A mild and efficient procedure for alkenols oxyselenocyclization by using ionic liquids

Article abstract of DOI:10.1002/poc.3928

A mild and efficient procedure for the oxyselenocyclization of unsaturated alcohols by treatment with phenylselenyl chloride using ionic liquids as solvents/catalyzers has been developed. The reaction proceeds instantaneously under mild conditions with ab

Full text of DOI:10.1002/poc.3928

Received: 30 July 2018
DOI: 10.1002/poc.3928
Revised: 31 October 2018
Accepted: 20 November 2018
R E S E A R C H A R T I C L E
A mild and efficient procedure for alkenols
oxyselenocyclization by using ionic liquids
Marina Kostić1
| Pedro Verdía2
| Verónica Fernández‐Stefanuto2
| Ralph Puchta3,4,5
|
Emilia Tojo2
1 Faculty of Science, Department of
Chemistry, University of Kragujevac,
Kragujevac, Serbia
2 Department of Organic Chemistry,
Universidade de Vigo, Marcosende, Vigo,
Spain
3 Inorganic Chemistry, Department of
Chemistry and Pharmacy, University of
Erlangen‐Nürnberg, Erlangen, Germany
4 Computer Chemistry Center,
Department of Chemistry and Pharmacy,
University of Erlangen‐Nuremberg,
Erlangen, Germany
Abstract
A mild and efficient procedure for the oxyselenocyclization of unsaturated
alcohols by treatment with phenylselenyl chloride using ionic liquids as
solvents/catalyzers has been developed. The reaction proceeds instanta-
neously under mild conditions with absolute regioselectivity, using primary,
secondary, tertiary, and aromatic alcohols, as well as monosubstituted, disub-
stituted, and trisubstituted alkenols. This procedure provides a new method
for the synthesis of substituted tetrahydrofurans and tetrahydropyrans ethers,
the precursors of many biologically active metabolites, avoiding the use of
toxic and corrosive catalysts. There are no previous reports of selenium‐
mediated cyclofuncionalization reactions in ionic liquids. Taking into the
account the good results obtained with [MMIM][MSO4], its ease preparation,
low viscosity, low price, and its capacity to be recovered and reused, it was
selected as the solvent/catalyzer. Quantum‐chemical calculations (MP2(fc)/
6‐311 + G**//B3LYP/6‐311 + G**) has shown that the intramolecular cycli-
zation is promoted by the hydrogen bond formed between the ionic liquid
anion and the hydroxyl group of the alkenol.
5 Central Instituite for Scientific
Computing (ZISC), Friedrich‐Alexander
University Erlangen‐Nürnberg
Martensstrasse 5a, Erlangen, Germany
Correspondence
Emilia Tojo, Department of Organic
Chemistry, Universidade de Vigo,
Marcosende, 36210 Vigo, Spain.
Email: etojo@uvigo.es
KEYWORDS
Funding information
catalysis, ionic liquids, oxyselenocyclization, quantum‐chemical calculations, sustainable chemistry
Consellería de Cultura, Educación e
Ordenación Universitaria, Xunta de
Galicia, Grant/Award Number: REGALIs
Network (ED431D 2017/06); University of
Vigo (CACTI); Ministry of Education and
Science of the Republic of Serbia, Grant/
Award Number: 172011
1 | INTRODUCTION
inflammatory, antitumor,[4] antimicrobial, or antiviral
agents.[1,5] During the last decades, organoselenium com-
Selenium is a fundamental element in life sciences; it
can be found in many active and natural compounds
such as carbohydrates, amino acids, and peptides.[1] Due
to their biological and pharmacological properties,
organoselenium compounds have emerged as important
therapeutic compounds, acting as antioxidant,[2,3] anti‐
pounds have also appeared as important reagents and
intermediates in organic synthesis.[6,7] They can partici-
pate in a wide number of reactions, usually under rela-
tively mild conditions[8] and presenting chemo‐, regio‐,
or stereo‐selectivity.[9] Thus, organoselenium compounds
have been widely employed as intermediates in the
J Phys Org Chem. 2019;e3928.
