One-Pot Multi-Component Synthesis of Triarylacrylonitriles Directly by Using CaC2 as a Concise Acetylene Source and K4[Fe(CN)6] as an Eco-Friendly Cyanide Source

Article abstract of DOI:10.1002/ejoc.201701711

An efficient method for the one-pot multicomponent synthesis of triarylacrylonitriles from various aryl iodides directly by using calcium carbide as a concise acetylene source and potassium hexacyanoferrate(II) as an eco-friendly cyanide source is described. This protocol benefits from safe, inexpensive and easy-to-handle starting materials, good substrate tolerance and simple work-up procedure.

Full text of DOI:10.1002/ejoc.201701711

A Journal of
Accepted Article
Title: One-Pot Multi-Component Synthesis of Triarylacrylonitriles Direct
Using CaC2 as a Concise Acetylene Source and K4[Fe(CN)6] as
an Eco-Friendly Cyanide Source
Authors: Geyang Song and Zheng Li
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201701711
Link to VoR: http://dx.doi.org/10.1002/ejoc.201701711
Supported by

10.1002/ejoc.201701711
European Journal of Organic Chemistry
FULL PAPER
One-Pot Multi-Component Synthesis of Triarylacrylonitriles Direct
Using CaC2 as a Concise Acetylene Source and K4[Fe(CN)6] as an
Eco-Friendly Cyanide Source
Geyang Song[a] and Zheng Li*[a]
Abstract: An efficient method for the one-pot multicomponent
synthesis of triarylacrylonitriles from various aryl iodides direct using
calcium carbide as a concise acetylene source and potassium
hexacyanoferrate(II) as an eco-friendly cyanide source is described.
This protocol has the features of use of safe, inexpensive and easy-
to-handle starting materials, good substrate tolerance and simple
work-up procedure.
antiagglutinating auxiliary for table salt (NaCl). Recently,
K4[Fe(CN)6] has been used as an eco-friendly cyanide source
for some organic reactions to synthesize important compounds
bearing cyano groups.[9]
Our recent research interests focused on the use of CaC2
and K4[Fe(CN)6] in the organic synthesis, respectively, and
reported the synthesis of 1,3,5-triaroylcyclohexanes[10] and N-
propargylation of secondary amines[11] directly using CaC2 as an
acetylene source, and the cyanation of unsaturated compounds
including C=O, C=N and/or C=C bonds by nucleophilic addition
reactions using K4[Fe(CN)6] as an eco-friendly cyanide
source.[12]
Introduction
Triarylacrylonitriles are of importance in medicinal
chemistry because of their biological activities and their
applications in the synthesis of biologically active compounds.[1]
For example, some triarylacrylonitriles can inhibit the growth of
certain tumors (breast and prostate cancer), and can also be
used to synthesize resveratrol, which suppresses the growth of
a number of tumor cell lines including those derived from
colorectal, liver, breast, pancreatic, and prostate tumors.[2] In
addition, triarylacrylonitriles also have comprehensive synthetic
applications in organic and material chemistry.[3] Over the years,
various methods have been developed to synthesize
triarylacrylonitriles.[4] The general methods include i) the
reactions of diaryl ketones with arylacetonitriles. However, the
arylacetonitriles used in this method must be synthesized using
the strong toxic NaCN[5] and HCN,[6] etc.; ii) the reactions of
In this work, we report an efficient method for the
simultaneous use of CaC2 as a concise acetylene source and
K4[Fe(CN)6] as an eco-friendly cyanide source in one reaction to
synthesize triarylacrylonitriles from various aryl iodides by one-
pot multi-component procedure. To the best our knowledge, this
is the first example to utilize both CaC2 and K4[Fe(CN)6] in one
organic reaction.
Results and Discussion
In the initial research, the reaction of iodobenzene, CaC2
and K4[Fe(CN)6] was selected as a model reaction to examine
the feasibility for the synthesis of 2,3,3-triphenylacrylonitrile (1).
Different catalysts, bases and solvents were screened for the
model reaction (Table 1). It was found that Pd(II) catalysts, such
as Pd(OAc)2, PdCl2 and Pd(PPh3)2Cl2, could catalyze the
reaction to give 1 in medium to good yield (Table1, entries 1−3).
