Synthesis of 5H-Selenopheno[3,2-c]isochromen-5-ones Promoted by Dialkyl Diselenides and Oxone

Article abstract of DOI:10.1002/adsc.201900288

We describe here for the first time the synthesis of isochromenones fused to selenophenes. 5H-Selenopheno[3,2-c]isochromen-5-ones were obtained through a double intramolecular cyclization of methyl 2-(organyl-1,3-diynyl)benzoate promoted by electrophilic species of selenium generated in situ by the reaction of dialkyl diselenides with Oxone, using ethanol as solvent. The reactions were conducted satisfactorily under mild conditions, using a range of 1,3-diynes and dialkyl diselenides as substrates. A total of sixteen unprecedent 5H-selenopheno[3,2-c]isochromen-5-ones were selectively obtained in moderate to good yields (40–86%) under reflux in an open flask and in short reaction times (1.0–2.5 h). (Figure presented.).

Full text of DOI:10.1002/adsc.201900288

Title: Synthesis of 5H-Selenopheno[3,2-c]isochromen-5-ones
Promoted by Dialkyl Diselenides and Oxone®
Authors: Helen A. Goulart, Jose Neto, Angelita M. Barcellos, Thiago
Barcellos, Márcio Silva, Diego Alves, Raquel Jacob, Eder
Lenardao, and Gelson Perin
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900288
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10.1002/adsc.201900288
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Synthesis of 5H-Selenopheno[3,2-c]isochromen-5-ones
Promoted by Dialkyl Diselenides and Oxone®
Helen A. Goulart,a José S. S. Neto,a Angelita M. Barcellos,a Thiago Barcellos,b Márcio
S. Silva,a Diego Alves,a Raquel G. Jacob,a Eder J. Lenardãoa and Gelson Perina,*
a LASOL - CCQFA - Universidade Federal de Pelotas - UFPel - P.O. Box 354 - 96010-900, Pelotas, RS, Brazil.
Phone/fax: +55 53 32757533, e-mail: gelson_perin@ufpel.edu.br (G. Perin).
b Laboratory of Biotechnology of Natural and Synthetic Products, Universidade de Caxias do Sul, Caxias do Sul, RS,
Brazil.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. We describe here for the first time the synthesis of The reactions were conducted satisfactorily under mild
isochromenones
Selenopheno[3,2-c]isochromen-5-ones
fused
to
selenophenes.
5H- conditions, using a range of 1,3-diynes and dialkyl
obtained diselenides as substrates. A total of sixteen unprecedent 5H-
were
through a double intramolecular cyclization of methyl 2- selenopheno[3,2-c]isochromen-5-ones were selectively
(organyl-1,3-diynyl)benzoate promoted by electrophilic obtained in moderate to good yields (40-86%) under reflux
species of selenium generated in situ by the reaction of in an open flask and in short reaction times (1.0-2.5 h).
dialkyl diselenides with Oxone®, using ethanol as solvent.
Keywords: electrophilic cyclization; dialkyl diselenides;
heterocycles; isochromenones; Oxone®; selenophenes.
interest in isochromenone derivatives are due to the
Introduction
variety of pharmacological activities reported for
these
compounds,
including
antifungal,[18]
Organochalcogen compounds are considered an
important class of molecules in organic synthesis, due
to their special structural characteristics and unique
reactivity. These compounds have been applied as
versatile synthetic intermediates in the synthesis of
different target molecules,[1] allowing selective
transformations,[2] and as catalysts in asymmetric
synthesis.[3] They also have shown interesting
biological activities, including antiparasitic,[4]
antioxidant,[5] anticholinesterase,[6] antinociceptive[7]
and anxiolytic effects.[8]
In particular, selenophenes are an interesting class of
bioactive compounds, presenting anticonvulsant,[9]
antioxidant,[10] hepatoprotective,[11] antinociceptive[12]
and antitumor[13] activities. Besides that, these
compounds are used to obtain new materials, like
semiconductors[14] and solar cells.[15] Regarding the
preparation of selenophenes, the most efficient
methods reported in the literature involve the addition
of either nucleophilic or electrophilic selenium
species to appropriate acyclic precursors containing
the π-system, followed by an intramolecular
cyclization.[16]
antimalarial,[19] antibacterial,[20] anticancer,[21] anti-
inflammatory,[22] and antioxidant[23] ones.
These aspects have stimulated the studies towards the
synthesis of isochromenone derivatives.[24] The
traditional approaches include transition-metal-
catalyzed
reactions[24c]
and
intramolecular
electrophilic cyclizations.[25] However, there are few
protocols describing the synthesis of isochromenones
decorated with organochalcogen groups.[26] In 2003,
Yao and Larock[26a] described the synthesis of
selenium- and sulfur-containing isochromenones via
the electrophilic cyclization of 2-alkynylaryl esters
with PhSeCl and 4-NO2C6H4SCl in DCM at room
temperature. In 2011, Zeni and co-workers[26b]
reported
a
FeCl3-mediated cyclization of 2-
alkynylaryl esters in the presence of diorganyl
dichalcogenides in DCM at room temperature to
prepare 4-chalcogen-substituted isochromenones. In
2012, Zhou and co-workers[26c] reported the synthesis
of sulfur-containing isochromenones by the FeCl3-
promoted intermolecular sulfoesterification of 2-
alkynylaryl esters with diorganyl disulfides in DCE at
80 ºC.
On the other hand, isochromenones represent an
important class of naturally occurring lactones. A
large number of these compounds are found in nature
as component of insect pheromones and venoms, and
as part of the structure of secondary metabolits of
plants, bacteria and fungi.[17] The reasons for the
In parallel, the use of Oxone® as an oxidant in
organic synthesis has been widely explored because
of its low cost, stability, water solubility and low
toxicity.[27] Oxone® is commercially available as a
triple salt (2KHSO5.KHSO4.K2SO4) and contains
about 50% of active oxidant per mol (anion
1
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10.1002/adsc.201900288
Advanced Synthesis & Catalysis
-
peroxymonosulfate, HSO5 ).[27] Recently, we and
others have explored the combination of Oxone® with
organoselenium chemistry. Oxone® was used in the
reaction of selenomethoxylation of alkenes,[28] in the
carbocyclization of alkynols to obtain 2-
organoselanyl-naphthalenes,[29] in the synthesis of
diorganyl selenides and tellurides,[30] in the oxidation
of vinyl selenides to selenones[31] and in the
No product 3a was obtained in the reactions using
DCM and glycerol as solvent, as indicated by GC/MS
analysis, and the starting materials were recovered
(Table 1, entries 7-8).
