Stereoselective One-Pot Synthesis of cis-1,2-Dicyanoalkenes from 1,1-Bis(benzenesulfonyl)alkenes and KCN

Article abstract of DOI:10.1002/ejoc.201801504

An efficient synthesis of cis-1,2-dicyanoalkenes by the reaction of 1,1-bis(benzenesulfonyl)alkenes with KCN was developed. This reaction was conducted in the presence of tetrabutylammonium bromide and NH₄Cl/K₃PO₄ under phase-transfer conditions. A series of cis-1,2-dicyanoalkenes were obtained in good to high yields. Further transformation of the obtained product allows for access to imide and dicarboxylic acid compounds.

Full text of DOI:10.1002/ejoc.201801504

DOI: 10.1002/ejoc.201801504
Full Paper
One-Pot Reaction
Stereoselective One-Pot Synthesis of cis-1,2-Dicyanoalkenes
from 1,1-Bis(benzenesulfonyl)alkenes and KCN
Yue Zhang,[a] Yi Wei,[a] Shen Li,*[a] and Jun-An Ma*[a]
Abstract: An efficient synthesis of cis-1,2-dicyanoalkenes by transfer conditions. A series of cis-1,2-dicyanoalkenes were ob-
the reaction of 1,1-bis(benzenesulfonyl)alkenes with KCN was tained in good to high yields. Further transformation of the
developed. This reaction was conducted in the presence of obtained product allows for access to imide and dicarboxylic
tetrabutylammonium bromide and NH4Cl/K3PO4 under phase- acid compounds.
Introduction
1,2-Dicyanoalkenes have found versatile applications in organic
synthesis.[1] They can serve not only as key intermediates for
the preparation of compounds with great value such as 1,2-
dicarboxylic acids,[2] 1,2-diamides[3] and 1,4-diamines,[4] but
also as 2π partners in cycloaddition reactions to build complex
cyclic structures.[5] In addition, the use of 1,2-dicyanoalkenes in
asymmetric catalysis has been described.[6] Despite their syn-
thetic utility, to date, only a limited number of methods are
available for the preparation of 1,2-dicyanoalkenes, and most
of them rely on multi-step synthesis.[6,7] In 2009, a significant
advance was achieved by Arai et al., who reported a palladium-
catalyzed dicyanation of alkynes under aerobic conditions to
access 1,2-dicyanoalkenes in two stereoisomers (Scheme 1,
Eq. a).[8] Very recently, Okamoto and Ohe et al. developed a
copper-catalyzed anti-selective dicyanation of alkynes
(Scheme 1, Eq. b).[9] However, certain drawbacks, such as the
requirement for transition-metal catalysts, limited scope of the
starting materials, and low stereoselectivity, cannot be com-
pletely overcome with these reported methods. The develop-
ment of an efficient and general protocol for the preparation
of 1,2-dicyanoalkenes under mild conditions is highly desired.
One-pot multi-step transformation[10] is considered to be
one of the most attractive procedures in organic synthesis due
to its high efficiency and avoidance of isolation or purification
steps. In 1991, Bailey and Jackson reported a one-pot synthesis
of 1,2-dicyanoalkane from a (benzenesulfonyl)alkene and LiCN
(Scheme 1, Eq. c).[11] This reaction was believed to proceed
through a sequential conjugate cyanation of (benzenesulf-
Scheme 1. Relevant previous studies and concept of this study.
onyl)alkene, desulphonylation, and conjugate cyanation of in
[a] Department of Chemistry, Tianjin Key Laboratory of Molecular
situ generated cyanoalkenes. Recently, Minakata et al. observed
Optoelectronic Sciences, and Collaborative Innovation Center of Chemical
similar results in the reaction of nitroalkenes with TMSCN
(Scheme 1, Eq. d).[12] Inspired by the above examples and our
previous work on the (benzenesulfonyl)alkene chemistry,[13]
herein, we reported our finding of the one-pot synthesis of 1,2-
dicyanoalkenes. The reaction of 1,1-bis(benzenesulfonyl)alkenes
with a cyanation reagent proceeds smoothly through a double
Science and Engineering, Tianjin University
Tianjin 300072, P. R. China
E-mail: shenli@tju.edu.cn
majun_an68@tju.edu.cn
http://tjmos.tju.edu.cn/majunan/
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201801504.