Pd(0) complex, for example Pd(PPh3)4, did not exhibit catalytic
effect on the reaction (Table 1, entry 4). In comparison,
Pd(PPh3)2Cl2 as a catalyst could give better yield (Table 1, entry
3).
Bases played a prominent role in the reaction. Some
organic bases, such as Et3N, DBU, DMAP and DABCO, and
some inorganic bases, such as NaOH, KOH, Na2CO3 and K2CO3,
were tested (Table 1, entries 5−12). Most of them exhibited low
activities. Especially only low yield of the desired product 1 were
obtained when Et3N and Na2CO3 alone were used as bases
(Table 1, entries 5, 11). However, the later research showed that
the combination of Et3N/Na2CO3 as bases was observed to give
high yield (Table 1, entry 3). In addition, the molar ratio of Et3N
over Na2CO3 could also influence the product yield (Table 1,
entries 17−19). The highest yield was obtained by using 2:1 of
Et3N over Na2CO3 (Table 1, entry 17).
diarylacetylenes,
aryl
bromides
and
potassium
hexacyanoferrate(II). However, the diarylacetylenes were
generally synthesized from highly flammable, complicated
handling acetylene gas.[7] Therefore it is necessary to explore a
more concise approach to synthesize triarylacrylonitriles.
Calcium carbide, CaC2, is a stable and inexpensive solid,
which is extensively used as a raw material to produce
acetylene gas by hydrolysis in chemical industry. The recent
reports have revealed that calcium carbide can be directly used
as a sustainable, easy-to-handle, and low-cost feedstock, and
efficient source of acetylene for in situ chemical
transformations.[8]
Potassium hexacyanoferrate(II), K4[Fe(CN)6], is
a
byproduct of the coal chemical industry and commercially
available on a ton scale. It is also used in the food industry for
metal precipitation. In addition, it has been described as an
[a]
College of Chemistry and Chemical Engineering, Northwest
Normal University, Lanzhou, Gansu, 730070, People’s Republic of
China.
Solvents also had certain effect on the yield of 1. The
reaction in DMSO, PhMe, and 1,4-dioxane almost could not give
product 1 (Table 1, entries 13−15). DMAc was selectable solvent
E-mail: lizheng@nwnu.edu.cn
Supporting information for this article is given via a link at the end
of the document.
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701711
European Journal of Organic Chemistry
FULL PAPER
(Table 1, entry 16). In contrast, DMF could afford the highest
yield (Table 1, entry 17).
Table 1. The effect of reaction conditions on the yield of 1[a]
Entry
Catalyst
Solvent
Base
Yield
(%)[b]
62
1[c]
2[c]
3[c]
4[c]
5
Pd(OAc)2
DMF
DMF
Et3N/Na2CO3
Et3N/Na2CO3
Et3N/Na2CO3
Et3N/Na2CO3
Et3N
PdCl2
43
69
Pd(PPh3)2Cl2
Pd(PPh3)4
DMF
DMF
0
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
DMF
25
6
DMF
DBU
Trace
Trace
Trace
0
7
DMF
DMAP
8
DMF
DABCO
9
DMF
NaOH
10
DMF
KOH
0
11
DMF
Na2CO3
16
12
DMF
K2CO3
Trace
Trace
0
13[c]
14[c]
15[c]
16[c]
17[d]
18[e]
19[f]
DMSO
PhMe
1,4-Dioxane
DMAc
DMF
Et3N/Na2CO3
Et3N/Na2CO3
Et3N/Na2CO3
Et3N/Na2CO3
Et3N/Na2CO3
Et3N/Na2CO3
Et3N/Na2CO3
Trace
56
77
DMF
71
DMF
53
[a] Reaction condition: Iodobenzene (1.5 mmol), K4[Fe(CN)6] (0.1 mmol),
CaC2 (1.0 mmol), H2O (0.5 mmol), base (0.5 mmol), palladium catalyst
(0.01 mmol) and CuI (0.1 mmol) in
3 mL of solvent under nitrogen
atmosphere stirred first at room temperature for 8 h, then at 110 °C for 4 h.
[b] Isolated yield. [c] Et3N/Na2CO3 (0.5 mmol/0.5 mmol). [d] Et3N/Na2CO3 ( 1
mmol/0.5 mmol). [e] Et3N/Na2CO3 ( 1 mmol/1 mmol). [f] Et3N/Na2CO3 ( 1.5
mmol/0.5 mmol).
