Synthesis of [3-(trimethylsilyl)prop-2-yn-1-yl] selenides

Article abstract of DOI:10.1134/S1070428017100049

Efficient and selective methods have been developed for the synthesis of previously unknown organyl [3-(trimethylsilyl)prop-2-yn-1-yl] selenides, organyl prop-2-yn-1-yl selenides, and bis[3-(trimethylsilyl) prop-2-yn-1-yl] selenide by reactions of 3-bromo

Full text of DOI:10.1134/S1070428017100049

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 10, pp. 1510–1513. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © M.V. Musalov, M.V. Andreev, S.V. Amosova, L.I. Larina, V.A. Potapov, 2017, published in Zhurnal Organicheskoi Khimii, 2017,
Vol. 53, No. 10, pp. 1483–1486.
Synthesis of [3-(Trimethylsilyl)prop-2-yn-1-yl] Selenides
M. V. Musalov, M. V. Andreev, S. V. Amosova,* L. I. Larina, and V. A. Potapov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*
e-mail: amosova@irioch.irk.ru
Received May 30, 2017
Abstract—Efficient and selective methods have been developed for the synthesis of previously unknown
organyl [3-(trimethylsilyl)prop-2-yn-1-yl] selenides, organyl prop-2-yn-1-yl selenides, and bis[3-(trimethyl-
silyl)prop-2-yn-1-yl] selenide by reactions of 3-bromo-1-(trimethylsilyl)prop-1-yne with the corresponding
organylselenolates and sodium selenide generated from diorganyl diselenides or elemental selenium by the
action of sodium tetrahydridoborate.
DOI: 10.1134/S1070428017100049
Unsaturated organoselenium compounds possess
a high synthetic potential and are extensively used as
intermediate products in organic synthesis [1–8].
Unsaturated diorganyl selenides can be synthesized by
reactions involving generation of organylselenolate
ions [1, 2, 9–11]. Organoselenium compounds exhibit
biological activity; in particular, like glutathione
peroxidase, they are capable of catalyzing peroxide
reduction in mammalians [3, 4].
selenolate and subsequent treatment with propargyl
bromide [18]. Analogous reactions with diorganyl
ditellurides afforded allenyl tellurides instead of
propargyl tellurides [19]. Base-catalyzed prototropic
rearrangement of methyl propargyl selenide gave
allenyl methyl selenide [18].
We have synthesized organyl [3-(trimethylsilyl)-
prop-2-yn-1-yl] selenides 1–3 in 80–92% yield by
reaction of the corresponding diorganyl diselenides
with sodium tetrahydridoborate and 3-bromo-1-(tri-
methylsilyl)prop-1-yne (Scheme 1). The action of
Propargyl selenides are important building blocks
for the synthesis of organic compounds [12–17].
However, only alkynyl aryl selenides, mostly phenyl
propargyl selenide [13, 16, 17], have been used so far.
A number of unsaturated ketones and sesquiterpene
NaBH on diorganyl diselenide generates in situ
4
sodium organylselenolate which reacts with 3-bromo-
1-(trimethylsilyl)prop-1-yne to give selenides 1–3;
here, 1 mol of the initial diselenide gives rise to 2 mol
of the product. It should be noted that no desilylation
products were formed when the reaction was carried
out in methanol or ethanol, so that compounds 1–3
were obtained with high selectivity.
7
-hydroxymyoporone were synthesized on the basis of
phenyl propargyl selenide [13].
Published data on the synthesis of alkyl propargyl
selenides are few in number [15–18]. We have recently
synthesized previously unknown methyl propargyl
selenide by reduction of dimethyl diselenide with
sodium tetrahydridoborate to sodium methane-
The reactions of dipropyl and dibenzyl diselenides
with 3-bromo-1-(trimethylsilyl)prop-1-yne in methanol
Scheme 1.
NaBH , EtOH (MeOH)
4
Br
SeR
RSeSeR
+
2
2
Me Si
Me Si
3
3
1
–3
Br
NaBH , EtOH (MeOH)
Me Si
4
3
2
[RSeNa]
1
, R = Ph; 2, R = PhCH
2
; 3, R = Pr.
1
510

