DABCO-promoted unexpected regioselective ring opening and stereoselective addition reactions of sulfonylaziridines with cyanoacetylenes: Access to functionalized enenitriles

Article abstract of DOI:10.1002/adsc.201300454

A highly regioselective ring opening and stereoselective addition reaction of sulfonylaziridines with cyanoacetylenes promoted by 1,4-diazabicyclo-[2.2.2] octane (DABCO) was investigated. A variety of functionalized (Z)-enenitriles could be obtained in good yields through regioselective cleavage of carbon-nitrogen bonds in sulfonylaziridines.

Full text of DOI:10.1002/adsc.201300454

FULL PAPERS
DOI: 10.1002/adsc.201300454
DABCO-Promoted Unexpected Regioselective Ring Opening
and Stereoselective Addition Reactions of Sulfonylaziridines with
Cyanoacetylenes: Access to Functionalized Enenitriles
Ling-Guo Menga and Lei Wanga,b,*
a
Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, Peopleꢀs Republic of China
Fax : (+86)-561-309-0518; phone: (+86)-561-380-2069; e-mail: leiwang@chnu.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, Peopleꢀs
b
Republic of China
Received: May 23, 2013; Revised: July 15, 2013; Published online: September 20, 2013
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300454.
Abstract: A highly regioselective ring opening and good yields through regioselective cleavage of
stereoselective addition reaction of sulfonylaziridines carbon-nitrogen bonds in sulfonylaziridines.
with cyanoacetylenes promoted by 1,4-diazabicyclo-
ACHTUNGTRENNUNG
Introduction
P nucleophiles to electron-deficient alkynes have
proven to be useful in the construction of multifunc-
Aziridines have received increasing attention as im- tional molecules.[11] In those reactions, attention was
portant intermediates due to the high strain energy frequently paid to the resulting electron-deficient al-
associated with the three-membered ring and have kynes, such as dialkyl acetylenedicarboxylates, termi-
undergone many interesting reactions,[1] such as ring nal alkynoates, alkynyl ketones, etc.[12] Cyanoacety-
expansion,[2] cyclization,[3] alkylation,[4] substitution,[5] lenes, easily prepared from bromoalkynes with
isomerization,[6] N-arylation,[7] N-acylation and N-alk- CuCN,[13] are one class of the important intermediates
ACHTUNGTRENNUNG
ylation,[8] etc. Apart from the above reactions, the and versatile building blocks in organic synthesis.[14]
ring opening of aziridines has also been studied inten- However, there are a few reports about the applica-
sively and applied to prepare a large number of func- tions of cyanoacetylenes as electron-deficient alkynes
tionalized nitrogen-containing compounds.[9] How- to form zwitterionic adducts in the presence of an or-
ACHTUNGTRENNUNG
ever, the ring opening pattern in the aziridines is the ganic base as catalyst.[15]
cleavage of the carbon-nitrogen bond often using
Most recently, we reported the Et3N-promoted
transition metals or Lewis acids as catalyst or promot- tandem ring opening reaction of N-tosylaziridines
er.[10]
with terminal alkynoates involving C N bond cleav-
À
Over the past decade, reactions based on nucleo- age to give functionalized enamines (Scheme 1, path
philic catalysis through conjugate additions of N and a).[16] To the best of our knowledge, there are only
À
Scheme 1. Regioselective C N bond cleavage of sulfonylaziridines.
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À
Table 1. Ring-opening reaction of 2-phenyl-1-tosylaziridine
(1a) with 3-phenylpropiolonitrile (2a).[a]
few reports about the C N bond cleavage in sulfonyl-
ACHTUNGTRENNUNGaziridines using organic bases as catalyst or promot-
er.[17] In continuation of our interest in developing C
N bond cleavage reactions, we further investigate the
possibility of the reaction between cyanoacetylenes
and sulfonylaziridines in the presence of an organic
base. To our delight, an unexpected regioselective
ring opening and stereoselective addition was ob-
À
served in the presence of 1,4-diazabicyclo
[2.2.2]octane
Entry
Solvent
Base
Yield [%][b]
À
(DABCO), through C N bond cleavage of aziridines
in a different way (Scheme 1, path b). The reaction
generated functionalized enenitriles, which are the
important intermediates in organic synthesis[18] under
simple reaction conditions and in good yields. Herein,
we wish to report this DABCO-promoted reaction of
sulfonylaziridines with cyanoacetylenes.