Table
2.
One-pot
one-step
synthesis
of
2,3,3-
triarylacrylonitriles using single aryl iodide for one reaction[a]
[a] Reaction condition: Ar1I (1.0 mmol), K4[Fe(CN)6] (0.1 mmol), CaC2 (1.0
mmol), Et3N (1.0 mmol), Na2CO3 (0.5 mmol), H2O (0.5 mmol), Pd(PPh3)2Cl2
(0.01 mmol) and CuI (0.1 mmol) in 3 mL of degassed DMF under nitrogen
atmosphere stirred first at room temperature for 10 h, then Ar2I (0.55 mmol)
was added and the system was stirred at 110 °C for 4 h.
Having the optimized conditions in hand, the substrate
scope using single aryl iodide for one reaction through one-pot
one-step procedure to synthesize 2,3,3-triarylacrylonitriles was
examined, and the results summarized in Table 2. The
reactions could tolerate a wide range of functional groups on
aromatic rings, and produce the corresponding products in
satisfactory yield. The substituents on the ortho-, meta- and
para- positions of aromatic rings of aryl iodides had no
obvious effect on the yield of products. The substrates bearing
Me, Br and Cl groups on the aromatic rings could afford good
yield (1−4, 9−11). In contrast, the substrates bearing methoxy
group gave the corresponding products in slightly lower yield
(5−6) possibly because of the resonance donation of electrons
from oxygen. The similar situations were observed for
substrates bearing F and CF3 groups (7−8) possibly due to the
[a] Reaction condition: ArI (1.5 mmol), K4[Fe(CN)6] (0.1 mmol), CaC2 (1.0
mmol), Et3N (1.0 mmol), Na2CO3 (0.5 mmol), H2O (0.5 mmol), Pd(PPh3)2Cl2
(0.01 mmol) and CuI (0.1 mmol) in 3 mL of degassed DMF under nitrogen
atmosphere stirred first at room temperature for 8 h, then at 110 °C for 4 h.
Table
3.
One-pot
two-step
synthesis
of
2,3,3-
triarylacrylonitriles using two aryl iodides for one reaction[a]
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701711
European Journal of Organic Chemistry
FULL PAPER
(0.01 mmol) and CuI (0.1 mmol) in 3 mL of degassed DMF under nitrogen
atmosphere stirred first at room temperature for 8 h, then at 110 °C for 4 h.
strong electron-withdrawing effect. The aryl iodide bearing
fused ring (naphthyl) could also give good yield (12). In
addition, the aryl iodides including heteroaromatic ring
(thienyl) was also effective for the reaction (13). Unfortunately,
the attempts for reactions of aliphatic iodides, such as methyl
iodide and isobutyl iodide, were not successful.
To our great delight, 2,3,3-triarylacrylonitriles bearing
two different aryls could be readily obtained by one-pot two-
step method using two aryl iodides for one reaction (Table 3,
14−63). The similar substituent effect was also observed for
these reactions.
Scheme 3. Synthesis of 1 using bromobenzene instead of iodobenzene.
Conditions: Bromobenzene (1.5 mmol), K4[Fe(CN)6] (0.1 mmol), CaC2 (1.0
mmol), Et3N (1.0 mmol), Na2CO3 (0.5 mmol), H2O (0.5 mmol), Pd(PPh3)2Cl2
(0.01 mmol) and CuI (0.1 mmol) in 3 mL of degassed DMF under nitrogen
atmosphere stirred first at room temperature for 24 h, then at 110 °C for 6 h.
In addition, the reactions using three different aryl
iodides for one reaction were also attempted by one-pot two-
step procedure. However, the reaction system was complex
and many products were observed for one system. For
example, the reaction system using iodobenzene, 4-
iodotoluene and 1-chloro-4-iodobenzene could produce 2,3,3-
triarylacrylonitrile bearing three different aryls 64, 2,3,3-
triarylacrylonitriles bearing two different aryls 23 and 35, and
other unidentified products in low yield (Scheme 1). Similarly,
the reaction system using iodobenzene, 4-iodotoluene and 1-
iodonaphthalene could obtain 2,3,3-triarylacrylonitrile bearing
three different aryls 65, 2,3,3-triarylacrylonitriles bearing two
different aryls 27 and 38, and other unidentified products in
low yield (Scheme 1)
The studied reaction could also be performed on gram
scale (Scheme 4). The reaction of 3.06 g of iodobenzene with
1.04 g of calcium carbide and 0.37 g of K4[Fe(CN)6] in DMF
(20 mL) was performed under the optimized condition to give
1 in 35% (0.49 g) isolated yield. The success of this gram
scale reaction further showed the potency of optimized
condition for the bulk processes.
