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Journal Name Dynamic Article Links ►

Cite this: DOI: 10.1039/c0xx00000x

www.rsc.org/advances ARTICLE TYPE
Ionic liquid/water mixtures promoted organic transformations
Pedavenkatagari Narayana Reddy,*a Pannala Padmaja,*b Basireddy V. Subba Reddy,c Gundla Rambabua

Ionic liquids (ILs) have been used in numerous applications in chemistry. Wet ILs constitutes a
5 new class of solvents with their own new and interesting properties. The properties of ILs are

RSC Advances Accepted Manuscript

significantly influenced by the addition of water and also affect reaction rates and selectivity. The
IL/water mixing makes it easy to control the properties of the solution and the formation of these
ionic liquid mixtures increases synthetic flexibility. In this review, mixtures of IL/water solvent
system promoted organic reactions have been described and the results are compared with other
10 solvent systems. In many cases IL/water combinations were superior compared to conventional
organic solvents and biphasic ILs/organic co-solvents media with respect to catalytic performance
as well as to catalyst separation and recycling.

1 Introduction 50 When these unique properties of both ILs and water are
suitably exploited by mixing them, the resulting mixtures should
15 Ionic liquids (ILs) have attracted intensive interests in recent provide numerous kinds of applications for many fields,
years due to their wide applications in synthesis, catalysis and especially for bioscience. Generally, hydrophobic ILs are
chemical separations.1-2 They possess a large array of fascinating immiscible with water and easily forms liquid/liquid biphasic
properties, such as a negligible vapor pressure, a high chemical 55 systems. On the other hand, ILs with hydrophilic ions are mostly
and thermal stability, a large temperature range and widely miscible with water. Cation species also affect the miscibility of
20 tunable thermophysical properties.3-8 Because of these properties, the ILs with water. In particular, the introduction of long alkyl
they can serve as a green recyclable alternative to the volatile chains into the cations dramatically lowers the miscibility of the
organic compounds that are traditionally used as industrial ILs with water. On the other hand, ILs having longer alkyl chains
solvents.9-10 In fact, ILs have been successfully used as green 60 are phase separated with water.44
solvents in many applications including organic and inorganic The properties of IL/water mixtures depend strongly on the
25 synthesis,11-13 polymer synthesis14-15, chemical separations16-24 ion species.45 The component ions of ILs interact strongly with
and electrochemistry.25-26 The range of research studies on ILs water via ion-dipole interactions. Even a small amount of water
have increased from the past decades and continually can dramatically influence the liquid properties of ILs such as
expanding.27-41 65 diffusion coefficient, viscosity, polarity, and surface tension.46-49
Multiphase processes employing binary mixtures of This may have an effect on reaction rates due to the coordinating
30 immiscible, or partly miscible, aqueous and organic phases are ability with a catalyst and also on the solubility of other
widely used in organic synthesis. The immiscibility of ionic substances in ILs. There have been several reports that studied
liquids with traditional solvents such as water, ether, hexane and the effect of water when IL/water mixtures used as solvent.50-54
benzene allowed for the formation of bi- and triphasic reaction 70 The other use of IL/water mixtures involves liquid/liquid phase-
systems which significantly facilitated purification and extraction separated systems. In particular, separated biphasic liquid
35 of the desired products.42 Furthermore, the mixing of ILs with mixtures are expected to be suitable media for separation,
other molecular liquids is much easier for tuning their properties condensation, and extraction.55 Employing water as the added
than the structural design of pure ILs. In this strategy, water is solvent to ILs enhanced the catalytic activities significantly,
now a very important partner for ILs because water also has a 75 ascribed to the creation of a well mixed emulsion-like system. An
wide variety of properties that pure ILs does not possess.43 insight at the molecular level into the state of water dissolved in
40 _________________________________________________________ ILs is needed for further understanding of ILs as media for
a
Department of Chemistry, Gitam School of Technology, Gitam chemical synthesis and separation. Recently attempts have been
University, Hyderabad (T.S), India- 502 102. E-mail: [email protected] made to take this idea further by using mixtures of IL/water.56-58
b
Department of Chemistry, JNTUH College of Engineering, Kukatpally, 80 The objective of this review is to draw attention to the recent
Hyderabad (T.S), India-500 085. E-mail: [email protected] trends of mixtures of IL/water solvent system promoted organic
c
45 CSIR- Indian Institute of Chemical Technology, Hyderabad, India-500 reactions such as hydrogenation, oxidation, reduction,
007. substitution, halogenations, three component coupling reactions
and other organic reactions.
85

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 RSC Advances Page 2 of 19

2 Ionic liquid/water mixtures promoted reactions other solvents. The authors attributed this clear beneficial effect
of water was due to the creation of a well mixed emulsion-like
2.1 Hydrogenation system. Similarly, Feng et al.61 focused on enantioselective
version of asymmetric hydrogenation of enamides in IL/water
5 Ionic liquids have been successfully used as reaction media for a 45 system (Scheme 3). The hydrogenation of methyl α-
wide variety of substrates for hydrogenation reactions. Ionic acetamidoacrylate (7) with rhodium-ferrocenyl diphosphine
liquids provide a stabilizing medium for catalysts and facilitate complexes afford the product (8) with better conversion and ee in
their immobilization, thereby facilitating recycling procedures. 1-methyl-3-octylimidazolium tetrafluoroborate
Biphasic hydrogenations have also demonstrated recyclability, ([omim][BF4])/H2O and 1-butyl-3-methylimidazolium bis
10 the substrates and products residing in a separate phase to the IL 50 (trifluoromethylsulfonyl)imide ([bmim][Tf2N])/H2O than in
and catalyst. conventional organic solvents and ionic liquid/organic systems. It
In 2003, Jessop and his group59 reported the asymmetric was shown that IL/water combination allow repeated catalyst

RSC Advances Accepted Manuscript

hydrogenation of tiglic acid (1) catalyzed by Ru(O2CMe)2((R)- recycling without significant loss of activity and that industrially
tolBINAP) in mixture of 1-butyl-3-methylimidazolium relevant turnover numbers of >10,000 can be obtained.
15 hexafluorophosphate ([bmim][PF6]) and water (3:2) to afford 2- 55

methylbutanoic acid (2) with high enantioselectivity (85%) and

conversion (99%) (Scheme 1). The product was extracted from
the IL by supercritical CO2. The enantioselectivity was shown to
be hydrogen pressure dependent in wet [bmim][PF6]. At low
20 pressure, the amount of water had no effect on the
enantioselectivity but at higher pressure adding water enhanced
the enantiomeric excess.

Scheme 3 Enantioselective hydrogenation of enamides.

More recently, Bouquillon et al.62 investigated the

60 tetrabutylammonium ionic liquids (TBA ILs) derived from with
natural organic anions and tetrabutylammonium hydroxide in
catalytic selective hydrogenation of 1,5-cyclooctadiene (9) into
25
cyclooctene (10) at room temperature under atmospheric H2
Scheme 1 The asymmetric hydrogenation of tiglic acid.
pressure in water (Scheme 4). They are more suitable for
65 selective hydrogenation of 1,5-COD into COE under milder
Afterwards, Wolfson et al.60 in 2005 examined the
conditions than commercial 1-butyl-3-methylimidazolium ionic
asymmetric hydrogenation of methyl 2-acetamidoacrylate (3)
liquids (BMIM ILs).
30 with Rh-EtDuPHOS and the hydrogenation of 2-cyclohexen-1-
one (5) with Wilkinson’s catalyst in [bmim][PF6] in the presence
of water (Scheme 2).

70

Scheme 4 Selective hydrogenation of 1,5-cyclooctadiene in

presence of TBA ILs/water.

