Ionic liquids as a reusable media for copper catalysis. Green access to alkenes using catalytic olefination reaction

Article abstract of DOI:10.1016/j.tet.2016.09.050

It was demonstrated that ionic liquids are superb recyclable media for copper catalyzed reactions using catalytic olefination reaction as an example. As a result a novel green access to the halogenoalkenes was elaborated. Possibility to perform up to five reaction cycles without catalyst leaching and decreasing of the yield was demonstrated. A number of various ionic liquids was screened and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim] [BF₄]) was found the solvent with highest efficiency. Mild conditions, high atom economy comparing to other known methods, low amounts of wastes and possibility to recover ionic liquid are the advantages of the proposed method.

Full text of DOI:10.1016/j.tet.2016.09.050

Accepted Manuscript
Ionic liquids as a reusable media for copper catalysis. Green access to alkenes using
catalytic olefination reaction
Vasily M. Muzalevskiy, Aleksey V. Shastin, Namiq G. Shikhaliev, Abel M.
Magerramov, Aytekin N. Teymurova, Valentine G. Nenajdenko
PII:
S0040-4020(16)30966-8
10.1016/j.tet.2016.09.050
TET 28121
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 24 June 2016
Revised Date: 8 September 2016
Accepted Date: 20 September 2016
Please cite this article as: Muzalevskiy VM, Shastin AV, Shikhaliev NG, Magerramov AM, Teymurova
AN, Nenajdenko VG, Ionic liquids as a reusable media for copper catalysis. Green access to alkenes
using catalytic olefination reaction, Tetrahedron (2016), doi: 10.1016/j.tet.2016.09.050.
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Ionic liquids as a reusable media for copper
catalysis. Green access to alkenes using
catalytic olefination reaction
Leave this area blank for abstract info.
Vasily M. Muzalevskiya, Aleksey V. Shastina,b, Namiq G. Shikhalievc, Abel M. Magerramovc, Aytekin N.
Teymurovac and Valentine G. Nenajdenkoc,*
a Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992, Russia
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow region, 142432 Russia.
cBaku State University, Department of Chemistry, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan.
NH2
CHal2XY
X
-CuCl immobilized in ionic liquid
-RT
-no catalyst leaching
-no loss of catalyst efficiency
-no contamination of the environment
Ar
N
Ar
[bmim] [BF4]
base
Y
up to 89%
10% CuCl
X=F, Cl, Br; Y=Cl, Br, CF3, CO2Et

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Ionic liquids as a reusable media for copper catalysis. Green access to alkenes using
catalytic olefination reaction
Vasily M. Muzalevskiya, Aleksey V. Shastina,b, Namiq G. Shikhalievc, Abel M. Magerramovc, Aytekin N.
Teymurovac and Valentine G. Nenajdenkoc,
a Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992, Russia
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow region, 142432 Russia.
cBaku State University, Department of Chemistry, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
It was demonstrated that ionic liquids are superb recyclable media for copper catalyzed reactions
using catalytic olefination reaction as an example. As a result a novel green access to the
halogenoalkenes was elaborated. Possibility to perform up to 5 reaction cycles without catalyst
leaching and decreasing of the yield was demonstrated. A number of various ionic liquids was
screened and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim] [BF4]) was found the
solvent with highest efficiency. Mild conditions, high atom economy comparing to other known
methods, low amounts of wastes and possibility to recover ionic liquid are the advantages of the
proposed method.
Available online
Keywords:
Ionic liquids
Alkenes
2009 Elsevier Ltd. All rights reserved
.
Olefination
Carbonyl compd.
Green Chemistry
1. Introduction
Both points lead to noticeable increase in the final price of the
products and decrease efficiency, which obstruct industrial
applications of such catalysts. Recycling and reusing of the
catalyst is a possible solution and efforts have been taken to
elaborate corresponding techniques. There are only a few
recyclable homogeneous catalysts reported, which can be settle
down and recycled by interphase,2 clathrate-enabled,3 silyl4- or
fluorous-tagged,5 redox,6 photo7 and phase-switchable8
techniques. Switching from homogeneous catalysis mode to
heterogeneous catalysis mode (immobilization of catalyst on
solid support) is more open to the possibility of repeatable use of
catalysts. However, very often immobilized catalyst show lower
catalytic efficiencies due to the higher diffusion limit, reduced
dispersion degree and unmatchable chemical microenvironment
of the active sites.9 Also many reactions lead to leaching of
catalyst even when metals are immobilized on inert surface.
Transition metal catalyzed transformations are of increasing
importance in modern organic chemistry, having numerous
applications in both academia and industry.1 The importance of
such transformations has been well acknowledged by several
Nobel prizes obtained during last decade (2010 Richard F. Heck,
Ei-ichi Negishi and Akira Suzuki "for palladium-catalyzed cross
couplings in organic synthesis"; 2005 Yves Chauvin, Robert H.
Grubbs and Richard R. Schrock "for the development of the
metathesis method in organic synthesis"; 2001 William S.
