Transition metal-catalyzed cross-coupling of 1,4-diiodobutadienes with thiols - A novel route to 1,4-bis(R-sulfanyl)buta-1,3-dienes

Article abstract of DOI:10.1134/s1070428008010028

Cross-coupling of 1,4-diiodobuta-1,3-dienes with thiols in the presence of Pd, Ni, and Cu complexes gives 1,4-bis[aryl(alkyl)sulfanyl]buta-1,3-dienes in high yields.

Full text of DOI:10.1134/s1070428008010028

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 1, pp. 24–30. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.G. Trostyanskaya, E.N. Maslova, M.A. Kazankova, I.P. Beletskaya, 2008, published in Zhurnal Organicheskoi Khimii, 2008,
Vol. 44, No. 1, pp. 32–38.
Transition Metal-Catalyzed Cross-Coupling
of 1,4-Diiodobutadienes with Thiols—A Novel Route
to 1,4-Bis(R-sulfanyl)buta-1,3-dienes
I. G. Trostyanskaya, E. N. Maslova, M. A. Kazankova, and I. P. Beletskaya
Faculty of Chemistry, Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
e-mail: beletska@org.chem.msu.ru
Received February 2, 2007
Abstract—Cross-coupling of 1,4-diiodobuta-1,3-dienes with thiols in the presence of Pd, Ni, and Cu com-
plexes gives 1,4-bis[aryl(alkyl)sulfanyl]buta-1,3-dienes in high yields.
DOI: 10.1134/S1070428008010028
α,ω-Bis(R-sulfanyl)alkadienes are poorly explored
and difficultly accessible compounds. On the other
hand, their use in the synthesis of functionally substi-
tuted carbo- [1, 2] and heterocyclic derivatives [3–5]
has been reported. Buta-1,3-diene-1,4-dithiols are pre-
cursors of important analogs of naturally occurring
compounds such as thiarubrines (1,2-dithiine deriva-
tives) [6–8] that exhibit a broad spectrum of biological
activity, including antiviral [9], antibacterial [10, 11],
and antitumor action [12]; they also showed a con-
siderable anti-HIV-1 effect [13].
diyl cation in Pd- or Ni-catalyzed cross-couplings with
carbon- and heteroelement-centered nucleophiles [39].
Taking into account synthetic importance of bis(sul-
fanyl)dienes and our interest in developing new cata-
lytic methods for building up sp2- and sp-carbon–
heteroelement bonds [40–44], in the present work we
examined cross-coupling reactions of (E,E′)-1,4-di-
iodobuta-1,3-diene and (Z,Z′)-1,4-diiodo-1,4-diphenyl-
buta-1,3-diene with benzene- and alkanethiols in the
presence of transition metal complexes. We anticipated
that this reaction will provide a simpler and general
procedure for the synthesis of bis(sulfanyl)butadienes.
1,4-Bis(sulfanyl)buta-1,3-dienes are usually syn-
thesized by addition of thiols to diacetylene [14] and
substituted diacetylenes [7, 8, 15] in the presence of
a base or by reaction of 1,4-dilithiobuta-1,3-diene with
disulfides or thiols [7, 16]. Nucleophilic replacement
of halogen in polyhalobutadienes by thiols in alkaline
medium was also reported [17–19]. However, the
yields of 1,4-bis(sulfanyl)buta-1,3-dienes thus obtained
were quite moderate, and the reactions were accom-
panied by formation of difficultly separable mixtures
of mono- and disubstitution and addition products.
Using the reaction of (E,E′)-1,4-diiodobuta-1,3-
diene (Ia) with benzenethiol (IIa) as an example
(Scheme 1), we tried to select optimal catalytic system,
base, and solvent. The results are collected in table.
Cross-coupling of alkenyl halides with thiols is com-
monly carried out in the presence of a palladium cata-
lyst and a base [24, 25]. We found that the nature of
the base is very important for the reaction of diiodo-
butadiene Ia with thiol IIa, catalyzed by Pd com-
plexes. No reaction occurred using 4 mol % of tetra-
kis(triphenylphosphine)palladium in the presence of
triethylamine even on prolonged heating in boiling
The use of transition metal complexes to catalyze
addition of thiols to alkynes [20, 21] and cross-cou-
plings of alkenyl halides with thiols, thiolates, or their
synthetic equivalents ensures chemo- and stereoselec-
tive syntheses of alkenyl sulfides in high yields. Palla-
dium [22–31], nickel [32, 33], and copper complexes
[34–38] were used for this purpose.
Scheme 1.
I
+
2PhSH
I
Ia
Catalyst, base, Δ
IIa
PhS
We recently showed that (E,E′)-1,4-diiodobuta-1,3-
SPh
IIIa
diene is a synthetic equivalent of buta-1,3-diene-1,4-
24

TRANSITION METAL-CATALYZED CROSS-COUPLING OF 1,4-DIIODOBUTADIENES
25
Cross-coupling of (E,E′)-1,4-diiodobuta-1,3-diene with benzenethiola
Run no.
