Stereoselective Synthesis of Z-Vinyl Selenides Through the Reaction of Sodium Selenide with Organic Halides and Alkynes

Article abstract of DOI:10.1002/ejoc.201900544

A practical synthetic approach to the stereoselective synthesis of Z-vinyl selenides is described through the reaction of sodium selenide with organic halides, followed by the addition to alkynes. The reaction conditions were also successfully applied to

Full text of DOI:10.1002/ejoc.201900544

A Journal of
Accepted Article
Title: Stereoselective Synthesis of Z-Vinyl Selenides through the
Reaction of Sodium Selenide with Organic Halides and Alkynes
Authors: Renan Pistoia, Davi Back, and Gilson Zeni
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10.1002/ejoc.201900544
European Journal of Organic Chemistry
FULL PAPER
DOI: 10.1002/ejoc.200((will be filled in by the editorial staff))
Stereoselective Synthesis of Z-Vinyl Selenides through the Reaction of Sodium
Selenide with Organic Halides and Alkynes
Renan P. Pistoia,[a] Davi F. Back,[b] and Gilson Zeni* [a]
Dedication ((optional))
Abstract.
approach
A
to
practical synthetic selenochromones
the stereoselective intramolecular
through
version of
the corresponding cross-coupled products
this
in good yields
.
synthesis of Z-vinyl selenides is methodology by the reaction of 2-
described through the reaction of chlorophenylynones with sodium
sodium selenide with organic halides, selenide. The synthetic utility of vinyl
followed by the addition to alkynes. selenides prepared was proven through
The reaction conditions were also the reaction with Kumada, Negishi and
Keywords: cyclization, • Z-vinyl
selenides, • selenium, • tellurium,
hydroselenation
successfully applied to the synthesis of Suzuky
substrates,
giving
the
Most general and efficient methods described for the preparation of
vinyl selenides involves hydroselenation of alkynes,17
hydrometallation of alkynyl selenides,18 halogenation of alkynyl
selenides,19 transition metal-catalyzed diorganyl diselenides
additions to alkynes,20 Horner, Wittig olefination,21 condensation
reactions,22 selenium electrophilic addition to alkynes23 and
selenium-radical addition to alkynes.24 However, these very
important methodologies require the use of metal transition, the
previous preparation of diorganyl diselenides or very unstable
selenols and the use of harsh reaction conditions, delivering serious
limitations. In this paper, we propose a solution to overcome these
disadvantages, which involves the preparation of vinyl selenides
through the reaction of sodium selenide with organic halides
followed by the addition to alkynes. Thus, the reaction of sodium
borohydride with elemental selenium in the presence of an
appropriate solvent led to the formation of sodium selenide, which
reacted with organic halides, giving the selenol. The nucleophilic
addition of selenol to alkynes afforded the vinyl selenides 2 in a
one-pot reaction, with good yields and high stereoselectivity
(Scheme 1).
Introduction
Organoselenium compounds have been consolidated in the last
decades as an essential class of compounds both in the chemistry
and biochemistry fields.1 In the biochemistry area, organoselenium
compounds became relevant because they prevent liver necrosis in
rats fed a selenium-deficient Torula yeast,2 the discovery that
selenium is a nutritionally important trace element3 and the
detection of selenocysteine in the active center of hepatic rat
glutathione peroxidase.4 Whereas in the chemistry area, these
compounds were highlighted because the introduction of an
organoselenium group to organic substrates is carried out in a highly
stereo and regioselective manner, using mild conditions and in many
cases without the need to protect sensitive functional groups.5 The
functionalization of organic molecules with selenium groups can be
easily performed using nucleophilic,6 electrophilic7 and radical
species8 of selenium compounds. Among the numerous classes of
organoselenium compounds described, without doubts, vinyl
selenides is probably the most important.9 They are useful building
blocks for a variety of stereoselective synthetic transformations
including, α-deprotonation,11 transition-metal-catalyzed cross-
coupling,12 cyclization transmetallation,13 nucleophilic vinylic
substitutions,14 oxidation15 and reduction.16 Because of these
applications in organic synthesis, much attention has been devoted
to the synthesis of vinyl selenides.