Welton and co-workers63 employed the concept of biphasic

75 systems of IL/water in the hydrogenation of 2-butyne-1,4-diol
(11) (Scheme 5). At room temperature, the ionic liquid
35 [omim][BF4], containing [Rh(η4-C7H8)(PPh3)2][BF4] catalyst,
Scheme 2 Asymmetric hydrogenation of methyl 2- forms a separate layer to water containing 2-butyne-1,4-diol. In a
acetamidoacrylate and 2-cyclohexen-1-one. stirred autoclave the mixture was pressurized with hydrogen to 60
80 atm and heated to 80 °C giving a homogeneous single phase
Employing water as second solvent the reaction rate in the solution. On cooling to room temperature, two phases reform,
40 biphasic system yielded much higher reaction rates than with the with the ionic liquid phase containing the catalyst and the

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Page 3 of 19 RSC Advances

aqueous phase containing a mixture of 2-butene-1,4-diol (12, 13) 2.2 Oxidation

and butane-1,4-diol (14) products that can be simply removed Ionic liquids are highly stable and have been evaluated as media
without catalyst contamination. for oxidation reactions.66 In 2003, Chen and co-workers67
reported a mild, efficient and eco-friendly procedure for the
55 oxidation of alcohols with IBX in 1-butyl-3-methylimidazolium
chloride ([bmim][Cl]) and water (Scheme 8). Simply stirring of a
solution of the alcohol (19) and IBX in [bmim][Cl]/H2O at room
temperature followed by extraction with ether or ethyl acetate and
removal of the solvent gave the corresponding carbonyl
60 compounds (20). Compared with the classical procedure in
DMSO, this procedure in [bmim][Cl] and water shares the

RSC Advances Accepted Manuscript

5
advantage of mild reaction conditions, homogeneous solution and
Scheme 5 Hydrogenations of 2-butyne-1,4-diol.
facile recovery of the oxidant and recycling of the ionic liquid.
Chen et al.64 prepared the TPPTS-stabilized Ru catalyst and
applied successfully for the asymmetric hydrogenation of
10 aromatic ketones (15) in (1-alkyl-3-methylimidazolium p-
methylphenylsulfonates ([RMIM]Ts)/water mixed solvent, which
gave the corresponding chiral alcohols (16) with good
enantioselectivity (Scheme 6).

15

65

Scheme 8 Oxidation of alcohols with IBX in [bmim][Cl]/water.

20
Recently, Lee and his group68 demonstrated the oxidation
Scheme 6 Asymmetric hydrogenation of aromatic ketones. reaction of benzylic alcohols (21) with trichloroisocyanuric acid
70 (22) and 1-butyl-3-methylimidazolium tetrafluoroborate
The authors observed that the addition of appropriate amounts of ([bmim][BF4]) in water at room temperature to afford the
water can increase the ee value from 45.1% to 80.3%. The corresponding carbonyl compounds (23) in good yields (Scheme
25 increase in the ee values can be attributed to the enhancement of 9). The use of pure water as reaction medium, mildness of
the solubility of the water-soluble catalyst in ionic liquid. reaction conditions and operational simplicity made this method
However, a lower activity and enantioselectivity are observed 75 an important alternative to the other methods previously reported.
when only water was used as a solvent. The same research
group65 further examined the asymmetric hydrogenation of α, β-
30 unsaturated ketones catalyzed by the achiral ruthenium
monophosphine complex RuCl2(TPPTS)2–(S,S)-DPENDS–KOH
in [RMIM]Ts/water mixture (Scheme 7). Under the optimized
conditions benzalacetone (17) afford the chiral alcohol (18) with
100% chemoselectivity and 75.9% ee. The addition of
35 appropriate amount of water was not only beneficial to exerting
the catalytic activity and chemoselectivity of the catalyst, but also
helps improve the enantioselectivity, because water enhances the
solubility of catalyst in ionic liquids. However, lower activity and
chemoselectivity are observed when only water was used as Scheme 9 TCCA-promoted oxidation of benzylic alcohols in
40 solvent. IL/water.
80

In 2005, Gao et al.69 reported the synthesis of a 2,2,6,6-

tetramethylpiperidine-1-oxyl (TEMPO) radical bearing an ionic
liquid and its use as catalyst for the metal-free, chemoselective
45
oxidation of primary and secondary alcohols (24) to aldehydes
85 and ketones (25) in aqueous-[bmim][PF6] biphasic conditions
respectively (Scheme 10). The new IL-supported radical proved
Scheme 7 Asymmetric hydrogenation of α, β-unsaturated to be an efficient, selective and recoverable catalyst for the
ketones. selective oxidation of alcohols and showed catalyst properties
50 similar to non-supported TEMPO in terms of activity and
90 selectivity.

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 RSC Advances Page 4 of 19

2.3 Suzuki-cross coupling

35

The Suzuki reaction is one of the most widely used catalytic

carbon-carbon bond forming tools in organic synthesis.
Palladium-catalyzed Suzuki cross-coupling reactions in ionic
liquids have been reported. However water was found to have a
40 remarkable rate accelerating effect on the Suzuki reaction in ionic
liquids.
In 2005, Zhang et al.72 successfully performed the Suzuki
reaction in a mixture of IL/water by using palladium(II) acetate
(Pd(OAc)2) as the catalyst in air (Scheme 13). The reactions of
arylhalides (30) with arylboronic acids (31) using Pd(OAc)2 as

RSC Advances Accepted Manuscript

45

the catalyst in mixture of IL/water provided the desired coupling

products (32) in good yields. The addition of the water
Scheme 10 Oxidation of alcohols by ionic liquid-supported dramatically improves the reactivity of the Suzuki reaction in ILs.
nitroxyl catalysts in water. The best yield was obtained when the mass ratio of water and
5 50 [bmim][PF6] was 1:3 and when the mass ratio of the [bmim][BF4]
Ansari and co-workers70 in 2005, found that a combination of and water was 1:1. The Pd(OAc)2–[bmim][PF6]-water system can
the ionic liquid ([bmim][BF4]) and water was an excellent solvent be reused seven times only with a small deactivation of reactivity.
system for the Wacker oxidation of different types of olefins (26)
to corresponding ketones (27) using the classical Pd/Cu catalysts
10 under an oxygen atmosphere (Scheme 11). The ionic liquid
[bmim][BF4] was selected for this study since it has an excellent
miscibility with H2O. The best yields were observed when the
IL/water ratio was 2:1 by volume. The Authors showed that
under these conditions it was not necessary to add any acid,
55
15 contrary to the classical Wacker process due to the hydrolysis of
Scheme 13 Suzuki cross-coupling reaction of aryl halides with
BF4- liberating HF during the reaction, which may act as the
phenylboronic acid in the mixture of [bmim][PF6]/water.
catalyst.
Recently, De Souza and co-workers73 reported the ionic liquid
60 1-butyl-4-methylpyridinium tetrafluoroborate (C4MPyBF4),
derived from 4-picoline was a very efficient solvent when mixed
with water for the Suzuki–Miyaura cross coupling promoted by
microwave irradiation (Scheme 14).

20 Scheme 11 Ionic liquid mediated Wacker oxidation of terminal

olefins in water.