Catalyst (mol %)
No catalyst
Base (solvent)
Temperature , °C (time, h)
Yield, %
01
02
03
04
05
06
07
08
09
10
11
t-BuOK (t-BuOH)
Et3N (toluene)
083 (20)
30
00
80
90
96
84
89
78
95
97
90
Pd(PPh3)4 (4)
100 (10)
Pd(PPh3)4 (4)
t-BuOK (toluene)
t-BuOK (toluene)
t-BuOK (toluene)
t-BuOK (toluene)
K2CO3 (DMF)
110–120 (10)
110 (2)
Pd2dba3 (2)/DPEphos (4)b
PdCl2 (BDPB) (4)c
PdCl2 (PPh3)2 (5)
Ni(cod)2 (5)
100–110 (2)
110–115 (10)
110–120 (23)
110–120 (12)
120 (12)
Ni[P(OEt)3]4 (5)
NiBr2 (5)
K2CO3 (DMF)
K2CO3 (DMF)
Ni(acac)2 (5)
K2CO3 (DMF)
120 (4)
CuI (10)/ethylene glycol
K2CO3 (i-C5H11OH)
120 (9)
a
b
c
1,4-Diiodobuta-1,3-diene, 0.5 mmol; benzenethiol, 1 mmol; t-BuOK, 1.1 mmol, or K2CO3, 2 mmol; solvent, 2 ml.
DPEphos is 2,2′-bis(diphenyl-λ3-phosphanyl)diphenyl ether.
BDPB is (Z,Z′)-1,4-bis(diphenyl-λ3-phosphanyl)-1,4-diphenylbuta-1,3-diene.
toluene (run no. 2). A stronger base, potassium tert-
butoxide ensured successful cross-coupling of ben-
zenethiol (IIa) with diiodobutadiene Ia in the presence
of both Pd(0) complex (run no. 3) and bis(triphenyl-
phosphine)palladium(II) dichloride (run. no. 6). All
Pd-catalyzed reactions with the use of potassium tert-
butoxide as a base gave 1,4-bis(phenylsulfanyl)buta-
1,3-diene (IIIa) in high yield, though they required
fairly high temperature.
phenylbuta-1,3-diene (IV) was synthesized by us for
the first time by cross-coupling of (Z,Z′)-1,4-diiodo-
1,4-diphenylbuta-1,3-diene (Ib) with diphenylphos-
phine in the presence of bis(diphenylphosphine)palla-
dium(II) dichloride and triethylamine (Scheme 2).*
The complex derived from diphosphine IV and PdCl2
successfully catalyzed the reaction of diiodobutadiene
Ia with benzenethiol (run. no. 5), and the yield of bis-
sulfide IIIa was as high as 96%.
Mann et al. [45] previously studied reactions of
vinyl halides with sodium thiolates and found that the
use of Pd complexes with bidentate chelating phos-
phine ligands shortens the reaction time and increases
the yield, presumably due to facilitation of the reduc-
tive elimination step. A positive effect of bidentate
ligands was also observed in the cross-coupling of di-
iodobutadiene Ia with benzenethiol (IIa). In the pres-
ence of the catalytic system Pd2dba3–DPEphos the
reaction time shortened from 10 to 2 h (run no. 4), and
the yield of IIIa increased to 90%. Another bidentate
ligand, (Z,Z′)-1,4-bis(diphenyl-λ3-phosphanyl)-1,4-di-
We recently showed [47–50] that nickel complexes
and salts are efficient catalysts in reactions leading to
formation of new Csp2–P bonds. Catalytic systems on
the basis of nickel complexes turned out to be efficient
in the cross-coupling of (E,E′)-1,4-diiodobuta-1,3-di-
ene with benzenethiol. Both Ni(0) (run nos. 7, 8) and
Ni(II) complexes (run no. 10), as well as nickel salt
containing no additional ligands (run no. 9), were tried.
In these cases, the best results were obtained using di-
methylformamide as solvent and potassium carbonate
as base. The yields of 1,4-bis(phenylsulfanyl)buta-1,3-
diene were comparable with those in Pd-catalyzed
reactions, while NiBr2 and Ni(acac)2 as catalyst pre-
cursors ensured considerably higher yields than in the
presence of Pd complexes with unidentate ligands.
Scheme 2.
Ph
Ph
+
2Ph2PH
It is known that sulfanylation of alkenyl halides can
be achieved using an equimolar amount of copper(I)
salts [37, 38] or a catalytic amount of copper(I) com-
plexes with nitrogen-containing ligands [36, 51, 52].
I
I
Ib
(Ph3P)2PdCl2 (4 mol %)
Et3N, toluene
* Tetrasubstituted (Z,Z′)-1,4-bis(diphenyl-λ3-phosphanyl)buta-1,3-
dienes and their complexes with PdCl2 and PtCl2 were reported
recently [46].
