(2) K, Z¼2, DC¼1.
ꢀ
ꢀ
227 mg/m3,
m
¼0.078 mmꢁ1
¼0.71073 A, F(000) 340, crystal size 0.20ꢂ0.10ꢂ0.
,
l
1H NMR, 13C NMR and HRMS spectra for all new compounds, 1H
NOESY NMR spectra of compound 5, X-ray crystal structures of
compounds 3am, 3ao and 4. Supplementary data associated with
this article can be found in the online version, at doi:10.1016/
j.tet.2012.03.049. These data include MOL files and InChIKeys of the
most important compounds described in this article.
10 mm3, 3175 independent reflections [R(int)¼0.0245], reflections collected
5319, refinement method: full-matrix least-squares on F2: goodness-of-fit on F2
1.013, final R indices [I>2 (I)], R1¼0.0569, wR2¼0.1270, largest diff. peak and
s
ꢀꢁ3
hole 0.170 and ꢁ0.157 e A
.
25. Crystal structure data for compound 3ap: CCDC number 850000, C20H19NO3,
ꢀ
triclinic, space group Pꢁ1, a¼6.6038(8), b¼10.0280(11), c¼12.7507(15) A,
3
ꢀ
ꢀ
a
¼85.679(2)ꢀ,
b
¼79.496ꢀ,
g
¼88.506(2) , V¼827.81(17) A , T¼298(2) K, Z¼2,
DC¼1.289 mg/m3,
m
¼0.087 mmꢁ1
¼0.71073 A, F(000) 340, crystal size 0.16ꢂ0.
,
l
ꢀ
12ꢂ0.10 mm3, 3236 independent reflections [R(int)¼0.0387], reflections col-
lected 8669, refinement method: full-matrix least-squares on F2: goodness-of-
References and notes
fit on F2 1.037, final R indices [I>2
peak and hole 0.134 and ꢁ0.159 e A
s
(I)], R1¼0.0594, wR2¼0.1178, largest diff.
ꢀꢁ3
.
1. Tandon, V. K.; Maurya, H. K. Tetrahedron Lett. 2009, 50, 5896e5902.
2. Laurieri, N.; Crawford, M.; Matthew, H. J.; Kawamura, A.; Westwood, I. M.;
Robinson, J.; Fletcher, A. M.; Davies, S. G.; Sim, E.; Russel, A. J. J. Am. Chem. Soc.
2010, 132, 3238e3239.
3. Benites, J.; Valderrama, J. A.; Bettega, K.; Pedrosa, R. C.; Calderon, P. B.; Verrax, J.
Eur. J. Med. Chem. 2010, 45, 6052e6057.
26. Yin, G. D.; Wang, Z. H.; Chen, A. H.; Gao, M.; Wu, A. X.; Pan, Y. J. J. Org. Chem.
2008, 73, 3377e3383.
27. Crystal structure data for compound 4: CCDC number 850001, C15H11ClO2S2,
ꢀ
triclinic, space group Pꢁ1, a¼7.8406(13), b¼11.8382(13), c¼17.047(2) A,
a
¼75.
3
ꢀ
778(2)ꢀ,
b
¼87.508(2)ꢀ,
g
¼81.0000(10)ꢀ, V¼1514.8(4) A , T¼298(2) K, Z¼4,
DC¼1.415 mg/m3,
m
¼0.525 mmꢁ1
,
l
¼0.71073 A, F(000) 664, crystal size 0.16ꢂ0.
ꢀ
4. Boteva, A. A.; Krasnykh, O. P.; Dubrovina, S. S.; Vakhrin, M. I.; Babushkina, E. B.;
Odegova, T. F.; Solova, I. V. Pharm. Chem. J. 2008, 42, 452e455.
5. Alizadeh, A.; Movahedi, F.; Masrouri, H.; Zhu, L. G. Synthesis 2006, 3431e3436.
6. Paradisi, C.; Prato, M.; Quintily, U.; Scorrano, G. J. Org. Chem. 1981, 46,
5156e5159.
7. Yavari, I.; Nasiri, F.;Moradi, L.; Djahaniani, H. TetrahedronLett. 2004, 45, 7099e7101.
8. Kumar, A.; Boykin, D. W. Synth. Commun. 1995, 25, 2071e2078.
9. Adib, M.; Mahdavi, M.; Abbasi, A.; Jahromi, A. H.; Bijanzadeh, H. R. Tetrahedron
Lett. 2007, 48, 3217e3220.