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conjugate addition-elimination pathway under the mild condi- within a shorten period when an equimolar amount of K3PO4
tions (Scheme 1, Eq. e). This method has the advantages of was added together with NH4Cl (Table 1, entry 5). Other quater-
substrate availability,[14] transition-metal free reaction condi- nary ammonium salts, such as tetramethylammonium bromide
tions, good functional group compatibility, as well as high (TMAB) and tetraethyl-ammonium bromide (TEAB) were evalu-
stereoselectivity, and may provide a complementary to the re- ated (Table 1, entries 6 and 7), and TBAB was still found to
ported routes to 1,2-dicyanoalkenes.
be the best catalyst. Screening of the organic solvent was also
conducted, with cyclopentane proving to be more suitable than
toluene, petroleum ether (60–90 °C), n-hexane and n-pentane
(Table 1, entries 8–11). Finally, elevating the temperature to
23 °C resulted in lower yield (Table 1, entry 12). Therefore, the
reaction conditions as shown in Table 1, entry 5 were selected
as the optimized conditions.
Having established the optimized conditions, the substrate
scope was investigated with a variety of 1,1-bis(benzene-
sulfonyl)alkenes. As revealed in Scheme 2, in the cases of 1,1-
bis(benzenesulfonyl)alkenes 1a–j derived from substituted
benzaldehydes, all the reactions proceeded smoothly to afford
the corresponding 1,2-dicyanoalkenes 2a–j in high yields. Gen-
erally, substituents on the phenyl ring at different position are
well tolerant. Moreover, 1,1-bis(benzenesulfonyl)alkenes with
Results and Discussion
Our study began with the model reaction of 1,1-bis(benzene-
sulfonyl)alkenes 1a with KCN in a biphasic solution of cyclo-
pentane and H2O at 0 °C in the presence of a catalytic amount
of tetrabutylammonium bromide (TBAB). After stirring for 29 h,
the desired product 2a was obtained in 39 % yield as a single
stereoisomer, along with 26 % yield of 3a (Table 1, entry 1). The
stereochemistry of 2a was confirmed by comparison with the
1H NMR spectra of literature,[8a] and the structure of 3a was
determined by X-ray crystallographic analysis.[15] It was re-
ported that in a phase-transfer catalyzed conjugate cyanation
with KCN as the cyanide source, Maruoka et al. observed that
the addition of a Brønsted acid additive, such as NH4Cl as the
proton source, is helpful for the acceleration of the reaction
rate.[16] To improve the efficiency of the model reaction, an
equimolar amount of NH4Cl was employed, and the yield of 2a
was dramatically increased to 72 % (Table 1, entry 2). Next, the
roles of TBAB and water in this reaction were examined. No
reaction occurred in the absence of TBAB or water (Table 1,
entries 3 and 4), which indicated that TBAB behaved as a phase-
transfer catalyst to promote the reaction via the extraction of a
cyanide anion from the aqueous phase. To our delight, we
found that the addition of a weak base could facilitate the elim-
ination of PhSO2H, hence a higher yield of 2a was achieved
Table 1. Condition optimization.[a]
.
Entry Cat.
Additives
Time (h)
Yield[b] of
Yield[b] of
2a [%]
3a [%]
1
2
3
TBAB
TBAB
–
–
29
72
72
72
29
21
21
36
36
12
12
21
39
72
0
26
–
–
–
–
45
33
–
–
–
NH4Cl
NH4Cl
NH4Cl
4[c]
5
TBAB
TBAB
TMAB
TEAB
TBAB
TBAB
TBAB
TBAB
TBAB
trace
81
19
22
49
61
58
40
45
NH4Cl/K3PO4
NH4Cl/K3PO4
NH4Cl/K3PO4
NH4Cl/K3PO4
NH4Cl/K3PO4
NH4Cl/K3PO4
NH4Cl/K3PO4
NH4Cl/K3PO4
6
7
8[d]
9[e]
10[f]
11[g]
12[h]
–
–
[a] Reaction conditions: 1a (0.1 mmol), KCN (0.2 mmol), catalyst (0.002 mmol)
and additives (0.1 mmol) in cyclopentane (2 mL)/H2O (0.1 mL) at 0 °C for
appropriate time. [b] Isolated yield. [c] Reaction was performed in the ab-
sence of H2O. [d] Toluene was used instead of cyclopentane. [e] Petroleum
ether (60–90 °C) was used instead of cyclopentane. [f] n-Hexane was used
instead of cyclopentane. [g] n-Pentane was used instead of cyclopentane.