Scheme 1. Preparation of vinyl selenides 2 from nucleophilic addition of selenol to
alkynes
[a]
Prof. Dr. G. Zeni and Dr. R. P. Pistoia, Laboratório de Síntese,
Toxicológica de Organocalcogênios,
Results and Discussion
Reatividade, Avaliação Farmacológica
e
CCNE, Universidade Federal de Santa Maria, Santa Maria, Rio Grande do Sul
97105-900, Brazil. gzeni@ufsm.br, www.ufsm.br
Because the reaction requires a hydrogen source to be completed,
we started the studies to determine the best reaction conditions,
using ethanol as solvent. Thus, in the model reaction we added
sodium selenide (2 equiv) to a solution of benzyl bromide (0.25
mmol) in ethanol (3 mL), at room temperature, under an inert
atmosphere. After 30 min, phenylacetylene (1 equiv) was added at
[b]
Prof. Dr. D. F. Back, Laboratório de Materiais Inorgânicos, CCNE,
Universidade Federal de Santa Maria, Santa Maria, Rio Grande do Sul 97105-900,
Brazil
Supporting information for this article is available on the WWW under
http://www.chemeurj.org/ or from the author.
0
room temperature and the reaction proceeded at 78 C. After 12 h,
the crude reaction was analyzed by CGMS indicating only the
presence of phenylacetylene, the absence of benzyl bromide and the
Submitted to the European Journal of Organic Chemistry
1
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10.1002/ejoc.201900544
European Journal of Organic Chemistry
formation of benzylselenide 4 (Table 1, entry 1). This result
indicates that this condition was very efficient only to promote the
reaction of sodium selenide with benzyl bromide; however, it was
ineffective in promoting the reduction of alkyne. When a mixture of
DMF and EtOH (3:1) was used as solvent, the vinyl selenide 2a was
obtained together with bis-vinyl selenide 3 in a 1:1 inseparable
mixture (Table 1, entry 2). The results demonstrate that changing
the reaction temperature of sodium selenide with benzyl bromide
and the addition of phenylacetylene to 0 0C favored the formation of
vinyl selenide 2a (Table 1, entry 3). However, the best result was
obtained with the reaction of sodium selenide and benzyl bromide at
to evaluate the effect of optimized conditions in the heteroaryl
halides, we used 2-halopyridines for the preparation of
corresponding 2-pyridineselenol. No significant difference was
observed in the reactivity of 2-bromopyridine and 2-chloropyridine,
which afforded the vinyl selenide 2r in 31% and 41% yields,
respectively (Scheme 2, entry 2r). 2-Bromoethanol was also
investigated as the halide source in the reaction with sodium
selenide, followed by the addition to alkyne, under the optimized
reaction conditions; leading to desired vinyl selenide 2s in 54%
yield (Scheme 2, entry 2s). Sodium telluride also reacted with butyl
bromide giving the corresponding n-butyltellurols, which were
added to terminal alkynes, affording the corresponding vinyl
tellurides in moderate yields (Scheme 2, t-v). These results are
significant because vinyl tellurides are reported in the literature as
important intermediates in organic synthesis, including for the
synthesis of natural products.25 We also extended the condition to
other alkynes, such as terminal alkyl alkynes, internal alkynes,
substituted propargyl alcohols and propargyl amines, but the
corresponding vinyl selenides or tellurides were not formed. The
reaction with terminal alkyl alkynes or internal alkynes gave only
the corresponding selenide 4, indicating that the selenol was formed,
but the reduction of carbon-carbon bond was hampered. The
reaction with propargyl alcohols and amines led to the formation of
product; however, a complete decomposition was observed. All
examples tested that did not give the products are shown in Scheme
S1, in the Supporting Information. In addition, all attempts to obtain
vinyl sulfides from Na2S, alkyl halides and terminal alkynes were
ineffective, even by changing the optimized reaction conditions. All
products were obtained with exclusive stereochemistry Z,
determined by the coupling constant between vinyl hydrogen. This
superior selectivity is attributed to the fact that this may be a
concerted reaction, in which the carbon-selenium bond and the
carbon-hydrogen bonds are formed in a single step (See mechanism
discussion, Scheme 5). The synthesis of functionalized alkenes with
exclusive Z-stereochemistry has important practical aspects, because
such compounds are difficult to prepare, are generally less unstable
and isomerize over the time or during the purification processes.