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https://doi.org/10.1002/poc.3928

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KOSTIĆ ET AL.
synthesis of complex molecules and in the development
of asymmetric synthesis.[8,10–15]
triphenyl phosphine,[34] palladium,[35] or the bimetallic
reagent Sn(II)/Cu(II).[14] The use of [bmim][BF4]
and [bmim][PF6] in the synthesis of diaryl selenides by
electrophilic substitution in arylboron reagents with
phenylselenyl halides has been also described.[36] In addi-
tion, a series of chiral seleno amino derivatives have been
synthesized employing CuO nanopowder in the IL [bmim]
[BF4].[8] Finally, 3‐arylselenylindoles have been prepared
in the selenium‐based IL [bmim][SeO2(OCH3)].[37] Those
reactions were usually performed with high yields
allowing the recovery and recycling of the IL. Neverthe-
less, to our knowledge, there are no previous reports of
selenium‐mediated cyclofuncionalization reactions in ILs.
As a continuation of our work on the application
of ILs as solvents and/or catalysts in organic synthe-
sis,[38–41] we report herein the use of different ILs as
solvents/catalyzers in the cycloetherification reaction of
unsaturated alcohols by means of phenylselenyl chloride.
To investigate the IL effect on the reaction mechanism,
quantum‐chemical methods (MP2(fc)/6‐311 + G**//
B3LYP/6‐311 + G**) have been applied.
Phenylselenyl halides (such as PhSeCl, PhSeBr, etc)
are some of the most studied organoselenium compounds
in organic synthesis; they have been widely employed as
electrophilic promoters in cyclofunctionalization reac-
tions. In particular, the synthesis of substituted tetrahy-
drofuran and tetrahydropyran cyclic ethers, which are
the key structural elements of many metabolites from
marine organisms, mycotoxins, and macrolides,[16–18]
can be approached by the cyclization of alkenes with
accessible hydroxyl groups induced by electrophilic sele-
nium species (reaction termed selenoetherification).[19]
The most commonly described selenocyclization reaction
involves the use of an excess of a phenylselenyl halide
(PhSeCl or PhSeBr) in CH2Cl2 as solvent, with tempera-
tures ranging from −78°C to room temperature.[20–23]
However, the use of phenylselenyl halides can give rise
to the undesired addition reaction on the double bond
of the unsaturated substrate, a process that gives smaller
yields of the cyclic products decreasing the reaction
chemoselectivity. Studies on these types of reactions have
shown that the presence of equimolar amounts of bases
(such as pyridine, triethylamine, or anhydrous potassium
carbonate) can catalyze the reaction, increasing the
rates and the yields to almost quantitative.[24] This is
especially evident for secondary and tertiary unsaturated
alcohols, where increased steric demands around the
carbinol atom induces the selenocyclization to proceed
in smaller extent.
Safety and environmental concerns demand new
sustainable synthetic methods that can operate under
mild reaction conditions while leading to high yields
and selectivity without undesired by‐products. Under
this context, ionic liquids (ILs) have been successfully
applied as alternative reaction media in a wide range
of chemical reactions, often showing better yields, reac-
tion rates, and selectivity than molecular solvents.[25,26]
Their unique properties such as negligible vapor
pressure, wide liquid range, chemical and thermal sta-
bility, recyclability, and high resistance to flammability
make them a safer and more environmentally friendly
reaction media compared with traditional molecular
solvents.
2 | EXPERIMENTAL
2.1 | Synthesis
All chemicals used in the synthesis were purchased
from Acros or Aldrich and used without any further
pre‐treatment or prepurification. Two unsaturated
alcohols (1‐phenyl‐4‐penten‐1‐ol and 1‐phenyl‐5‐hexen‐
1‐ol) were prepared by the procedures described in
literature.[42,43] All ILs used in these studies (1‐methyl‐
3‐methylimidazolium
methyl
sulfate
[MMIM]
[MSO4],[38,44] 1‐methyl‐3‐methylimidazolium bis(trifluo-
romethylsulfonyl) imide [MMIM][NTf2],[45] 1,2,3‐
trimethyl imidazolium methyl sulfate [MMMIM]
[MSO4],[46] 1,1,3,3‐tetramethylguanidinium trifluoro ace-
tate [TMG][TFA],[40] bis(trifluoromethylsulfonyl)imide
[Chol][NTf2],[47] N‐butylpyridinium bis(trifluorome-
thanesulfonyl)imide [BPy][NTf2],[48] and N‐butyl‐
pyridinium dicyanamide [BPy][DCA][49]) were prepared
by procedures previously described in literature.