SYNTHESIS OF [3-(TRIMETHYLSILYL)PROP-2-YN-1-YL] SELENIDES
1511
Scheme 2.
NaBH , EtOH (MeOH)
4
Br
Se
Se
+
2
2
Me Si
Me Si
SiMe3
3
3
4
Br
NaBH , EtOH (MeOH)
Me Si
3
4
[
Na Se]
2
at room temperature were accompanied by formation
of up to 10% of bis[3-(trimethylsilyl)prop-2-yn-1-yl]
selenide (4) as by-product. When these reactions were
carried out in ethanol on cooling to ‒20°C, the yield of
EXPERIMENTAL
The NMR spectra were recorded from solutions in
CDCl on a Bruker DPX-400 spectrometer operating at
3
1
13
29
4
(
00.13 ( H), 100.61 ( C), 79.5 ( Si), or 76.3 MHz
4
was reduced to 2%. No selenide 4 was detected in
7
7
29
77
Se); the Si and Se chemical shifts were measured
the reaction with diphenyl diselenide. Presumably,
selenide 4 is formed via side dealkylation of 2 and 3 by
the action of phenylmethane- or propane-1-selenolate
ion. We have synthesized selenide 4 in 81% yield by
reaction of 3-bromo-1-(trimethylsilyl)prop-1-yne with
sodium selenide in ethanol (Scheme 2).
relative to hexamethyldisiloxane and dimethyl sele-
nide, respectively. The solvents used were prelimi-
narily dried and distilled. The elemental analyses were
obtained on a Thermo Flash EA1112 analyzer.
Phenyl [3-(trimethylsilyl)prop-2-yn-1-yl] sele-
nide (1). Sodium tetrahydridoborate, 100 mg
2.63 mmol), was added in small portions under argon
Desilylation of 1–3 by the action of K CO in
2
3
(
ethanol afforded the corresponding organyl propargyl
to a solution of 200 mg (0.64 mmol) of diphenyl
diselenide and 260 mg (1.36 mmol) of 3-bromo-1-
(trimethylsilyl)prop-1-yne in 7 mL of methanol. The
mixture was stirred for 4 h at room temperature in
a closed vessel, diluted with degassed water (10 mL),
and extracted with carbon tetrachloride (3×10 mL).
The extract was dried over Na SO and filtered, the
selenides 5–7 in high yields (90–94%; Scheme 3).
Scheme 3.
K CO , EtOH
SeR
2
3
SeR
HC
Me Si
3
1
–3
5–7
2
4
5
2
, R = PhCH ; 6, R = Pr; 7, R = Ph.
solvent was distilled off from the filtrate on a rotary
evaporator, and the residue was dried under reduced
The reaction in ethanol at room temperature was
chemoselective, and compounds 5‒7 were the only
products. Desilylation of 1 in methanol, other condi-
tions being equal, gave 50% of propargyl selenide 7
and 45% of allenyl phenyl selenide 8 (Scheme 4).
pressure. Yield 315 mg (92%), yellowish liquid.
1
H NMR spectrum, δ, ppm: 0.13 s (9H, Me Si), 3.52 s
3
2
(
2H, CH , J
= 13.5 Hz), 7.29–7.31 m (3H, p-H,
2
Se–H
1
3
m-H), 7.61–7.63 m (2H, o-H). C NMR spectrum, δ ,
C
ppm: 0.02 (CH Si), 13.86 (CH ), 88.88 (SiC≡), 102.70
3
2
p
m
i
(
≡CCH ), 127.88 (C ), 129.05 (C ), 129.58 (C ),
Scheme 4.
2
o
29
1
34.10 (C ). Si NMR spectrum: δSi –18.2 ppm.
K CO , MeOH
SePh
2
3
SePh
77
HC
Se NMR spectrum: δSe 381.0 ppm. Found, %:
C 53.85; H 6.14; Se 29.83; Si 10.35. C H SeSi. Cal-
Me Si
3
12
16
1
7
culated, %: C 53.92; H 6.03; Se 29.54; Si 10.51.
·
SePh
Compounds 2 and 3 were synthesized in a similar
way.
+
H C
2
8
Benzyl [3-(trimethylsilyl)prop-2-yn-1-yl] selenide
1
The structure of the synthesized compounds was
(
2). Yield 83%, yellowish liquid. H NMR spectrum, δ,
1
13
28
77
2
confirmed by H, C, Si, and Se NMR spectra and
ppm: 0.22 s (9H, Me Si), 3.11 s (2H, CH C≡, J =
3
2
Se–H
1
3
2
elemental analyses. Signals in the C NMR spectra
were assigned using HMBC technique.
1
4.8 Hz), 3.98 s (2H, CH Ph, J
= 13.9 Hz).
Se–H
2
1
3
C NMR spectrum, δ , ppm: 0.22 (CH Si), 8.63
C
3
Thus, we have proposed efficient and selective
methods for the preparation of previously unknown
propargyl selenides that are promising as intermediate
products in organic synthesis.
(CH C≡), 27.56 (CH Ph), 88.60 (SiC≡), 102.76
2 2
p
m
o
(≡CCH ), 126.96 (C ), 128.68 (C ), 129.04 (C ),
2
i
29
138.99 (C ). Si NMR spectrum: δSi –18.2 ppm.
7
7
Se NMR spectrum: δSe 345.2 ppm. Found, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 10 2017