0
room temperature and the addition of phenylacetylene at 0 C, after
that the reaction was maintained under reflux (Table 1, entry 4).
The reduction of sodium selenide amount from 2.0 equiv to 1.5 and
1.0 equiv negatively influenced the efficiency of the reaction (Table
1, entries 5 and 6). The decrease in the yields of vinyl selenide 2a
was also observed by decreasing the final reaction temperature to 50
and 25 0C (Table 1, entries 7 and 8). Monitoring the chemical
reactions by TLC and CGMS, it was revealed that 2.3 h was the
time required for the reaction to be completed, delivering the
product in good yield (Table 1, entry 9).
Table 1. Effects of different reaction parameters on the preparation of vinyl selenide
2a.a
entry
1
Na2Se (equiv)
T1 (0C)/ t1 (h)
-78/12
-78/12
2/3/4b
0/0/100
1:1:0
2.0
2.0
2.0
2.0
1.5
1.0
2
2c
3
0/12
3:0:1
4c, d
5
6
reflux/12
reflux/12
reflux/12
50/12
100:0:0
8.4:1:0.6
6:3:1
7
8:1:1
8
2
2
r.t./12
reflux/2.3
8:1:1
100:0:0
9c, d
Scheme
2.
Synthesis
of
vinyl
selenides
and
tellurides
2.a
[a] The reaction was performed by the addition of benzyl bromide (0.25 mmol) in EtOH
(3 mL) to a solution of sodium selenide at r.t., under an inert atmosphere. After 30 min,
phenylacetylene (1 equiv) was added at 0 0C and the reaction proceeded at -78 0C for
the time indicated in the Table.
[b] Determined by CGMS.
[c]
DMF/EtOH (4 mL, 3:1) was used as solvent and DMF (1 mL) was used for the
organic halide.
[d] Sodium selenide was added at room temperature and phenylacetylene was added at 0
0C.
We next explored the effect of optimized reaction conditions to
other alkynes and halides (Scheme 2). As shown in Scheme 2, the
optimized reaction conditions could be applied to a variety of
alkynes with electron-withdrawing and electron-donating groups as
well as to benzyl, heteroaryl and alkyl halides. For example, benzyl
halides bearing electron-donating or electron-withdrawing groups in
the aromatic ring gave similar yields to unsubstituted benzyl
bromide, indicating that the electronic effect did not have a severe
influence on the formation of corresponding vinyl selenides
(Scheme 2, 2a-c). Alkyl bromides were also suitable substrates to
the preparation of vinyl selenides under the optimized reaction
conditions. The study on the influence of the linear alkyl chain
length indicated that alkyl halides from 3 to 12 carbons were
efficient to give the products (Scheme 2, 2d-l). The use of
secondary halides; however, did not lead to the formation of vinyl
selenide derivatives (Scheme 2, 2m and n). In these cases, the
halides were recovered, indicating that the product formation was
hampered in the selenol generation step. This probably occurs
because the secondary halides provided a steric hindrance in the
reaction with sodium selenide. In addition to phenylacetylene,
substituted aryl alkynes afforded the vinyl selenides 2o and 2p in
good yields (Scheme 2, 2o and 2p). Under the same reaction
conditions, propynol reacted with selenol, giving 3-
(butylselanyl)prop-2-en-1-ol in 50% yield (Scheme 2, 2q). In order
[a]
The reaction was performed by the addition of halides (0.25 mmol) in DMF (1 mL) to a
sodium selenide (2 equiv), at 0 0C, under an inert atmosphere. After 30 min, phenylacetylene
(1 equiv) was added at 0 0C and the reaction proceeded at reflux for the time indicated in the
Scheme
2
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10.1002/ejoc.201900544
European Journal of Organic Chemistry
Having prepared vinyl selenides, via an intermolecular addition of
selenol to alkynes, we then examined the intramolecular version of
this methodology by the reaction of 2-chlorophenylynones with
sodium selenide for the preparation of selenochromones 5.