Ph
Ph
Ph2P PPh2
IV
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TROSTYANSKAYA et al.
26
We examined the reactions of diiodobutadiene Ia with
thiols in the presence of a copper-based catalyst. Cop-
per(I) iodide in combination with 2 equiv of ethylene
glycol in isopropyl alcohol is an active catalytic system
for the amination [53] and sulfenylation [54] of aryl
halides. Probably, ethylene glycol acts simultaneously
as co-solvent and ligand. This simple catalytic system
turned out to be efficient in the cross-coupling of
1,4-diiodobuta-1,3-diene with benzenethiol (run
no. 12). Here, either potassium carbonate or potassium
phosphate may be used as base, and high-boiling iso-
pentyl alcohol, as solvent.
buta-1,3-dienes with thiols in the presence of both Pd
complexes and very simple, accessible, and low-ex-
pensive catalytic systems such as nickel(II) acetyl-
acetonate and copper(I) iodide–ethylene glycol.
EXPERIMENTAL
The progress of reactions was monitored by thin-
layer chromatography on Silufol plates using ethyl
1
13
31
acetate–hexane as eluent. The H, C, and P NMR
spectra were recorded on a Varian VXR-400 instru-
ment at 400, 100.6, and 162 MHz, respectively, using
CDCl3 as solvent and reference (1H, 13C); the 31P
chemical shifts were measured relative to 85% H3PO4.
The optimal conditions found were applied to the
synthesis of (E,E′)- and (Z,Z′)-1,4-bis[alkyl(aryl)sul-
fanyl]buta-1,3-dienes IIIb–IIIe via cross-coupling of
Ia and Ib with alkanethiols and benzenethiol (Schemes
3, 4). The reactions occurred with conservation of the
original double bond configuration. 1,4-Bis(benzylsul-
fanyl)-1,4-diphenylbuta-1,3-diene (IIIe) [8] was re-
ported previously. Newly synthesized compounds
IIIa–IIId were isolated as colorless crystalline sub-
stances which can be stored in an inert atmosphere.
Their structure was confirmed by elemental analysis
and 1H and 13C NMR spectroscopy.
All operations with readily hydrolyzable and oxi-
dizable compounds and transition metal complexes
were carried out under dry argon (it was dried by
passing through a column filled with phosphoric anhy-
dride). The solvents used were purified and dehydrated
according to standard procedures: benzene, toluene,
THF, hexane, and petroleum ether were heated under
reflux over metallic sodium in the presence of benzo-
phenone; methylene chloride was distilled over phos-
phoric anhydride; DMF was preliminary held over
anhydrous copper sulfate and distilled over calcium
hydride; isopropyl and isopentyl alcohols and ethylene
glycol were subjected to fractional distillation.
Scheme 3.
I
+
2RSH
I
(E,E′)-1,4-Diiodobuta-1,3-diene [55], (Z,Z′)-1,4-di-
iodo-1,4-diphenylbuta-1,3-diene [56], diphenylphos-
phine [57], bis(triphenylphosphine)palladium(II) di-
chloride [58], tetrakis(triphenylphosphine)palladium(0)
[59], bis(triphenylphosphine)nickel(II) dibromide [60],
tetrakis(triethyl phosphite)nickel(0) [61], bis(cyclo-
octadienyl)nickel(0) [62], and (dibenzylideneacetone)-
palladium(0) [63] were prepared by known methods.
Benzenethiol, phenylmethanethiol, hexane-1-thiol, and
2,2′-bis(diphenylphosphino)diphenyl ether (DPEphos)
were commercial reagents (Aldrich).
Ia
Catalyst, K2CO3
RS
SR
IIIb, IIIc
DMF, 5 mol % of Ni(acac)2; R = n-C6H13 (b, 69%), PhCH2
(c, 96%); i-C5H11OH, 10 mol % of CuI, 2 equiv of ethylene
glycol; R = n-C6H13 (b, 96%), PhCH2 (c, 86%).
Scheme 4.
Ph
Ph
Ph
+
2RSH
(E,E′)-1,4-Bis(phenylsulfanyl)buta-1,3-diene
(IIIa) (noncatalytic synthesis). Benzenethiol (IIa),
0.743 g (6.75 mmol) and potassium tert-butoxide,
0.302 g (2.7 mmol), were added to a solution of
0.415 g (1.35 mmol) of (E,E′)-1,4-diiodobuta-1,3-di-
ene (Ia) in 15 ml of tert-butyl alcohol. The mixture
was heated to the boiling point, stirred for 20 h at
that temperature, and cooled, and a saturated aqueous
solution of sodium carbonate and 40 ml of ethyl ace-
tate were added. The organic layer was separated, the
solvent was removed under reduced pressure, and the
solid residue was dried and recrystallized from petro-
leum ether. Yield 0.11 g (30%), mp 63–64°C.