1
2
3
4
5
6
7
8
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
DABCO
DABCO
DABCO
DABCO
DABCO
DMAP
pyridine
N-methylimidazole
Et3N
DBU
PPh3
AHCTUNGTERN(GNUN n-Bu)3P
DABCO
DABCO
DABCO
DABCO
DABCO
DABCO
72
53[c]
72[d]
30[e]
17[f]
NR[g]
NR[g]
NR[g]
NR[g]
NR[g]
ND[h]
ND[h]
55
9
Results and Discussion
10
11
12
13
14
15
16
17
18
In the initial exploration of the regioselective ring
opening and stereoselective addition of sulfonylaziri-
dines with cyanoacetylenes, 2-phenyl-1-tosylaziridine
(1a) and 3-phenylpropiolonitrile (2a) were chosen as
model substrates for our investigation and the results
are summaried in Table 1. The reaction of 1a with 2a
in the presence of DABCO (1.0 equiv.) at room tem-
perature for 36 h afforded 3a as a pale yellow oil in
72% yield (Table 1, entry 1), and it was characterized
CH3CN
toluene
CHCl3
DMF
21
18
<5
<5
DMSO
ND[h]
[a]
Reaction conditions: 1a (0.30 mmol), 2a (0.20 mmol),
base (0.20 mmol), solvent (2.0 mL), room temperature, in
1
by H and 13C NMR spectroscopy and HR-MS analy-
air, 36 h.
Isolate yields.
DABCO (0.50 equiv.).
DABCO (1.2 equiv.).
At 08C.
At 608C.
NR=no reaction observed.
ND=no desired product detected.
[b]
[c]
[d]
[e]
[f]
sis. The amount of DABCO has an obvious effect on
this ring opening reaction. When 0.5 equiv. of
DABCO was used, the desired product 3a was isolat-
ed in 53% yield, and the yield of 3a was not improved
by further increasing the amount of DABCO
(Table 1, entries 2 and 3). The yield of 3a was not suc-
cessfully improved when the reaction was conducted
at 08C or 608C, respectively (Table 1, entries 4 and 5).
[g]
[h]
DABCO as a promoter was crucial in the model reac- could react with 3-phenylpropiolonitrile (2a) smoothly
tion. No reaction was observed when other tertiary to give the desired functionalized enenitriles in mod-
amines, such as DMAP, pyridine, N-methylimidazole, erate to good yields (Scheme 2). Clearly, aromatic N-
Et3N and DBU, were used instead of DABCO tosylaziridines with an electron-withdrawing group on
(Table 1, entries 6–10). Meanwhile, no desired prod- the aromatic ring gave better yields than those with
uct was detected when the reaction was run in the an electron-donating group on the aromatic ring. For
presence of tertiary phosphines (Table 1, entries 11 example, 1 with an electron-withdrawing group, such
and 12). On the other hand, when the model reaction as F, Cl or Br at the para-position of benzene ring re-
was carried out in the presence of DABCO, a signifi- acted with 2a, providing the desired products 3b–d in
cant solvent effect was observed (Table 1, entries 13– good yields. On the other hand, the reaction of sub-
18). Among the tested solvents, CH2Cl2 was found to strate 1 with a CH3 group attached on the benzene
be the best one. THF, CH3CN and toluene were infe- ring with 2a generated the corresponding product 3e
rior and afforded 18–55% yields of 3a. When the sol- in 55% yield; only a trace amount of the product 3f
vent was switched to CHCl3 or DMF, only a trace was detected when a CH3O group was on the para-
amount of 3a was detected. No desired product was position of the benzene ring. The ortho-position effect
detected when DMSO was used as solvent.
of N-tosylaziridines was observed in the reaction of 2-
Under the optimized reaction conditions, the reac- (2-chlorophenyl)-1-tosylaziridine with 2a. Treatment
tion scope of aromatic N-tosylaziridines was exam- of 2-(3-chlorophenyl)-, 2-(3-bromophenyl)-, and 2-
ined. Basically, a variety of aromatic N-tosylaziridines (naphthalen-2-yl)-1-tosylaziridines with 2a afforded
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DABCO-Promoted Unexpected Regioselective Ring Opening and Stereoselective Addition Reactions
Scheme 3. DABCO-promoted ring-opening reaction of aziri-
dines with cyanoacetylenes. Reaction conditions: aziridine
(0.30 mmol), cyanoacetylene (0.20 mmol), DABCO
(0.20 mmol), CH2Cl2 (2.0 mL), room temperature, in air,
36 h.