Qian and co-workers71 disclosed the chemoselective oxidation

of sulfides (28) to sulfoxides (29) using 1-(4-
25 diacetoxyiodobenzyl)-3-methylimidazolium tetrafluoroborate
([dibmim][BF4]) in water under mild conditions (scheme 12). The
addition of small amount of water to ionic liquid shortened the
65
reaction time. Aliphatic and aromatic sulfides are selectively
oxidized to the corresponding sulfoxides at room temperature in
Scheme 14 Microwave assisted Suzuki reaction.
30 excellent yields.
The resulting phosphine-free catalytic system was able to activate
70 both iodo and bromoarenes toward reaction conditions. Reactions
between haloarenes (33) with phenylboronic acids (34) catalyzed
by Pd(OAc)2 in the presence of C4MPyBF4/H2O system and
triethylamine as base under microwave activation resulted the
desired cross coupling products (35). The presence of the ionic
75 liquid seems to be crucial because a drop in the catalytic activity
was verified when water was used as the unique solvent. High
Scheme 12 Oxidation of sulfides with [dibmim][BF4] in water. performances obtained in C4MPyBF4/H2O system may stem from

4 | Journal Name, [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
Page 5 of 19 RSC Advances

an increase in the fluidity of the reaction media allowing energy [bmim][BF4] and water (1:1) can afford the products (45) in good
and mass transference between organic (substrates) and aqueous- yields. The ionic liquid plays the dual role of solvent and catalyst
ionic (catalytic system) and easy the work-up of the product. in this transformation. When the reaction was carried out in water
Later on, Kosmrlj et al.74 effectively used 1,4-disubstituted-3- 55 the reaction does not proceed at all. But when the reaction was
5 methyl-1,2,3-triazolium salts as ionic liquids in palladium- performed in [bmim][BF4]/water in a 1:1 ratio the best yeild was
catalyzed Suzuki–Miyaura catalysis in the environmentally obtained.
benign solvent water (Scheme 15). The reaction of 4-bromo-
benzaldehyde (36) and phenyl boronic acid (37) with catalyst
Pd(OAc)2 and 1,4-disubstituted-3-methyl-1,2,3-triazolium salt in
10 water at room temperature afford 4-phenylbenzaldehyde (38).

RSC Advances Accepted Manuscript

60 Scheme 17 Multicomponent synthesis of furopyranopyridine
using ionic liquid [bmim][BF4] and water in one-pot.
Scheme 15 Performance of triazolium salts in Suzuki-Miyaura
15 catalysis. 2.5 Substitution reaction

2.4 Diels-Alder Reaction 65 The nucleophilic substitution reaction is one of the important
method for inserting functional groups into a carbon skeleton.
Diels–Alder reactions conducted in the presence of an ionic Many nucleophilic substitution reactions have been found with
20 liquid are known and quite effective.75-81 In 2011, Nino et al.82 enhanced reactivity and selectivity in ionic liquid.84 In 2003,
investigated the MacMillan iminium catalyst for asymmetric Afonso and his co-workers85 demonstrated the nucleophilic
Diels–Alder cycloadditions in methylpyridinium triflate 70 substitution reactions of alkyl halide (46) with various
([mpy][OTf])/water homogeneous phase (Scheme 16). nucleophiles (47) under aqueous-RTIL phase transfer conditions
at room temperature (Scheme 18).
25

30

75

Scheme 18 Nucleophilic substitution reactions in aqueous-RTIL

35 Scheme 16 Diels–Alder reaction of different dienes and system.
dienophiles using the chiral iminium salt in IL/water.
The use of this biphasic aqueous-RTIL procedure, in opposition
Diels–Alder reactions between dienes (39) and dienophiles (40) 80 to the reported method seems particularly appealing, since it
were carried out at 0 0C, using MacMillan iminium in mixture of avoids the use of less friendly solvent DMSO.
40 [mpy][OTf]:H2O to afford the corresponding products (41). Chi and co-workers86 reported a facile hydroxylation of
Water plays a fundamental role in this reaction both as the co- haloalkanes (49) at the primary and secondary aliphatic and
solvent, allowing a homogeneous phase for transformations benzylic positions using water as a nucleophile in the presence of
carried out in [mpy][OTf] and for mechanistic reasons in 85 ionic liquids (Scheme 19).
facilitating the iminium ion hydrolysis. The protocol provided
45 good yields, selectivity and shorter reaction times in comparison
with classical organic solvents.
Recently, Siddiqui and co-workers83 developed the
multicomponent one pot synthesis of furopyranopyridines (45) in 90

IL/water mixture (scheme 17). The synthetic strategy involves a

50 reaction between N-methylpiperidinone (42), an aromatic Scheme 19 Hydroxylation of various alkyl halides and sulfonate
aldehydes (43) and 2,3-dihydrofuran (44) using the ionic liquid using H2O in [bmim][BF4].

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 RSC Advances Page 6 of 19

water. Between the two ionic liquids used, [bmim][BF4] was a

The use of ionic liquid as an alternative reaction medium not only 60 better solvent as the reaction in [bmim][PF6] was sluggish be
enhanced the nucleophilicity of water but also reduced the because [bmim][PF6] and water are immiscible.
formation of elimination products predominantly formed under Yi-Qun and co-workers reported89 the reduction reactions of a
5 the conventional basic reaction conditions. series of aldehydes and ketones (56) by potassium borohydride
Later on, Liang et al.87 developed an efficient microwave (57) in an IL/water ([bmim][PF6]/H2O) biphasic system to afford
assisted Tsuji-Trost reaction for allylic substitution with various 65 the corresponding alcohols (58) with high purity in excellent
carbon and heteronucleophiles catalyzed by Pd(OAc)2/TPPTS in yields (Scheme 22). The IL/water biphasic system could promote
an ethylmethylimidazolium tetrafluoroborate ([emim][BF4])/H2O the chemoselectivity and the substituents such as nitro group and
10 system (Scheme 20). The reactions of allylic acetates (51) with chlorine remained intact. Aromatic ketones were not as active as
various nucleophiles (52) catalyzed by palladium(0)-TPPTS in an aromatic aldhydes and cyclic ketones owing to their higher steric
IL/water medium via microwave irradiation are proceeded well to hindrance. The reduction in the IL/water biphasic system starts

RSC Advances Accepted Manuscript

70

afford the corresponding products (53). The water plays from the transport of the anion BH4− from the water phase by the
presumably an important role in the process because of good onium cation of the ionic liquid either between the interface of
15 water solubility to Pd(OAc)2 and TPPTS. The catalyst system the ionic liquid phase and water phase or slightly amount of ionic
was very easy to separate from the reaction product, so it can be liquid dissolved in water.
used repeatedly. 75
O OH
[bmim][PF6]/ H2O
R1 R2 KBH4
rt R1 R2
20

56 57 58
80
R1 = Ph, 4-OMeC6H4, etc. (Up to 96% yield)
R2 = H, Me

25 Scheme 22 Reductions of carbonyl compounds in

Scheme 20 Tsuji-Trost reaction of allylic substrates with various [bmim][PF6]/H2O.
nucleophiles in a mixture of IL/water. 85

Khan and co-workers reported90 the chemoselective reduction

2.6 Reduction of nitroarenes (59) to the corresponding amines (60) using zinc
30 and aqueous ammonium salts in IL/water mixture as a safe and
The most studied ionic liquids in reduction reactions have recyclable reaction medium (Scheme 23). The combination of
been simple salts of N,N'-dialkylimidazolium tetrafluoroborates 90 Zn/NH4Cl in [bmim][PF6] or Zn/HCO2NH4 in [bmim][BF4] were
or hexafluorophosphates, usually hydrophobic and immiscible the suitable conditions for the reduction of nitroarenes.
with some organic solvents such as alkanes, isopropyl alcohol, Azobenzenes (61) were also smoothly reduced to
35 and toluene. Khan and co-workers88 have investigated the hydrazobenzenes (62) with Zn/HCO2NH4 in recyclable
efficient reduction of mono- and disubstituted norbornyl α- [bmim][BF4] without any over reduction to the corresponding
diketones (54) with zinc in [bmim][BF4]:H2O (10:1) to afford the 95 anilines. Use of 4 equivalents of Zn, 3 equivalents of ammonium
corresponding acyloins (55) in excellent yields and salt in 10:1 ionic liquid and water gave a clean reaction profile.
diastereoselectivities (Scheme 21).
40

100

45

105

50

Scheme 21 Zn mediated reduction of diketones in mixture of IL/

water. 110 Scheme 23 Zinc-mediated reduction of aromatic nitro
compounds and azobenzenes in mixture of IL/water.
In case of the monosubstituted norbornyl α-diketones, very high
55 regioselectivities ranging from 90:10 to 100:0, in favor of Nagaiah et al.91 demonstrated that [bmim][BF4]/water (2:1)
diastereomer possessing endo-hydroxyl diagonal to endo- system was an efficient reaction medium for one-pot reductive
substituent were observed. It was necessary that water be used as 115 amination of carbonyl compounds (63) with sodium borohydride
a co-solvent as the reactions did not proceed in the absence of

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Page 7 of 19 RSC Advances

at ambient temperature (Scheme 24). Several aldimines obtained

by the condensation of carbonyl compounds (63) with primary 60

amines (64) yielded the desired products (65) in excellent yields.