Scheme 4. Gram-scale synthesis of 1. Conditions: Iodobenzene (15 mmol),
K4[Fe(CN)6] (1 mmol), CaC2 (12 mmol, 1.04 g for 74% purity), Et3N (10
mmol), Na2CO3 (5 mmol), H2O (5 mmol), Pd(PPh3)2Cl2 (0.1 mmol) and CuI
(1 mmol) in 20 mL of degassed DMF under nitrogen atmosphere stirred first
at room temperature for 15 h, then at 110 °C for 6 h.
A plausible mechanism is proposed for the synthesis of
triarylacrylonitriles (Scheme 5). CaC2 first reacts with water to
give acetylene in situ. Simultaneously, Pd(0)L2 from the
reaction of Pd(II)L2 with Cu(I) combines with Ar1I through
oxidative addition to produce arylpalladium(II) intermediate A.
A exchanges ion with acetylene in the presence of Et3N and
Na2CO3 to give an ethynyl palladium intermediate B and co-
product HI, which can react with calcium carbide to generate
more acetylene in the reaction. The trans/cis-isomerization of
B produces intermediate C. The reductive elimination of C
gives diarylacetylene (D) and releases Pd(0)L2 to continue the
cycle. D reacts with another arylpalladium(II) intermediate E
formed from Ar2I by cis-addition to afford a vinylic palladium
intermediate F. F exchanges ligand with cyanide ion of
K4[Fe(CN)6] to form a new intermediate G. G conducts
reductive elimination to produce triarylacrylonitrile as a final
product and release Pd(0)L2 to continue the cycle or by Cu(II)
oxidation to produce Pd(II)L2 catalyst.
Scheme 1. One-pot two-step synthesis of 2,3,3-triarylacrylonitriles using
three aryl iodides for one reaction. Conditions: Iodobenzene (0.5 mmol),
K4[Fe(CN)6] (0.1 mmol), CaC2 (1.0 mmol), 1-iodo-4-methylbenzene (0.5
mmol), Et3N (1.0 mmol), Na2CO3 (0.5 mmol), H2O (0.5 mmol), Pd(PPh3)2Cl2
(0.01 mmol) and CuI (0.1 mmol) in 3 mL of degassed DMF under nitrogen
atmosphere stirred first at room temperature for 10 h, then 1-chloro-4-
iodobenzene or 1-iodonaphthalene (0.55 mmol) was added and the system
was stirred at 110 °C for 6 h.
It is noteworthy to mention that reaction substrates and
reagents could also be extended. When K3[Fe(CN)6] was used
to replace K4[Fe(CN)6] in the reaction, the product 1 could also
be obtained in 49% yield (Scheme 2). When bromobenzene
was used to replace iodobenzene in the reaction, the product
1 could be obtained in 12% yield (Scheme 3).
Conclusions
In conclusion, we have developed a novel method for
the synthesis of triarylacrylonitriles from various aryl iodides
using calcium carbide as a concise acetylene source and
potassium hexacyanoferrate(II) as an eco-friendly cyanide
source by one-pot multi-component procedure. The selective
use of one, two or three kinds of aryl iodides could obtain
Scheme 2. Synthesis of
Conditions: Iodobenzene (1.5 mmol), K3[Fe(CN)6] (0.1 mmol), CaC2 (1.0
mmol), Et3N (1.0 mmol), Na2CO3 (0.5 mmol), H2O (0.5 mmol), Pd(PPh3)2Cl2
1 using K3[Fe(CN)6] instead of K4[Fe(CN)6].