Scheme 2. DABCO-promoted ring-opening reaction of aro-
matic N-tosylaziridines with 3-phenylpropiolonitrile (2a).
Reaction conditions:
1
(0.30 mmol), 2a (0.20 mmol),
DABCO (0.20 mmol), CH2Cl2 (2.0 mL), room temperature,
in air, 36 h.
phenyl-1-tosylaziridine or 2-butyl-1-tosylaziridine was
used as the aziridine substrate.
The structure of compound 3d was determined as
the desired products (3h–j) in 50–71% yields. 4-(1- having the Z-configuration and this was confirmed
Tosylaziridin-2-yl)phenyl acetate also could be con- unambiguously by single crystal X-ray analysis and
verted to the corresponding product 3k, albeit the the corresponding CIF data were presented in the
ACHTUNGTRENNUNG
yield was so low.
Supporting Information.[19]
To further evaluate the scope of this reaction, other
aziridines and cyanoacetylenes were examined under
the optimized reaction conditions. As can be seen Conclusions
from Scheme 3, sulfonylaziridines with other different
groups, e.g., 1-(4-chlorophenyl)sulfonyl-, 1-(4-bromo- In conclusion, a novel regioselective ring opening and
phenyl)sulfonyl- and 1-(4-nitrophenyl)sulfonyl-2-phe- stereoselective addition of sulfonylaziridines with cya-
nylaziridines, reacted with 2a smoothly to generate noacetylenes promoted by DABCO has been devel-
the desired products (3l–n) in 70–75% yields. As ex- oped. This reaction has simple conditions and produ-
pected, other cyanoacetylenes with different function- ces functionalized enenitriles in moderate to good
al groups, including F, CH3, and t-Bu groups on the yields. Further studies on reactions with electron-defi-
para-position of the benzene rings, also gave the de- cient alkynes and aziridines catalyzed or promoted by
sired products (3o–q) in 41–62% yields. However, the organic bases are currently underway.
reactions gave the poor results when 2-methyl-2-
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(100 MHz, CDCl3): d=163.2 (d, J=245.1 Hz), 154.3, 145.1,
135.2, 133.7, 131.6, 131.5 (d, J=3.3 Hz), 130.0, 129.0, 127.9,
127.3, 127.2, 126.7 (d, J=2.1 Hz), 115.7 (d, J=21.7 Hz),
114.7, 113.3, 99.8, 21.6; HR-MS (ESI): m/z=441.1044, calcd.
for C24H19N2O2SFNa (M+Na)+: 441.1043.
Experimental Section
General Remarks
All reactions were conducted in oven-dried glassware with
magnetic stirring. Chromatographic purification was per-
formed on silica gel (100~200 mesh) and analytical thin
layer chromatography (TLC) on silica gel 60-F254 (Qindao),
which was detected by fluorescence. 1H NMR (400 MHz)
and 13C NMR (100 MHz) spectra were measured with
a Bruker AC 400 spectrometer with CDCl3 as solvent and
recorded in ppm relative to internal tetramethylsilane stan-
dard. 1H NMR data are reported as follows: d, chemical
shift; coupling constants (J are given in Hertz, Hz) and inte-
gration. Abbreviations to denote the multiplicity of a partic-
ular signal were s (singlet), d (doublet), t (triplet), q (quar-
tet), m (multiplet), and br (broad singlet). High resolution
mass spectra were obtained with a Micromass GCT-TOF
mass spectrometer. Melting points were determined on a dig-
ital melting point apparatus and temperatures were uncor-
rected.