The role of water can be explained by the solubility of NaBH4 in
5 the ionic medium. Furthermore, the reduction process also
requires protic solvents such as alcohol or water.
65

Scheme 26 Ionic liquid catalyzed aza-Michael reaction of

10 aliphatic amines with α, β-unsaturated compounds in water.

70 Recently, Lu et al.94 employed a functionalized ionic liquid,

RSC Advances Accepted Manuscript

3-(N,N-dimethyldodecylammonium) propanesulfonic acid
hydrogen sulphate ([DDPA][HSO4]) as catalyst in water for the
15 Scheme 24 Reductive amination in ionic liquid aza-Michael reactions of aromatic amines (74) with α, β-
[bmim][BF4]/H2O system with NaBH4. unsaturated compounds (75) at room temperature to produce β-
75 amino compounds (76) in good yields (Scheme 27). The catalyst
2.7 Michael addition can be reused for several times without obvious loss of the
catalytic activity.
20 The Michael addition reaction is a one of the most important
classes of new carbon-carbon bond-forming reactions for the
preparation of organic target products in synthetic organic 80

chemistry. Recently, room-temperature ionic liquids have been

used as alternate catalysts to carry out Michael addition.
25 In 2003, Yadav and co-workers reported92 the conjugate
addition α, β-unsaturated ketones (66, 69) with thiols (67) rapidly
in a hydrophobic ionic liquid [bmim][PF6]/H2O solvent system 85

(2:1) in the absence of any acid catalyst to afford the

corresponding Michael adducts (68, 70) in high to quantitative
30 yields with excellent 1,4-selectivity under mild and neutral Scheme 27 Aza-Michael addition of aromatic amines in the
conditions (Scheme 25). Authors observed that, the combination presence of [DDPA][HSO4] and water.
90
of IL/water was found to be the most effective solvent system for
this conversion. In this reaction, the efficiency of ionic liquid was Yadav and co-workers reported95 the hydrothiocyanation of
strongly influenced by the nature of the anion. chalcones (77) with the task-specific ionic liquid (TSIL), 1-n-
butyl-3-methylimidazolium thiocyanate ([bmim][SCN]) (78) in
35
water to afford the corresponding products (79) (Scheme 28).
95

40

100

Scheme 28 Hydrothiocyanation of chalcones with TSIL in water.

45
A highly efficient organocatalyst in combination with ILs-
105 benzoic acid as a catalytic system for Michael additions of
aldehydes (80) to nitroolefins (81) in water has been developed
Scheme 25 Conjugate addition of thiols to enones in IL/H2O. by Ni and his group96 (Scheme 29). A notable feature of this
50
organocatalytic system was that the catalyst can be recycled more
Thereafter, Xia et al.93 reported the efficient conjugate than 12 times without significant loss of enantioselectivity
addition of aliphatic amines (71) to α, β-unsaturated compounds 110 (Scheme 29).
(72) catalyzed by simple quaternary ammonium salts and ionic
liquids in the green solvent, water to afford the corresponding
55 products (73) (Scheme 26). The feasibility of recovery and reuse
of the catalyst in the water was also examined through a series of
sequential Michael reactions and the recovered [bmim][BF4] 115

catalyst was reused five times without loss of activity.

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 RSC Advances Page 8 of 19

O [bmim][BF4]-H2O OH O
60 O
Ar
Ar H catalyst 89 or 90
R R R R
86 87 88
5
Ar = 4-O2NC6H4, 2-pyridyl, etc. (Up to 99% yield)
R = H, (CH2)3 (dr > 75/25)
65

O
O O NH
10 HN NH NH HN
Scheme 29 Organocatalytic asymmetric Michael reaction using
NH HN OHN
aldehydes and nitroolefins. 70

RSC Advances Accepted Manuscript

89 Catalyst 90
97
The same research group further examined another highly
15 efficient asymmetric Michael addition of ketones and aldehyde Scheme 31 Synthesis of aldols in the [bmim][BF4]-H2O medium
(83) to nitroolefins (84) catalyzed by a water-compatible chiral catalyzed by amide 89 or 90.
pyrrolidine-based organocatalyst, in combination with ILs 75

sulfonic acid in water (Scheme 30). The hydrophobicity of the In 2008, Zlotin and co-workers99 designed and synthesized a
catalyst forces it into close contact with hydrophobic reactants in novel chiral (S)-proline-modified task-specific ionic liquid as an
20 water and excludes the reaction transition state from water. efficient recoverable organocatalyst for the direct asymmetric
aldol reaction between cycloalkanones (91) and aromatic
80 aldehydes (92) in the presence of water to afford aldol products
(93) (Scheme 32). The catalyst retains its activity and selectivity
over at least five reaction cycles.
25

85

30

90

Scheme 30 Michael addition of ketones to nitroolefins.

35

2.8 Aldol Reaction

95 Scheme 32 The catalytic asymmetric aldol reaction in the
Asymmetric aldol condensation of unmodified aldehydes with presence of water catalyzed by amphiphilic organocatalyst.
ketones is used for the preparation of β-hydroxy carbonyl
40 compounds, valuable synthons in organic synthesis. Asymmetric The same research group100 further studied chiral ionic liquids
aldol reactions in the presence of water, is the most cost-effective bearing a prolinamide motif as organocatalysts in asymmetric
and environment-friendly reaction medium. 100 aldol reactions in water (Scheme 33).
Kucherenko et al.98 reported the asymmetric aldol
condensation of selected aldehydes (86) with ketones (87)
45 catalyzed by 1(R),2(R)-bis((S)-prolinamido)cyclohexane (89) or
(Rax)-2,2´-bis((S)-prolinamido)-1,1´-binaphtyl (90) in an IL-
water system (1:1, v/v) proceeds with high reaction rate and 105

diastereoselectivity (Scheme 31). The dependence of ее of the

dominating anti-diastereomer of aldol on the percentage of water
50 has a maximum at 50 vol%. Addition of water allows decreasing
the consumption of expensive IL twofold and in some cases
110
increasing the reaction rate.

55
Scheme 33 Aldol reactions between cycloalkanones and aromatic
115 aldehydes in the presence of prolinamide derivatives in water.

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Page 9 of 19 RSC Advances

In the presence of a hydrophobic organocatalyst, cyclic ketones technology (Scheme 36). Aldol reaction of benzaldehyde (104)
and methylketones (94) react with aromatic aldehydes (95) in the and acetone (105) in the amine-functionalized
aqueous medium affording respective aldols (96, 97) in high 60 tetraethylammonium ethylamino-propanesulfonic ionic liquid
yields and with excellent regio-, diastereo- and ([N2222][EtNHC3SO3]) offered the desired 4-phenylbut-3-en-2-
5 enantioselectivities. The reactions were run in excess water (100 one (106) in yield of 28% (Scheme 36). In contrast, when 50 wt
equivalents relative to aldehyde) at 3-25 0C. % of H2O was added to the reaction system, aldol product was
In 2008 Lombardo et al.101 reported imidazolium- obtained in a conversion of more than 99% with high selectivity.
tagged trans-4-hydroxy-L-proline, as an efficient catalyst for the 65 Hence, all aldol condensation reactions in this work were carried
asymmetric cross-aldol reaction in water. Reaction of out in a solution of 50 wt % IL and 50 wt % water. In addition,
10 cyclohexanones (98) and aromatic aldehydes (99) catalyzed by this catalytic system can be successfully extended to the Henry
imidazolium-tagged trans-4-hydroxy-L-proline under aqueous reactions.
biphasic conditions afford the aldols (100) with anti/syn ratios up

RSC Advances Accepted Manuscript

to 98:2 and ee (anti) up to 99% (Scheme 34). 70

15

75

20

Scheme 36 Aldol reaction of benzaldehyde and acetone.