Selenochromones are not found in natural products; however, the
synthetic selenochromones were recently reported as anticancer26
and neuroprotective drugs.27 Further exploration of optimized
reaction conditions (Table 1, entry 9) for the reaction of 2-
chlorophenylynone, having a phenyl group directly bonded to the
alkyne, with sodium selenide led to the corresponding
selenochromone 5a in an isolated yield of 72% (Scheme 3, 5a). As
shown in Scheme 3, electron-donating or electron-withdrawing
groups on the aromatic ring of 2-chlorophenylynone had no
significant influence in the yields (Scheme 3, 5b-d). However, the
presence of an alkyl group directly bonded to alkyne led to a
decrease in the yield, probably because the absence of π bonds in
the alkyne decreases the reactivity of the carbon-carbon triple bond
for the selenium nucleophilic attack (Scheme 3, 5e). The
nucleophilic cyclization of 2-chlorophenylynone with sodium
sulfide proceeded smoothly to give thiochromone 5f in 41% yield
(Scheme 3, 5f). When sodium telluride was used, under the same
reaction conditions a complete decomposition of tellurochromones
was observed. The NMR experiments showed that only the 6-endo-
dig product was obtained, which was confirmed by X-ray diffraction
analysis (see Supporting Information).
Scheme 5, Plausible reaction mechanism for the formation of vinyl selenides
2.
Vinyl selenides are useful building blocks for a variety of
stereoselective synthetic transformations, as mentioned in the
introduction of this study. The vinyl selenides have a Csp2-selenium
bond in the structure, which makes them suitable for oxidative
addition on transition metal catalyst and consequently, applicable as
substrates in cross-coupling reactions.28 In order to prove the
synthetic application of compounds prepared in this study, we
subjected the vinyl selenide 2e to the conditions of Kumada, Negishi
and Suzuki cross-coupling reactions and the results are shown in
Scheme 6. Thus, the reaction of vinyl selenide 2e with 4-
methoxyphenyl magnesium bromide catalyzed by Pd(PPh3)4 (10
mol%) in THF (3 mL) at 60 0C gave the styrene derivative 8 in 77%
yield (Scheme 6, eq 1). Conversely, the vinyl selenide 2e underwent
Negishi cross-coupling with 4-methoxyphenyl zinc chloride also
affording the styrene derivative 8 in moderate yields (Scheme 6, eq
2). Finally, the vinyl selenide 2e reacted with 3-acetylphenylboronic
acid under a Suzuki condition giving Z-(3-acetylaryl) styrene 9 in
48% yield (Scheme 6, eq 3).
Scheme 3: Synthesis of selenochromones 5.a
Scheme 6. Synthetic application of vinyl selenide 2e
[a]The reaction was performed by the addition of 2-chlorophenylynones
(0.25 mmol) in DMF (1 mL) to sodium selenide (2 equiv) at 0 0C, under
an inert atmosphere. After 30 min, the reaction proceeded at reflux for 12
h.
Conclusion
In summary, we developed a straightforward procedure for the
steroselective synthesis of Z-vinyl selenides through the reaction of
sodium selenide with organic halides, followed by the addition to
alkynes. The stereodefined Z-double bond was selectively formed
through the anti-Markovnikov addition of selenolate to the carbon-
carbon triple bond with simultaneous trapping of the vinyl anion
with hydrogen from the solvent. Additionally, we applied the same
reaction conditions to a one-pot synthesis of selenochromones
through an intramolecular version of this methodology by the
reaction of 2-chlorophenylynones with sodium selenide. The vinyl
selenides prepared were successfully applied as substrates in the
Kumada, Negishi and Suzuky reactions, giving the cross-coupled
products in good yields. The advantages of this method over the
previously reported hydroselenation reactions are that diorganyl
diselenides and selenol do not need to be previously prepared or
Because the addition of selenol to alkyne led to Z-vinyl selenides
with a high stereoselectivity, we propose that it could involve an
anti-addition of selenol across the triple bond with a concomitant
capture of hydrogen from EtOH, and that the formation of
intermediate 7 (Scheme 5) should be the key step for this procedure.