Knowles and Ryoji Noyori "for their work on chirally catalyzed
hydrogenation reactions", K. Barry Sharpless "for his work on
chirally catalyzed oxidation reactions"). High universality,
chemo-, regio- and stereoselectivity are distinct advantages of
these transformations. On the other hand there are some
difficulties, restricting more wide industrial use of transition
metals catalyzed transformations. First one is a quite high price
of most effective noble metals (Pt, Pd, Ir, Rh) as well as some
ligands (e.g. phosphorous derivatives), therefore repeatable use
of catalysts is highly desirable. In addition the toxicity of these
compounds can not be ignored and demands special precautions
to prevent or eliminate contamination of reaction products as well
as the environment.
A promising strategy for many catalytic reactions is the
application of ionic liquids as a reaction media. Ionic liquids
have been shown as a valuable immobilizing media for transition
metal catalyst, allowing several repeated reaction cycles without
significant decreasing of catalytic activity and catalyst leaching.
Another benefit of this strategy is a possibility to recycle
transition metal catalyst and prevent both the reaction product
and the environment from heavy metal contamination.10 Due to
their low volatility, immiscibility with non-polar organic
———
Corresponding author. Tel.: +7-495-939-2276; fax: +7-495-9328846; e-mail: nenajdenko@org.chem.msu.ru

2
Tetrahedron
ACCEPTED MANUSCRIPT
2. Results and discussion
solvents, stability and possibility to be easily recovered ionic
liquids (ILs) are very attractive replacement to conventional
solvents especially for use in green reactions.11,12
To start our investigation several ILs were tested as solvents
for COR. Hydrazone of 4-chlorobenzaldehyde 1a and CBrCl3
were used as a model system for catalytic olefination (10% of
CuCl). It was found that reaction of 1a with CBrCl3 in ILs leads
to target dichloroalkene 2a in good to high yields (Figure 2).
Imidazolium as well as pyrrolidinium ILs show comparable
results to give target alkene 2a in high yields. We tried to track
influence of reaction efficiency (yield of model product in
multiple runs) from nature of ionic liquids. Several parameters of
ionic liquids (nature of cation and anion, dielectric constants,
viscosity, electrolytic conductivity, hydrophobicity16) were
analysed. However, the reaction is appeared to be most sensitive
to the anion nature and hydrophobicity of IL as its function.
Thus, the yields of alkene 2a are lower in case of extremely
lipophilic (hydrophobic) tris(pentafluoroethyl)trifluorophosphate
Halogenated alkenes are versatile reagents in organic
synthesis, which is used for synthesis of various alkenes, alkynes,
derivatives of carboxylic acids, carbo- and heterocyclic
compounds.13 In 1999 a novel catalytic olefination reaction
(COR) was elaborated in our laboratory. COR is a transformation
of N-unsubstituted hydrazones into alkenes under treatment with
polyhalogenated alkanes (PHAs) in the presence of a base and
catalytic amounts of copper salts (Figure 1). Having a wide
synthetic scope, the reaction allows to synthesize both alkyl and
aryl substituted alkenes, including fluorinated ones and
derivatives with functional groups.14 Simple experimental
procedure, which does not require using of organometallics or
toxic organophosphorus compounds, affordable price and
availability of starting materials, high yields and stereoselectivity
are distinct advantages of the reaction. Because of application of
hydrazine derivatives is necessary for COR, copper forms soluble
complexes. We attempted to use heterogeneous copper catalysts,
however highly aggressive leaching of copper has been observed
to lead to significant loss of catalyst effectiveness even after first
cycle.15 Therefore, COR is one of the most difficult reaction in
terms of control of catalyst leaching and its multiple use.
−
anion (P(C2F5)3F3 ), never downing lower 40-50% however. The
−
−
−
−
other anions (BF4−, CF3SO3 , B(CN)4 , PF6 , CF3CO2 ,
CH3OSO3 , (CF3SO2)2N−) show yields up to 80% in first run and
−
average yields around 70% for 3-5 runs. Possible explanation can
be contributed to the delicate balance of hydrophilic and
lipophilic properties of the ILs. The most lipophilic ionic liquids,
IL2 and IL3, can not dissolve aqueous ammonia (using as a
base), which lead to formation of water-IL two phase system to
give lower yields. In contrast, being mixed with aqueous
ammonia, most hydrophilic IL1 lost its ability to dissolve
effectively hydrazone 1a, which also lead to decreasing of the
yields. Recently it was demonstrated that water can form
complex aggregates with some ILs to change significantly
properties of the solvent.17
R1
R1
X
R1
R1
Hal2CXY
+
N
N2
+
N
N
base, cat. CuCl
DMSO or EtOH
R2
NH2
R2
Y
R2
R2
easily separable
isomers ratio up to 21/1
up to 90-95%
R1 = Ar, Alk; R2= Alk, H
Hal = Cl, Br X = F, Cl, Br, H; Y = F, Cl, Br, CN, CO2Et
High yields were also obtained then reactions were performed
in repeated manner. In some case up to 5 runs were carried out
with no significant decrease in the yields. The best results were
obtained for ionic liquids IL 6-8, 10, 11. Among those 1-butyl-3-
methylimidazolium tetrafluoroborate ([bmim] [BF4]) IL10
showed almost no decrease of the yield and was chosen as a
reaction media for further investigations (Figure 2).
Figure 1. Catalytic olefination reaction (COR).