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701711
European Journal of Organic Chemistry
FULL PAPER
The general procedure for the preparation of 2,3,3-
triarylacrylonitriles 1−13: The mixture of ArI (1.5 mmol), K4[Fe(CN)6]
(0.1 mmol, 0.037 g), CaC2 (1.0 mmol, 0.086 g for 74% purity),
Pd(PPh3)2Cl2 (0.01 mmol, 0.007 g), CuI (0.1 mmol, 0.020 g), Et3N (1
mmol, 0.101 g), Na2CO3 (0.5 mmol, 0.053 g) and H2O (0.5 mmol, 0.009
g) in 3 mL of degassed DMF was stirred at room temperature under
nitrogen atmosphere for 8 h. Then the system was warmed to 110 °C
and continued to stir for 4 h. The resulting mixture was filtered, and the
solid was washed with ethyl acetate (3×10 mL). The liquor was washed
with saturated brine (3×10 mL), dried over anhydrous sodium sulfate, and
concentrated under reduced pressure. The residue was isolated by
column chromatography using petroleum ether and ethyl acetate (v/v
125:1) as eluent to give pure product.
various different aryl substituted triarylacrylonitriles. The
application of safe, inexpensive and eco-friendly raw
materials, mild conditions, good substrate tolerance and
simple work-up procedure made this protocol
alternative for the synthesis of many
triarylacrylonitriles.
a
good
desired
The general procedure for the preparation of 2,3,3-
triarylacrylonitriles 14−63: The mixture of Ar1I (1.0 mmol), K4[Fe(CN)6]
(0.1 mmol, 0.037 g), CaC2 (1.0 mmol, 0.086 g for 74% purity),
Pd(PPh3)2Cl2 (0.01 mmol, 0.007 g), CuI (0.1 mmol, 0.020 g), Et3N (1
mmol, 0.101 g), Na2CO3 (0.5 mmol, 0.053 g) and H2O (0.5 mmol, 0.009
g) in 3 mL of degassed DMF was stirred at room temperature under
nitrogen atmosphere for 10 h. Then Ar2I (0.55 mmol) was added and the
system was warmed to 110 °C and continued to stir for 4 h. The resulting
mixture was filtered, and the solid was washed with ethyl acetate (3×10
mL). The liquor was washed with saturated brine (3×10 mL), dried over
anhydrous sodium sulfate, and concentrated under reduced pressure.
The residue was isolated by column chromatography using petroleum
ether and ethyl acetate (v/v 125:1) as eluent to give pure product.
The general procedure for the preparation of 2,3,3-
triarylacrylonitriles 64, 65: The mixture of Ar1I (0.5 mmol), Ar2I (0.5
mmol), K4[Fe(CN)6] (0.1 mmol, 0.037 g), CaC2 (1.0 mmol, 0.086 g for
74% purity), Pd(PPh3)2Cl2 (0.01 mmol, 0.007 g), CuI (0.1 mmol, 0.020 g),
Et3N (1 mmol, 0.101 g), Na2CO3 (0.5 mmol, 0.053 g) and H2O (0.5 mmol,
0.009 g) in 3 mL of degassed DMF was stirred at room temperature under
nitrogen atmosphere for 10 h. Then Ar3I (0.55 mmol) was added and the
system was warmed to 110 °C and continued to stir for 6 h. The resulting
mixture was filtered, and the solid was washed with ethyl acetate (3×10
mL). The liquor was washed with saturated brine (3×10 mL), dried over
anhydrous sodium sulfate, and concentrated under reduced pressure.
The residue was isolated by column chromatography using petroleum
ether and ethyl acetate (v/v 125:1) as eluent to give pure product.
Acknowledgements
The authors thank the National Natural Science Foundation of
China (21462038) and Key Laboratory of eco-environment
Related Polymer Materials of Ministry of Education of China for
the financial support of this work.
Scheme 5. The proposed mechanism for the synthesis of triarylacrylonitriles
Keywords: calcium carbide, potassium hexacyanoferrate(II),
triarylacrylonitrile, one-pot reaction, multicomponent synthesis
Experimental Section
[1] a) B. Eric, P. Michel, J. Med. Chem. 1989, 32, 2092–2103; b) G. Jacques,
J. Miquel, C. Andre, J. Med. Chem. 1983, 26, 693–699; c) J. Dore, J.
Gilbert, E. Bignon, J. Med. Chem. 1992, 35, 573–583; d) C. Colleen, J.
Roderick, D.S. Hollis, Bioorg. Med. Chem. 2016, 21, 5495–5504; e) M.R.