To our satisfaction, the expected product 3a could be
isolated in 82% yield under refluxing ethanol in only
2.5 h (Table 1, entry 1 vs 10). The effect of using
different quantities of Oxone® was evaluated and a
little influence was observed when larger amounts
were used (1.25, 0.75 and 0.69 mmol), with the
corresponding product 3a being isolated in 83%, 82%
and 86% yields, respectively (Table 1, entries 11-13).
However, the yields have decreased when the amount
of Oxone® was reduced to 0.63 and 0.50 mmol, and
3a was obtained in 77% and 69% yields, respectively
(Table 1, entries 14-15). A similar behavior was
observed regarding the amounts of dibutyl diselenide
arylselenylation
of
imidazo[2,1-b]thiazoles,
imidazo[1,2-a]pyridines and 1H-pyrazoles.[32]
Considering the importance of selenophenes and
isochromenone derivatives, and our interest in the
synthesis of organochalcogen compounds, we
describe herein the first synthesis of isochromenones
fused to selenophenes. The developed protocol
involves a simple, practical, and selective tandem
cyclization of 1,3-diynes 1 with dialkyl diselenides 2
to obtain 5H-selenopheno[3,2-c]isochromen-5-ones 3. 2a, with the better result (82% yield) being obtained
The electrophilic species of selenium (ES) was
generated in situ, through the reaction of dialkyl
diselenides with Oxone® using ethanol as the solvent
(Scheme 1).
using 0.38 mmol (1.5 equiv) (Table 1, entries 16-18).
Table 1. Optimization of the conditions to prepare 3a.[a]
Scheme
1.
Synthesis
of
5H-selenopheno[3,2-
c]isochromen-5-ones 3.
2a
(mmol) (mmol)
Oxone®
Solvent
T
(°C)
78
-
Time
(h)
12
1
12
12
12
12
12
Yield
(%)[b]
85
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.44
0.50
0.38
0.25
0.38
0.38
0.38
0.38
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
EtOH
EtOH
AcOEt
CH3CN
DMF
1,4-dioxane
DCM
glycerol
PEG-400
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
20c
Results and Discussion
77
82
153
101
40
100
100
78
78
78
78
78
78
78
78
78
50
25
78
78
70
65
[d]
Methyl 2-(phenylbuta-1,3-diyn-1-yl)benzoate 1a
(0.25 mmol) and dibutyl diselenide 2a were chosen as
standard starting materials to perform the
optimization studies in the reaction with Oxone®
under argon atmosphere (Table 1). We examined the
effect of the nature of the solvent, the amounts of
diselenide and Oxone® and the temperature.
In our first experiment, 1,3-diyne 1a (0.25 mmol) and
Oxone® (1.0 mmol) were added to a solution of
dibutyl diselenide 2a (0.44 mmol) in 3.0 mL of
ethanol. The resulting yellowish mixture was stirred
at reflux for 12 h to deliver the desired product 3a in
85% yield (Table 1, entry 1). Aiming to improve the
reaction yield and reduce the time, the reaction was
performed under ultrasonic irradiation (US) at 60% of
amplitude and, unfortunately, the expected product
3a was obtained in only 20% yield after 1 h (Table 1,
entry 2). By setting the conventional heating method
(oil bath), a range of solvents were tested, such as
AcOEt, CH3CN, DMF, 1,4-dioxane and DCM, as
well as, green solvents like glycerol and PEG-400
(Table 1, entries 3-9).
-
30
nr[e]
nr[e]
20
82
83
82
86
77
69
12
12
1.0
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
12
1.25
0.75
0.69
0.63
0.50
0.69
0.69
0.69
0.69
0.69
0.69
0.69
82
82
35
75
EtOH
EtOH
EtOH
EtOH
12
2.5
2.5
14
80[f]
86[g]
[a] A mixture of 1,3-diyne 1a (0.25 mmol), Oxone® and dibutyl
diselenide 2a in the solvent (3.0 mL) under argon atmosphere was
stirred at the temperature and time indicated;
purification by column chromatography; Reaction performed
[b]
Yields after
[c]
[d]
under ultrasonic irradiation (US) at 60% of amplitude;
A
complex mixture of products was obtained; [e] The product was
not formed and the starting material was recovered; Oxone®
[f]
was added to a solution of dibutyl diselenide 2a in ethanol (3.0
mL) at room temperature, under argon atmosphere. After 15 min,
1,3-diyne 1a (0.25 mmol) was added. The resulting mixture was
In the reactions using AcOEt, CH3CN, 1,4-dioxane
and PEG-400, the isochromenone 3a was obtained in
lower yields compared to the reaction performed in
ethanol (Table 1, entry 1 vs 3, 4, 6 and 9). When the
reaction was carried out using DMF, a complex
mixture of products was obtained (Table 1, entry 5).
[g]
refluxed for 2.5 h; Reaction performed under air atmosphere.
nr = no reaction.
Next, we investigated the possibility of performing
the reaction at lower temperatures, i.e., 50 C and
o
2
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10.1002/adsc.201900288
Advanced Synthesis & Catalysis
25 °C. The expected product 3a was obtained,
however in lower yields, of 75% and 14%,
respectively (Table 1, entries 19-20). Additionally, in
an attempt to improve the yield of 3a, we performed
two steps, one-pot experiment. Firstly, Oxone® was
added to a solution of dibutyl diselenide 2a in ethanol
compounds 3h (R1 = 4-CH3OC6H4), 3j (R1 = 4-
CH3C6H4) and 3l (R1 = 4-ClC6H4) were isolated in
74%, 81% and 72% yields, respectively (Table 2,
compounds 3h, 3j and 3l). Surprisingly, when 1,3-
diyne 1c (R1 = 2-CH3OC6H4) was used as substrate in
the reaction with 2a, the expected 5H-
and the mixture was stirred at room temperature for selenopheno[3,2-c]isochromen-5-one 3i was
15 min to generate the electrophilic selenium species.
Following, the 1,3-diyne 1a was added and the
reaction mixture was refluxed for 2.5 h, affording the
desired product 3a in 80% yield (Table 1, entry 21).
Finally, the reaction was carried out under an air
atmosphere (open flask) and a similar yield of 3a was
obtained (Table 1, entry 22 vs 17).