Thus, sulfates were obtained by a direct quaternization
reaction with a diakyl sulfate, trifluoroacetate derivative
by treatment of the amine with and acid, and the rest
by treatment with and alkyl halide followed by a
methatesis reaction.
A series of reactions of organoselenium compounds
employing ILs have been tested. Potewar et al
described the condensation of selenourea with different
phenacyl bromides employing mixtures of different
alkylimidazolium ILs with water.[27] Different groups pre-
pared diorganyl selenides and selenolesters in a series of
dialkylimidazolium ILs employing different promoters
and catalysts as Zn dust,[28,29] ZnO nanopowder,[30]
CuO nanopowder,[9,13] NaBF4,[31] Indium[32] and InI,[33]
The detailed synthetic procedures as well as 1H
NMR, 13C NMR, and HRMS spectral data of the synthe-
sized compounds, are available in Supplementary Infor-
mation (SI).

KOSTIĆ ET AL.
3 of 8
with an appropriate solvent. The collected organic phases
were washed and dried, and after the removal of the sol-
vent, the residue was purified by column chromatography.
The results are shown in Table 1. As it can be seen, the best
reaction conditions were obtained when [MMIM][NTf2]
(time: less than 1 min, yield: 92%) and [MMIM][MSO4]
(time: 7 min, yield: 95%) were used as solvents/catalyzers.
In view of the successful results, a recycling study
with these two ILs was performed, observing that both
ILs can be reused up to five times without loss of activity.
A comparison between the results obtained in entries
4, 5, and 6, keeping the same anion combined with differ-
ent cations, indicated that in this process the main IL cat-
alytic effect resides in the anion. Modifying the cation of
an IL has shown to not affect the outcome of some other
reactions, as for example SN2.[54]
2.2 | Computational details
All structures were fully optimized at B3LYP/6‐311 + G**
and characterized as local minimum or transition state
structures by computation of vibrational frequencies (for
transition state structures, exactly one imaginary fre-
quency is present, NImag = 1).[50] Being well aware of
the limitations of Density Functional Theory (DFT)
calculations,[51] we evaluated the energies by MP2(fc)/
6‐311 + G** calculations (MP2(fc)/6‐311 + G**//B3LYP/
6‐311 + G** + ZPE(B3LYP/6‐311 + G**)).[52] Gaussian
16 suites of programs were used throughout.[53]
3 | RESULTS AND DISCUSSION
To investigate the scope of the reaction, it was
also carried out with other substrates, using primary,
secondary, tertiary, and aromatic alcohols, as well
as monosubstituted, disubstituted, and trisubstituted
alkenols (Table 2). Taking into the account the good
results obtained with [MMIM][MSO4] in the first reaction,
its ease of preparation, low viscosity, and price, it was
selected to be used as solvent. As it can be observed in
Table 2, low reaction times and high yields were obtained
for all substrates. In addition, a very high level of regiose-
lectivity was achieved, since none other products
were observed by TLC. The reaction products structures
A
series of ILs derived from different cations
(imidazolium, pyridinium, guanidinium, and cholinium)
and different anions (methylsulfate, bistriflamide,
dicyanoamide, and trifluoracetate) (Figure 1) were synthe-
sized according to procedures previously described as indi-
cated in the Section 2.