With green applications of COR in mind, we decided to
examine various ILs as a reusable reaction media for the reaction.
Here we would like to report a novel green approach towards
alkenes based on COR in ILs.
NH2
Cl
CBrCl3
IL1-11
NH3(aq)
N
Cl
Cl
Cl
2a
1a
10% CuCl
-
-
CF3SO3
PF3(C2F5)3
(CF3SO2)2N-
-
-
PF3(C2F5)3
B(CN)4
N
N
N+
N+
N
N+
IL1
IL2
IL5
N+
IL3
IL4
N+
65 /70 /48%
44 /42 /46%
62 /66 /59%
58 /47 /51%
51 /58 /50%
-
(CF3SO2)2N-
CF3SO3
N+
-
-
-
-
MeOSO3
BF4
CF3CO2
N+
PF6
N
N
N
N
N+
IL9
IL10
IL6
IL8
IL7
IL11
N+
N+
N+
77 /72 /71 /63 /60%
63 /58 /58 /55 /53%
70 /68 /68 /67 /66%
71 /68 /69 /61 /63%
77 /71 /74%
80 /78 /63%
Figure 2. COR of hydrazone 1a with CBrCl3 in ILs 1-11.
To investigate the synthetic scope of the method, we
performed the reaction of various hydrazones with CBrCl3 in
IL10 as a solvent. The corresponding dichloroalkenes with both
electron-withdrawing and electron-donating substituents were
prepared in good yields. Diene 2i was also synthesized from bis-
hydrazone of terephthalic aldehyde. Hydrazones of some
acetophenones were also involved effectively into the reaction to
give tetrasubstituted alkenes 2g,2h in a similar way (Scheme 1).
In principle, non-aromatic hydrazones can also be involved in
this olefination.14 However, due to low stability of aliphatic

3
hydrazones the reaction performed in repeated manner is less
efficient, therefore we investigated only aromatic derivatives in
this study.
Several improvements of the experimental technique were
ACCEPTED MANUSCRIPT
also made. Thus, the “conventional COR” is carried out in polar
solvent (DMSO, EtOH or ethylene glycol), then diluted with 10-
20 fold amount of water and extracted with dichloromethane.
After drying of the extract and evaporation of the solvent, the
residue obtained is purified by chromatography on silica gel
eluting with hexane (or hexane-dichloromethane mixtures). In
contrast, COR in ionic liquids does not require quenching of the
reaction mixture with water and extraction is carried out by
hexane. Since byproducts of the reaction (azines) are poor
soluble in hexane, the extract thus obtained contains almost pure
target alkene and purification can be carried out using minimal
amount of silica gel. Moreover, repeated use of silica gel column
as well as recovery of hexane makes the process very simple and
economical. Another important advance of this method is the
immobilization of copper salts in the IL layer. As a result no
waste contaminated water with copper is formed. At the same
time, CuCl does not decrease its catalytic activity in up to 5
repeated reaction runs. Very important also is purity of formed
alkenes which contain no copper traces after silica gel column
(Figure 3).
R
CBrCl3
R
Cl
NH2
[bmim] [BF4]
NH3(aq)
10% CuCl
Ar
Ar
N
Cl
2
1
O2N
Cl
Cl
Cl
Cl
Cl
Cl
2d 67 /69 /64%
Cl
Cl
O
O2N
2b 53 /54 /51%
2c 55 /48 /43%
Cl
Cl
Cl
Cl
Cl
Cl
S
2g 72 /74 /70%
2f 74 /70 /67%
2e 89 /85 /85%
Cl
Cl
Cl
Cl
Cl
2h 71 /67 /60%
Br
Cl
2i 64 /53 /48%
Hal2CXY
Scheme 1. Synthesis of alkenes 2 by COR with CBrCl3 in IL10.
base
extraction
by hexane
Next, the reaction of hydrazone 1a with set of
a
polyhalogenated alkanes was also investigated. 1-Butyl-3-
methylimidazolium tetrafluoroborate IL10 has been chosen again
as a reaction media. It was found, that other PHAs can be also
involved successfully into the COR in 1-butyl-3-
methylimidazolium tetrafluoroborate to give the corresponding
alkenes 3a and 4a in high yields (Scheme 2). The reaction
proceeded stereoselectively to afford mostly the less hindered
isomer with aryl and most bulky substituent in trans-position (in
cases, there formation of isomers is possible) and the ratio of E/Z
isomers was equal to the usual COR selectivity. Configurations
of the isomers were determined by comparison with literature
data.
SiO2
multiple use
Ar
N
elueting
by hexane
NH2
R
recovery
of hexane
cat. CuCl
IL
-CuCl immobilized in ionic liquid
-RT
-no catalyst leaching
-no loss of catalyst efficiency
-no contamination of the environment
X
Ar
Y
R
green procedure
metal free product
Utilization of freons, which are suspected to be active agents
of the ozone layer depletion, is an urgent problem to solve.14e
One the best possible solutions is to find out simple and
environmentally friendly chemical transformations of freons into
useful products. Using olefination with freons in ILs
corresponding fluorinated styrenes 5a-7a can be also prepared
effectively (Scheme 2). Styrenes 5a-7a have been shown to be
versatile building blocks for the synthesis of various fluorinated
molecules.13,18,19 So, olefination in ILs provides a very convenient
way for freons utilization as well.