[h] Reaction was conducted at 23 °C.
Scheme 2. Reaction scope. Unless otherwise specified, all reactions were car-
ried out with 1 (0.2 mmol), KCN (0.4 mmol), TBAB (0.004 mmol), NH4Cl
(0.2 mmol) and K3PO4 (0.2 mmol) in cyclopentane (4 mL)/H2O (0.2 mL) at
0 °C for appropriate time, yields are given for isolated products. [a] Reaction
was conducted at 30 °C.
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electron-donating groups (1b, 1c, 1e, 1f, 1h–j) exhibited higher reaction could be possibly explained by the difference of steric
activity than those with electron-withdrawing substituents (1d, hindrance between cis- and trans-isomer, the more stable cis-2
1g). Substrates with other aryl or heteroaryl units, including is preferentially formed.
1,3-benzodioxol-5-yl (1k), 1-naphthyl (1l), 2-naphthyl (1m), 2-
thienyl (1n), and 3-thienyl (1o), were equally reactive under the
optimized conditions, providing the desired products 2k–o in
good yields ranging from 71 % to 88 %. This transformation
also works well with 1,1-bis(benzenesulfonyl)alkene 1p contain-
ing an unsaturated moiety, delivering 2p in 45 % yield.
1,2-Dicyanoalkenes are versatile synthetic intermediates and
can be readily transformed into highly functionalized com-
pounds. Some examples are illustrated in Scheme 5. Treatment
of 2a with 2.0 equiv. of NaBH4 in methanol afforded 1,2-di-
cyanoalkane 4 in 90 % yield. Compound 4 could be converted
to cyclic imide 5 or dicarboxylic acid 6 in one step. Our method-
To gain the mechanistic information, 3a was isolated and ology complements Arai's elegant approach to the cyclic an-
subjected to standard conditions, the desired product 2a was hydride 7.[8a]
obtained in a comparable yield under standard conditions
(Scheme 3), thus suggesting the involvement of cyanoalkenes
3 in the reaction pathway. From this result and together with
the previous reports,[11,12,16] we proposed a reaction mecha-
nism for the formation of 1,2-dicyanoalkenes 2 as shown in
Scheme 4. The quaternary ammonium salt TBAB acts as a
phase-transfer catalyst to initiate the reaction via the extraction
of a cyanide anion from the aqueous phase. The resulting
ammonium cyanide I reacts with 1,1-bis(benzenesulfonyl)-
alkenes 1 to provide the adduct II, which then undergoes pro-
tonation by NH4+ to give III, along with the regeneration of the
phase-transfer catalyst. In the presence of a base, elimination
of PhSO2H from III leads to the formation of the intermediate 3.
Subsequently, a second conjugate addition of the regenerated
Scheme 5. Synthetic transformation.
ammonium cyanide I to cyanoalkenes 3 occurs, followed by
protonation and base-induced elimination, yielding the final
product 2. At last, the high stereoselectivity obtained in this
Conclusions
In conclusion, we have developed a one-pot, transition-metal
free transformation for the synthesis of cis-1,2-dicyanoalkenes
from 1,1-bis(benzenesulfonyl)alkenes and KCN. This reaction is
characterized by the availability of starting materials, transition-
Scheme 3. Mechanistic experiment.
metal free reaction conditions, good functional group compati-
bility, as well as high stereoselectivity. Mechanistic experiments
indicated that the reaction proceeds through a double conju-
gate addition-elimination pathway. In addition, further transfor-
mation of the obtained product allows for access to imide and
dicarboxylic acid compounds.
Experimental Section
General Methods: NMR spectroscopic data were recorded on
Bruker AV 400 MHz instrument at 400 MHz (1H NMR) and 100 MHz
(
13C NMR), or Bruker AV 600 MHz instrument at 600 MHz (1H NMR)
and 150 MHz 13C NMR). Chemical shifts are reported in ppm from
tetramethylsilane with the solvent resonance as the internal stan-
dard (CDCl3: δH = 7.26 ppm, δC = 77.2 ppm; [D4]methanol: δH
3.31 ppm, δC = 49.0 ppm; [D6]DMSO: δH = 2.50 ppm, δC
=
=
39.5 ppm). High-resolution mass spectrometry (HRMS) spectra were
obtained on a Bruker micrOTOF-QII Instrument. Melting points were
measured on a WRS-1A digital melting point apparatus and are
uncorrected. X-ray structural analyses were conducted on a Rigaku
XtaLAB mini (600 W, SHINE, CCD, 75 mm, 0.1 electrons/pixel/sec).