The study of phenylselenocyclofunctionalization in
ILs was initially tested with the reaction of the primary
alkenol pent‐4‐en‐1‐ol 1 with PhSeCl (1.1 equiv.) in the
presence of each of the previously synthesized ILs as
solvents/catalyzers room temperature. The reaction
mixture was stirred for a certain time as required to
complete the reaction (monitored by Thin Layer Chroma-
tography (TLC)), and the reaction product was extracted
1
were determined by H and 13C NMR spectroscopy and
TABLE 1 Optimization of the reaction conditions for the ionic
liquid‐mediated phenylselenocyclofunctionalization
Entry
Ionic liquid
Yield, %a
Time, min
1
2
3
4
5
6
7
[MMIM][MSO4]b
[MMMIM][MSO4]
[TMG][TFA]
95
7
10
55c
65
360
1
[Chol][NTf2]
Not isolatedd
[MMIM][NTf2]b
92
82
78
<1
<1
90
[BPy][NTf2]
[BPy][DCA]
aTLC and NMR evaluation showed complete transformation of starting
material, while presented yields correspond to the yields determined after
purification by column chromatography.
b[MMIM][MSO4] and [MMIM][NTf2] were reused up to five times without
significant loss of activity.
cThe lower yield was due to difficulties encountered to extract the product
from the IL.
dThe product extraction was not possible due to the high IL solubility in all
tested solvents.
FIGURE 1 Structure of ionic liquids (ILs) synthesized to be used
in this work

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KOSTIĆ ET AL.
TABLE 2 Phenylselenocyclofunctionalization reaction of different unsaturated alcohols in [MMIM][MSO4]
Substrate
Product
Yield, %a
Time, min
Ref.
95
7
Konstantinovic et al[22] and Bugarčić et al[55]
88
10
5
Konstantinovic et al[22] and Bugarčić et al[55]
86b
Konstantinovic et al[22]
Konstantinovic et al[22]
91 (52:48)c
81 (50:50)c
1
10
Tiecco et al[56]e
77 (45:55)c
20
‐
88
60
90
Konstantinovic et al[22]
Nicolaou[20]
76d
79
30
Nicolaou[21]
71d
120
Wodrich et al[57]
aYields determined after purification by column chromatography.
bErythro‐2‐(1‐phenylselenoethyl)tetrahydrofuran.
cRatio of cis/trans isomers determined by NMR from crude reaction mixture.
dThe reaction was performed in the presence of 1 equivalent of pyridine.
eOur compound was obtained as mixture of cis‐ and trans‐ while in the referenced article the 4 enantiomers are described separately.
confirmed by comparison with the data previously report
in literature, except in the case of 6a whose data were
not found in the bibliography. Its structure was confirmed
A comparative study of the results obtained in this
work with those previously described using a different
reaction medium showed that the effect of the IL is very
similar to that observed when the reaction is carried out
in CH2Cl2 and an equimolecular amount of pyridine.[24]
Thus, primary (1, 3), secondary (5), and aromatic (8)
Δ4‐alkenols gave five‐membered cyclic ethers (1a, 3a,
5a, and 8a), except when the terminal double bond is E
disubstituted (4) or trisubstituted (7), that favor the
tetrahydropyran derivative (4a and 7a). The cyclic tertiary
Δ4‐alkenol with a trisubstituted double bond 10 also gave
the six‐membered cyclic ether (10a). Quantum‐chemical
calculations on the phenylselenoetherification of (Z) and
(E)‐hex‐4‐en‐1‐ols (3 and 4)[55] have shown that the cycli-
zation of (Z)‐hex‐4‐en‐1‐ol (3) is kinetically controlled by
the activation energy to afford the five‐membered cyclic
ether (3a), while the cyclization of the (E)‐alkenol (4) is
thermodynamically controlled to yield the more stable
1
by H and 13C NMR spectroscopy as well as high resolu-
tion mass spectrometry.
The accepted mechanism for the organoselenium‐
mediated cyclization reactions between unsaturated
alcohols and electrophilic selenium reagents as PhSeCl
involves the initial formation of a cyclic seleniranium
ion intermediate by the electrophilic attack on the double
bond. The later intramolecular nucleophilic attack of the
hydroxyl group at one of the carbons of the seleniranium
ring gives the cyclic ether product. As result of the
seleniranium intermediate formation, the reaction is
antistereospecific.[58] Depending on the chain length
and the substitution pattern of the alkenol, the reaction
can follow an exo‐ and/or endo‐pathway to give a five
or a six membered cyclic ether (Scheme 1).

KOSTIĆ ET AL.