I
I
Ib
Catalyst, K2CO3
Ph
RS SR
IIId, IIIe
i-C5H11OH, 10 mol % of CuI, 2 equiv of ethylene glycol;
R = Ph (d, 97%), PhCH2 (e, 78%).
Thus we have developed a procedure for the syn-
thesis of difficultly accessible 1,4-bis[aryl(alkyl)sul-
fanyl]buta-1,3-dienes via cross-coupling of 1,4-diiodo-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008

TRANSITION METAL-CATALYZED CROSS-COUPLING OF 1,4-DIIODOBUTADIENES
27
sealed and heated for 2 h at 85°C. When the reaction
was complete (31P NMR), the precipitate was filtered
off and washed with 5 ml of benzene–petroleum ether
(1:1), the solvent was removed under reduced pres-
sure, and the residue was recrystallized from methanol.
Yield of (Z,Z′)-1,4-bis(diphenyl-λ3-phosphanyl)-1,4-di-
phenylbuta-1,3-diene (IV) 0.250 g (87%), colorless
Catalytic system (Ph3P)4Pd. a. In the presence of
triethylamine. An ampule was flushed with argon and
charged with 0.07 g (0.23 mmol) of compound Ia,
0.05 g (0.46 mmol) of benzenethiol, 0.051 g (0.5 mmol)
of triethylamine, and 0.011 g (4 mol %) of tetrakis-
(triphenylphosphine)palladium(0) in 2 ml of toluene.
The ampule was flushed again with argon, sealed, and
heated for 10 h at 100°C. According to the TLC data
(hexane–diethyl ether, 3 :1), the mixture contained
only 1,4-diiodobuta-1,3-diene (Ia) and benzenethiol.
1
crystals, mp 115.8–116.5°C. H NMR spectrum
(CDCl3), δ, ppm: 7.19 m (C6H5), 7.31 d.d (2H,
=CHCH=, 3JPH = 20, 3JHH = 8 Hz). 13C NMR spectrum
(CDCl3), δC, ppm: 127.28, 127.99, 128.22, 134.96
b. In the presence of potassium tert-butoxide.
An ampule was flushed with argon and charged with
0.153 g (0.5 mmol) of compound Ia, 0.11 g (1.0 mmol)
of benzenethiol, 0.123 g (1.1 mmol) of potassium tert-
butoxide, and 0.023 g (4 mol %) of tetrakis(triphenyl-
phosphine)palladium(0) in 5 ml of toluene. The am-
pule was flushed again with argon, sealed, and heated
for 10 h at 110–120°C. When the reaction was com-
plete (TLC, hexane–ethyl acetate, 3:1), the mixture
was filtered, the precipitate was washed with hexane
(2×15 ml), the solvent was distilled off under reduced
pressure, and the residue was recrystallized. Yield
0.108 g (80%), mp 63.8–64.5°C (from hexane).
1H NMR spectrum (CDCl3), δ, ppm: 6.31 m (2H,
=CHS), 6.34 m (2H, =CHCH=), 7.28 m (10H, C6H5).
13C NMR spectrum (CDCl3), δC, ppm: 125.73 (=CC=),
130.44 (=CS), 126.98, 129.10, 129.88, 134.78 (C6H5).
Found, %: C 71.09; H 5.47. C16H14S2. Calculated, %:
C 70.95; H 5.19.
(C6H5), 129.67 d (4JPC = 8 Hz), 133.09 d (3JPC
=
=
19.0 Hz), 134.30 d (2JPC = 20.0 Hz), 136.20 d (1JPC
2
12.1 Hz), 138.60 d (PC=C, JPC = 22.3 Hz), 142.32 d
1
(PC=C, JPC = 13.1 Hz). 31P NMR spectrum:
δP –9.42 ppm. Found, %: C 83.61; H 5.65; P 10.75.
C40H32P2. Calculated, %: C 83.62; H 5.57; P 10.80.
A Schlenk vessel was charged with a solution of
0.345 g (0.6 mmol) of (Z,Z′)-1,4-bis(diphenyl-λ3-
phosphanyl)-1,4-diphenylbuta-1,3-diene in 5 ml of
methylene chloride, a solution of bis(acetonitrile)pal-
ladium(II) dichloride in 10 ml of methylene chloride
was added, and the mixture was kept for 1.5 h at 20°C.
When the reaction was complete, the solvent was
distilled off under reduced pressure, and the residue
was recrystallized from methylene chloride–ethanol
(1 : 5). Yield of [(Z,Z′)-1,4-bis(diphenyl-λ3-phos-
phanyl)-1,4-diphenylbuta-1,3-diene]palladium(II) di-
31
chloride 0.395 g (88%), mp 209.0–210.5°C. P NMR
spectrum: δP 16.4 ppm. Found, %: C 63.48; H 4.16.