Lashley, C.W. Dicus, K. Brown, M.H. Nantz, Org. Prep. Proced. Int. 2003,
35, 231–238.
General Information: 1H NMR and 13C NMR spectra were obtained with
Mercury–400 MB or Mercury–600 MB instrument using CDCl3 as solvent
and Me4Si as the internal standard. The Elemental analyses were
performed on a Vario El Elemental Analysis instrument. Melting points
were observed in an electrothermal melting point apparatus. The
solvents (DMF and the others) were degassed. All reagents were
purchased from Energy Chemical Company (China). Calcium carbide
[2] J. Ma, J. Li, Y. Tian, Bioorg. Med. Chem. Lett. 2017, 27, 81–85.
[3] a) F. Roberto, G. Pablo, V. Jose, Organometallics 2012, 31, 3361−3372; b)
Y. Tan, Y. Gong, P. Lu, X.Y. Shen, C. Feng, Y. Zhang, Z.B. Tang, Adv.
Mater. 2013, 25, 2837–2843; c) Z. Fu, X. Lv, B. Hu, P. Wang, C. Zhang,
Integr. Ferroelectr. 2013, 145, 146–150; d) Y. Gong, Y. Tan, J. Liu, P. Lu,
(purity
≥ 74 %) was ground into fine powder prior to use.
K4[Fe(CN)6]·3H2O was dehydrated at 80oC under vacuum for 24 h and
finely powdered before use.
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701711
European Journal of Organic Chemistry
FULL PAPER
G. He, Y. Zhang, Chem. Commun. 2013, 49, 4009−4011; e) G.F. Zhang,
H. Wang, Z.Q. Chen, X. Meng, M.Q. Zhu, Chem. Mater. 2014, 26,
4433−4446; f) Y. Zhang, Q. Song, K. Wang, W. Mao, C. Zhang, J. Mater.
Chem. 2015, 3, 3049−3054; g) W. Dong, Y. Pan, U. Scherf, Polymer 2015,
76, 173−181; h) Y. Qi, Y. Wang, Y. Yu, Z. Liu, C. Zhou, J. Mater. Chem. C
2016, 4, 11291−11297; i) Y. Zhan, P. Gong, P. Yang, Z. Jin, Y. Bao, Y. Xu,
RSC Adv. 2016, 6, 32697−32704; j) M. Ouyang, L. Zhan, X. Lv, F. Cao, W.
Li, C. Zhang, RSC Adv. 2016, 6, 1188−1193; k) Z. Ma, Y. Ji, Z. Wang, G.
Kuang, X. Jia, J. Mater. Chem. C 2016, 4, 10914−10918.
2017, 82, 9479−9486; p) A. Samzadeh-Kermani, Synlett 2017, 28, 2126–
2130; q) A. Hosseini, A. Pilevar, E. Hogan, B. Mogwitz, A. S. Schulze, P.
R. Schreiner, Org. Biomol. Chem. 2017, 15, 6800–6807; r) G. Werner, K.
S. Rodygin, A. A. Kostin, E. G. Gordeev, A. S. Kashin, V. P. Ananikov,
Green Chem. 2017, 19, 3032–3041.
[9] a) T. Schareina, A. Zapf, M. Beller, J. Organomet. Chem. 2004, 689, 4576–
4583; b) T. Schareina, A. Zapf, M. Beller, Chem. Commun. 2004, 1388–
1389; c) T. Schareina, A. Zapf, M. Beller, Tetrahedron Lett. 2005, 46,
2585–2588; d) S.A. Weissman, D. Zewge, C. Chen, J. Org. Chem. 2005,
70, 1508–1510; e) O. Grossman, D. Gelman, Org. Lett. 2006, 8, 1189–
1191; f) L.H. Li, Z.L. Pan, X.H. Duan, Y.M. Liang, Synlett 2006, 2094–
2098; g) T. Schareina, A. Zapf, M. Beller, Tetrahedron Lett. 2007, 48,
1087–1090; h) S. Velmathi, N.E. Leadbeater, Tetrahedron Lett. 2008, 49,
4693–4694; i) G. Chen, J. Weng, Z. Zheng, X. Zhu, Y. Cai, J. Cai, Y. Wan,
Eur. J. Org. Chem. 2008, 3524–3528; j) A.W. Franz, L.N. Popa, T.J.J.