Thin layer chromatography (TLC) was performed on 0.20 mm Qing-
dao Haiyang silica gel plates. Flash column chromatography was
performed on silica gel (200–300 mesh, Qingdao Haiyang Chem.
Company, Ltd.).
Scheme 4. Proposed reaction pathway.
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General Procedure for the Synthesis of Compounds 2: To a mix- 2-(3-Methoxyphenyl)maleonitrile[6] (2i): Yellow solid, 25.8 mg,
1
ture of 1,1-bis(benzenesulfonyl)alkenes
1
(0.2 mmol), KCN
70 % yield, m.p. 100–101 °C. H NMR (400 MHz, CDCl3): δ = 7.42 (t,
J = 8.0 Hz, 1 H), 7.26–7.24 (m, 1 H), 7.13–7.09 (m, 2 H), 6.37 (s, 1 H),
3.87 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 160.5, 133.6, 131.3,
131.0, 119.2, 118.7, 114.8, 114.3, 112.2, 107.8, 55.8. HRMS (ESI): m/z
calcd. for C11H8N2NaO+ 207.0529, found 207.0531 [M + Na]+.
(0.4 mmol), NH4Cl (0.2 mmol), K3PO4 (0.2 mmol) and tetrabutyl-
ammonium bromide (0.004 mmol, 2 mol-%) in cyclopentane (4 mL)/
H2O (0.2 mL) was stirred at 0 °C until the starting material disap-
peared as evidenced by TLC. The reaction mixture was diluted with
water (10 mL) and extracted with ethyl acetate (10 mL × 3). The
combined organic layers were dried with anhydrous Na2SO4 and
concentrated under vacuum. The residue was purified by flash chro-
matography on silica gel (PE/EA = 30:1 to 5:1 as eluent) to give the
corresponding product 2.
2-Mesitylmaleonitrile (2j): White solid, 27.9 mg, 71 % yield, m.p.
1
80–81 °C. H NMR (400 MHz, CDCl3): δ = 6.95 (s, 2 H), 5.94 (s, 1 H),
2.31 (s, 3 H), 2.29 (s, 6 H). 13C NMR (100 MHz, CDCl3): δ = 140.9,
136.0, 133.7, 129.5, 127.8, 115.7, 114.3, 113.9, 21.3, 20.2. HRMS (ESI):
m/z calcd. for C13H12N2Na+ 219.0893, found 219.0892 [M + Na]+.
2-Phenylmaleonitrile[8a] (2a): Yellow solid, 24.9 mg, 81 % yield,
2-(Benzo[d][1,3]dioxol-5-yl)maleonitrile (2k): Orange solid,
34.8 mg, 88 % yield, m.p. 170–171 °C. 1H NMR (400 MHz, [D6]DMSO):
δ = 7.44 (s, 1 H), 7.29–7.24 (m, 2 H), 7.10 (d, J = 8.2 Hz, 1 H), 6.17
(s, 2 H). 13C NMR (100 MHz, [D6]DMSO): δ = 151.4, 148.8, 131.0,
124.2, 124.0, 116.4, 115.0, 109.0, 107.4, 105.5, 102.7. HRMS (ESI): m/z
1
m.p. 85–86 °C. H NMR (400 MHz, CDCl3): δ = 7.67 (d, J = 7.4 Hz, 2
H), 7.58 (t, J = 7.3 Hz, 1 H), 7.51 (t, J = 7.4 Hz, 2 H), 6.39 (s, 1 H). 13C
NMR (100 MHz, CDCl3): δ = 133.6, 133.1, 130.0, 129.9, 126.9, 114.9,
114.3, 107.6. HRMS (ESI): m/z calcd. for C10H6N2Na+ 177.0423, found
177.0427 [M + Na]+.
calcd. for C11H6N2NaO2 221.0321, found 221.0323 [M + Na]+.