80 2.9 Biocatalysis

25 Scheme 34 Asymmetric cross-aldol reactions under aqueous Enzymatic reactions in ILs comprise another important category
biphasic conditions. of environmentally benign processes.104-107 Recently, the use of
ionic liquids as reaction media has been extended to biocatalytic
Han and co-workers102 employed a new functional IL (2- 85 processes.
hydroxyethyl)-trimethyl-ammonium (S)-2-pyrrolidinecarboxylic Lye and coworkers108 examined the use of a biphasic
30 acid salt ([Choline][Pro]) to catalyze direct aldol reactions [bmim][PF6]/H2O medium for the conversion of 1,3-
between a variety of ketones (101) and aromatic aldehydes (102) dicyanobenzene to 3-cyanobenzamide and 3-cyanobenzoic acid
efficiently in water to afford aldols (103) (Scheme 35). catalyzed by a nitrile hydratase contained in a whole cells of
90 Rhodococcus R312. Stephens and co-workers109 conducted the
N hydrogenation of caffeate with the whole cells of Sporomusa
HO
35 N COO OH O
termitida in a biphasic system 0.2:1 [bmim][PF6]/H2O. The yields
O H were very low, suggesting that [bmim][PF6] became toxic for the
R3CHO [choline][Pro] R3
cells. The feasibility of using isolated enzymes in ionic liquid
H2O R1 R2
R1 R2 95 media has also been demonstrated. Thus, Erbeldinger et al.110
101 102 103 reported the thermolysin-catalysed synthesis of Z-aspartame
40
R1 = H, CH3, etc. (Up to >97.9% yield) (109) from L-phenylalanine methyl ester hydrochloride (107) and
R2 = H, CH3, etc. carbobenzoxy-L-aspartate (108) in [bmim][PF6]/H2O (95/5, v/v)
R3 = Ph, p-nitrophenyl, etc. as shown in Scheme 37. To fully dissolve the reactants, it was
100 essential to add the water to a suspension of ionic liquid.
Scheme 35 Direct aldol reactions of aromatic aldehydes and
ketones catalyzed by [Choline][Pro] in water. O
45 O O NHZ
NH OH
OMe HO OH [bmim][PF6] + H2O
NH2 + O NHZ O
The reaction mixtures separate into an aqueous phase and an thermolysin O OMe
L-Phe Z-L-Asp 37 0C, 50h
organic phase after reaction. After simple separation and
105 107 108 109
extraction, the IL-containing aqueous phase can be reused (95% yield)

50 without any obvious decrease in activity. Therefore, using water Scheme 37 Thermolysin-catalyzed reaction of carbobenzoxy-L-
as the solvent made the separation easier. The aldol reactions aspartate and L-phenylalanine methyl ester hydrochloride in
catalyzed by this IL can be finished in a very short time with [bmim][PF6]/H2O.
good yields and there was no dehydrated product produced in 110
most cases. Bjlirkling et al.111 developed the epoxidation of cyclohexene
55 Recently, a green and efficient functionalized IL catalytic (110) by peroctanoic acid, generated in situ by Novozym 435-
system was developed by Gao et al.103 to facilitate the aldol catalyzed reaction of octanoic acid with commercially available
condensation reactions through the use of microwave heating 60% aqueous hydrogen peroxide in [bmim][BF4], afforded

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 RSC Advances Page 10 of 19

cyclohexene oxide (111) in 83% yield in 24 h (Scheme 38). For 2.11 Halohydroxylation
comparison, a yield of 93% was observed in 24 h in acetonitrile.
60 In 2005, Yadav and co-workers reported114 the use of IL/water
system for bromo- and iodohydroxylation of olefins (117) with
5 N-bromo- and N-iodosuccinimides, to produce the corresponding
halohydrins (118) respectively in high to quantitative yields
(Scheme 41). N-Halosuccinimides showed enhanced reactivity in
65 ionic liquids thereby reducing the reaction times and improving
the yields considerably. The ionic liquid plays a dual role as
10 Scheme 38 Epoxidation of cyclohexene. solvent and activator of the N-halosuccinimides.

Brautigam and co-workers112 demonstrated the ionic liquids

RSC Advances Accepted Manuscript

such as [bmim][PF6] and 1-butyl-3-methylimidazolium 70
bis(trifluoromethylsulfonyl)imide ([bmim][NTf]) are good
15 alternatives to organic solvents in biphasic biotransformation
(Scheme 39). Asymmetric reductions of several prochiral ketones
(112) were performed with the use of a recombinant Escherichia
coli as biocatalyst in biphasic IL/water system to offered chiral 75

alcohols (113).
20 Scheme 41 Synthesis of bromohydrins from olefins using
O E.Coli (LB-ADH MV -FDH) OH [bmim][BF4]/water.
R1 R2 [bmim]PF6/H2O R1 R2
80 2.12 Dihydroxylation
112 113
Afonso and co-workers reported the use of room-temperature
R1 = Ph, 4-ClC6H4, etc. (Up to >99.5% ee)
25 ionic liquids (RTILs) in the Sharpless catalytic asymmetric
R2 = CH3, etc.
dihydroxylation (AD) as a cosolvent (Scheme 42).115 The
85 asymmetric dihydroxylation of styrene (119) using cooxidant
Scheme 39 Asymmetric whole cell biotransformations in NMO and ligand (DHQD)2PHAL with catalyst K2OsO2(OH)4
biphasic IL/water system. under IL/water biphasic conditions afford the dihydroxy
30
derivative (120). The AD reaction was faster in 1-n-butyl-3-
2.10 Halogenation methylimidazolium hexafluorophosphate ([C4mim][PF6]) as a
90 cosolvent with higher yields and enantiomeric excess (ee)
Primerano and co-workers113 developed a novel one-pot method
compared to the conventional solvent system. Due to high affinity
for chemo- and diastereo-selective dibromination of electron-rich
of the catalytic osmium/quiral ligand system to the ionic liquid,
35 and electron-poor alkenes (114) with bromine (115) in water in
the use of IL/water (biphasic) solvent systems provides a
the presence of amino-functionalized basic ionic liquids (BILs) to
recoverable, reusable, robust, efficient, and simple system for the
afford dibromo derivatives (116) (Scheme 40). Addition of water
95 AD reaction.
(ratio BIL/water = 1:3) improved the reaction yield, likely
making more homogeneous and less dense the reaction mixture.
40 It was noteworthy that the water does not interfere on the final
product, rather it accelerates the progress of the reaction.
R2 BIL/H2O Br 100
Br2 Br
R1
114 115 116
45
R1 = Ph, n-hexyl, etc. (Up to 98% yield)
R2 = Ph, COOEt, etc.
105

Scheme 42 Asymmetric dihydroxylation of olefins RTIL/H2O.

R N N N
50
X 2.13 Resolution
R= Me, n-Bu
X= PF6, BF4, ClO4 110 Zhao et al.116 devloped the enzymatic resolution of amino acid
BILs ester (121) to obtain enantiomeric amino acid homophenylalanine
(122, 123) (Scheme 43). The use of mixed solvents such as
55
IL/water led to lower enantioselectivity than water alone. It was
Scheme 40 Bromination of alkenes in aqueous media and basic
assumed that high concentration of ionic liquid in water denatures
ionic liquids.
115 the enzyme and thus decreases the enantioselectivity.