Thus, from the results presented on Table 1, the best
reaction conditions to prepare compound 3a involve
the stirring of a mixture of 1,3-diyne 1a (0.25 mmol),
Oxone® (0.69 mmol) and diselenide 2a (0.38 mmol)
in refluxing EtOH (3.0 mL) for 2.5 h in an open flask
(Table 1, entry 22).
isolated in only 40% yield (Table 2, compound 3i).
This can be explained by two competing reactions of
the intermediate 8c formed in the first step of the
reaction (see Scheme 7, for the reaction mechanism):
the intramolecular Se-cyclization and the O-
cyclization. As a consequence, the benzofuran
derivative 3i’ was formed in 50% yield as a co-
product of the reaction (Scheme 2).[25a] The steric
hindered ortho-substituted diynes 1e (R1 = 2-
CH3C6H4), 1g (R1 = 2-CH3OCOC6H4) and 1h (R1 = 1-
naphthyl) satisfactorily reacted with 2a to afford the
respective products 3k, 3m and 3n in 76%, 80% and
75% yields, respectively (Table 2, compounds 3k,
3m and 3n). Interestingly, when using the dimer 1g,
the double intramolecular O-cyclization product was
not formed. Alkyl-substituted 1,3-diynes 1i and 1j
were good substrates for the reaction with 2a, giving
the respective products 3o and 3p in 73% and 84%
yield, under the optimal conditions (Table 2,
compounds 3o and 3p). The scope of products was
extended further by the reaction of diethyl diselenide
2b (R2 = C2H5) with 1,3-diynes 1d, 1f and 1j. In all
cases the reaction proceeded smoothly, giving the
corresponding isochromenones 3q, 3r and 3s in 74%,
76% and 80% yields, respectively (Table 2,
compounds 3q, 3r and 3s). Finally, the 1,3-diyne tri-
substituted on the ring of the ester group 1k was
investigated in the reaction with dibutyl diselenide 2a,
giving the expected product 3t in 84% yield after 2.5
h.
Scope of the Reaction
With the optimal conditions in hand, we decided to
explore the scope and limitations of the reaction
using different 1,3-diynes 1 and various dialkyl
dichalcogenides 2 (Table 2). Besides dibutyl
diselenide 2a, our protocol was suitable to dialkyl
n
diselenides 2b (R2 = C2H5) and 2c (R2 = C8H17),
which reacted with 1a to give the expected
isochromenones 3b and 3c in 77% and 82% yields,
respectively (Table 2, compounds 3b and 3c). No
product was observed starting from dibenzyl
diselenide 2d or bis(2-naphthylmethyl) diselenide 2e,
even after 3 h of reaction, as indicated by GC/MS
analysis and the starting materials were recovered
(Table 2, compounds 3d and 3e). No product was
observed when diphenyl diselenide was used as
substrate in the reaction with 1a, and a complex
mixture was obtained in the end of the reaction.. Also,
we examined the reaction between 1,3-diyne 1a and
dibutyl telluride or dimethyl disulfide. Unfortunately,
in both cases the desired products 3f and 3g were not
obtained, even after 3 h of reaction (Table 2).
Regarding the 1,3-diyne counterpart 1, both electron-
releasing and electron-withdrawing groups in the
pendent phenyl ring of 1 were tolerated in the
reaction with dibutyl diselenide 2a. There is no a
remarkable electronic effect caused by the
introduction of substituents in the para-position, and
The synthetic potential of this new class of
compounds
was
demonstrated
using
5H-
selenopheno[3,2-c]isochromen-5-one 3a, which was
subjected to a Sonogashira-type cross-coupling
reaction.[33] The reaction of 3a (0.25 mmol) with
phenylacetylene 4a (1.0 mmol) in the presence of
PdCl2(PPh3)2 (10 mol%), Cu(OAc)2.H2O (20 mol%),
and Et3N (0.25 mmol) in DMF (3.0 mL) for 24 h at
80 °C gave the product 5a in 70% yield (Scheme 3).
Scheme 2. Selenocyclization competition reaction.
3
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10.1002/adsc.201900288
Advanced Synthesis & Catalysis
Table 2. Scope of the reaction to prepare compounds 3.[a,b]
[a] A mixture of 1,3-diyne 1a-k (0.25 mmol), Oxone® (0.69 mmol) and diorganyl dichalcogenides 2 (0.38 mmol) in EtOH (3.0 mL) was stirred under
[b]
air atmosphere and reflux. The progress of the reaction was monitored by gas chromatography.
Yields after purification by column
chromatography. [c] Products 3c and 3q are quite unstable. After purification, the solvent was quickly removed under vacuum and the NMR spectra
were collected. [d] No product was detected and the starting materials were recovered. [e] Benzofuran 3i’ (50% yield) was isolated as a co-product. nr
= no reaction.
4
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10.1002/adsc.201900288
Advanced Synthesis & Catalysis
The formation of nbutylseleninic acid 6a is a result of
the overoxidation of dibutyl diselenide 2a by Oxone®
n
-
and it could pass by the intermediates C4H9SeOSO3
n
(I) and C4H9SeOH (II) (See Scheme 7 for a
plausible mechanism).
Scheme 3. Sonogashira cross-coupling reaction.
Mechanism Discussion
After the synthesis of compounds 3, we performed a
series of control experiments to collect evidences to
understand the mechanism of this process. Firstly, the
reaction was conducted in the presence of 2 equiv of
the radical inhibitors 2,2,6,6-tetramethylpiperidin-1-
oxyl (TEMPO) and benzene-1,4-diol (hydroquinone).
In these experiments, the product 3a was formed in
82% yield using TEMPO and in 68% yield using
hydroquinone. These findings suggest that a radical
pathway is not involved in the reaction (Scheme 4).
Scheme 5. Formation of methyl butane-1-seleninate
7a.
All attempts to isolate the intermediate 4-
nbutylselanyl isochromen-1-one intermediate 8a,
formed in the first step of the reaction between the
1,3-diyne 1a and diselenide 2a, were unsuccessful,
once compound 8a was inseparable from the product
3a (Scheme 6). To obtain more information to
support a plausible mechanism for the reaction of 1a
with 2a in the presence of Oxone®, the reaction was
monitored by GC/MS. Aliquots of the reaction
mixture were collected, pre-treated by a “micro work-
up” and injected into the GC/MS spectrometer. This
experiment was carried out under the optimal
conditions and the aliquots were collected at 15, 30,
60 and 120 min (Figure 1). After 15 min of reaction,
only starting materials 1a and 2a were present
[Figures 1(a) and 1(b)]. After 30 min, we observed a
partial consumption of the starting materials, with the
appearance of a peak at 21.38 min, which mass and
fragmentation correspond to the intermediate 8a
[Figure 1(c)]. At this stage of the reaction, the amount
of the product 3a is around the triple of 8a, indicating
that the formation of 3a from 8a is fast [Figure 1(c)].