Figure 3. Green access to halogenoalkenes using catalytic
olefination reaction (COR)
Comparing to other methods such as Corey-Fuchs20 or
Horner-Wadsworth-Emmons21 reactions, the method proposed
has also several advantages. First of all, simplicity and safety of
experimental technique should be mentioned. The reaction is
performed at room temperature with no need to exclude air. In
contrast to mentioned methods, our method does not produce
stoichiometric amounts of toxic phosphorous compounds or zinc
salts. Side products of the reaction (azines) are low toxic
compounds. Stoichiometrically formed ammonium halogenides
are even less toxic and nitrogen gas is not toxic at all. In addition,
these products are immobilized in IL phase, which prevent their
leaking to the environment. Atom economy of the reaction is
0.53 (in case of dibromide), which is much higher than the
corresponding values of Corey-Fuchs reaction (0.23 with PPh3,
0.29 with PPh3 and Zn), which is used mostly for synthesis of
dibromides from aldehydes. The possibility to recover easily
hexane and IL are also benefits of the reaction. Taking all
mentioned facts into account, one can conclude, that COR in ILs
goes very well with the principals of green chemistry and can be
used as a greener alternative to known methods.11,12
NH2
Hal2CXY
X
N
[bmim] [BF4]
base
10% CuCl
Y
Cl
Cl
2-7
1a
CO2Et
Br
Z/E 86:14
Cl
Br
Cl
Cl
4a CCl3CO2Et / NEt3
3a CBr4 / NH3
78 /71 /72%
89 /81 /73%
CF3
Br
CF3
Cl
F
Br
Cl
Cl
Cl
Z/E 79:21
E/Z 85:15
Z/E 92:8
7a CCl3CF3 / en
6a CBr3F / en
5a CBr3CF3 / NH3
3. Conclusion
64 /61 /61%
76 /66 /57%
60 /57 /61%
ILs were found to be prospective solvents for COR, providing
convenient pathway to a number of substituted alkenes, which
en = H2N(CH2)2NH2
Scheme 2. Synthesis of alkenes 2-7 in IL10.

4
Tetrahedron
ACCEPTED MANUSCRIPT
1
are valuable materials for organic synthesis. Effective
Yellow solid; mp 53-54 °C (lit.30 53-55 °C). H NMR (600
MHz CDC13) 6.92 (s, 1H, CH=CCl2), 7.55 (t, 1Н, Ar, J = 8.0),
7.81-7.83 (m, 1H), 8.16 (ddd, 1Н, Ar, J = 8.0, J = 2.2, J = 1.0).
1H NMR spectra of 2d are in agreement with literature25.
immobilization of transition metal catalyst in ionic liquid allows
performing up to 5 repeated reaction cycles without significant
decrease of the yields and prevents contamination of the
environment. Simple experimental procedure, low toxicity and
low amounts of wastes, higher atom economy comparing to
known methods (Corey-Fuchs or Horner-Wadsworth-Emmons
reactions) are the advantages of proposed approach.
4.5. 2,4-Dichloro-1-(2,2-dichlorovinyl)benzene (2e)
Colorless crystals; mp 49-50 °C (lit.23 47-48 °C), H NMR
(400 MHz CDC13) 6.99 (s, 1H, CH=CCl2), 7.28 (dd, 1Н, Ar, J =
8.5, J = 2.1), 7.43 (d, 1Н, Ar, J = 2.1), 7.65 (d, 1Н, Ar, J = 8.5).
1H NMR spectra of 2e are in agreement with literature23.
1
4. Experimental Section
General details
4.6. (4-(2,2-Dichlorovinyl)phenyl)(methyl)sulfane (2f)
Ionic liquids IL1-11 were received from Merck. All solvents
and reagents were of reagent grade and used without additional
purification. Hydrazones of carbonyl compounds were obtained
by reaction with hydrazine hydrate in refluxing ethanol as
reported previously.14a All reactions were monitored by thin-layer
chromatography carried out on Merck silica gel plates (Silufol
UV-254). Column chromatography was performed on silica gel
1
Brown crystals; mp 57-58 °C; H NMR (600 MHz CDC13)
2.48 (s, 3H, SMe), 6.79 (s, 1H, CH=CCl2), 7.22 (d, 2Н, Ar, J =
8.4), 7.46 (d, 2Н, Ar, J = 8.4); 13C NMR (150 MHz CDC13) 15.3,
120.3, 126.0, 128.0, 128.9, 129.9, 139.4; ESI-MS: MH+, found
218.9790. C9H8Cl2SH requires 218.9797.
4.7. 1-(1,1-Dichloroprop-1-en-2-yl)benzene (2g)
1
(Merck, 63–200 mesh). H NMR spectra were recorded at 400
1
and 600 MHz in CDCl3. 13C NMR spectra were recorded at 150
MHz in CDCl3. HRMS spectra were measured at Orbitrap Elite
instrument. 1H NMR spectra of compounds 2a22, 2b23, 2c24, 2d25,
2e23, 2i14d, 2g26, 3a27, 4a28, 5a14b, 6a19d, 7a29 are in agreement with
those in the literature.