+
2-(p-Tolyl)maleonitrile[6] (2b): Light yellow solid, 26.9 mg, 80 %
yield, m.p. 134–135 °C. 1H NMR (400 MHz, CDCl3): δ = 7.55 (d, J =
8.2 Hz, 2 H), 7.31 (d, J = 8.1 Hz, 2 H), 6.32 (s, 1 H), 2.43 (s, 3 H). 13C
NMR (100 MHz, CDCl3): δ = 144.2, 133.5, 130.6, 127.4, 126.8, 115.1,
114.4, 106.1, 21.8. HRMS (ESI): m/z calcd. for C11H8N2Na+ 191.0580,
found 191.0585 [M + Na]+.
2-(Naphthalen-1-yl)maleonitrile[6] (2l): Yellow solid, 29.0 mg, 71 %
yield, m.p. 119–120 °C. 1H NMR (400 MHz, CDCl3): δ = 8.09 (d, J =
8.3 Hz, 1 H), 8.03 (d, J = 6.7 Hz, 1 H), 7.95 (d, J = 7.9 Hz, 1 H), 7.69–
7.60 (m, 2 H), 7.55–7.51 (m, 2 H), 6.33 (s, 1 H). 13C NMR (100 MHz,
CDCl3): δ = 133.9, 133.5, 132.8, 129.7, 129.3, 129.1, 128.5, 128.1,
127.5, 125.3, 123.7, 115.1, 114.4, 114.1. HRMS (ESI): m/z calcd. for
C
14H8N2Na+ 227.0580, found 227.0582 [M + Na]+.
2-(4-Methoxyphenyl)maleonitrile[6] (2c): Yellow solid, 36.4 mg,
99 % yield, m.p. 149–150 °C. 1H NMR (400 MHz, CDCl3): δ = 7.61 (d,
J = 8.9 Hz, 2 H), 6.99 (d, J = 8.9 Hz, 2 H), 6.21 (s, 1 H), 3.88 (s, 3 H).
13C NMR (100MHz, CDCl3): δ = 163.6, 132.9, 128.8, 122.7, 115.4,
115.3, 114.5, 104.1, 55.9. HRMS (ESI): m/z calcd. for C11H8N2NaO+
207.0529, found 207.0523 [M + Na]+.
2-(Naphthalen-2-yl)maleonitrile[6] (2m): Yellow solid, 30.6 mg,
1
75 % yield, m.p. 145–146 °C. H NMR (400 MHz, CDCl3): δ = 8.23 (s,
1 H), 7.96–7.88 (m, 3 H), 7.66–7.60 (m, 3 H), 6.47 (s, 1 H). 13C NMR
(100 MHz, CDCl3): δ = 135.1, 133.6, 133.0, 130.1, 129.7, 129.5, 129.3,
128.1, 128.1, 127.4, 121.1, 115.1, 114.4, 107.0. HRMS (ESI): m/z calcd.
for C14H8N2Na+ 227.0580, found 227.0581 [M + Na]+.
2-(4-Chlorophenyl)maleonitrile (2d): Light yellow solid, 25.7 mg,
68 % yield, m.p. 176–177 °C. 1H NMR (400 MHz, [D6]DMSO): δ = 7.79
(d, J = 8.5 Hz, 2 H), 7.64 (d, J = 8.5 Hz, 2 H), 7.45 (s, 1 H). 13C NMR
(100 MHz, [D6]DMSO): δ = 137.5, 130.5, 129.7, 128.8, 128.8, 115.9,
114.7, 111.1. HRMS (ESI): m/z calcd. for C10H5ClN2Na+ 211.0033,
found 211.0031 [M + Na]+.
2-(Thiophen-2-yl)maleonitrile[6] (2n): Brown solid, 25.6 mg, 80 %
yield, m.p. 118–119 °C. 1H NMR (400 MHz, CDCl3): δ = 7.59–7.56 (m,
2 H), 7.18 (t, J = 4.3 Hz, 1 H), 6.10 (s, 1 H). 13C NMR (100 MHz, CDCl3):
δ = 135.0, 133.2, 132.0, 129.4, 126.9, 114.8, 113.4, 103.8. HRMS (ESI):
m/z calcd. for C11H6N2NaO2 182.9987, found 182.9985 [M + Na]+.