10. (a) Pratapan, S.; Scaria, P. M.; Bhattacharyya, K.; Das, P. K.; George, M. V. J. Org.
Chem. 1986, 51, 1972e1976; (b) Yavari, I.; Nasiri, F.; Moradi, L.; Djahaniani, H.
Tetrahedron Lett. 2004, 45, 7099e7102.
11. Rao, H. S. P.; Senthilkumar, S. P. Synth. Commun. 2005, 35, 1707e1714.
12. (a) Ollis, W. D.; Rey, M.; Sutherland, I. O. J. Chem. Soc., Perkin Trans. 1 1983,
1009e1027; (b) Seko, S.; Miyake, K. Synth. Commun. 1999, 29, 2487e2492; (c)
Benati, L.; Montevecchi, P. C.; Spagnolo, P. J. Chem. Soc., PerkinTrans.11991, 71e77.
13. Tamura, Y.; Matsushima, H.; Ikeda, M.; Sumoto, K. Tetrahedron 1976, 32,
431e435.
12ꢂ0.10 mm3, 5270 independent reflections [R(int)¼0.0173], reflections col-
lected 8005, refinement method: full-matrix least-squares on F2: goodness-of-
fit on F2 1.129, final R indices [I>2
s
.
(I)], R1¼0.0687, wR2¼0.1481, largest diff. peak
ꢀꢁ3
and hole 0.238 and ꢁ0.256 e A
28. Crystal data for compound 5: CCDC number 850002, C20H14ClNO2S, mono-
¼90ꢀ,
ꢀ
clinic, space group P2(1)/c, a¼14.788(3), b¼6.3291(13), c¼19.418(4) A;
a
3
ꢀ
3
ꢀ
b
¼101.59(3)ꢀ,
g
¼90 , V¼1780.4(6) A , T¼293(2) K, Z¼4, DC¼1.372 mg/m , ¼0.
m
3
344 mmꢁ1
,
l
¼0.71073 A, F(000) 760, crystal size 0.16ꢂ0.12ꢂ0.10 mm , 2262
ꢀ
independent reflections [R(int)¼0.0360], reflections collected 7966, refinement
method: full-matrix least-squares on F2: goodness-of-fit on F2 1.059, final R
indices [I>2 (I)], R1¼0.0414, wR2¼0.1240, largest diff. peak and hole 0.218 and
s
ꢀꢁ3
ꢁ0.292 e A
.
29. (a) Ram, V. J.; Agarwal, N. Tetrahedron Lett. 2001, 42, 7127e7130; (b) Goel, A.;
Singh, F. V.; Verma, D. Synlett 2005, 2027e2030; (c) Goel, A.; Verma, D.; Dixit,
M.; Raghunandan, R.; Maulik, P. R. J. Org. Chem. 2006, 71, 804e807; (d) Singh, F.
V.; Kumar, V.; Kumar, B.; Goel, A. Tetrahedron 2007, 63, 10971e10978; (e) Zhang,
L.; Liang, F. S.; Cheng, X.; Liu, Q. J. Org. Chem. 2009, 74, 899e902.
30. (a) Tamura, Y.; Sumoto, K.; Matsushirna, H.; Taniguchi, H.; Ikeda, M. J. Org.
Chem. 1973, 38, 4324e4328; (b) Nitta, M.; Miyano, H. J. Chem. Soc., Perkin Trans.
1 1986, 595e600; (c) Ramaiah, D.; Muneer, M.; Gopidas, K. R.; Das, P. K.; Rath,
N. P.; George, M. V. J. Org. Chem. 1996, 61, 4240e4246.
14. Hayashi, Y.; Watanabe, T.; Oda, R. Tetrahedron Lett. 1970, 11, 605e608.
15. Ghandi, M.; Jamea, A. H. Tetrahedron Lett. 2011, 52, 4005e4007.
16. Prakash, O.; Batra, A.; Chaudhri, V.; Prakash, R. Tetrahedron Lett. 2005, 46,
2877e2878.
17. Rosa, R.; Martinez-Barrasa, V.; Burgos, C.; Alvarez-Builla, J. Tetrahedron Lett.
2000, 41, 5837e5840.
31. Lahiri, S.; Mahajan, M. P.; Prasad, R.; George, M. V. Tetrahedron 1977, 33,
3159e3170.