To support this hypothesis, we carried out the reaction of butyl
bromide with sodium selenide and phenylacetylene, under optimized
reaction conditions, using EtOD as solvent, and the Z-deuterated
vinyl selenide 6 was obtained in 54% yield (Scheme 4). This
experiment proved that the reaction occurs via a Michael-type
addition of a selenolate anion onto the triple bond followed by
trapping of the vinyl anion with a proton from the alcohol. In
addition, the use of DMF as solvent could stabilize the selenolate
anion favoring the addition to alkyne over nucleophilic substitution,
which gave the undesired diorganyl selenides.
handled. All compounds prepared were characterized by 1H and 13
C
NMR spectroscopy, and the structures of 5c (CCDC 1880377) and
5d (CCDC 1880339) were elucidated by X-ray crystallography,
which indicated that the cyclization occurred via 6-endo-dig mode.
Scheme 4, Preparation of Z-deuterated vinyl selenide 6
3
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10.1002/ejoc.201900544
European Journal of Organic Chemistry
131.72, 130.19, 129.58, 128.29, 128.15, 127.99, 125.90. 77Se NMR (77 MHz, in CDCl3
with diphenyl diselenide as external reference): δ = 394. MS (EI, 70 eV; m/z (relative
intensity)): 320 (57), 285 (14), 207 (25), 183 (100), 132 (49). HRMS (ESI-TOF) m/z
calcd for C15H10ClOSe (M + H+): 320.9585, found: 320.9591: 552.0378.
Experimental Section
General procedure for the synthesis of Vinylic Selenides 2
Acknowledgements
To a Schlenck tube, under a nitrogen atmosphere, containing solution of Na2Se (0.5
mmol) which was prepared from selenium powder (0.5 mmol) and NaBH4 (1.0 mmol)
in DMF (3 mL) at 70 0C for 0.5 h, were added (0.25 mmol) organic halide in 1 mL of
DMF was added dropwise at 0 0C. The solution was stirred for 0.5 h and then warmed
to room temperature. The solution was cooled to 0 0C, and the alkyne (0.25 mmol) in 1
mL of EtOH was added dropwise. The mixture was then heated in oil bath for 1.5-12 h
at 70 0C. After the reaction was cooled to room temperature and diluted with ethyl
acetate (10 mL) and then washed with saturated solution of NH4Cl (20 mL). The
organic phase was separated, dried over MgSO4 and concentrated under vacuum. The
residue was purified by flash chromatography.
We are grateful to FAPERGS, CAPES and CNPq for financial support. CNPq and
CAPES are also acknowledged for the fellowships (R. P. P and G. Z.).
[1]
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Compounds (Eds.: Z. Rappoport), John Wiley & Sons, Chichester, 2012, vol. 3,
pp 1-1370.
(Z)-benzyl(styryl)selane (2a). The product was isolated by column chromatography
(hexane as eluent) as a yellow oil. Yield: 0.45g (66 %). 1H NMR (400 MHz, CDCl3): δ
(ppm) 7.39-7.19 (m, 10H), 6.86 (d, J = 10.6 Hz, 1H), 6.62 (d, J = 10.6 Hz, 1H), 4.00 (s,
2H). 13C NMR (100 MHz, CDCl3): δ (ppm) 138.16, 137.42, 129.59, 128.97, 128.65,
128.45, 128.25, 127.07, 126.95, 121.96, 31.53. MS (EI, 70 eV; m/z (relative intensity)):
274 (10), 183 (8), 102 (10), 91 (100), 65 (11). HRMS (ESI-TOF) m/z calcd for
[2]
[3]
P. von R. Schleyer, J. Am. Chem. Soc. 1957, 79, 3292-3293.
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15H15Se (M + H+): 275.0339, found: 275.0313.
(Z)-(4-methylbenzyl)(styryl)selane (2b). The product was isolated by column
chromatography (hexane as eluent) as a yellow oil. Yield: 0.036g (50 %). 1H NMR (400
MHz, CDCl3): δ (ppm) 7.30-7.39 (d, J = 6.5 Hz, 4H), 7.25-7.19 (m, 3H), 7.12 (m, 2H),
6.86 (d, J = 10.6 Hz, 1H), 6.62 (d, J = 10.6 Hz, 1H), 3.98 (s, 2H), 2.32 (s, 3H).13C NMR
(100 MHz, CDCl3): δ (ppm), 137.57, 136.82, 135.12, 129.57, 129.40, 128.91, 128.32,
128.28, 126.96, 122.16, 31.39, 21.14. MS (EI, 70 eV; m/z (relative intensity)): 288 (40),
182 (72), 115 (20), 102 (14), 88 (10) HRMS (ESI-TOF) m/z calcd for C16H17Se (M +
H+): 289.0495, found: 289.0481.