Colorless oil; H NMR (400 MHz CDC13) 2.21 (s, 3H, Me),
7.26-7.40 (m, 5Н, Ar). H NMR spectra of compounds 2g are in
1
agreement with literature26.
4.8. 1-Bromo-4-(1,1-dichloroprop-1-en-2-yl)benzene (2h)
Colorless oil; 1H NMR (600 MHz CDC13) 2.18 (s, 3H, Me),
7.14 (d, 2Н, Ar, J = 7.9), 7.49 (d, 2Н, Ar, J = 7.9); 13C NMR (150
MHz CDC13) 22.8, 117.6, 121.8, 129.5, 131.6, 134.6, 138.9;
ESI-MS: MH+, found 264.9171. C9H7BrCl2H requires 264.9181.
COR in ILs (general procedure):
First run: 10 mL glass vial was equipped with stirring bar, IL
(1 mL), hydrazone of the corresponding carbonyl compound (1
mmol), base (NH3 or ethylenediamine (2 mmol)), CuCl (0.1
mmol) and stirred at room temperature for 2 min. Next,
polyhalogenated alkane (2 mmol) was added under cold water
(10-15 °C) bath cooling. Reaction mixture was stirred overnight,
then hexane (2 mL) was added and two phase mixture obtained
was stirred for 5 min. Hexane layer was separated via suction by
pipette, the operation was repeated another 3 times. Combined
hexane phases were passed through short silica gel pad using
hexane or hexane-CH2Cl2 1:1 mixture (4a) as eluents.
4.9. 1,4-bis(2,2-Dichlorovinyl)benzene (2i)
Colorless crystals; mp 77-78 °C (lit.14d 77-78 °C), H NMR
1
1
(400 MHz CDC13) 6.86 (s, 2H, C=CH), 7.57 (s, 4H, Ar). H
NMR spectra of 2i are in agreement with literature14d
.
4.10. 1-(2,2-Dibromovinyl)-4-chlorobenzene (3a)
Colorless crystals; mp 35-37 °C (lit.27 35-36 °C), H NMR
(400 MHz CDC13) 7.26 (d, 2Н, Ar, J = 8.7), 7.35 (s, 1H,
CH=CBr2), 7.39 (d, 2Н, Ar, J = 8.7). H NMR spectra of 3a are
1
1
Second and subsequent runs: To the mixture left from the
previous run, hydrazone of aryl aldehyde (1mmol), base (2
mmol) were added and stirred at room temperature for 2 min.
Next, polyhalogenated alkane (5 mmol) was added under water
bath cooling and stirred overnight. The product was isolated and
purified as in the first run.
in agreement with literature27.
4.11. Ethyl 2-chloro-3-(4-chlorophenyl)acrylate (4a)
1
Yellow oil; mixture of Z/E isomers in ratio 86:14; H NMR
(400 MHz CDC13) 1.31 (t, 3H, CH3, J = 7.1), 4.33 (q, 2H, CH2, J
= 7.1), 7.32 (d, 2Н, Ar, J = 8.7), 7.71 (d, 2Н, Ar, J = 8.7), 7.77 (s,
4.1. 1-Chloro-4-(2,2-dichlorovinyl)benzene (2a)
1
1H, CH=CClCO2Et). H NMR spectra of compounds 4a are in
agreement with literature28.
Colorless oil; 1H NMR (400 MHz CDC13) 6.81 (s, 1H,
CH=CCl2), 7.30 (d, 2Н, Ar, J = 8.3), 7.49 (d, 2Н, Ar, J = 8.4). 1H
NMR spectra of 2a are in agreement with literature 22.
4.12. 1-(2-Bromo-3,3,3-trifluoroprop-1-enyl)-4-
chlorobenzene (5a)
4.2. 1-(2,2-Dichlorovinyl)-4-nitrobenzene (2b)
1
Colorless oil; mixture of Z/E isomers in ratio 92:8; H NMR
1
Yellow solid; mp 88-90 °C (lit.23 88-89 °C). H NMR (400
(400 MHz CDC13) Z-isomer: 7.40 (d, 2Н, Ar, J = 8.8), 7.55 (s,
1H, CH=CBrCF3), 7.66 (d, 2Н, Ar, J = 8.8). E-isomer: 7.20 (d,
2Н, Ar, J = 8.5), 7.34 (d, 2Н, Ar, J = 8.5), 7.45 (s, 1H,
MHz CDC13) 6.93 (s, 1H, CH=CCl2), 7.69 (d, 2Н, Ar, J = 8.8),
8.22 (d, 2Н, Ar, J = 8.8). 1H NMR spectra of 2b are in agreement
with literature23.
1
CH=CBrCF3). H NMR spectra of 5a are in agreement with
literature14b
.