After 60 min, product 3a is the major component of
the mixture [Figure 1(d)], and after 120 min the
starting materials 1a and 2a were almost totally
consumed [Figure 1(e)].
Scheme 4. Reactions in the presence of 2 equiv of
2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) or
benzene-1,4-diol (hydroquinone).
Turning our attention to the identity of the active
electrophilic selenium species involved in the
77
reaction, we have collected the Se NMR spectrum
of the reaction between Oxone® and dibutyl
diselenide 2a in an NMR tube, using MeOD-d4 as the
solvent. It was observed a signal at 984 ppm (Figure
S59), which is due to methyl butane-1-seleninate
7a,34 formed from the reaction between
nbutylseleninic acid 6a and MeOD-d4 (Scheme 5).34
Scheme 6. Formation of the mono-cyclized intermediate 8a.
5
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10.1002/adsc.201900288
Advanced Synthesis & Catalysis
intramolecular cyclization of 1,3-diynes promoted by
electrophilic species of organoselenium, generated in
situ by the oxidative cleavage of the Se-Se bond of
dialkyl diselenides by Oxone®. The protocol is
versatile and was successfully applied to dialkyl
diselenides with open chains containing 2, 4 and 8
carbon atoms and a range of 1,3-diynes. Control
experiments, GC/MS and 77Se NMR analysis gave
insights on the reaction intermediates involved in the
reaction mechanism.
Experimental Section
Materials and methods
The reactions were monitored by gas chromatography or
TLC carried out on Merck silica gel (60 F254) by using UV
light as visualization agent and the mixture between 5% of
vanillin in 10% of H2SO4 under heating conditions as
developing agents. Merck silica gel (particle size 0.040-
0.063 mm) was used to flash chromatography. High-
resolution mass spectra (HRMS) were recorded in positive
ion mode (ESI) using a Q-TOF spectrometer. Low-
resolution mass spectra (MS) were measured on a
Shimadzu GC-MS-QP2010 mass spectrometer. Hydrogen
nuclear magnetic resonance spectra (1H NMR) were
obtained at 400 MHz spectrometer. The spectra were
recorded in CDCl3 solutions. The chemical shifts (δ) are
reported in ppm, referenced to tetramethylsilane (TMS) as
the internal pattern. Coupling constants (J) are reported in
Hertz. Carbon-13 nuclear magnetic resonance spectra (13C
NMR) were obtained at 100 MHz spectrometer.
Abbreviations to denote the multiplicity of a particular
signal are s (singlet), d (doublet), t (triplet), q (quartet),
quint (quintet), sext (sextet), dd (double doublet), ddd
(double double doublet), td (triple doublet) and m
(multiplet). Melting point (m.p.) values were measured in a
Marte PFD III instrument with a 0.1 ºC precision. Oxone®
was purchased from Sigma-Aldrich. Compounds 1a-k were
prepared according to a procedure described in SI.
Figure 1. GC/MS studies monitoring a time reaction
for product formation. Chromatogram of the mixture at
(a): 15 min. (b): 15 min (zoom). (c): 30 min (zoom).
(d): 60 min (zoom). (e): 120 min.
Based on the control experiments and in the
literature,34-36 a plausible mechanism for the reaction
of 1a with 2a promoted by Oxone® is presented in
Scheme 7. Firstly, dibutyl diselenide 2a reacts with
n
-
Oxone® to form two intermediates: C4H9SeOSO3
n
(I
)
and C4H9SeOH (II) (Scheme 7, path
a
).35 The
species (II) can react with H+ from the reaction
medium, leading to nC4H9SeOH2 (V). The
+
General procedure for the synthesis of 3
intermediates
active electrophiles in the reaction with substrate
1a 36
The reaction of 1a with I and V leading to the
I and V are most probably the
To a 25.0 mL two-neck round-bottomed flask containing a
solution of the appropriate dialkyl diselenide 2a-c (0.38
mmol) in ethanol (3.0 mL), 1,3-diyne 1a-k (0.25 mmol)
and Oxone® (0.69 mmol, 0.211 g) were added under air
atmosphere. The resulting mixture was refluxed for the
time indicated in Table 2. The progress of the reaction was
monitored by gas chromatography. After this time, the
resulting solution was received in water (10.0 mL) and the
aqueous phase was extracted with ethyl acetate (3x 10.0
mL). The organic layer was separated, dried with MgSO4
and concentrated under vacuum. The residue was purified
by column chromatography using silica gel 60Å (0.060-
0.200 mm) and hexane/ethyl acetate (96:04) as eluent to
afford 3 (40-86% yield).
.
-
cyclic intermediate VI, releasing HSO4 and H2O to
the medium. The displacement of the methyl group
from VI by a nucleophile (HSO4- from previous step
and SO4 of Oxone®), affords the intermediate 8a.
2-
Following, 8a reacts in the same way with I and V to
give the fused-selenophene cation intermediate VII.
The displacement of the nbutyl group from the
selenonium cation affords the expected product 3a.
Conclusion
In resume, 5H-selenopheno[3,2-c]isochromen-5-ones
were prepared for the first time, by the reaction
between
methyl
2-(organylbuta-1,3-diyn-1-
yl)benzoates and dialkyl diselenides using Oxone® as
oxidant. This method involves a selective, sequential
6
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10.1002/adsc.201900288
Advanced Synthesis & Catalysis
Scheme 7. Proposed mechanism for the synthesis of 3a.
+
(ESI-QTOF) Calculated mass for C19H14O2Se2 [M+H] :
434.9403, found: 434.9407.
3-(nButylselanyl)-2-phenyl-5H-selenopheno[3,2-
c]isochromen-5-one (3a): Yield: 0.099 g (86%); yellow
solid, m.p: 80-82 ºC. 1H NMR (CDCl3, 400 MHz)  (ppm)
= 8.34 (ddd, J = 8.0, 1.3 and 0.6 Hz, 1H); 7.74-7.70 (m,
1H); 7.60-7.58 (m, 2H); 7.50-7.48 (m, 1H); 7.47-7.41 (m,
4H); 2.89 (t, J = 7.4 Hz, 2H); 1.52 (quint, J = 7.4 Hz, 2H);
1.27 (sext, J = 7.4 Hz, 2H); 0.79 (t, J = 7.4 Hz, 3H). 13C
NMR (CDCl3, 100 MHz)  (ppm) = 161.7, 152.5, 148.5,
135.5, 135.3, 135.2, 130.8, 129.6, 128.8, 128.4, 127.9,
123.5, 119.1, 117.9, 114.1, 32.1, 28.0, 22.5, 13.4. MS (rel.
int., %) m/z: 462 (43.0), 406 (47.8), 326 (51.3), 281 (27.9),
207 (100.0). HRMS (ESI-QTOF) Calculated mass for
C21H18O2Se2 [M+H]+: 462.9716, found: 462.9710.
3-(nOctylselanyl)-2-phenyl-5H-selenopheno[3,2-
c]isochromen-5-one (3c): Yield: 0.106 g (82%); yellow
1
oil. H NMR (CDCl3, 400 MHz)  (ppm) = 8.37-8.33 (m,
1H); 7.74-7.70 (m, 1H); 7.61-7.57 (m, 2H); 7.51-7.48 (m,
1H); 7.47-7.41 (m, 4H); 2.88 (t, J = 7.4 Hz, 2H); 1.52
(quint, J = 7.4 Hz, 2H); 1.27-1.15 (m, 10H); 0.83 (t, J = 7.2
Hz, 3H). 13C NMR (CDCl3, 100 MHz)  (ppm) = 161.7,
152.5, 148.6, 135.6, 135.3, 135.2, 130.8, 129.6, 128.8,
128.4, 127.9, 123.5, 119.1, 117.9, 114.1, 31.7, 30.0, 29.4,
29.0, 28.9, 28.4, 22.6, 14.0. MS (rel. int., %) m/z: 518
(17.2), 406 (32.8), 326 (25.5), 281 (40.8), 207 (100.0).
HRMS (ESI-QTOF) Calculated mass for C25H26O2Se2
[M+H]+: 519.0341, found: 519.0341.
3-(Ethylselanyl)-2-phenyl-5H-selenopheno[3,2-
c]isochromen-5-one (3b): Yield: 0.084 g (77%); yellow
3-(nButylselanyl)-2-(4-methoxyphenyl)-5H-
1
solid, m.p: 155-157 ºC. H NMR (CDCl3, 400 MHz) 
selenopheno[3,2-c]isochromen-5-one (3h): Yield: 0.091 g
1
(ppm) = 8.34 (ddd, J = 8.0, 1.3 and 0.6 Hz, 1H); 7.74-7.70
(m, 1H); 7.60-7.57 (m, 2H); 7.50-7.41 (m, 5H); 2.92 (q, J
= 7.5 Hz, 2H); 1.28 (t, J = 7.5 Hz, 3H). 13C NMR (CDCl3,
100 MHz)  (ppm) = 161.7, 152.5, 148.6, 135.5, 135.2,
135.1, 130.8, 129.6, 128.9, 128.4, 128.0, 123.5, 119.1,
117.9, 113.9, 21.8, 15.4. MS (rel. int., %) m/z: 434 (100.0),
406 (29.0), 326 (56.3), 297 (46.8), 207 (47.6). HRMS
(74%); yellow solid, m.p: 95-98 ºC. H NMR (CDCl3, 400
MHz)  (ppm) = 8.36-8.33 (m, 1H); 7.71 (td, J = 7.8 and
1.3 Hz, 1H); 7.54 (d, J = 8.8 Hz, 2H); 7.49-7.42 (m, 2H);
6.97 (d, J = 8.8 Hz, 2H); 3.87 (s, 3H); 2.89 (t, J = 7.4 Hz,
2H); 1.52 (quint, J = 7.4 Hz, 2H); 1.28 (sext, J = 7.4 Hz,
2H); 0.80 (t, J = 7.4 Hz, 3H). 13C NMR (CDCl3, 100 MHz)
 (ppm) = 161.8, 160.1, 152.5, 148.7, 135.4, 135.2, 130.9,
130.8, 128.0, 127.8, 123.5, 119.1, 117.2, 113.8, 113.3, 55.3,
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900288
Advanced Synthesis & Catalysis
32.1, 28.0, 22.6, 13.4. MS (rel. int., %) m/z: 492 (38.9),
434 (23.1), 356 (50.4), 281 (36.3), 207 (100.0). HRMS
(ESI-QTOF) Calculated mass for C22H20O3Se2 [M+H]+:
492.9821, found: 492.9828.
3-(nButylselanyl)-2-(4-chlorophenyl)-5H-
selenopheno[3,2-c]isochromen-5-one (3l): Yield: 0.089 g
1
(72%); yellow solid, m.p: 84-87 ºC. H NMR (CDCl3, 400
MHz)  (ppm) = 8.34 (ddd, J = 8.0, 1.2 and 0.5 Hz, 1H);
7.75-7.71 (m, 1H); 7.54-7.51 (m, 2H); 7.50-7.45 (m, 2H);
7.43-7.39 (m, 2H); 2.90 (t, J = 7.4 Hz, 2H); 1.52 (quint, J =
7.4 Hz, 2H); 1.28 (sext, J = 7.4 Hz, 2H); 0.80 (t, J = 7.4 Hz,
3H). 13C NMR (CDCl3, 100 MHz)  (ppm) = 161.6, 152.4,
146.9, 135.2, 135.1, 135.0, 134.0, 130.83, 130.8, 128.7,
128.1, 123.5, 119.2, 118.1, 114.7, 32.1, 28.2, 22.5, 13.4.
MS (rel. int., %) m/z: 496 (17.4), 440 (24.5), 360 (24.1),
281 (36.0), 207 (100.0). HRMS (ESI-QTOF) Calculated
mass for C21H17ClO2Se2 [M+H]+: 496.9326, found:
496.9324.
3-(nButylselanyl)-2-(2-methoxyphenyl)-5H-
selenopheno[3,2-c]isochromen-5-one (3i): Yield: 0.049 g
1
(40%); yellow solid, m.p: 86-89 ºC. H NMR (CDCl3, 400
MHz)  (ppm) = 8.31-8.27 (m, 1H); 7.67-7.62 (m, 1H);
7.43-7.31 (m, 4H); 6.99-6.91 (m, 2H); 3.78 (s, 3H); 2.80 (t,
J = 7.4 Hz, 2H); 1.43 (quint, J = 7.4 Hz, 2H); 1.18 (sext, J
= 7.4 Hz, 2H); 0.72 (t, J = 7.4 Hz, 3H). 13C NMR (CDCl3,
100 MHz)  (ppm) = 162.0, 156.6, 152.0, 144.1, 135.6,
135.1, 131.7, 130.8, 130.6, 127.8, 124.3, 123.5, 120.3,
119.1, 118.3, 116.5, 111.0, 55.5, 32.2, 27.3, 22.6, 13.5. MS
(rel. int., %) m/z: 492 (46.9), 434 (12.6), 356 (59.8), 281
(32.9), 207 (100.0). HRMS (ESI-QTOF) Calculated mass
for C22H20O3Se2 [M+H]+: 492.9821, found: 492.9824.
Methyl
2-(3-butylselanyl-5-oxo-5H-selenopheno[3,2-
c]isochromen-2-yl)benzoate (3m): Yield: 0.104 g (80%);
1
yellow oil. H NMR (CDCl3, 400 MHz)  (ppm) = 8.38-
8.35 (m, 1H); 8.03-8.00 (m, 1H); 7.75-7.70 (m, 1H); 7.61-
7.56 (m, 1H); 7.54-7.48 (m, 2H); 7.46-7.40 (m, 2H); 3.76
(s, 3H); 2.80 (t, J = 7.3 Hz, 2H); 1.48 (quint, J = 7.3 Hz,
2H); 1.29-1.21 (m, 2H); 0.79 (t, J = 7.3 Hz, 3H). 13C NMR
(CDCl3, 100 MHz)  (ppm) = 166.9, 161.8, 151.8, 147.9,
136.2, 135.4, 135.2, 132.1, 131.4, 131.2, 130.8, 130.4,
129.0, 127.9, 123.5, 119.2, 118.3, 116.0, 52.3, 32.2, 27.6,
22.5, 13.4. MS (rel. int., %) m/z: 520 (8.3), 383 (100.0),
168 (12.9), 41 (41.4). HRMS (ESI-QTOF) Calculated mass
for C23H20O4Se2 [M+H]+: 520.9769, found: 520.9753.
3-(nButylselanyl)-4-(3-nbutylselanylbenzofuran-2-yl)-
1H-isochromen-1-one (3i’): Yield: 0.067 g (50%); yellow
1
oil. H NMR (CDCl3, 400 MHz)  (ppm) = 8.41-8.38 (m,
1H); 8.28-8.26 (m, 1H); 7.89-7.84 (m, 1H); 7.74-7.72 (m,
1H); 7.65-7.61 (m, 1H); 7.57-7.54 (m, 1H); 7.44-7.40 (m,
1H); 7.38-7.34 (m, 1H); 2.84 (t, J = 7.4 Hz, 2H); 2.63 (t, J
= 7.4 Hz, 2H); 1.61-1.54 (m, 2H); 1.49-1.42 (m, 2H);
1.37-1.27 (m, 2H); 1.23-1.14 (m, 2H); 0.80 (t, J = 7.4 Hz,
3H); 0.74 (t, J = 7.4 Hz, 3H). 13C NMR (CDCl3, 100 MHz)
 (ppm) = 161.2, 154.6, 150.5, 148.0, 137.9, 135.2, 130.3,
130.0, 129.4, 128.7, 126.3, 123.5, 121.7, 121.6, 111.8,
111.1, 109.2, 32.5, 31.8, 29.3, 28.3, 22.6, 22.5, 13.4, 13.3.
MS (rel. int., %) m/z: 534 (15.2), 397 (16.8), 340 (100.0),
207 (34.5). HRMS (ESI-QTOF) Calculated mass for
C25H26O3Se2 [M+H]+: 535.0291, found: 535.0292.
3-(nButylselanyl)-2-(naphthalen-1-yl)-5H-
selenopheno[3,2-c]isochromen-5-one (3n): Yield: 0.096 g
1
(75%); yellow solid, m.p: 142-144 ºC. H NMR (CDCl3,
400 MHz)  (ppm) = 8.41-8.38 (m, 1H); 7.96-7.90 (m,
2H); 7.84-7.80 (m, 1H); 7.73 (td, J = 7.7 and 1.3 Hz, 1H);
7.55-7.45 (m, 6H); 2.79 (t, J = 7.4 Hz, 2H); 1.44 (quint, J =
7.4 Hz, 2H); 1.16 (sext, J = 7.4 Hz, 2H); 0.73 (t, J = 7.4 Hz,
3H). 13C NMR (CDCl3, 100 MHz)  (ppm) = 161.8, 151.9,
146.0, 135.4, 135.2, 133.4, 133.0, 131.9, 130.9, 129.6,
128.6, 128.3, 128.1, 126.6, 126.3, 125.7, 124.9, 123.6,
119.2, 118.9, 117.4, 32.2, 27.5, 22.5, 13.4. MS (rel. int., %)
m/z: 512 (31.9), 453 (28.4), 376 (15.7), 281 (42.1), 207
(100.0). HRMS (ESI-QTOF) Calculated mass for
C25H20O2Se2 [M+H]+: 512.9872, found: 512.9872.
3-(nButylselanyl)-2-(4-tolyl)-5H-selenopheno[3,2-
c]isochromen-5-one (3j): Yield: 0.096 g (81%); yellow
1
solid, m.p: 102-104 ºC. H NMR (CDCl3, 400 MHz) 
(ppm) = 8.37-8.34 (m, 1H); 7.75-7.70 (m, 1H); 7.51-7.44
(m, 4H); 7.27-7.24 (m, 2H); 2.90 (t, J = 7.4 Hz, 2H); 2.41
(s, 3H); 1.53 (quint, J = 7.4 Hz, 2H); 1.28 (sext, J = 7.4 Hz,
2H); 0.80 (t, J = 7.4 Hz, 3H). 13C NMR (CDCl3, 100 MHz)
 (ppm) = 161.8, 152.5, 148.9, 139.0, 135.4, 135.2, 132.7,
130.8, 129.5, 129.2, 127.9, 123.5, 119.2, 117.5, 113.8, 32.1,
28.1, 22.6, 21.3, 13.5. MS (rel. int., %) m/z: 476 (71.1),
420 (66.8), 340 (88.6), 281 (42.8), 207 (100.0). HRMS
(ESI-QTOF) Calculated mass for C22H20O2Se2 [M+H]+:
476.9872, found: 476.9874.
2-nButyl-3-(nbutylselanyl)-5H-selenopheno[3,2-
c]isochromen-5-one (3o): Yield: 0.081 g (73%); yellow
solid, m.p: 60-62 ºC. 1H NMR (CDCl3, 400 MHz)  (ppm)
= 8.31 (ddd, J = 8.0, 1.2 and 0.6 Hz, 1H); 7.71-7.66 (m,
1H); 7.46-7.42 (m, 1H); 7.39-7.36 (m, 1H); 3.11 (t, J = 7.6
Hz, 2H); 2.92 (t, J = 7.4 Hz, 2H); 1.73-1.57 (m, 4H); 1.51-
1.37 (m, 4H); 0.98 (t, J = 7.3 Hz, 3H); 0.88 (t, J = 7.4 Hz,
3H). 13C NMR (CDCl3, 100 MHz)  (ppm) = 162.0, 154.4,
152.1, 135.6, 135.1, 130.8, 127.5, 123.1, 119.0, 115.4,
114.6, 34.4, 32.8, 32.4, 28.0, 22.7, 22.2, 13.8, 13.5. MS
(rel. int., %) m/z: 442 (76.0), 385 (45.6), 343 (61.4), 305
(36.7), 263 (100.0). HRMS (ESI-QTOF) Calculated mass
for C19H22O2Se2 [M+H]+: 443.0029, found: 443.0026.
3-(nButylselanyl)-2-(2-tolyl)-5H-selenopheno[3,2-
c]isochromen-5-one (3k): Yield: 0.090 g (76%); yellow
1
solid, m.p: 119-121 ºC. H NMR (CDCl3, 400 MHz) 
(ppm) = 8.37 (ddd, J = 8.0, 1.4 and 0.6 Hz, 1H); 7.75-7.71
(m, 1H); 7.52-7.44 (m, 2H); 7.37-7.25 (m, 4H); 2.85 (t, J =
7.4 Hz, 2H); 2.28 (s, 3H); 1.52 (quint, J = 7.4 Hz, 2H);
1.27 (sext, J = 7.4 Hz, 2H); 0.81 (t, J = 7.4 Hz, 3H). 13C
NMR (CDCl3, 100 MHz)  (ppm) = 161.8, 151.9, 147.7,
137.1, 135.4, 135.2, 135.0, 130.8, 130.5, 130.2, 129.2,
127.9, 125.4, 123.5, 119.2, 118.4, 116.1, 32.3, 27.4, 22.6,
20.4, 13.4. MS (rel. int., %) m/z: 476 (100.0), 420 (79.9),
340 (42.4), 281 (26.5), 207 (46.9). HRMS (ESI-QTOF)
Calculated mass for C22H20O2Se2 [M+H]+: 476.9872,
found: 476.9876.
3-(nButylselanyl)-2-nhexyl-5H-selenopheno[3,2-
c]isochromen-5-one (3p): Yield: 0.099 g (84%); yellow
1
oil. H NMR (CDCl3, 400 MHz)  (ppm) = 8.34-8.30 (m,
1H); 7.73-7.65 (m, 1H); 7.47-7.42 (m, 1H); 7.40-7.37 (m,
1H); 3.11 (t, J = 7.6 Hz, 2H); 2.92 (t, J = 7.4 Hz, 2H);
1.74-1.66 (m, 2H); 1.64-1.57 (m, 2H); 1.46-1.38 (m, 4H);
8
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900288
Advanced Synthesis & Catalysis
1.36-1.31 (m, 4H); 0.93-0.86 (m, 6H). 13C NMR (CDCl3,
100 MHz)  (ppm) = 162.0, 154.5, 152.1, 135.6, 135.1,
130.8, 127.5, 123.2, 118.9, 115.4, 114.5, 33.1, 32.4, 32.3,
31.5, 28.7, 28.0, 22.7, 22.5, 14.0, 13.5. MS (rel. int., %)
m/z: 470 (52.3), 413 (30.0), 343 (43.3), 263 (100.0).
HRMS (ESI-QTOF) Calculated mass for C21H26O2Se2
[M+H]+: 471.0340, found: 471.0315.
General procedure for the synthesis of 5a
Compound 5a was prepared according to a published
procedure.[34] A mixture of 3a (0.25 mmol, 0.116 g),
PdCl2(PPh3)2 (0.025 mmol, 0.0175 g), phenylacetylene 4a
(1.0 mmol, 0.102 g) and triethylamine (0.25 mmol, 0.025
g) were dissolved in DMF (3.0 mL). After this, the
Cu(OAc)2.H2O (0.05 mmol, 0.010 g) was added. The
resulting mixture was stirred for 24 h at 80 °C. After the
reaction was cooled to ambient temperature, the crude
reaction mixture was received in a saturated aqueous
NH4Cl solution (10.0 mL) and the product was extracted
with ethyl acetate (3x 10.0 mL). The organic layer was
separated, dried with MgSO4 and concentrated under
vacuum. The residue was purified by column
chromatography using silica gel 60Å (0.060-0.200 mm)
and hexane/ethyl acetate (90:10) as eluent to afford 5a as
an orange solid (0.075 g, 70% yield).
3-(Ethylselanyl)-2-(4-tolyl)-5H-selenopheno[3,2-
c]isochromen-5-one (3q): Yield: 0.083 g (74%); yellow
1
solid, m.p: 129-131 ºC. H NMR (CDCl3, 400 MHz) 
(ppm) = 8.36 (ddd, J = 8.0, 1.3 and 0.6 Hz, 1H); 7.75-7.71
(m, 1H); 7.51-7.45 (m, 4H); 7.27-7.25 (m, 2H); 2.93 (q, J
= 7.4 Hz, 2H); 2.42 (s, 3H); 1.29 (t, J = 7.4 Hz, 3H). 13C
NMR (CDCl3, 100 MHz)  (ppm) = 161.9, 152.5, 149.0,
139.1, 135.4, 135.2, 132.7, 130.9, 129.5, 129.2, 127.9,
123.5, 119.2, 117.6, 113.5, 21.9, 21.4, 15.4. MS (rel.
int., %) m/z: 448 (15.0), 281 (24.5), 207 (56.7), 44 (100.0).
HRMS (ESI-QTOF) Calculated mass for C20H16O2Se2
[M+H]+: 448.9559, found: 448.9561.
2-Phenyl-3-(phenylethynyl)-5H-selenopheno[3,2-
c]isochromen-5-one (5a): Yield: 0.075 g (70%); orange
1
solid, m.p: 192-195 ºC. H NMR (CDCl3, 400 MHz) 
2-(4-Chlorophenyl)-3-(ethylselanyl)-5H-
(ppm) = 8.27-8.23 (m, 1H); 7.85-7.81 (m, 2H); 7.65-7.61
(m, 1H); 7.48-7.46 (m, 2H); 7.41-7.32 (m, 5H); 7.29-7.26
(m, 3H). 13C NMR (CDCl3, 100 MHz)  (ppm) = 161.5,
151.1, 150.4, 135.2, 134.9, 134.8, 131.7, 130.9, 129.3,
128.8, 128.6, 128.3, 128.1, 128.0, 123.3, 122.7, 119.3,
116.4, 112.4, 94.9, 82.4. MS (rel. int., %) m/z: 426 (100.0),
318 (23.1), 289 (43.5), 202 (41.7). HRMS (ESI-QTOF)
Calculated mass for C25H14O2Se [M+H]+: 427.0237, found:
427.0239.
selenopheno[3,2-c]isochromen-5-one (3r): Yield: 0.089 g
1
(76%); yellow solid, m.p: 133-135 ºC. H NMR (CDCl3,
400 MHz)  (ppm) = 8.35 (ddd, J = 8.0, 1.3 and 0.5 Hz,
1H); 7.75-7.71 (m, 1H); 7.54-7.51 (m, 2H); 7.50-7.43 (m,
2H); 7.42-7.40 (m, 2H); 2.93 (q, J = 7.5 Hz, 2H); 1.28 (t, J
= 7.5 Hz, 3H). 13C NMR (CDCl3, 100 MHz)  (ppm) =
161.6, 152.4, 147.0, 135.3, 135.1, 135.0, 134.0, 130.8,
128.7, 128.2, 123.6, 119.2, 118.1, 114.4, 22.0, 15.4. MS
(rel. int., %) m/z: 468 (100.0), 440 (32.2), 281 (26.9), 207
(65.8). HRMS (ESI-QTOF) Calculated mass for
C19H13ClO2Se2 [M+H]+: 468.9013, found: 468.9015.
Acknowledgements
3-(Ethylselanyl)-2-nhexyl-5H-selenopheno[3,2-
We are grateful for the financial support and scholarships from
the Brazilian agencies CNPq and FAPERGS. CNPq is also
acknowledged for the fellowship for D.A., R.G.J., E.J.L. and G.P.
This study was financed in party by the Coordenação de
Aperfeiçoamento de Pessoal de Nivel Superior - Brasil (CAPES)
- Finance Code 001.
c]isochromen-5-one (3s): Yield: 0.088 g (80%); yellow oil.
1H NMR (CDCl3, 400 MHz)  (ppm) = 8.32-8.29 (m, 1H);
7.71-7.67 (m, 1H); 7.46-7.42 (m, 1H); 7.39-7.36 (m, 1H);
3.10 (t, J = 7.5 Hz, 2H); 2.92 (q, J = 7.5 Hz, 2H); 1.70
(quint, J = 7.2 Hz, 2H); 1.40-1.30 (m, 9H); 0.92-0.88 (m,
3H). 13C NMR (CDCl3, 100 MHz)  (ppm) = 162.0, 154.8,
152.0, 135.5, 135.1, 130.7, 127.4, 123.1, 118.8, 115.4,
114.1, 33.0, 32.2, 31.5, 28.7, 22.5, 21.7, 15.7, 14.0. MS
(rel. int., %) m/z: 442 (42.8), 290 (35.5), 263 (100.0), 41
(59.5). HRMS (ESI-QTOF) Calculated mass for
C19H22O2Se2 [M+H]+: 443.0027, found: 443.0015.
References
[1] a) A. J. Mukherjee, S. S. Zade, H. B. Singh, R. B.
Sunoj, Chem. Rev. 2010, 110, 4357–4416; b) I. P.
Beletskaya, V. P. Ananikov, Chem. Rev. 2011, 111, 1596–
1636; c) B. Godoi, R. F. Schumacher, G. Zeni, Chem. Rev.
2011, 111, 2937–2980; d) Z.-J. Yang, B.-L. Hu, C.-L.
Deng, X.-G. Zhang, Adv. Synth. Catal. 2014, 356, 1962-
1966.
3-(nButylselanyl)-8-fluoro-2-phenyl-5H-
selenopheno[3,2-c]isochromen-5-one (3t): Yield: 0.101 g
1
(84%); yellow solid, m.p: 103-105 ºC. H NMR (CDCl3,
400 MHz)  (ppm) = 8.41-8.37 (m, 1H); 7.61-7.58 (m,
2H); 7.49-7.44 (m, 3H); 7.21-7.16 (m, 1H); 7.13-7.10 (m,
1H); 2.89 (t, J = 7.4 Hz, 2H); 1.52 (quint, J = 7.4 Hz, 2H);
1.32-1.29 (m, 2H); 0.79 (t, J = 7.4 Hz, 3H). 13C NMR
(CDCl3, 100 MHz)  (ppm) = 166.90 (d, J = 256.0 Hz),
160.9, 153.5, 149.7, 137.9 (d, J = 10.9 Hz), 135.4, 134.3 (d,
J = 10.5 Hz), 129.6, 129.1, 128.5, 117.0 (d, J = 2.7 Hz),
116.1 (d, J = 23.0 Hz), 115.6 (d, J = 2.1 Hz), 114.3, 109.5
(d, J = 23.3 Hz), 32.1, 28.1, 22.6, 13.4. MS (rel. int., %)
m/z: 480 (60.9), 424 (77.4), 344 (84.1), 41 (100.0). HRMS
(ESI-QTOF) Calculated mass for C21H17FO2Se2 [M+H]+:
480.9620, found: 480.9613.
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FULL PAPER
Synthesis of 5H-Selenopheno[3,2-c]isochromen-5-
one Promoted by Dialkyl Diselenides and Oxone®
Adv. Synth. Catal. Year, Volume, Page – Page
Author(s), Corresponding Author(s)*
Helen A. Goulart, José S. S. Neto, Angelita M.
Barcellos, Thiago Barcellos, Márcio S. Silva,
Diego Alves, Raquel G. Jacob, Eder J. Lenardão
and Gelson Perin*
12
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