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(a) L. Flohe, W. A. Günzler, H. H. Schock, FEBS Lett. 1973, 32, 132-134; (b) J.
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Compounds (Eds.: Z. Rappoport), John Wiley & Sons, Chichester, 2012, vol. 3,
pp 623-688.
(Z)-(4-chlorobenzyl)(styryl)selane (2c). The product was isolated by column
chromatography (hexane as eluent) as a yellow oil. Yield: 0.038g (50 %). 1H NMR (400
MHz, CDCl3): δ (ppm) 7.33 (d, J = 4.4 Hz, 4H), 7.27-7.14 (m, 5H), 6.87 (d, J = 10.6 Hz,
1H), 6.55 (d, J = 10.6 Hz, 1H), 3.94 (s, 2H). 13C NMR (100 MHz, CDCl3): δ (ppm),
137.37, 136.85, 132.88, 130.28, 130.15, 128.80, 128.63, 128.29 127.11, 121.44, 30.67.
MS (EI, 70 eV; m/z (relative intensity)): 308 (11), 184 (11), 125 (100), 102 (12), 89 (11).
HRMS (ESI-TOF) m/z calcd for C15H14ClSe (M + H+): 308.9949, found: 308.9938.
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8040.
(Z)-propyl(styryl)selane (2d). The product was isolated by column chromatography
(hexane as eluent) as a yellow oil. Yield: 0.038g (68 %). 1H NMR (400 MHz, CDCl3): δ
(ppm) 7.45-7.31 (m, 4H), 7.26-7.20 (m, 1H), 6.88 (d, J = 10.6 Hz, 1H), 6.61 (d, J = 10.6
Hz, 1H), 2.77 (t, J = 7.3 Hz, 2H), 1.79 (Sex, J = 7.3 Hz, 2H), 1.02 (t, J = 7.3 Hz, 3H).
13C NMR (100 MHz, CDCl3): δ (ppm) 137.65, 129.30, 128.32, 128.28, 126.89, 123.24,
31.25, 24.06, 14.34. MS (EI, 70 eV; m/z (relative intensity)): 226 (73), 183 (100), 102
(78), 91 (46), 77 (50). HRMS (ESI-TOF) m/z calcd for C11H15Se (M + H+): 227.0339,
found: 227.0347.
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2-phenyl-4H-selenochromen-4-one (5a). The product was isolated by column
chromatography (hexane and ethyl acetate 99:1 as eluent) as a yellow solid. Yield:
0.051g (72 %); mp 150-152. 1H NMR (400 MHz, CDCl3): δ (ppm) 8.65-8.57 (m, 1H),
7.72-7.64 (m, 1H), 7.66-7.59 (m, 2H), 7.58-7.43 (m, 5H), 7.36 (s, 1H). 13C NMR (100
MHz, CDCl3): δ (ppm), 182.74, 153.94, 138.15, 136.83, 131.78, 131.54, 130.63, 130.09,
129.27, 128. 77Se NMR (77 MHz, in CDCl3 with diphenyl diselenide as external
reference): δ = 391. MS (EI, 70 eV; m/z (relative intensity)): 286 (67), 207 (23), 183
(100), 102 (13), 75 (12). HRMS (ESI-TOF) m/z calcd for C15H11OSe (M + H+):
286.9975, found: 286.9983.
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2-(p-tolyl)-4H-selenochromen-4-one (5b). The product was isolated by column
chromatography (hexane and ethyl acetate 99:1 as eluent) as a yellow solid. Yield:
0.051g (68 %); mp 140-142 oC. 1H NMR (400 MHz, CDCl3): δ 8.63-8.56 (m, 1H), 7.71-
7.63 (m, 1H), 7.55-7.48 (m, 4H), 7.37 (s, 1H), 7.29-7.25 (m, 2H), 2.40 (s, 3H). 13C
NMR (100 MHz, CDCl3): δ (ppm), 182.72, 154.25, 141.18, 136.88, 135.24, 131.73,
131.47, 130.03 129.96, 128.25, 127.73, 126.70, 124.92, 21.27. MS (EI, 70 eV; m/z
(relative intensity)): 301 (55), 272 (15), 207 (36), 183 (100), 115 (39). HRMS (ESI-
TOF) m/z calcd for C16H13OSe (M + H+): 301.0132, found: 301.0150.