4.3. 1-(2,2-Dichlorovinyl)-4-methoxybenzene (2c)
4.13. (2-Bromo-2-fluorovinyl)-4-chlorobenzene (6a)
Colorless oil; 1H NMR (400 MHz CDC13) 3.78 (s, 3H,
Colorless oil; mixture of E/Z isomers in ratio 85:15; 1H NMR
(400 MHz CDC13) E-isomer: 5.92 (d, 1H, CH=CBrF, J = 32.3),
7.31 (m, 4Н, Ar). Z-isomer: 6.60 (d, 1H, CH=CBrF, J = 14.9),
OCH3), 6.80 (s, 1H, CH=CCl2), 6.83 (d, 2Н, Ar, J = 8.5), 7.21 (d,
1
2Н, Ar, J = 8.5). H NMR spectra of 2c are in agreement with
literature24.
1
7.32 (d, 2Н, Ar, J = 8.4), 7.40 (d, 2Н, Ar, J = 8.4). H NMR
spectra of 6a are in agreement with literature19d
.
4.4. 1-(2,2-Dichlorovinyl)-3-nitrobenzene (2d)

5
H.; Harms, K.; Sundermeyer, J. J. Am. Chem. Soc. 2004, 126,
9550-9551.
4.14. 1-(2-Chloro-3,3,3-trifluoroprop-1-enyl)-4-
chlorobenzene (7a)
ACCEPTED MANUSCRIPT
11. (a) Dupont, J.; de Souza, R. F.; Z. Suarez, P. A. Chem. Rev. 2002,
102, 3667–3692; (b) Pˆarvulescu, V. I.; Hardacre, C. Chem. Rev.
2007, 107, 2615–2665; (c) Liu, S. F.; Xiao, J. L. J. Mol. Catal. A:
Chem. 2007, 270, 1–43; (d) Śledź, P.; Mauduit, M.; Grela, K.
Chem. Soc. Rev. 2008, 37, 2433–2442; (e) Šebesta, R.; Kmentová,
I.; Toma, S. Green Chem. 2008, 10, 484–496; (f) Miao, W.; Chan,
T. H. Acc. Chem. Res. 2006, 39, 897–908.
12. (a) Sheldon, R. A.; Arends, I.; Hanefeld, U. Green Chemistry and
Catalysis, Wiley-VCH, Weinheim, 2007; (b) Green chemistry, in
special issue, Chem. Rev. 2007, 107, 2167-2820.
Colorless oil; mixture of Z/E isomers in ratio 79:21; 1H NMR
(400 MHz CDC13) Z-isomer: 7.07 (s, 1H, CH=CClCF3), 7.20 (d,
2Н, Ar, J = 8.7), 7.48 (d, 2Н, Ar, J = 8.7). E-isomer: 7.02 (s, 1H,
CH=CClCF3), 7.03 (d, 2Н, Ar, J = 8.4), 7.17 (d, 2Н, Ar, J = 8.4).
1H NMR spectra of 7a are in agreement with literature29.
Acknowledgments
13. Chelucci, G. Chem. Rev. 2012, 112, 1344–1462.
14. (a) Nenajdenko, V. G.; Korotchenko, V. N.; Shastin, A. V.;
Balenkova, E. S. Russ. Chem. Bull. 2004, 53, 1034-1064; (b)
Nenajdenko, V. G.; Varseev, G. N.; Shastin, A. V.; Balenkova, E.
S. J. Fluorine Chem. 2005, 126, 907-913; (c) Goldberg, A. A.;
Muzalevskiy, V. M.; Shastin, A. V.; Balenkova, E. S.;
Nenajdenko, V. G. J. Fluorine Chem. 2010, 131, 384-388; (d)
Muzalevskiy, V.M.; Shikhaliev, N. Q.; Magerramov, A.M.;
Gurbanova, N.V.; Geydarova, S.D.; Balenkova, E.S.; Shastin,
A.V.; Nenajdenko, V.G. Russ. Chem. Bull. 2013, 62, 678–682; (e)
Nenajdenko, V. G.; Muzalevskiy, V. M.; Shastin, A. V. Chem.
Rev. 2015, 115, 973–1050.
15. Nenajdenko, V. G.; Vasil'kov, A. Y.; Goldberg, A. A.;
Muzalevskiy, V. M.; Naumkin, A. V.; Podshibikhin, V. L.;
Shastin, A. V.; Balenkova, E. S. Mendeleev Comm. 2010, 20, 200-
202.
16. (a) Ignat’ev, N.V.; Finze, M.; Sprenger, J.A.P.; Kerpen, C.;
Bernhardt, E.; Willner, H. J. Fluorine Chem. 2015, 177, 46–54;
(b) Ignat’ev, N.V.; Welz-Biermann, U.; Kucheryna, A.; Bissky,
G.; Willner, H. J. Fluorine Chem. 2005, 126, 1150-1159; (c)
Ignat’ev, N.V.; Barthen, P.; Kucheryna, A.; Willner, H.; Sartori, P.
Molecules 2012, 17, 5319-5338; (d) Wasserscheid, P.; Welton, T.
(Eds.), Ionic Liquids in Synthesis, Wiley-VCH Verlag Gmbh,
Weinheim, 2008.
This work was supported by Russian Science Foundation
(grant no. 14-13-00083 for V.N.
(synthesis of alkenes 2-7,
purchasing of some starting materials, silica gel and
chromatography)), Russian Foundation for the Basic Research
(Grant no 16-03-00936-a for V.M. (synthesis of starting
hydrazones, purchasing of deuterated solvents and measuring of
NMR)). Special thanks to Merck KGaA (Darmstadt, Germany)
and Dr. N.V. Ignat’ev for provided ionic liquids.