Catalytic system Pd2dba3–DPEphos. A Schlenk
vessel was charged with 0.020 g (2 mol %) of Pd2dba3,
0.026 g (4 mol %) of DPEphos in 5 ml of toluene was
added, the mixture was stirred for 5 min, and 0.306 g
(1 mmol) of compound Ia, 0.220 g (2 mmol) of ben-
zenethiol, and 0.246 g (2.2 mmol) of potassium tert-
butoxide in 11 ml of toluene were added to the result-
ing solution. The mixture was heated for 2 h at 110°C
(TLC, hexane–ethyl acetate, 3:1) and filtered, the pre-
cipitate was washed with hexane (2×15 ml), the sol-
vent was distilled off under reduced pressure, and the
solid residue was recrystallized from hexane. Yield
0.243 g (90%), mp 63–64°C.
Catalytic system [(Z,Z′)-1,4-bis(diphenyl-λ3-phos-
phanyl)-1,4-diphenylbuta-1,3-diene]palladium(II)
dichloride. An ampule was charged with a solution of
0.230 g (0.5 mmol) of (Z,Z′)-1,4-diiodo-1,4-diphenyl-
buta-1,3-diene, 0.101 g (1 mmol) of triethylamine, and
0.014 g (4 mol%) of bis(triphenylphosphine)palladi-
um(II) dichloride in 5 ml of benzene, 0.186 g (1 mmol)
of diphenylphosphine was added, and the ampule was
C40H32Cl2P2Pd. Calculated, %: C 63.91; H 4.26.
A Schlenk vessel was charged with a solution of
0.153 g (0.5 mmol) of compound Ia, 0.11 g (1 mmol)
of benzenethiol, and 0.123 g (1.1 mmol) of potassium
tert-butoxide in 10 ml of toluene, a solution of 0.015 g
(4 mol %) of [(Z,Z′)-1,4-bis(diphenyl-λ3-phosphanyl)-
1,4-diphenylbuta-1,3-diene]palladium(II) dichloride in
6 ml of toluene was added, and the mixture was heated
for 2 h at 100–110°C. When the reaction was com-
plete, the precipitate was filtered off and washed with
hexane (2×5 ml), the solvent was distilled off under
reduced pressure, and the residue was recrystallized.
Yield of compound IIIa 0.130 g (96%), mp 63.5–
64.0°C (from hexane).
Catalytic system (PPh3)2PdCl2. An ampule was
flushed with argon and charged with 0.153 g
(0.5 mmol) of compound Ia, 0.11 g (1.0 mmol) of
benzenethiol, 0.123 g (1.1 mmol) of potassium tert-
butoxide, and 0.018 g (5.1 mol %) of (PPh3)2PdCl2 in
6 ml of toluene. The ampule was sealed, heated for
10 h at 110–115°C, cooled, and opened, the precipitate
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008

TROSTYANSKAYA et al.
28
was filtered off and washed with hexane (2×5 ml), the
solvent was distilled off under reduced pressure, and
the residue was recrystallized. Yield of IIIa 0.113 g
(84%), mp 63.5–64.5°C (from hexane).
was charged with 0.153 g (0.5 mmol) of compound Ia,
0.120 g (1.0 mmol) of hexane-1-thiol, 0.28 g (2 mmol)
of K2CO3, and 0.006 g (5 mol %) of nickel(II) acetyl-
acetonate in 2 ml of DMF, and the mixture was heated
for 50 h at 120°C. When the reaction was complete,
the precipitate was filtered off, the solvent was dis-
tilled under reduced pressure, and the residue was
recrystallized. Yield 0.097 g (69%), mp 67–68°C (from
Catalytic system Ni(cod)2. A Schlenk vessel was
charged with 0.153 g (0.5 mmol) of compound Ia,
0.007 g (5 mol %) of Ni(cod)2, 0.28 g (2.0 mmol) of
K2CO3, 2 ml of DMF, and 0.11 g (1 mmol) of
benzenethiol. The mixture was heated for 23 h at 110–
115°C and cooled, the precipitate was filtered off, the
solvent was distilled off under reduced pressure, and
the residue was recrystallized from hexane. Yield of
IIIa 0.120 g (89%), mp 63.5°C.
1
hexane). H NMR spectrum (CDCl3), δ, ppm: 0.89 t
(6H, CH3), 1.26–1.65 m (16H, CH2), 2.68 t (4H,
CH2S), 6.07 m (2H, =CHS), 6.13 m (2H, =CHCH=).
13C NMR spectrum (CDCl3), δC, ppm: 13.95, 22.48,
29.65, 31.32, 32.78, 37.97 (C6H13), 125.23 (=CC=),
127.39 (=CS). Found, %: C 66.92; H 10.62. C16H30S2.
Calculated, %: C 67.13; H 10.49.