[13] H. J. Reich, M. D. Bowe, J. Am. Chem. Soc. 1990, 112, 8994-8995.
[14] L. Testaferri, M. Tiecco, M. Tingoli, D. Chianelli, Tetrahedron 1985, 41, 1401-
1408.
[15] M. Palomba, F. Trappetti, L. Bagnoli, C. Santi, F. Marini, Eur. J. Org. Chem.
2018, 2018 3914-3919.
2-(4-methoxyphenyl)-4H-selenochromen-4-one (5c). The product was isolated by
column chromatography (hexane and ethyl acetate 99:1 as eluent) as a yellow solid:
0.050g (63 %); mp 118-120 oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 8.66-8.58 (m,
1H), 7.74-7.66 (m, 1H), 7.66-7.57 (m, 2H), 7.59-7.48 (m, 2H), 7.35 (s, 1H), 7.06 -6.97
(m, 2H), 3.89 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm), 182.86, 161.76, 153.71,
136.73, 131.76, 131.46, 130.41, 130.01, 129.30, 128.26, 127.72, 124.32, 114.69, 55.46.
MS (EI, 70 eV; m/z (relative intensity)): 316 (75), 288 (12), 207 (25), 183 (87), 132
(100). HRMS (ESI-TOF) m/z calcd for C16H13O2Se (M + H+): 317.0081, found:
317.0089.
[16] Y. Sumino, N. Harato, Y. Tomisaka, A. Ogawa, Tetrahedron 2003, 59, 10499-
10508.
[17] (a) V. A. Potapov, M. V. Musalova, R. S. Ishigeev, M. V. Musalov, V. A. Panov,
A. G. Khabibulina, S. V. Amosova, K. K. Bhasin, Tetrahedron Lett. 2016, 57,
5341-5343. (b) G. Zeni, M. P. Stracke, C. W. Nogueira, A. L. Braga, P. H.
Menezes, H. A. Stefani, Org. Lett. 2004, 6, 1135-1138. (c) V. A. Potapov, S. V.
Amosova, Phosphorus, Sulfur Silicon Relat. Elem. 1993, 79, 277-280.
2-(4-chlorophenyl)-4H-selenochromen-4-one (5d). The product was isolated by
column chromatography (hexane and ethyl acetate 99:1 as eluent) as a yellow solid.
Yield: 0.059g (74 %); mp 128-130 oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 8.63-8.56
(m, 1H), 7.73-7.62 (m, 1H), 7.60-7.48 (m, 4H), 7.47-7.43 (m, 2H), 7.37-7.24 (m, 1H).
13C NMR (100 MHz, CDCl3): δ (ppm), 182.62, 152.29, 136.97, 136.64, 136.52, 132.98,
[18] R. Kadikova, I. Ramazanov, A. Vyatkin, U. Dzhemilev, Synthesis 2017, 49,
4523-4534.
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10.1002/ejoc.201900544
European Journal of Organic Chemistry
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Compounds (Ed.: Z. Rappoport) John Wiley & Sons, Chichester, 2013, vol. 4,
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1032-1076.
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10.1002/ejoc.201900544
European Journal of Organic Chemistry
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Entry for the Table of Contents (Please choose one layout only)
Layout 2:
Heterocycle −−−−−−−−−−−−−−−
Renan P. Pistoia,[a] Davi F. Back,[b]
and Gilson Zeni*[a] ………..… Page
– Page
Stereoselective Synthesis of Z-
Vinyl Selenides through the
Reaction of Sodium Selenide
with Organic Halides and
Alkynes
We
have
developed
an
with organic halides, followed by
the addition of alkynes.
stereoselective synthesis of Z-
vinyl selenides through the
reaction of sodium selenide
3
6
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