References and notes
1. (a) Wang, Y.-M.; Lackner, A. D.; Toste, F. D. Acc. Chem. Res.
2014, 47, 889–901; (b) Prier, C. K.; Rankic, D. A.; MacMillan, D.
W. C. Chem. Rev. 2013, 113, 5322–5363; (c) Huang, J.-L.; Dai,
X.-J.; Li, C.-J. Eur. J. Org. Chem. 2013, 6496–6500; (d)
Yamaguchi, J.; Yamaguchi, A. D.; Itami, K. Angew. Chem., Int.
Ed. 2012, 51, 8960–9009.
2. (a) Wu, D. Y.; Marzini, M.; Lindner, E.; Mayer, H. A. Z. Anorg,
Allg. Chem. 2005, 631, 2538–2539; (b) Gelman, F.; Blum, J.;
Avnir, D. J. Am. Chem. Soc. 2002, 124, 14460–14463; (c)
Akiyama, R.; Kobayashi, S. Angew. Chem., Int. Ed. 2002, 41,
2602–2604.
17. Kashin, A. S.; Galkin, K. I.; Khokhlova, E. A.; Ananikov, V. P.
Angew. Chem. Int. Ed. 2016, 55, 2161–2166.
3. Dioumaev, V. K.; Bullock, R. M. Nature 2003, 424, 530–532.
4. Huang, J.-L.; Wang, J.-Zh.; Li, H.-X.; Guo, H.; O'Doherty, G. A.
Green Chem. 2015, 17, 1473-1478.
18. (a) Mokrushin, M. G.; Shastin, A. V.; Muzalevskiy, V. M.;
Balenkova, E. S.; Nenajdenko, V. G. Mendeleev Comm. 2008,
327-328; (b) Nenajdenko, V. G.; Muzalevskiy, V. M.; Shastin, A.
V.; Balenkova, E. S.; Kondrashov, E. V.; Ushakov, I. A.; Rulev,
A. Y. J. Org. Chem. 2010, 75, 5679-5688; (c) Muzalevskiy, V.
M.; Shastin, A. V.; Balenkova, E. S.; Nenajdenko, V. G. Russ.
Chem. Bull. 2007, 56, 1526-1533; (d) Rulev, A. Y.; Muzalevskiy,
V. M.; Kondrashov, E. V.; Ushakov, I. A.; Shastin, A. V.;
Balenkova, E. S.; Haufe, G.; Nenajdenko, V. G. Eur. J. Org.
Chem., 2010, 300-310; (e) Wang, C.; Chen, L.-H.; Deng, C.-L.;
Zhang, X.-G. Synthesis 2014, 46, 313-319; (f) Jiang, B.; Zhang,
F.; Xiong, W. Tetrahedron 2002, 58, 261-264; (g) Zhou, H.; Niu,
J.-J.; Xu, J.-W.; Hu, S.-J. Synth. Comm. 2009, 39, 716-732; (h)
Sun, L.-L.; Liao, Zh.-Y.; Tang, R.-Y.; Deng, C.-L.; Zhang, X.-G.
J. Org. Chem. 2012, 77, 2850-2856; (i) Sun, L.-L.; Hu, B.-L.;
Tang, R.-Y.; Deng, C.-L.; Zhang, X.-G. Adv. Synth. Catal. 2013,
355, 377-382; (j) Dong, S.-X.; Zhang, X.-G.; Liu, Q.; Tang, R.-Y.;
Zhong, P.; Li, J.-H. Synthesis 2010, 1521-1525; (k) Li, C.-L.;
Zhang, X.-G.; Tang, R.-Y.; Zhong, P.; Li, J.-H. J. Org. Chem.
2010, 75, 7037-7040; (l) Shi, S.; Sun, L.-L.; Liao, Z.-Y.; Zhang,
X.-G. Synthesis 2012, 44, 966-972.
19. (a) Nenajdenko, V. G.; Muzalevskiy, V. M.; Shastin, A. V.;
Balenkova, E. S.; Haufe, G. J. Fluorine Chem. 2007, 128, 818-
826; (b) Eddarir, S.; Kajjout, M.; Rolando, C. Tetrahedron 2012,
68, 603-607; (c) Schneider, C.; Masi, D.; Couve-Bonnaire, S.;
Pannecoucke, X.; Hoarau, C. Angew. Chem. Int. Ed. 2013, 52,
3246-3249; (d) Rouse, K.; Schneider, C.; Bouillon, J.-P.;
Levacher, V.; Hoarau, C.; Couve-Bonnaire, S.; Pannecoucke, X.
Org. Biomol. Chem. 2015, 14, 353-357.
20. Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 13, 3769–3772.
21. a) Horner, L.; Hoffmann, H. M. R.; Wippel, H. G.; Klahre, G. Ber.
1959, 92, 2499–2505; b) Wadsworth, W. S., Jr.; Emmons, W. D.