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Page 11 of 19 RSC Advances

allylation reaction are avoided. The small amount of water

NHAc BL alcalase, rt, 24h NHAc NHAc 60 seemed to cause the hydrolysis of the Sn(IV)–Cl bonds to activate
H H H
Ph COOEt NaHCO3, water/IL Ph COOEt Ph COOEt the allylic tin intermediate. The authors observed that ketones,
121 which are less reactive than aldehydes, can also be allylated in
(1) Ethylacetate
(1) HCl
5 extraction
(2) reflux
high yields with this system. Furthermore, when H2O was
(2) NaOH
(3) HCl employed as solvent instead of ionic liquid, no allylation for
65 ketones occurred.
NH2 NH2
H H
Ph COOH Ph COOH
D L 2.16 1,2,3 Triazole synthesis
10
122 123
Liang et al.119 disclosed the IL/H2O was a good reaction medium
Scheme 43 Enzymatic resolution of amino acid ester in mixture 70 for the one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles using

RSC Advances Accepted Manuscript

of IL/water. either halides at sp3-hybridized carbon atoms or halides at sp2-
hybridized carbon atoms in good yields (Scheme 46). Reaction of
15 2.14 Epoxidation various halides (129), sodium azide with terminal alkynes (130)
in [bmim][BF4]/H2O afforded corresponding triazoles (131) in
In 2003, Yang et al.117 conducted the epoxidation reactions of α,
75 good to excellent yields. Better performance was obtained than
β-unsaturated carbonyl compounds (124) in [C4mim][PF6]/H2O
that of conventional reaction condition. Authors observed that,
biphasic system using hydrogen peroxide as an oxidant at room
using [bmim][BF4]/H2O (1:1) instead of [bmim]BF4, the product
20 temperature (Scheme 44). Under optimized reaction conditions,
was obtained in excellent yield due to good water solubility of
unsaturated carbonyl compounds such as mesityl oxide,
sodium azide.
benzylideneacetone and chalcone have been almost completely
80
converted to the corresponding epoxyketones (125). Compared
with traditional organic solvent/H2O phase transfer catalyst
25 (PTC) systems, [C4mim][PF6]/H2O biphasic catalytic system has
exhibited excellent selectivity to epoxyketones.
85

Scheme 46 Synthesis of 1,4-disubstituted 1,2,3-triazoles in

IL/water system.
30

2.17 Prins reaction

90

Li and co-workers120 reported a facile and direct formation of

tetrahydropyranols (134) by the reaction of an aldehyde (132) and
35
homoallyl alcohol (133) in the presence of a catalytic amount of
cerium triflate, in IL/water media (Scheme 47).
Scheme 44 Epoxidation of α, β- unsaturated carbonyl compounds
95
in IL/water biphasic system.

40 2.15 Allylation

Li and co-workers118 disclosed an efficient SnCl2-mediated

carbonyl allylation of allyl bromide (127) to aldehydes and 100
ketones (126) in IL/water mixture (Scheme 45).
45 Scheme 47 Direct formation of tetrahydropyranols in IL//water.

2.18 Pinacol coupling

105

Manchanayakage et al.121 investigated the electrochemical

50 pinacol coupling reactions of aromatic carbonyl compounds (135)
using an 80% [bmim][BF4]-H2O mixture as the electrolytic
medium (Scheme 48). The corresponding diols (136, 137) were
110 obtained in good to excellent yields with moderate
Scheme 45 Carbonyl allylation of aldehydes and ketones diastereoselectivity. The authors observed that the combination of
55 IL/water mixture. the ionic liquid ([bmim][BF4]) with the co-solvent water, resulted
in the best yields. The conductivity and viscosity of RTILs can be
By applying ionic liquid, some previously reported serious
changed by adding a co-solvent H2O. The viscosity for the 80%
operational problems associated with the SnCl2-mediated
115 [bmim][BF4]-H2O mixture which gave the best yields was

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 RSC Advances Page 12 of 19

determined to be substantially lower than that of the pure ionic The products could simply be separated from the catalyst/water,
liquid. The conductivity for the 80% [bmim]BF4-H2O mixture and the catalyst could be reused at least 7 times without
was measured to be about ten times higher than the conductivity noticeably decreasing the catalytic activity.
of pure ionic liquid. 60

5 2.21 Three component coupling reactions

The IL-three component coupling reactions are extremely useful

for the rapid entry to highly functionalized heterocyclic
65 molecules of potentials use in medicianl chemistry. Thus, Su et
al.124 reported the three-component reactions of 4-
10
hydroxycoumarin (144), aldehydes (145) and cyclic 1,3-
dicarbonyl compounds (146) prompted by novel sulfonic acid

RSC Advances Accepted Manuscript

Scheme 48 Electrochemical Pinacol coupling of aromatic functionalized ionic liquids 1,3-dimethyl-2-oxo-1,3-bis(4-
carbonyl compounds in a [bmim][BF4]/H2O mixture.
70 sulfobutyl)imidazolidine-1,3-diium hydrogen sulfate
([DMDBSI].2HSO4) in water at reflux temperature to provide a
15 2.19 Beackmann rearrangement
novel series of 10,11-dihydrochromeno[4,3-b]chromene-6,8(7H,
9H)-dione derivatives (147) in high yields (Scheme 51).
Sun et al.122 performed the Beckmann rearrangement of
ketoximes (138) to the corresponding amine or cyanide (139) in a
75
novel task-specific ionic liquid consisting sulfonyl chloride
20 (TISC) (Scheme 49). Especially for the conversion of
cyclohexanone oxime to ε-caprolactam, ε-caprolactam has good
solubility in water while the task-specific ionic liquid was
immiscible with water, therefore, ε-caprolactam could be easily
80
separated from the reaction system by water extraction.
25
TISC: H2O
O2N O 2N N
N OH
138 139 85
(72% yield)
30
Scheme 51 [DMDBSI].2HSO4 promoted synthesis of 10,11-
N N
SO2Cl . PF dihydrochromeno[4,3-b]chromene-6,8(7H,9H)-dione derivatives
6
in H2O.
TISC 90

Liu and co-workers125 synthesized the halogen-free acyclic

35 Scheme 49 Beckmann rearrangement of oxime in TISC: H2O task-specific ionic liquids (TSILs) such as N,N,N-triethyl-N-
butanesulfonic acid ammonium hydrogen sulfate
2.20 Mannich reaction ([TEBSA][HSO4]), N,N,N-tributyl-N-propanesulfonic acid
95 ammonium hydrogen sulfate ([TBPSA][HSO4]) and used an
Zu-liang and co-workers123 developed an acyclic Bronsted
efficient catalysts for synthesis of 5-oxo-5,6,7,8-tetrahydro-4H-
40 acidic task-specific ionic liquid N, N, N-trimethyl-N-
benzo[b]pyrans (152) by one-pot three-
butanesulfonic acid ammonium hydrogen sulphate
component condensation of aromatic aldehyde (149),
([TMBSA][HSO4]) was an efficient catalyst for one-pot three-
malononitrile (or ethyl cyanoacetate) (150),
component Mannich reaction of aromatic aldehydes (140),
100 and dimedone (or 1,3-cyclohexanedione) (151) in water (Scheme
aromatic amines (141) and ketones (142) at room temperature in
52). After the reaction, the products could simply be separated
45 water to afford β-amino carbonyl compounds (143) in good
from the catalyst/water and the catalyst could be reused at least
yields (Scheme 50).
10 times without noticeably decreasing the catalytic activity.

105

50

110

55 Scheme 50 Mannich reaction catalyzed by [TMBSA][HSO4] in

Scheme 52 Synthesis of 5-oxo-5,6,7,8-tetrahydro-4H-
water.
benzo[b]pyrans catalyzed by acidic ionic liquids.

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Page 13 of 19 RSC Advances

Guo et al.126 described the ionic liquid 2- Heydari et al.130 developed a sulfonic acid functionalized
(hydroxyl)ethylammonium acetate (HEAA) catalyzed a three- ionic liquid (TSIL) catalyzed one-pot, three-component synthesis
component, one-pot condensation of quinone or ninhydrin (153), 60 of α-aminophosphonates (168) from aldehydes or ketones (165),
malononitrile/ethyl cyanoacetate (154) and 1,3-dicarbonyl amines (166) and trimethyl phosphate (167) at room temperature
5 compound/enol (155) in water to afford a spiropyran derivative in water (Scheme 56). This homogeneous catalytic procedure is
(156). This method has advantages of mild reaction conditions, simple and efficient and the catalyst can be reused at least six
short reaction time and environmental friendliness (Scheme 53). times without any noticeable decrease in catalytic activity. The
65 authors found that the reaction in the absence of water did not
take place, but in the presence of water the product formed
10 rapidly.