Muller, Tetrahedron Lett. 2008, 49, 3300–3303; k) Y.L. Ren, Z.F. Liu, S.
Zhao, J.J. Wang, Catal. Commun. 2009, 10, 768–771; l) Y.L. Ren, W.
Wang, S. Zhao, X.Z. Tian, J.J. Wang, Tetrahedron Lett. 2009, 50, 4595–
4597; m) Y.L. Ren, W. Wang, S. Zhao, X.Z. Tian, J.J. Wang, Org. Process
Res. Dev. 2009, 13, 764–768; n) P.Y. Yeung, C.P. Tsang, F.Y. Kwong,
Tetrahedron Lett. 2011, 52, 7038−7041; o) P. Anbarasan, H. Neumann, M.
Beller, Chem. Eur. J. 2011, 17, 4217−4222; p) P.Y. Yueng, M.S. Chau,
P.L. Chak, Org. Lett. 2011, 13, 648−651; q) D.Y. Zhang, H.F. Sun, L.
Zhang, Y. Zhou, C.P. Li, H.L. Jiang, K.X. Chen, H. Liu, Chem. Commun.
2012, 48, 2909–2911; r) L. Liu, J. Li, J. Xu, J.T. Sun, Tetrahedron Lett.
2012, 53, 6954–6956; s) I.A. Azath, P. Suresh, K. Pitchumani, New J.
Chem. 2012, 36, 2334–2339; t) X.Z. Tian, Y.P. Sun, C.H. Dong, K.X.
Zhang, T.F. Liang, Y. Zhang, C.D. Hou, Chem. Lett. 2012, 41, 719–721; u)
R. Gerber, M. Oberholzer, C.M. Frech, Chem. Eur. J. 2012, 18,
2978−2986; v) Y.L. Ren, C.H. Dong, S. Zhao, Y.P. Sun, J.J. Wang, J.Y.
Ma, C.D. Hou, Tetrahedron Lett. 2012, 53, 2825−2827; w) D. Saha, L.
Adak, M. Mukherjee, B.C. Ranu, Org. Biomol. Chem. 2012, 10, 952−957;
x) W.Z. Yin, R. Liu, G.K. He, W.J. Lv, H.J. Zhu, RSC Adv. 2014, 4,
37773−37778; y) T. Chatterjee, R. Dey, B. C. Ranu, J. Org. Chem. 2014,
79, 5875−5879.
[4] a) W. Stanley, M.S. Edwin, Org. Synth. 1951, 31, 52; b) K. Tsugio, M.
Mahito, K. Shinjiro, T. Hiroshi, Tetrahedron Lett. 1986, 27, 3885−3888; c)
Y. Cheng, Z. Duan, L. Yu, Y. Zhu, Y. Wu, Org. Lett. 2008, 10, 901−904; d)
B. Klaus, H. Manfred, P. Tom, F. Joachim, Chem. Eur. J. 2015, 21,
14911–14923; e) M. Yasunori, Y. Hirofumi, N. Yoshiaki, H. Tamejiro,
Angew. Chem. Int. Ed. 2013, 52, 883–887; f) J. Li, H. Chen, Y. Du, K.
Zhao, RSC Adv. 2013, 3, 4311–4320; g) V. Sivan, V. Reena, P.P.
Ravindra, V. Ajayan, Catal. Lett. 2010, 135, 148–151.
[5] a) M.N.S. Rad, A. Khalafi-Nezhad, S. Behrouz, M.A. Faghihi, Tetrahedron
Lett. 2007, 48, 6779−6784; b) M. Chidambaram, S.U. Sonavane, J. Zerda,
Y. Sasson, Tetrahedron 2007, 63, 7696−7701; c) B.M. Godajdar, B.
Ansari, J. Mol. Liq. 2015, 202, 34−39; d) A.R. Kiasat, S. Nazari, J. Mol.
Catal. A: Chem. 2012, 365, 80−86; e) A.R. Kiasat, S. Nazari, Catal.
Commun. 2012, 18, 102−105.
[6] H. Mahdavi, M. Amirsadeghi, J. Iranian Chem. Soc. 2013, 10, 791−797.