J. Am. Chem. Soc. 1961, 83, 1733.
5. For a review, see: (a) Gladysz, J. A.; Curran, D. P.; Horvath, I. T.
Handbook of Fluorous Chemistry, Wiley-VCH, Weinheim, 2004;
(b) Horváth, I. T.; Rábai, J. Science 1994, 266, 72–75; (c) Curran,
D. P.; Hadida, S. J. Am. Chem. Soc. 1996, 118, 2531–2532; (d)
Wende, M.; Gladysz, J. A. J. Am. Chem. Soc. 2003, 125, 5861–
5872; (e) Yao, Q.; Zhang, Y. J. Am. Chem. Soc. 2004, 126, 74–75.
6. (a) Liu, G.; He, H.; Wang, J. Adv. Synth. Catal. 2009, 351, 1610–
1620; (b) Süner, M.; Plenio, H. Angew. Chem., Int. Ed. 2005, 44,
6885–6888.
7. (a) Yang, Y.; Zhang, B.; Wang, Y. Z.; Yue, L.; Li, W.; Wu, L. X.
J. Am. Chem. Soc. 2013, 135, 14500–14503; (b) Liu, G. Y.; Wang,
J. H. Angew. Chem., Int. Ed. 2010, 49, 4425–4429.
8. (a) Xi, Z. W.; Zhou, N.; Sun, Y.; Li, K. L. Science 2001, 292,
1139–1141; (b) Hourdin, G.; Germain, A.; Moreau C.; Fajula, F.
J. Catal. 2002, 209, 217–224; (c) Desset, S. L.; Cole-Hamilton, D.
J. Angew. Chem., Int. Ed. 2009, 48, 1472–1474; (d) Uk Son, S.;
Jang, Y. J.; Park, J. N.; Na, H. B.; Park, H. M.; Yun, H. J.; Lee, J.
H.; Hyeon, T. J. Am. Chem. Soc. 2004, 126, 5026–5027; (e )
Astruc, D.; Lu, F.; Aranzaes, J. R. Angew. Chem., Int. Ed. 2005,
44, 7852–7872.
9. (a) Lu, J. N.; Toy, P. H. Chem. Rev. 2009, 109, 815–838; (b)
Clavier, H.; Grela, K.; Kirschning, A.; Mauduit, M.; Nolan, S. P.
Angew. Chem., Int. Ed. 2007, 46, 6786–6801; (c) Sheldon, R. A.
Green Chem. 2005, 7, 267-278; (d) McMorn, P.; Hutchings, G. J.
Chem. Soc. Rev. 2004, 33, 108-122; (e) De Vos, D. E. ; Dams,
M. ; Sels, B. F. ; Jacobs, P. A. Chem. Rev. 2002, 102, 3615-3640;
(f) Metivier, P. Fine Chemicals through Heterogeneous Catalysis,
Wiley, Weinheim, 2001, pp. 211; (g) De Vos, D. E. ; Vankelecom,
F. J. ; Jabobs, P. A. Chiral Catalyst Immobilization and Recycling,
Wiley-VCH, Weinheim, 2000, pp. 640; (h) Corma, A. Chem. Rev.
1997, 97, 2373-2419.
22. Arthuis, M.; Lecup, A.; Roulland, E. Chem. Comm. 2010, 46,
7810-7812.
23. Newman, S. G.; Bryan, C. S.; Perez, D.; Lautens, M. Synthesis
2011, 342-346.
24. Liron, F.; Fosse, C.; Pernolet, A.; Roulland, E. J. Org. Chem.
2007, 72, 2220-2223.
25. Ando A.; Miki, T.; Kumadaki, I. J. Org. Chem. 1988, 53, 3637-
3639.
10. (a) Zhou, Zh.-M.; Li, Zh.-H.; Hao, X.-Y.; Dong, X.; Li, X.; Dai,
L.; Liu, Y.-Q.; Zhang, J.; Huang, H.-F.; Li, X.; Wang, J.-L. Green
Chem. 2011, 13, 2963–2971; (b) Cotugno, P.; Monopoli, A.;
Ciminale, F.; Milella, A.; Nacci, A. Angew. Chem. Int. Ed. 2014,
53, 13563–13567; (c) Khan, N.-H.; Prasetyanto, E. A.; Kim, Y.-
K.; Ansari, M. B.; Park, S.-E. Catal. Lett. 2010, 140, 189–196; (d)
Park, S. B.; Alper, H. Chem. Commun. 2005, 1315–1317; (e) Sun,

6
Tetrahedron
26. Chien, C.-T.; Tsai, C.-C.; Tsai, C.-H.; Chang, T.-Y.; Tsai, P.-K.;
file. That file can then be transformed into PDF format and
ACCEPTED MANUSCRIPT
Wang, Y.-C.; Yan, T.-H. J. Org. Chem. 2006, 71, 4324-4327.
submitted along with the manuscript and graphic files to the
appropriate editorial office.
27. Sha,Q.; Wei, Y. Synthesis 2013, 45, 413-420.
28. Huang, Z.; Yu, X.; Huang, X. J. Org. Chem. 2002, 67, 8261-8264.
29. Fujita, M.; Hiyama, T. Bull. Chem. Soc. 1987, 60, 4377–4384.
30. Krabbenhoft, H. O. J. Org. Chem. 1978, 43, 1305-1310.
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