Catalytic system Ni[P(OEt)3]4. A Schlenk vessel
was charged with 0.018 g (5 mol %) of tetrakis(triethyl
phosphite)nickel(0), 0.28 g (2.0 mmol) of K2CO3,
0.153 g (0.5 mmol) of compound Ia, 2 ml of DMF, and
0.11 g (1 mmol) of benzenethiol. The mixture was
heated for 12 h at 110–120°C and cooled, the precip-
itate was filtered off and washed with benzene, the
solvent was distilled off under reduced pressure, and
the residue was recrystallized. Yield of IIIa 0.105 g
(78%), mp 64.0–64.5°C (from hexane).
b. Catalytic system CuI. Following a similar proce-
dure, a mixture of 0.153 g (0.5 mmol) of compound Ia,
0.120 g (1.0 mmol) of hexane-1-thiol, 0.28 g (2 mmol)
of potassium carbonate, 0.010 g (10 mol %) of cop-
per(I) iodide, 2 ml of isopentyl alcohol, and 0.124 g
(0.1 ml, 2 mmol) of ethylene glycol was heated for
50 h at 120°C and subjected to appropriate treatment to
isolate 0.136 g (96%) of compound IIIb with mp 67–
68°C (from hexane).
Catalytic system NiBr2. Following a similar proce-
dure, the reaction was carried out with 0.005 g
(5 mol %) of nickel(II) bromide, 0.28 g (2.0 mmol)
of K2CO3, 0.153 g (0.5 mmol) of compound Ia, and
0.11 g (1 mmol) of benzenethiol in 2 ml of DMF. The
mixture was heated for 12 h at 120°C. Yield of IIIa
0.128 g (95%), mp 63.5–64.0°C (from hexane).
(E,E′)-1,4-Bis(benzylsulfanyl)buta-1,3-diene
(IIIc). a. Catalytic system Ni(acac)2. A Schlenk vessel
was charged with 0.153 g (0.5 mmol) of compound Ia,
0.124 g (1.0 mmol) of phenylmethanethiol, 0.28 g
(2 mmol) of potassium carbonate, and 0.006 g
(5 mol %) of nickel(II) acetylacetonate in 2 ml of
DMF, and the mixture was heated for 32 h at 120°C.
When the reaction was complete, the precipitate was
filtered off, the solvent was distilled off under reduced
pressure, and the residue was recrystallized. Yield
Catalytic system Ni(acac)2. Likewise, a mixture of
0.006 g (5 mol %) of nickel(II) acetylacetonate, 0.28 g
(2.0 mmol) of K2CO3, 0.153 g (0.5 mmol) of com-
pound Ia, and 0.11 g (1 mmol) of benzenethiol in 2 ml
of DMF was heated for 4 h at 120°C. Yield of IIIa
0.130 g (97%), mp 64.0–64.5°C.
1
0.142 g (96%), mp 56–57°C (from hexane). H NMR
spectrum (CDCl3), δ, ppm: 3.81 s (4H, CH2S), 5.98 m
(2H, =CHS), 6.10 m (2H, =CHCH=), 7.20 m (10H,
Ph). 13C NMR spectrum (CDCl3), δC, ppm: 38.30
(CH2S), 125.06 (=CC=), 129.07 (=CS), 128.65, 128.81,
129.03, 138.18 (Ph). Found, %: C 72.65; H 6.10.
C18H18S2. Calculated, %: C 72.48; H 6.04.
Catalytic system CuI. A Schlenk vessel was
charged with 0.010 g (10 mol %) of copper(I) iodide,
0.28 g (2.0 mmol) of K2CO3, 0.153 g (0.5 mmol) of
compound Ia, 2 ml of isopentyl alcohol, 0.11 g
(1 mmol) of benzenethiol, and 0.124 g (0.1 ml,
2.0 mmol) of ethylene glycol. The mixture was heated
for 9 h at 120°C. When the reaction was complete, the
precipitate was filtered off and washed with benzene,
the solvent was removed under reduced pressure, and
the residue was recrystallized. Yield of IIIa 0.123 g
(90%), mp 63.5–64.0°C (from hexane).
b. Catalytic system CuI. Likewise, a mixture of
0.153 g (0.5 mmol) of compound Ia, 0.124 g
(1.0 mmol, 0.12 ml) of phenylmethanethiol, 0.28 g
(2 mmol) of potassium carbonate, 0.010 g (10 mol %)
of copper(I) iodide, 2 ml of isopentyl alcohol, and
0.124 g (0.1 ml, 2 mmol) of ethylene glycol was
heated for 50 h at 120°C. Yield of IIIc 0.127 g (86%),
mp 56–57°C (from hexane).
(E,E′)-1,4-Bis(hexylsulfanyl)buta-1,3-diene
(IIIb). a. Catalytic system Ni(acac)2. A Schlenk vessel
(Z,Z′)-1,4-Diphenyl-1,4-bis(phenylsulfanyl)buta-
1,3-diene (IIId). A Schlenk vessel was charged with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008

TRANSITION METAL-CATALYZED CROSS-COUPLING OF 1,4-DIIODOBUTADIENES
29
7. Schroth, W., Spitzner, R., and Bruhn, C., Eur. J. Org.
Chem., 1998, p. 2365.