+
2-(o-Tolyl)maleonitrile[6] (2e): Light yellow solid, 30.9 mg, 92 %
yield, m.p. 65–66 °C. 1H NMR (400 MHz, CDCl3): δ = 7.38–7.34 (m, 1
H), 7.26–7.19 (m, 3 H), 6.05 (s, 1 H), 2.43 (s, 3 H). 13C NMR (100 MHz,
CDCl3): δ = 136.5, 134.3, 131.8, 130.9, 129.2, 127.2, 114.5, 114.3,
113.6, 20.5. HRMS (ESI): m/z calcd. for C11H8N2Na+ 191.0580, found
191.0579 [M + Na]+.
2-(Thiophen-3-yl)maleonitrile (2o): Green solid, 23.0 mg, 72 %
yield, m.p. 132–133 °C. 1H NMR (600 MHz, CDCl3): δ = 7.88 (d, J =
1.1 Hz, 1 H), 7.48 (dd, J = 4.9, 2.9 Hz, 1 H), 7.29 (d, J = 4.8 Hz, 1 H),
6.20 (s, 1 H). 13C NMR (150 MHz, CDCl3): δ = 133.1, 130.6, 129.5,
127.6, 123.7, 114.9, 114.3, 105.5. HRMS (ESI): m/z calcd. for
+
C
11H6N2NaO2 182.9987, found 182.9989 [M + Na]+.
2-(2-Methoxyphenyl)maleonitrile[6] (2f): Yellow solid, 29.1 mg,
79 % yield, m.p. 130–131 °C. 1H NMR (600 MHz, CDCl3): δ = 7.68–
7.66 (m, 1 H), 7.50 (t, J = 7.4 Hz, 1 H), 7.09 (t, J = 7.6 Hz, 1 H), 7.03
(d, J = 8.4 Hz, 1 H), 7.00 (s, 1 H), 3.96 (s, 3 H). 13C NMR (150 MHz,
CDCl3): δ = 158.9, 133.9, 131.5, 130.7, 121.6, 119.0, 115.8, 115.0,
112.1, 111.3, 56.1. HRMS (ESI): m/z calcd. for C11H8N2NaO+ 207.0529,
found 207.0531 [M + Na]+.
2-((E)-Styryl)maleonitrile (2p): Yellow solid, 16.2 mg, 45 % yield,
m.p. 147–148 °C. H NMR (400 MHz, CDCl3): δ = 7.53–7.50 (m, 2 H),
7.44–7.42 (m, 3 H), 7.35 (d, J = 15.8 Hz, 1 H), 6.84 (d, J = 15.8 Hz, 1
H), 5.92 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 143.3, 134.0, 132.4,
131.2, 129.4, 128.3, 121.6, 115.1, 113.0, 107.5. HRMS (ESI): m/z calcd.
for C12H8N2Na+ 203.0580, found 203.0578 [M + Na]+.
1
(Z)-2-Phenyl-3-(phenylsulfonyl)acrylonitrile (3a): Yellow solid,
1
2-(2-Bromophenyl)maleonitrile (2g): White solid, 24.2 mg, 52 %
yield, m.p. 64–65 °C. 1H NMR (600 MHz, CDCl3): δ = 7.70 (d, J =
8.1 Hz, 1 H), 7.47–7.44 (m, 1 H), 7.41–7.39 (m, 2 H), 6.34 (s, 1 H). 13C
NMR (150 MHz, CDCl3): δ = 134.5, 133.2, 133.0, 131.8, 130.8, 128.6,
121.8, 115.5, 113.9, 113.8. HRMS (ESI): m/z calcd. for C10H5BrN2Na+
254.9528, found 254.9529 [M + Na]+.
m.p. 125–126 °C. H NMR (400 MHz, CDCl3): δ = 8.11 (d, J = 7.5 Hz,
2 H), 7.72 (t, J = 7.3 Hz, 1 H), 7.66–7.61 (m, 4 H), 7.56–7.49 (m, 1 H),
7.46 (t, J = 7.3 Hz, 2 H), 7.35 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ =
139.5, 139.4, 134.9, 132.6, 130.7, 129.9, 129.7, 128.6, 127.4, 125.0,
113.1. HRMS (ESI): m/z calcd. for C15H12NO2S+ 270.0583, found
270.0589 [M + H]+.