RSC Advances Accepted Manuscript

70

15 Scheme 53 Ionic liquid catalyzed three-component synthesis of

spiropyran derivatives reaction in water.

Su and co-workers127 synthesized a series of 2,3- 75

dihydroquinazolin-4(1H)-ones (160) in high to excellent yields

20 through one-pot three-component cyclocondensation of isatoic
anhydrides (157), ammonium acetate (158) and aldehydes (159) Scheme 56 Three-component reaction catalyzed by a TSIL in
in IL/water solvent system without the use of any additional water.
catalyst (Scheme 54). The volume ratio of IL/ water was 80

examined and the best results were obtained by carrying out the 2.22 Other organic reactions
25 reaction in [bmim][BF4]-H2O with a ratio of 3:2 (v/v). The
desired product was obtained in good yield in IL/water solvent In 2012, Chen and co-workers131 developed the first example of
system instead of ionic liquid. The water presumably plays an Sc(OTf)3-catalyzed sulfenylation of sodium sulfinates (170) with
important role in the process due to the good water solubility of 85 N-(organothio)succinimides (169) in IL/water solvent system to
ammonium acetate. achieve the thiosulfonates (171) in moderate to excellent yields
30
(Scheme 57). They recovered Sc(OTf)3/IL easily after the
reactions and reused without a significant loss in the catalytic
activity. The water plays an important role in the reaction due to
90 the good water solubility of sodium sulfinates.

35

Scheme 54 One-pot synthesis of 2,3-dihydroquinazolin-4(1H)-

ones in [Bmim][BF4]-H2O. 95

40 Yavari and co-workers128-129 demonstrated a basic

functionalized ionic liquid, 1-butyl-3-methylimidazolium
hydroxide ([bmim][OH]), catalyzed the three-component
condensation reaction of acid chlorides (161), amino acids (162), 100 Scheme 57 Sc(OTf)3-catalyzed synthesis of thiosulfonates in
and dialkyl acetylenedicarboxylates (163) in water to afford IL/water.
45 functionalized pyrroles (164) in high yields (Scheme 55). The
[bmim][OH]-H2O system was found to be a much better catalytic Siddiqui et al.132 achieved an expeditious, facile, ionic liquid
medium for this reaction and the catalyst can be recycled for catalyzed, water accelerated synthesis of substituted
subsequent reactions without appreciable loss of efficiency. 105 benzothiazole-2(3H)-one derivatives (174) from readily available
2-iodoanilines (172) and potassium thiocayanate (173) under
50
basic conditions (Scheme 58). The strategy involves nucleophilic
substitution forming N-C and S-C bond resulting the desired
heterocyclic scaffold. The reactions proceeded smoothly at an
110 ambient condition with high yield, using water a green reaction
medium and basic 1-butyl-3-methylimidazolium bromide
55 ([bmim][Br]) as recyclable catalyst system.
Scheme 55 One-pot synthesis of pyrroles in aqueous media
catalyzed by task-specific basic ionic liquid.

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 RSC Advances Page 14 of 19

BAILs O
60 R1 R2 + H2O R2
333K, 10h R1
183 184
5
R1 = Ph, Propyl, etc. (Up to 100% yield)
R2 = H, Ph, Propyl, etc.
Scheme 58 Synthesis of benzothiazole-2(3H)-one in water and 65

ionic liquid synergy. Scheme 61 Hydration reaction of alkynes using BAILs.

10 Srinivasan and co-workers133 established a highly efficient Recently, Pan et al.136 employed an efficient copper catalyzed
synthesis of 4-aryl-2-amino-1,3-selenazole (177) by the tandem reaction for the synthesis of benzanilide (187) in water.
condensation of various phenacyl bromide (175) with selenourea 70 Ionic liquid was used as a phase transfer catalyst and this method

RSC Advances Accepted Manuscript

(176) in 1-n-butylimidazolium tetrafluoroborate could be applied in the N-arylation between benzonitriles (186)
([Hbim][BF4])/H2O solvent system (Scheme 59). The role of IL and aryl halides (185) (or alkenyl bromides) (Scheme 62).
15 may be postulated in terms of Lewis/Brønsted acidity, thereby Advantages of this reaction include the use of water as the
promoting the reaction. The addition of water to IL may environmental friendly solvent, short reaction time and the
presumably play an important role in the process due to the good 75 tolerance of various functional groups.
water solubility of the selenoureas.
H
CN [Cu], Ligand, IL, H2O N O
20
X
R1 R2 R1
+ M2CO3, NaOH, N2, 100 C 0
R2
80
185 186 187
(Up to 94% yield)
R1 = Me, OMe, Br, etc.
25 R2 = Ph, Napthyl, etc.
X = Br, Cl

Scheme 59 Synthesis of 2-amino-1,3-selenazoles in IL/water 85 Scheme 62 N-Arylation between aryl halides and nitriles in IL/
system. water.

30 Parac-Vogt and co-workers134 reported the reaction of ceric In 2005, Yadav et al.137 proved an IL/water solvent system
ammonium nitrate ((NH4)2[Ce(NO3)6 or CAN), with naphthalene was an effective reaction medium for the synthesis of 2-
(178) in the ionic liquid 1-ethyl-3-methylimidazolium triflate 90 azidoalcohols (189, 190) from epoxides (188) by playing the dual
([C2mim][OTf]). The reaction products 1-nitronaphthalene (179), role of solvent as well as promoter. The epoxides showed a
2-nitronaphthalene (180), 1,4-naphthoquinone (181) and phthalic significant increase in reactivity thereby reducing the reaction
35 acid (182) are strongly dependent on the water content of the times and improving the yields substantially (Scheme 63). The
ionic liquid and that cerium(IV) in the ionic liquid can combination of IL/water as solvent system (2:1) was found to be
electrochemically be regenerated (Scheme 60). 95 an effective reaction media for this conversion.

[bmim][PF6]/H2O
or
40 O [bmim][BF4]/H2O OH N3
NaN3 N3 OH
R 65 0C R R
100

188 189 190

R = Ph, Benzyl, etc. (Up to 95% yield)
45

Scheme 63 Synthesis of 2-azidoalcohols in 1-butyl-3-

105 methylimidazolium IL/water.
Scheme 60 Reaction of CAN with naphthalene in [C2mim][OTf]
and water. Recently same group138 examined the use of [bmim][PF6]-
50 H2O or [bmim][BF4]-H2O (2:1) solvent system as an alternative
Srivastava and co-workers135 disclosed an efficient, non-toxic, reaction medium for the synthesis of episulfides (193) from
noble metal free, and Bronsted acidic ionic liquid (BAIL) based 110 epoxides (191) with potassium thiocyanate (192) (Scheme 64).
economical route for the hydration reaction of alkynes (183) to The ionic liquid plays a dual role of solvent as well as catalyst.
afford ketones (184). N-SO3H functionalized BAIL The use of ionic liquids for this transformation avoids the use of
55 ([SO3Hmim][Cl]) was found to be more active than the N-R- heavy metal halides as promoters and chlorinated hydrocarbons
SO3H (R=alkyl/benzyl) functionalized BAILs. These reactions as solvents. The ionic liquid was recycled in five to six
are easy to perform and the purification protocol was simple 115 subsequent runs with gradual decrease in activity.
(Scheme 61).

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Page 15 of 19 RSC Advances

1,2-diketones (205) to synthesis 1,2-disubstituted benzimidazoles

60 (203) and quinoxalines (206) in water, respectively (Scheme 67).