N-[(E)-4-Chlorostyryl]-N-[(Z)-2-cyano-1-phenylvinyl]-4-
1
methylbenzenesulfonamide (3c): Pale yellow oil; H NMR
(400 MHz, CDCl3): d=7.75 (d, J=8.0 Hz, 2H), 7.56 (d, J=
14.4 Hz, 1H), 7.50–7.45 (m, 3H), 7.39–7.17 (m, 8H), 6.08 (s,
1H), 5.83 (d, J=14.4 Hz, 1H), 2.44 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=154.1, 145.2, 135.1, 133.9, 133.5,
132.5, 131.7, 130.0, 129.1, 128.7, 127.9, 127.3, 127.2, 126.9,
114.6, 112.7, 99.9, 21.6; HR-MS (ESI): m/z=457.0752, calcd.
for C24H19N2O2S35ClNa (M+Na)+: 457.0748.
N-[(E)-4-Bromostyryl]-N-[(Z)-2-cyano-1-phenylvinyl]-4-
methylbenzenesulfonamide (3d): Yellow solid; mp 128–
1308C; H NMR (400 MHz, CDCl3): d=7.74 (d, J=7.6 Hz,
Typical Procedure for the Regioselective Ring
Opening and Stereoselective Addition Reaction of
Aziridines with Cyanoacetylenes Promoted by
DABCO
1
2H), 7.58 (d, J=14.4 Hz, 1H), 7.50–7.45 (m, 3H), 7.40–7.27
To a solution of aziridine (0.30 mmol) with cyanoacetylene
(0.20 mmol) in CH2Cl2 (2.0 mL) was added DABCO
(22.4 mg, 0.20 mmol). The mixture was then stirred at room
temperature for 36 h in a reaction flask. Then the solvent
was removed under vacuum and residue was purified by
column chromatography on silica gel (10:1, petroleum ether/
EtOAc) to give the desired product.
(m, 6H), 7.13 (d, J=7.6 Hz, 2H), 6.08 (s, 1H), 5.80 (d, J=
14.4 Hz, 1H), 2.44 (s, 3H); 13C NMR (100 MHz, CDCl3):
d=154.1, 145.3, 135.0, 134.3, 133.5, 131.7, 131.7, 130.1, 129.1,
127.8, 127.4, 127.2, 127.2, 120.6, 114.6, 112.6, 99.9, 21.7; HR-
MS (ESI): m/z=501.0243, calcd. for C24H19N2O2S79BrNa
(M+Na)+: 501.0242.
Characterization Data for all Products
N-[(Z)-2-Cyano-1-phenylvinyl]-4-methyl-N-[(E)-styryl]ben-
1
zenesulfonamide (3a): Pale yellow oil; H NMR (400 MHz,
CDCl3): d=7.76 (d, J=7.6 Hz, 2H), 7.59 (d, J=14.0 Hz,
1H), 7.52–7.45 (m, 3H), 7.39–7.20 (m, 9H), 6.08 (s, 1H),
N-[(Z)-2-Cyano-1-phenylvinyl]-4-methyl-N-[(E)-4-methyl-
1
styryl]benzenesulfonamide (3e): Pale yellow oil; H NMR
(400 MHz, CDCl3): d=7.73 (d, J=8.0 Hz, 2H), 7.48–7.41
(m, 4H), 7.35–7.24 (m, 4H), 7.14 (d, J=8.0 Hz, 2H), 7.08
5.89 (d, J=14.0 Hz, 1H), 2.44 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=154.3, 145.1, 135.3, 135.2, 133.6, 131.6, 130.0,
129.0, 128.7, 127.9, 127.2, 127.1, 126.8, 125.7, 114.7, 114.3,
99.8, 21.7; HR-MS (ESI): m/z=423.1142, calcd. for
C24H20N2O2SNa (M+Na)+: 423.1137.
(d, J=8.0 Hz, 2H), 6.02 (s, 1H), 5.87 (d, J=14.4 Hz, 1H),
2.41 (s, 3H), 2.29 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
154.5, 145.0, 137.0, 135.4, 133.8, 132.4, 131.5, 129.9, 129.3,
129.0, 127.9, 127.3, 126.0, 125.7, 115.0, 114.8, 99.6, 21.6, 21.1;
HR-MS (ESI): m/z=437.1299, calcd. for C25H22N2O2SNa
(M+Na)+: 437.1294.