2-(m-Tolyl)maleonitrile[6] (2h): Light yellow solid, 28.6 mg, 85 % Procedure for the Synthesis of Compound 4: To a solution of 2a
yield, m.p. 81–82 °C. 1H NMR (400 MHz, CDCl3): δ = 7.46 (s, 2 H),
7.41–7.38 (m, 2 H), 6.36 (s, 1 H), 2.42 (s, 3 H). 13C NMR (100 MHz,
CDCl3): δ = 140.0, 134.0, 133.8, 130.0, 129.7, 127.5, 124.0, 115.0,
(92.5 mg, 0.6 mmol) in MeOH (2 mL) was added NaBH4 (27.2 mg,
0.72 mmol) at 0 °C. After 10 min, the reaction was quenched by
addition of water (1 mL) and the resulting mixture was extracted
114.4, 107.2, 21.5. HRMS (ESI): m/z calcd. for C11H8N2Na+ 191.0580, with EtOAc (10 mL × 3). The combined organic layers were washed
found 191.0582 [M + Na]+.
with brine, dried with anhydrous Na2SO4 and concentrated under
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vacuum. The residue was purified by flash chromatography on silica
gel to give compound 4.
21772142) and the National Basic Research Program of China
(973 Program: 2014CB745100).
2-Phenylsuccinonitrile[12] (4): White solid, 84.3 mg, 90 % yield,
m.p. 60–61 °C. 1H NMR (400 MHz, CDCl3): δ = 7.47–7.40 (m, 5 H),
4.19 (t, J = 6.8 Hz, 1 H), 2.96 (d, J = 6.8 Hz, 2 H). 13C NMR (100 MHz,
CDCl3): δ = 132.3, 129.7, 129.6, 127.3, 118.1, 115.6, 34.0, 24.7. HRMS
(ESI): m/z calcd. for C10H8N2Na+ 179.0580, found 179.0585 [M +
Na]+.
Keywords: Synthetic methods · Alkenes · Cyanides ·
Phase-transfer catalysis
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3-Phenylpyrrolidine-2,5-Dione[17] (5): White solid, 24.2 mg, 69 %
yield, m.p. 78–80 °C. 1H NMR (400 MHz, CDCl3): δ = 9.02 (br. s, 1 H),
7.32–7.28 (m, 2 H), 7.26–7.22 (m, 1 H), 7.18–7.16 (m, 2 H), 3.99 (dd,
J = 9.6, 5.1 Hz, 1 H), 3.15 (dd, J = 18.6, 9.6 Hz, 1 H), 2.78 (dd, J =
18.6, 5.1 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 178.7, 177.0, 136.8,
+
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176.0706, found 176.0715 [M + H]+.
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24 h. After cooling, NaOH aqueous solution (2
The aqueous layer was washed with diethyl ether (10 mL × 1), acidi-
fied by HCl (2 ), and extracted with ethyl acetate (10 mL × 3). The
combined organic layers were dried with anhydrous Na2SO4 and
concentrated under vacuum to give compound 6.
M, 5 mL) was added.
M
2-Phenylsuccinic Acid[18] (6): White solid, 25 mg, 85 % yield, m.p.
1
161–162 °C. H NMR (400 MHz, [D4]methanol): δ = 7.24–7.13 (m, 5
H), 3.91 (dd, J = 10.2, 5.2 Hz, 1 H), 3.00 (dd, J = 17.0, 10.2 Hz, 1 H),
2.51 (dd, J = 17.0, 5.2 Hz, 1 H). 13C NMR (100 MHz, [D4]methanol):
δ = 176.4, 175.0, 139.6, 129.6, 128.7, 128.3, 48.4, 38.5. HRMS (ESI):
m/z calcd. for C10H9O4 193.0506, found 193.0506 [M–H]–.
–
Acknowledgments
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This research was supported financially by the National Natural
Science Foundation of China (No. 21472137, 21532008, and
Received: October 3, 2018
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
One-Pot Reaction
Y. Zhang, Y. Wei, S. Li,*
J.-A. Ma* ............................................... 1–6
Stereoselective One-Pot Synthesis
of cis-1,2-Dicyanoalkenes from 1,1-
cis-1,2-Dicyanoalkenes can be synthe- 1,1-bis(benzenesulfonyl)alkenes with
sized in good to high yields by a tran- KCN under phase-transfer conditions.
sition-metal-free one-pot reaction of
Bis(benzenesulfonyl)alkenes
KCN
and
DOI: 10.1002/ejoc.201801504
Eur. J. Org. Chem. 0000, 0–0
www.eurjoc.org
6
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim