Stereoselective synthesis of (Z,E)-bis(2-chloroethenyl)tellanes

Article abstract of DOI:10.1134/S1070428017100177

A procedure for the stereoselective synthesis of dichloro[(Z)-2-chloro-2-phenylethenyl][(4E)-5- chlorooct-4-en-4-yl]-λ⁴-tellane and [(Z)-2-chloro-2-phenylethenyl][(4E)-5-chlorooct-4-en-4-yl]tellane has been developed on the basis of anti-additi

Full text of DOI:10.1134/S1070428017100177

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 10, pp. 1593–1595. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © M.V. Musalova, A.G. Khabibulina, V.A. Potapov, S.V. Amosova, 2017, published in Zhurnal Organicheskoi Khimii, 2017, Vol. 53,
No. 10, pp. 1557–1559.
SHORT
COMMUNICATIONS
Stereoselective Synthesis of (Z,E)-Bis(2-chloroethenyl)tellanes
M. V. Musalova, A. G. Khabibulina, V. A. Potapov, and S. V. Amosova*
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—A procedure for the stereoselective synthesis of dichloro[(Z)-2-chloro-2-phenylethenyl][(4E)-5-
chlorooct-4-en-4-yl]-λ4-tellane and [(Z)-2-chloro-2-phenylethenyl][(4E)-5-chlorooct-4-en-4-yl]tellane has been
developed on the basis of anti-addition of tellurium tetrachloride–phenylacetylene monoadduct to oct-4-yne.
DOI: 10.1134/S1070428017100177
Vinyl tellurides containing a halogen atom at the
double bond with a predetermined configuration are
important intermediate products in organic synthesis
[1]. In particular, they are used for stereoselective
synthesis of alkenes via successive substitution of the
halogen atom and tellurium-containing group at the
double bond in cross-coupling reactions with retention
of the double bond configuration [1, 2].
propargyl ether [14] were reported to produce E
isomers as a result of anti-addition.
In this communication we describe the synthesis of
the first representatives of bis(2-haloethenyl)-λ4-tel-
lanes and -λ2-tellanes having Z,E-configuration of the
double bonds. The reaction of tellurium tetrachloride
with phenylacetylene in CCl4‒PhH (9:1) followed the
syn-addition path, presumably through four-membered
cyclic transition state, with quantitative formation of
trichloro[(Z)-2-chloro-2-phenylethenyl]-λ4-tellane (1)
[4]. The subsequent stereoselective reaction of 1 with
oct-4-yne (anti-addition) afforded dichloro[(4E)-5-
chlorooct-4-en-4-yl][(Z)-2-chloro-2-phenylethenyl]-λ4-
tellane (3) in 92% yield.
Tellane 1 reacted with oct-4-yne on heating in
boiling benzene. The anti-addition of 1 to oct-4-yne is
likely to proceed through three-membered tellurire-
nium intermediate 2, by analogy with the reaction of
tellurium tetrachloride with oct-4-yne [13]. The forma-
tion of such intermediates was presumed in a number
of addition reactions of tellurium-containing electro-
Development of procedures for stereoselective syn-
thesis of 2-halovinyl tellurides is an important problem
of organotellurium chemistry. These compounds can
be obtained by addition of tellurium tetrachloride to
acetylenic compounds, which is often characterized by
high regio- and stereoselectivity [1–14]. Tellurium
tetrachloride reacts with phenylacetylene [3, 4], phenyl-
(alkyl)acetylenes [5], and diphenylacetylene [3], as
well as with alkylacetylenes and their derivatives
[6–9], to give the corresponding syn-addition products
with Z configuration of the double bond. The reactions
of tellurium tetrachloride with unsubstituted acetylene
[10, 11], hex-3-yne [12], oct-4-yne [13], and phenyl
Ph
Pr
PhH
Pr
Pr
Ph
H
Cl
CCl4–PhH
TeCl4
+
Ph
CH
Cl–
Cl3Te
Te
Cl
Cl
Ph
Cl
Cl TeCl3
Pr
1
2
Pr
Pr
Na2S2O5, PhH–H2O
Cl
Ph
Cl
Ph
Te
Te
Cl
Cl
Pr
Cl
Pr
Cl
3
4
1593

MUSALOVA et al.
1594
philes with alkynes [3, 12–15]; and in some cases they
were isolated and characterized [15].
tellane 3 in 25 mL of benzene, and the mixture was
stirred for 2 h at room temperature. The organic layer
was separated and dried over Na2SO4, the solvent was
removed on a rotary evaporator, and the residue was
dried under reduced pressure. Yield 0.711 g (94%),
By reduction of tellane 3 with sodium metabisulfite
(Na2S2O5) in a two-phase system (water–benzene) we
obtained 94% of [(Z)-2-chloro-2-phenylethenyl]-[(4E)-
5-chlorooct-4-en-4-yl]tellane (4). The synthesis of 4
can be accomplished in a one-pot manner without
isolation of λ4-tellane 3. In this case, an aqueous
solution of Na2S2O5 was added to the benzene solution
containing compound 3, and the mixture was stirred
for 2 h at room temperature.
1
yellowish oily material. H NMR spectrum, δ, ppm:
1.05‒1.16 m (6H, CH3), 1.72‒1.85 m (4H, CH2), 2.87 t
(2H, CH2), 2.96 t (2H, CH2), 7.34‒7.47 m (3H, Ph),
7.59‒7.66 m (2H, Ph). 13C NMR spectrum, δC, ppm:
13.78 (CH3), 14.74 (CH3), 21.99 (CH2), 23.19 (CH2),
42.77 (=CCH2), 45.77 (=CCH2), 106.48 (TeCH=),
115.67 (TeC=), 126.51 (CHarom), 128.71 (CHarom),
128.76 (CHarom); 138.04, 138.28, 138.87 (Carom, ClC=).
Found, %: C 47.06; H 5.09; Cl 16.98. C16H20Cl2Te.
Calculated, %: C 46.78; H 4.91; Cl 17.26.
The structure of compounds 3 and 4 was proved by
1H and 13C NMR spectra and elemental analyses; the
configuration of the double bonds therein was deter-
mined by NOESY experiments. Compounds 3 and 4
are the first representatives of (Z,E)-bis(2-halo-
ethenyl)tellanes that are promising intermediate
products for organic synthesis.
The solvents were preliminarily dried and distilled
just before use. The NMR spectra were recorded on
a Bruker DPX-400 spectrometer at 400.13 (1H) and
100.61 MHz (13C) using CDCl3 as solvent and hexa-
methyldisiloxane as internal standard.
Dichloro[(4E)-5-chlorooct-4-en-4-yl]-
[(Z)-2-chloro-2-phenylethenyl]-λ4-tellane (3). A solu-
tion of 0.204 g (2 mmol) of phenylacetylene in 4 mL
of benzene was added to a mixture of 0.539 g
(2 mmol) of tellurium tetrachloride and 36 mL of
carbon tetrachloride. The mixture was refluxed for
10 h with stirring under argon, the solvent was
removed on a rotary evaporator, and the residue was
dried under reduced pressure. We thus isolated 0.743 g
(quantitative yield) of tellane 1 as an off-white mate-
rial. Compound 1, 0.743 g (2 mmol), was mixed with
20 mL of benzene, a solution of 0.25 g (2.27 mmol) of
oct-4-yne in 5 mL of benzene was added, and the mix-
ture was refluxed for 10 h with stirring. The mixture
was filtered, the solvent was distilled off on a rotary
evaporator, and the residue was dried under reduced
pressure. Yield 0.886 g (92%), off-white material.
1H NMR spectrum, δ, ppm: 0.92‒1.01 m (6H, CH3),
1.76‒1.87 m (4H, CH2), 2.83 m (2H, CH2), 3.12 m
(2H, CH2), 7.39‒7.52 m (3H, Ph), 7.68‒7.76 m (2H,
Ph), 8.27 s (1H, =CHTe). 13C NMR spectrum, δC, ppm:
13.72 (CH3), 13.93 (CH3), 21.33 (CH2), 22.09 (CH2),
36.29 (=CCH2), 44.01 (=CCH2), 121.81 (TeCH=),
127.44 (CHarom), 128.94 (CHarom), 129.09 (CHarom),
131.56 (CHarom), 133.85 (Carom), 135.31 (ClC=), 147.42
(ClC=). Found, %: C 40.27; H 4.03; Cl 29.72.
C16H20Cl4Te. Calculated, %: C 39.89; H 4.18;
Cl 29.44.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 16-33-60199 mol_a_dk). The spectral studies were
carried out at the Baikal Joint Analytical Center
(Siberian Branch, Russian Academy of Sciences).
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