N-[(Z)-2-Cyano-1-phenylvinyl]-N-[(E)-4-fluorostyryl]-4-
methylbenzenesulfonamide (3b):
Yellow oil; 1H NMR
(400 MHz, CDCl3): d=7.76 (d, J=8.0 Hz, 2H), 7.51–7.45
(m, 4H), 7.39–7.21 (m, 6H), 6.99 (t, J=8.4 Hz, 2H), 6.07 (s,
1H), 5.88 (d, J=14.4 Hz, 1H), 2.44 (s, 3H); 13C NMR
N-[(E)-2-Chlorostyryl]-N-[(Z)-2-cyano-1-phenylvinyl]-4-
1
methylbenzenesulfonamide (3g): Pale yellow oil; H NMR
(400 MHz, CDCl3): d=7.74 (d, J=8.4 Hz, 2H), 7.55–7.45
(m, 5H), 7.39–7.13 (m, 7H), 6.23 (d, J=14.4 Hz, 1H), 6.08
(s, 1H), 2.44 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
154.3, 145.2, 135.1, 133.8, 133.7, 132.7, 131.6, 130.0, 129.6,
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DABCO-Promoted Unexpected Regioselective Ring Opening and Stereoselective Addition Reactions
129.0, 128.8, 128.1, 127.9, 127.3, 126.9, 126.2, 114.5, 110.5,
2H), 6.05 (s, 1H), 5.87 (d, J=14.4 Hz, 1H), 2.44 (s, 3H),
100.0, 21.6; HR-MS (ESI): m/z=457.0746, calcd. for
2.29 (s, 3H); 13C NMR (100 MHz, CDCl3): d=169.3, 154.3,
149.6, 145.1, 135.2, 133.7, 133.1, 131.6, 130.0, 129.0, 127.9,
127.2, 127.0, 126.7, 121.8, 114.6, 113.6, 99.7, 21.6, 21.0.; HR-
MS (ESI): m/z=481.1211, calcd. for C26H22N2O4SNa (M+
Na)+: 481.1206.
C24H19N2O2S35ClNa (M+Na)+: 457.0748.
N-[(E)-3-Chlorostyryl]-N-[(Z)-2-cyano-1-phenylvinyl]-4-
methylbenzenesulfonamide (3h):
Yellow oil; 1H NMR
(400 MHz, CDCl3): d=7.76 (d, J=8.4 Hz, 2H), 7.59 (d, J=
14.4 Hz, 1H), 7.50–7.45 (m, 3H), 7.39–7.31 (m, 4H), 7.27–
4-Chloro-N-[(Z)-2-cyano-1-phenylvinyl]-N-[(E)-styryl]-
1
benzenesulfonamide (3l): Yellow oil; H NMR (400 MHz,
CDCl3): d=7.80 (d, J=8.4 Hz, 2H), 7.58 (d, J=14.4 Hz,
1H), 7.51–7.47 (m, 5H), 7.40–7.23 (m, 7H), 6.09 (s, 1H),
7.12 (m, 4H), 6.09 (s, 1H), 5.80 (d, J=14.4 Hz, 1H), 2.45 (s,
3H); 13C NMR (100 MHz, CDCl3): d=154.0, 145.2, 137.3,
135.1, 134.6, 133.5, 131.7, 130.0, 129.8, 129.1, 127.9, 127.9,
127.1, 126.9, 125.6, 123.8, 114.5, 112.2, 100.0, 21.6; HR-MS
(ESI): m/z=457.0753, calcd. for C24H19N2O2S35ClNa (M+
Na)+: 457.0748.
N-[(E)-3-Bromostyryl]
methylbenzenesulfonamide (3i):
(400 MHz, CDCl3): d=7.75 (d, J=8.0 Hz, 2H), 7.59 (d, J=
14.4 Hz, 1H), 7.49–7.45 (m, 3H), 7.40–7.30 (m, 6H), 7.19–
ACHTUNGTRENNUNG
5.98 (d, J=14.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
154.1, 140.6, 136.8, 135.0, 133.4, 131.8, 129.7, 129.2, 129.1,
128.7, 127.3, 127.2, 126.4, 125.9, 115.3, 114.7, 100.1; HR-MS
(ESI): m/z=443.0596, calcd. for C23H17N2O2S35ClNa (M+
Na)+: 443.0591.