8. Schroth, W., Dunger, S., Billing, F., Spitzner, R.,
Herzschuh, R., Jende, T., Jstael, G., Barche, J., and
Strohl, D., Tetrahedron, 1996, vol. 52, p. 12677.
9. Hundson, J.B., Graham, E.A., Fong, R., Finlayson, A.J.,
and Towers, G.H., Planta Med., 1985, vol. 51, p. 225.
10. Constabel, C.P. and Towers, G.H., Planta Med., 1989,
0.010 g (10 mol %) of copper(I) iodide, 0.28 g
(2.0 mmol) of potassium carbonate, 0.229 g (0.5 mmol)
of (Z,Z′)-1,4-diiodo-1,4-diphenylbuta-1,3-diene, 2 ml
of isopropyl alcohol, 0.11 g (1 mmol) of benzenethiol,
and 0.124 g (0.1 ml, 2.0 mmol) of ethylene glycol. The
mixture was heated for 30 h at 80°C and cooled, the
precipitate was filtered off and washed with benzene,
the solvent was removed under reduced pressure, and
the residue was recrystallized. Yield 0.205 g (97%),
vol. 55, p. 35.
11. Bierer, D.E., Dener, J.M., Dubenko, L.G., Gerber, R.E.,
Litvak, J., Peterli, S., Peterli-Roth, P., Truong, T.V.,
Mao, G., and Bauer, B.E., J. Med. Chem., 1995, vol. 38,
p. 2628.
13
mp 128–128.5°C (from hexane). C NMR spectrum
(CDCl3), δC, ppm: 125.80 (=CC=), 127.83, 128.25,
128.25, 128.65, 128.74, 133.35, 135.54, 138.12 (C6H5),
139.57 (=CS). Found, %: C 79.38; H 5.22. C28H22S2.
Calculated, %: C 79.62; H 5.21.
12. Wang, Y., Koreeda, M., Chatterji, T., and Gates, K.S.,
J. Org. Chem., 1998, vol. 63, p. 8644.
13. Hadson, J.B., Balza, F., Harris, L., and Towers, G.H.,
Photochem. Photobiol., 1993, vol. 57, p. 675.
14. Koreeda, M. and Wang, Y., J. Org Chem., 1997, vol. 62,
(Z,Z′)-1,4-Bis(benzylsulfanyl)-1,4-diphenylbuta-
1,3-diene (IIIe). A Schlenk vessel was charged with
0.229 g (0.5 mmol) of (Z,Z′)-1,4-diiodo-1,4-diphenyl-
buta-1,3-diene, 0.124 g (1.0 mmol) of phenylmethane-
thiol, 0.28 g (2 mmol) of potassium carbonate, 0.010 g
(10 mol %) of copper(I) iodide, 2 ml of isopentyl alco-
hol, and 0.124 g (0.1 ml, 2 mmol) of ethylene glycol,
and the mixture was heated for 40 h at 120°C. When
the reaction was complete, the precipitate was filtered
off, the solvent was distilled off under reduced pres-
sure, and the residue was recrystallized. Yield 0.174 g
(78%), mp 116–117°C (from hexane); published data
p. 446.
15. Freeman, F., Lu, H., and Rodriquez, E., Sulfur Lett.,
1995, vol. 18, p. 243.
16. Reich, H.J. and Reich, I.L., J. Org. Chem., 1975,
vol. 40, p. 2248.
17. Zapol’skii, V.A. and Kaberdin R.V., Zh. Org. Khim.,
1994, vol. 30, p. 1368.
18. Zapol’skii, V.A., Potkin, V.I., and Kaberdin, R.V.,
Zh. Org. Khim., 1994, vol. 30, p. 193.
19. Ibis, C. and Sayil, C., Phosphorus, Sulfur Silicon, 1994,
1
[8]: mp 117–118°C. H NMR spectrum (CDCl3), δ,
vol. 92, p. 39.
ppm: 3.59 s (4H, CH2S), 7.13 s (=CH), 7.02 m (4H,
Ph), 7.20 m (6H, Ph), 7.50 m (4H, Ph). 13C NMR spec-
trum (CDCl3), δC, ppm: 37.5 (SCH2), 132.1 (=CH),
140.0 (C=), 126.8, 128.0, 128.2, 128.3, 128.5, 128.7,
138.2, 139.2 (Ph).
20. Kondo, T. and Mitsudo, T., Chem. Rev., 2000, vol. 100,
p. 3205.
21. Ananikov, V.P., Orlov, N.V., and Beletskaya, I.P.,
Organometallics, 2006, vol. 25, p. 1970.
22. Murahashi, S.-I., Masaaki, Y., Yanagusawa, K.-I., and
Mita, N., J. Org. Chem., 1979, vol. 44, p. 2408.
23. Prim, D., Campagne, J.-M., Joseph, D., and Andrio-
letti, B., Tetrahedron, 2002, vol. 58, p. 2041.