[7] a) C.J. Li, D.L. Chen, C.W. Costello, Org. Process Res. Devel. 1997, 1,
325−327; b) M. Pal, N.G. Kandu, J. Chem. Soc., Perkin Trans. 1 1996,
449−51.
[8] a) W. Zhang, H. Wu, Z. Liu, P. Zhong, L. Zhang, X. Huang, J. Cheng,
Chem. Commun. 2006, 4826–4828; b) Y. Jiang, C. Kuang, Q. Yang,
Synlett 2009, 3163−3166; c) P. Chuentragool, K. Vongnam, P.
Rashatasakhon, M. Sukwattanasinitt, S. Wacharasindhu, Tetrahedron
2011, 67, 8177–8182; d) Q. Yang, Y. Jiang, C. Kuang, Helv. Chim. Acta
2012, 95, 448−454; e) Z. Lin, D. Yu, Y.N. Sum, Y. Zhang, ChemSusChem.
2012, 5, 625−628; f) D. Yu, Y.N. Sum, A.C.C. Ean, M.P. Chin, Y. Zhang,
Angew. Chem., Int. Ed. 2013, 52, 5125−5128; g) Y.N. Sum, D. Yu, Y.
Zhang, Green Chem. 2013, 15, 2718−2721; h) N. Thavornsin, M.
Sukwattanasinitt, S. Wacharasindhu, Polym. Chem. 2014, 5, 48−52; i) A.
Hosseini, D. Seidel, A. Miska, P. R. Schreiner, Org. Lett. 2015, 17,
2808−2811; j) N. Kaewchangwat, R. Sukato, V. Vchirawongkwin, T.
Vilaivan, M. Sukwattanasinitt, S. Wacharasindhu, Green Chem. 2015, 17,
460−465; k) K.S. Rodygin, V.P. Ananikov, Green Chem. 2016, 18,
482−486; l) K.S. Rodygin, G. Werner, F.A. Kucherov, V.P. Ananikov,
Chem. Asian J. 2016, 11, 965–976; m) S.P. Teong, D. Yu, Y.N. Sum, Y.
Zhang, Green Chem. 2016, 18, 3499−3502; n) E. Rattanangkool, T.
Vilaivan, M. Sukwattanasinitt, S. Wacharasindhu, Eur. J. Org. Chem. 2016,
4347–4353; o) Y. Yu, Y. Chen, W. Huang, W. Wu, H. Jiang, J. Org. Chem.
[10] Z. Li, L.L. He, R.G. Fu, G.Y. Song, W.L. Song, D.M. Xie, J.Y. Yang,
Tetrahedron 2016, 72, 4321–4328.
[11] R.G. Fu, Z. Li, J. Chem. Res. 2017, 41, 341–345.
[12] a) Z.X. Zhao, Z. Li, Eur. J. Org. Chem. 2010, 5460−5463; b) Z. Li, G.Q.
Tian, Y.H. Ma, Synlett 2010, 14, 2164−2168; c) Z. Li, C.H. Liu, Y.P. Zhang,
R.Z. Li, B. Ma, J.Y. Yang, Synlett 2012, 23, 2567−2571; d) Z. Li, J.J. Yin,
T.P Li, G. Wen, X.L. Shen, J.Y. Yang, Tetrahedron 2014, 70, 5619−5625;
e) X.C. Hu, H.B. Li, J.Y. Yang, Z. Li, Synlett 2014, 25, 1786−1790; f) Z. Li,
F. Wen, J.Y. Yang, Chin. J. Chem. 2014, 32, 1251−1254; g) Z. Li, F. Wen,
J.Y. Yang, J. Chem. Sci. 2016, 128, 1849−1853.
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701711
European Journal of Organic Chemistry
FULL PAPER
Table of Contents
FULL PAPER
An efficient method for the one-pot
Triarylacrylonitriles
multicomponent
synthesis
of
Geyang Song, Zheng Li*
triarylacrylonitriles from various aryl
iodides direct using calcium carbide
as a concise acetylene source and
potassium hexacyanoferrate(II) as an
Page 1 – Page 6
One-Pot Multi-Component Synthesis
of Triarylacrylonitriles Direct Using
CaC2 as a Concise Acetylene Source
and K4[Fe(CN)6] as an Eco-Friendly
Cyanide Source
eco-friendly
described.
cyanide
source
is
This article is protected by copyright. All rights reserved.