5 of 8
SCHEME 1 General accepted
mechanism of the
phenylselenocyclofunctionalization
reaction between unsaturated alcohols
and PhSeX
six‐membered tetrahydropyran cyclic ether (4a). As
expected, the γ,δ‐unsaturated carboxylic acid 9 yields
the corresponding seleno‐substituted lactone 9a, showing
the efficiency of the procedure when using unsaturated
carboxylic acids instead of alkenols.
Therefore, we decided to perform additional quantum
chemical calculations at molecular level in order to get
deeper insight into the NTf2 influence on the reaction
pathway. For comparability with our previously pub-
lished results for uncatalyzed‐ and pyridine‐facilitated
selenoetherification of pent‐4‐en‐1‐ol,[60] the same level
of theory (B3LYP/6‐311 + G**) has been utilized for
our quantum chemical calculation of the NTf2‐suported
reaction. Again, the same concept as already successfully
applied was followed. The mechanistic survey started
with the seleniranium ion formation (Figures 2A and 3A).
As it was expected, there is no significant difference
for the bond lengths at this point in the reaction and very
similar values have been obtained. The length of C–C
bond of 1.44 Å in newly formed seleniranium intermedi-
ate is identical to those observed in unsupported‐ and
pyridine‐facilitated reactions.[60] Slightly different bond
lengths have been noticed for the Se–CCH– bond, which
is 2.23 Å (unsupported reaction: 2.13 Å; with pyridine:
2.17 Å) and for the C4‐O distance (2.56 Å for IL‐mediated
reaction, 2.79 Å for the unsupported reaction, and 2.64 Å
in pyridine case). Through the molecular rearrangement
In the case of Δ5‐alkenols, primary (2), or secondary
(6), the reaction always affords a six‐membered cyclic
ether (6a).
Although the reaction yields when using ILs or
CH2Cl2/Py as solvents/catalyzers are very similar, and
both proceed at room temperature, the use of ILs affords
a series of advantages. Thus, besides avoiding the use of
the traditional contaminating volatile organic solvents
and toxic bases, they can be recycled and reused without
losing their activity.
Mechanistic studies of cycloetherifications of
pent‐4‐en‐ols by treatment with PhSeCl in the presence
of a base (pyridine, trimethylamine, quinolone, and 2,2'‐
bipyridine) have shown that the catalytic effect of the base
is caused by the hydrogen bond formed with the hydroxyl
group, which increases the oxygen nucleophilic charac-
ter.[59,60] It has been also reported that solvents with
higher polarity can better stabilize the charged transition
state for the cyclization, increasing the reaction rate. Sim-
ilar effects can be attributed to the catalytic role of the ILs,
which present a very high polarity and would form hydro-
gen bonds with the hydroxyl group through the anion.
In order to determine the effect of the cation when
acidic protons are present (H‐2 of 1,2‐dimethyli-
midazolium cation), the reaction between pent‐4‐en‐1‐ol
1 and PhSeCl in 1,2,3‐trimethylimidazolium sulfate
([MMMIm][MSO4]) was carried out (Table 1, entry 2),
but no significant differences were observed in the reac-
tion rate.
As mentioned above, the decision to investigate reac-
tions in [MMIm][MeSO4] was driven by the economical
demands for the preparation of ILs, as well as by the reac-
tion yields and rates observed during the optimization
process. However, a pertinent effect of the NTf2‐based
ILs on the reaction rates still remained to intrigue our
research attention. As it can be seen in Table 1, the
application of all NTf2‐based ILs as reaction media have
afforded almost instantaneous formation of the cyclic
ether product, regardless cationic part of the IL applied.
FIGURE 2 Calculated reaction pathway (MP2(fc)/6‐311 + G**//
B3LYP/6‐311 + G** + ZPE(B3LYP/6‐311 + G**) for the
cycloselenoetherification of pent‐4‐en‐1‐ol mediated by the Ph‐Se+
with hydrogen bond bound [NTf2] anion (Values in brackets:
B3LYP/6‐311 + G** + ZPE(B3LYP/6‐311 + G**

6 of 8
KOSTIĆ ET AL.
FIGURE 3 B3LYP/6‐311 + G**‐calculated (A) seleniranium ion; (B) transition state; and (C) cyclic ether product for the
cycloselenoetherification mediated by the Ph‐Se+ with hydrogen bond bound NTf2 anion
required for the final formation of the cyclic ether prod-
uct, the first significant differences for unsupported and
NTf2‐faciliated reaction are disclosed at the transition
state (Figures 2B and 3B). The transition state of the
unsupported reaction is associated with an energy barrier
of 8.8 kcal/mol (B3LYP/6‐311 + G**) (11.8 kcal/mol for
MP2(fc)), while the presence of NTf2 hydrogen bound
by the OH group in the structure influences the signifi-
cant decrease of energetic demands—more precisely, a
barrier of 1.7 kcal/mol at the B3LYP level of theory
(or 7.5 kcal/mol in the case of MP2(fc)) is calculated. It
is noteworthy to mention that such differences in the
activation barriers are already mentioned in literature
for the B3LYP and MP2(fc) calculation and are not
unexpected.[52]
observation of energetic destiny for the hydrogen bond
between nitrogen form NTf2‐anion and OH‐alkenol
group. Although in the framework of the seleniranium
ion‐transition state pass, this bond does not change its
length, the migration of the proton from OH group to
the negatively charged nitrogen in NTf2 in the cyclic
product is likely to have strong influence on the stability
of calculated pathways. The liberated energies of
19 kcal/mol (B3LYP) and 18 kcal/mol (MP2(fc)) for the
formation of the five‐membered heterocyclic product C
are very similar to those achieved by the pyridine‐
supported concept (around 20 kcal/mol). In contrast to
the stabilization of the cyclic ether product caused by
the NTf2 acceptance of the proton, the protonated cyclic
ether form in unsupported reaction is energetically very
unfavorable in its transformation to the final product by
later deprotonation. This behavior has been observed for
other reported reactions in ILs, where the IL effect is cor-
related with the hydrogen bond accepting ability of the IL
anion,[61] as well as the transition state IL solvation.[62]
The distance of the C4–O bond that is responsible for
the cyclic ether formation is getting shorter in transition
state by around 0.1 Å and reduces to the 1.47 Å in the
final selenocyclic product C (Figures 2 and 3). Another
relevant conclusion has been derived from the

KOSTIĆ ET AL.
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4 | CONCLUSIONS
A new application of ILs in organic synthesis is reported.
The oxyselenocyclization of unsaturated alcohols by
treatment with phenylselenyl chloride is carried out by
using ILs as solvents/catalyzers, without the need of any
other promoter. The reaction proceeds in a regiospecific
fashion, mild conditions, broad scope, and in general very
good yields, using primary, secondary, tertiary, and aro-
matic alcohols, as well as monosubstituted, disubstituted,
and trisubstituted alkenols. Taking into the account the
good results obtained with [MMIM][MSO4], its ease
preparation, low viscosity, low price, and its capacity to
be recovered and reused, it was selected to be used as
the solvent/cataliser. This procedure provides an
improved method for the synthesis of substituted tetrahy-
drofurans and tetrahydropyrans ethers, the precursor of
many biologically active metabolites isolated from marine
organisms, polyene mycotoxines, and macrolides. The
reaction mechanism was investigated by Quantum‐
chemical calculations (MP2(fc)/6‐311 + G**//B3LYP/6‐
311 + G**), which has shown that the intramolecular
cyclization is promoted by the hydrogen bond formed
between the IL anion and the HO group of the alkenol.
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We thank the Consellería de Cultura, Educación e
Ordenación Universitaria, Xunta de Galicia (REGALIs
Network [ED431D 2017/06]), the scientific activity of the
international and multidisciplinary network “SeS Redox
and Catalysis,” and the Ministry of Education and Science
of the Republic of Serbia (Grant: 172011) for funding. We
also thank the research support services of the University
of Vigo (CACTI) for the NMR divisions work. R.P. would
like to thank the Regionales Rechenzentrum Erlangen
(RRZE) for a generous allotment of computer time and
Prof Tim Clark for hosting this work at the CCC.
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ORCID
Lysenko, M. M. Joullie, J. Am. Chem. Soc. 1980, 102(11), 3784.
Marina Kostić https://orcid.org/0000-0001-8981-4470
Pedro Verdía https://orcid.org/0000-0001-6471-6305
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