1
512
MUSALOV et al.
C 55.74; H 6.65; Se 27.83; Si 10.14. C H SeSi.
Calculated, %: C 55.50; H 6.45; Se 28.07; Si 9.98.
Compounds 6 and 7 were synthesized in a similar
way.
1
3
18
Propyl [3-(trimethylsilyl)prop-2-yn-1-yl] selenide
3). Yield 80%, yellowish liquid. H NMR spectrum, δ,
Propyl prop-2-yn-1-yl selenide (6). Yield 90%,
1
1
(
yellowish liquid. H NMR spectrum, δ, ppm: 1.02 t
4
ppm: 0.16 s (9H, Me Si), 1.02 t (3H, CH ), 1.72 m
(3H, CH ), 1.69 m (2H, CH ), 2.08 t (1H, CH, J =
3
3
3
2
4
(
2H, CH ), 2.75 t (2H, SeCH ), 3.22 s (2H, (≡CCH ).
2.6 Hz), 2.68 t (2H, SeCH ), 3.08 d (2H, SeCH , J =
2
2
2
2 2
1
3
13
C NMR spectrum, δ , ppm: 0.18 (CH Si), 7.84
2.6 Hz). C NMR spectrum, δ , ppm: 6.83 (SeCH ),
C 2
C
3
(
8
SeCH ), 14.87 (CH ), 23.68 (CH ), 26.89 (CH ),
14.93 (CH ), 23.66 (CH ), 26.98 (CH ), 71.39 (≡CH),
81.17 (≡C). Found, %: C 44.57; H 6.43; Se 48.76.
2
3
2
2
3 2 2
2
9
8.57 (SiC≡), 102.78 (≡CCH ). Si NMR spectrum:
2
δSi –18.2 ppm. Found, %: C 46.05; H 8.02; Se 34.15;
C H Se. Calculated, %: C 44.73; H 6.26; Se 49.01.
6
10
Si 11.85. C H SeSi. Calculated, %: C 46.34; H 7.78;
9
18
Phenyl prop-2-yn-1-yl selenide (7). Yield 93%,
yellowish liquid.
Se 33.85; Si 12.04.
Bis[3-(trimethylsilyl)prop-2-yn-1-yl] selenide (4).
Sodium tetrahydridoborate, 70 mg (1.85 mmol), was
added in small portions under argon to a mixture of
Allenyl phenyl selenide (8). Potassium carbonate,
28 mg (6 mmol), was added to a solution of 267 mg
1 mmol) of selenide 1 in 15 mL of anhydrous
8
(
5
0 mg (0.63 mmol) of selenium and 5 mL of methanol
methanol, and the mixture was stirred for 24 h at room
temperature under argon. The mixture was diluted with
cold degassed water (30 mL) and extracted with
carbon tetrachloride (3 ×15 mL). The extract was
washed with water and dried over Na SO , the solvent
until the mixture became colorless. A solution of
2
1
10 mg (1.1 mmol) of 3-bromo-1-(trimethylsilyl)prop-
-yne in 1 mL of methanol was added, and the mixture
was stirred for 4 h at room temperature in a closed
vessel. The mixture was then diluted with degassed
water (15 mL) and extracted with carbon tetrachloride
2
4
was removed on a rotary evaporator, and the residue
was dried under reduced pressure. The product was
85 mg of a mixture of selenides 7 (98 mg, 50%) and 8
87 mg, 45%) which were separated by column
chromatography on silica gel (hexane–chloroform,
:1). Compounds 7 and 8 were described previously
(
3×15 mL). The extract was dried over Na SO and
2 4
1
(
filtered, the solvent was distilled off from the filtrate
on a rotary evaporator, and the residue was dried under
reduced pressure. Yield 135 mg (81%), yellowish
6
[
1
liquid. H NMR spectrum, δ, ppm: 0.16 s (18H,
13, 16, 17].
2
13
Me Si), 3.41 s (4H, CH , J
= 14.0 Hz). C NMR
3
2
Se–H
1
The spectral studies were performed using the
facilities of the Baikal Joint Analytical Center, Siberian
Branch, Russian Academy of Sciences.
spectrum, δ , ppm: 0.16 (CH Si), 9.57 (CH , J
47.9 Hz), 88.58 (SiC≡), 102.00 (≡CCH ). Si NMR
spectrum: δSi –18.1 ppm. Se NMR spectrum:
δSe 339.6 ppm. Found, %: C 48.07; H 7.53; Se 25.92;
Si 18.34. C H SeSi . Calculated, %: C 47.81; H 7.36;
=
C
3
2
CH
2
9
1
2
7
7
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22
2
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SYNTHESIS OF [3-(TRIMETHYLSILYL)PROP-2-YN-1-YL] SELENIDES
1513
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