4-Bromo-N-[(Z)-2-cyano-1-phenylvinyl]-N-[(E)-styryl]-
benzenesulfonamide (3m): Yellow solid; mp 50–528C;
1H NMR (400 MHz, CDCl3): d=7.72 (d, J=8.4 Hz, 2H),
7.12 (m, 2H), 6.09 (s, 1H), 5.79 (d, J=14.4 Hz, 1H), 2.44 (s,
3H); 13C NMR (100 MHz, CDCl3): d=153.9, 145.2, 137.6,
135.1, 133.4, 131.7, 130.1, 130.0, 129.8, 129.1, 128.6, 127.9,
127.9, 127.1, 124.2, 122.8, 114.5, 112.1, 100.0, 21.6; HR-MS
(ESI): m/z=501.0247, calcd. for C24H19N2O2S79BrNa (M+
Na)+: 501.0242.
N-[(Z)-2-Cyano-1-phenylvinyl[-4-methyl-N-[(E)-2-(naph-
thalen-2-yl)vinyl]benzenesulfonamide (3j): Yellow solid;
1
mp 55–588C; H NMR (400 MHz, CDCl3): d=7.80–7.75 (m,
7.65 (d, J=8.4 Hz, 2H), 7.56 (d, J=14.4 Hz, 1H), 7.50–7.46
(m, 3H), 7.40–7.36 (m, 2H), 7.30–7.22 (m, 5H), 6.08 (s, 1H),
5.97 (d, J=14.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
154.1, 137.3, 135.0, 133.4, 132.6, 131.8, 129.2, 129.2, 129.1,
128.7, 127.3, 127.2, 126.3, 125.9, 115.4, 114.6, 100.0; HR-MS
(ESI): m/z=487.0087, calcd. for C23H17N2O2S79BrNa (M+
Na)+: 487.0086.
5H), 7.74 (d, J=14.4 Hz, 1H), 7.60 (s, 1H), 7.55–7.31 (m,
N-[(Z)-2-Cyano-1-phenylvinyl]-4-nitro-N-[(E)-styryl]ben-
zenesulfonamide (3n): Yellow oil; 1H NMR (400 MHz,
CDCl3): d=8.35 (d, J=8.8 Hz, 2H), 8.05 (d, J=8.8 Hz, 2H),
7.58–7.48 (m, 4H), 7.42 (t, J=7.6 Hz, 2H), 7.31–7.24 (m,
10H), 6.11 (s, 1H), 6.08 (d, J=14.4 Hz, 1H), 2.44 (s, 3H);
13C NMR (100 MHz, CDCl3): d=154.3, 145.1, 135.3, 133.7,
133.6, 132.8, 132.6, 131.6, 130.0, 129.0, 128.3, 127.9, 127.6,
127.3, 127.1, 126.4, 125.7, 125.3, 123.1, 114.7, 114.6, 99.9,
21.6;
C28H22N2O2SNa (M+Na)+: 473.1294.
4-((E)-2-{N-[(Z)-2-Cyano-1-phenylvinyl]-4-methylphenyl-
HR-MS
(ESI):
m/z=473.1300,
calcd.
for
sulfonamido}vinyl)-phenyl acetate (3k):
Yellow oil;
1H NMR (400 MHz, CDCl3): d=7.75 (d, J=8.0 Hz, 2H),
7.50–7.44 (m, 4H), 7.39–7.25 (m, 6H), 7.02 (d, J=8.4 Hz,
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5H), 6.10 (s, 1H), 6.02 (d, J=14.4 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=153.9, 150.7, 143.8, 134.6, 133.2,
132.0, 129.2, 129.0, 128.8, 127.7, 127.2, 126.0, 125.7, 124.6,
116.6, 114.5, 100.1; HR-MS (ESI): m/z=432.1012, calcd. for
C23H18N3O4S (M+H)+: 432.1018.
Acknowledgements
We gratefully acknowledge the financial support by the Na-
tional Natural Science Foundation of China (No. 21172092,
21072152) and the Anhui Provincial Natural Science Founda-
tion (1208085QB40).
N-[(Z)-2-Cyano-1-(4-fluorophenyl)vinyl]-4-methyl-N-
1
[(E)-styryl]benzenesulfonamide (3o): Yellow oil; H NMR
(400 MHz, CDCl3): d=7.78 (d, J=8.0 Hz, 2H), 7.54–7.49
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