65

Scheme 64 Conversion of oxiranes to thiiranes in 1-butyl-3-

10 methylimidazolium IL/water.

Zhang and co-workers139 developed the palladium acetate- 70

RSC Advances Accepted Manuscript

catalyzed coupling reaction of carboxylic anhydride (194) or acyl
chloride (195) with aryl boronic acid (196) in water in the
15 presence of [bmim][PF6] to gave high yields of ketones (197)
without the use of phosphine ligands. The Pd(OAc)2-H2O- Scheme 67 Synthesis of benzimidazoles and quinoxalines using
[bmim][PF6] catalytic system can be recovered and reused eight 75 IL/water.
times with high efficiency for both carboxylic anhydride and acyl
chloride (Scheme 65). The ratio of water and [bmim]PF6 acted on In 1998, Dupont et al.142 investigated the hydrodimerization
20 the reactivity and best yield was obtained when the ratio of of 1,3-butadiene (207) catalyzed by bis(1-butyl-3-
[bmim][PF6] and water achieved 3:2.5. methylimidazolium) tetrachloropalladate ([BMI]2PdCl4) in 1-n-
80 butyl-3-methylimidazolium tetrafluoroborate (BMI.BF4) and
water (1:1). In addition to the dimer, 1,3,6-octatriene (208), 2,7-
octadienol (209) was also produced (Scheme 68). The products
25 selectivity and catalytic activity depend on the reaction
conditions. 1,3-Butadiene conversion up to 28%, a turnover
85 frequency (TOF) of 118 h-1, and a selectivity of 94% on telomer
were achieved with (BMI)2PdCl4 dissolved in BMI.BF4. The 1,3-
butadiene conversion and TOF were significantly increased to
30 49% and 204 h-1, respectively, by a 5-atm pressure of carbon
dioxide. The recovered ionic catalyst solution can be reused
Scheme 65 Cross-coupling of carboxylic anhydrides with aryl 90 several times without any significant changes in the catalytic
boronic acids. performance.

35 Dabiri et al.140 employed a new procedure for the rapid and

selective synthesis of 2-aryl-1-arylmethyl-1H-1,3-benzimidazoles
(200) from ortho phenylenediamines (198) and aldehydes (199) 95

in the presence of 1-methylimidazoluim triflouroacetate

([HMIM][TFA]) as a Bronsted acidic ionic liquid (BAIL) at room Scheme 68 Hydrodimerization of 1,3-butadiene catalyzed by
40 temperature (Scheme 66). The authors observed that in the (BMI)2PdCl4 in BMI.BF4 and water.
presence of water an inconceivable decrease in the reaction time
was observed. 100 Chattopadhyay and co-workers143 developed novel
application of ionic liquid for selective debromination of gem-α-
H2N R1 R1 N dibromoketones (210) to monobromo (211) and debromoketones
[HMIM][TFA]
2 R2-CHO R2
45 N (212) by proper control of reaction time (Scheme 69). The use of
H2N R1 water, rt R1
R2 1-methyl-3-pentylimidazolium tetrafluoroborate ([pmim][BF4])
198 199 200 105 in water was also found suitable for the dehalogenation of α-halo
R1 = H, Me, Cl (Up to 95% yield) ketones and esters and of vic-bromoacetals.
R2 = Ph, 2-Furyl, etc.
50

Scheme 66 Synthesis of 2-substituted benzimidazoles catalyzed

by ionic liquid in water. 110

Beheshtiha and co-workers141 reported the ionic liquid 1-(4-

55 sulfonic acid)butyl-3-methylimidazolium hydrogen sulphate
([(CH2)4SO3HMIM][HSO4]) catalyzed reaction of o- Scheme 69 Selective debromination of dibromo compounds
phenylenediamine (201) with different aromatic aldehydes (202) 115 catalyzed by [pmim][BF4] in water.
and also the reaction of 1,2-diaminoarene derivatives (204) with

This journal is © The Royal Society of Chemistry [year] Journal Name, [year], [vol], 00–00 | 15
 RSC Advances Page 16 of 19

Kamal et al.144 demonstrated the direct one-pot synthesis of β- excellent yields. After isolation of the product, the ionic liquid
hydroxysulfides (215) from alkenes (213) and thiophenols (214) [bmim][OH] could be easily recovered and reused without any
in the presence of aerial oxygen using a mixture of ionic liquid 60 loss of efficiency.
[bmim][BF4] and water under neutral conditions (Scheme 70).
5 The thiophenol attacks the alkene in an anti-Markonikov manner
resulting in the formation of β-hydroxysulfides in a mixture of IL/
water in presence of oxygen. This protocol tolerates a wide
variety of functional groups or substrates and does not require the 65

use of either acid or base catalysts. Ionic liquid can be recovered

10 and reused for a number of runs with negligible loss of its
activity. Scheme 72 Ionic liquid promoted one-pot synthesis of α-
mercapto-γ-lactones in water.

RSC Advances Accepted Manuscript

70

Salunkhe et al.147 prepared 1,8-dioxo-octahydroxanthenes (223)

efficiently from 1,3-cyclohexanediones (221) and aldehydes
15
(222) by a recyclable carboxyl-functionalized 1-carboxymethyl 3-
methylimidazolium tetrafluoroborate ([cmmim][BF4]) task
75 specific ionic liquid [TSIL] in aqueous media in high yield. The
ionic liquid can be recycled at least 6 times without significant
20
loss of activity (Scheme 73). The best results were obtained in
Scheme 70 One-pot synthesis of β-hydroxysulfides from terminal presence of 20 mol% TSIL and water as solvent.
olefins in a mixture of [bmim][BF4] and water.
80

Rahatgaonkar et al.145 accomplished the convenient synthesis

25 of a library of pyrimidine-isoxazoline hybrids (217) in
[bmim][PF6]-water/potassium hydroxide at ambient temperature
(Scheme 71). The IL/water biphasic system proved to be effective
at enhancing the efficiency of the reaction. The ionic liquid 85

[bmim][PF6], immiscible in water, can be easily recycled for

30 reuse after separation of the products without any noticeable
diminution in its activity. The ionic liquid [bmim][PF6] stabilized
the hydrophobic reactant, and water stabilized hydroxylamine Scheme 73 Ionic liquid promoted synthesis of privileged 1,8 -
hydrochloride. The reaction presumably occurs at the junction of 90 dioxo-octahydroxanthene in water.
the two immiscible phases.
Kowsari and co-workers148 reported the basic ionic liquid
35
(BIL) catalyzed condensation reaction of isatin (224) with
ketones (225) by ultrasonic irradiation in aqueous media for
95 quinoline (226) synthesis (Scheme 74). The reaction was
favoured in IL/water medium compared other solvent mixtures.
When two different α-protons are available in a ketone, a mixture
40
of two quinolines was obtained.

100

45

Scheme 71 convenient synthesis of a library of pyrimidine-

105
isoxazoline hybrids in [bmim][PF6]-water biphasic system.

50 Yadav and his group146 reported the task-specific ionic liquid 1-

butyl-3-methyl imidazolium hydroxide ([bmim][OH]) promoted
one-pot synthesis of α-mercapto-γ-lactones (Scheme 72). The Scheme 74 Ultrasound promoted synthesis of quinolines using
present protocol involves regioselective epoxide ring opening and 110 basic ionic liquids in aqueous media.
intramolecular translactonisation cascade. A variety of epoxides
Zhang et al.149 developed the homocoupling reaction of the
55 (218) undergo this ring-opening-ring-closing cascade with 2-
arylboronic acids (227) in a mixture of IL/water in the presence
methyl-2-phenyl-1,3-oxathiolan-5-one (219) to afford α-
of ethyl bromoacetate ester using Pd(OAc)2 as catalyst to afford
mercapto-γ-lactones (220) diastereoselectively in good to
115 biaryls (228) in high yield (Scheme 75). The separation of desired

16 | Journal Name, [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
Page 17 of 19 RSC Advances

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