24. Li, G.Y., Angew. Chem., Int. Ed., 2001, vol. 40, p. 1513.
25. Li, G.Y., J. Org. Chem., 2002, vol. 67, p. 3643.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 04-03-32709).
REFERENCES
26. Rane, A.M., Miranda, E.I., and Soderquist, J.A., Tetra-
hedron Lett., 1994, vol. 35, p. 3225.
1. Glass, R.S. and Smith, D.L., Synthesis, 1977, p. 886.
2. Shostakovskii, M.F., Bogdanova, A.V., and Plotniko-
27. Kosugi, M., Ogata, T., Terada, M., Sano, H., and
va, G.I., Izv. Akad. Nauk SSSR, Ser. Khim., 1960, p. 1514.
Migita, T., Bull. Chem. Soc. Jpn., 1985, vol. 58, p. 3657.
3. Okauchi, T., Fukamachi, T., Nakamura, F., Ichikawa, J.,
and Minami, T., Bull. Soc. Chim. Belg., 1997, vol. 106,
p. 525.
28. Carpita, A., Rossi, R., and Scamuzzi, B., Tetrahedron
Lett., 1989, vol. 30, p. 2699.
29. Rossi, R., Bellina, F., and Carpita, A., Synlett, 1996,
p. 356.
4. Ibis, C., Phosphorus, Sulfur Silicon, 1997, vol. 130, p. 79.
30. Rossi, R., Bellina, F., and Mannina, L., Tetrahedron,
1997, vol. 53, p. 1025.
5. Everhardus, R., Eluworst, H.G., and Brandsma, L.,
J. Chem. Soc., Chem. Commun., 1977, p. 801.
31. Ishiyama, T., Mori, M., Suzuki, A., and Miyaura, N.,
J. Organomet. Chem., 1996, vol. 525, p. 225.
32. Cristau, H.J., Chabaund, B., Labaundiniere, R., and
6. Sato, R., Six-Membered Hetarenes with Two Identical
Heteroatoms (Science of Synthesis: Houben–Weyl
Methods of Molecular Transformations), Yamamoto, Y.,
Ed., Stuttgart: Thieme, 2003, vol. 16, p. 39.
Christol, H., J. Org. Chem., 1986, vol. 51, p. 875.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008

TROSTYANSKAYA et al.
30
47. Kazankova, M.A., Efimova, I.V., Kochetkov, A.N.,
Afanas’ev, V.V., Beletskaya, I.P., and Dixneuf, P.H.,
Synlett, 2001, p. 497.
33. Foa, M., Santi, R., and Garavaglia, F., J. Organomet.
Chem., 1981, vol. 206, p. C29.
34. Herradura, P., Pendola, K., and Guy, R., Org. Lett.,
48. Shulyupin, M.O., Kazankova, M.A., and Beletskaya, I.P.,
2000, vol. 2, p. 2019.
Org. Lett., 2002, vol. 4, p. 761.
35. Savarin, C., Srogl, J., and Liebeskind, L., Org. Lett.,
49. Kazankova, M.A., Shulyupin, M.O., and Beletskaya, I.P.,
2001, vol. 3, p. 91.
36. Savarin, C., Srogl, J., and Liebeskind, L., Org. Lett.,
Synlett, 2003, p. 2155.
50. Shulyupin, M.O., Trostyanskaya, I.G., Kazankova, M.A.,
and Beletskaya, I.P., Russ. J. Org. Chem., 2006, vol. 42,
p. 17.
51. Beletskaya, I.P. and Cheprakov, A.V., Coord. Chem.
Rev., 2004, vol. 248, p. 2352.
2002, vol. 4, p. 4309.
37. Ogawa, T., Hayami, K., and Suzuki, H., Chem. Lett.,
1989, p. 768.
38. Adams, R. and Ferretti, A., J. Am. Chem. Soc., 1959,
vol. 81, p. 4927.
52. Bates, C.G., Saejueng, P., Doherty, M.Q., and Venkata-
39. Trostyanskaya, I.G., Titskii, D.Yu., Anufrieva, E.A., Bo-
risenko, A.A., Kazankova, M.A., and Beletskaya, I.P.,
Izv. Ross. Akad. Nauk, Ser. Khim., 2001, p. 2003.
raman, D., Org. Lett., 2004, vol. 6, p. 5005.
53. Kwong, F.Y., Klapars, A., and Buchwald, S.L., Org.
Lett., 2002, vol. 4, p. 581.
40. Kazankova, M.A., Trostyanskaya, I.G., Lutsenko, S.V.,
and Beletskaya, I.P., Tetrahedron Lett., 1999, vol. 40,
p. 569.
54. Kwong, F.Y. and Buchwald, S.L., Org. Lett., 2002,
vol. 4, p. 3517.
55. Mitchenko, S.A., Ananikov, V.P., Beletskaya, I.P., and
Ustynyuk, Y.A., Mendeleev Commun., 1997, p. 130.
56. Yamaguchi, S., Jin, R.-Z., Tamao, K., and Sato, F.,
J. Org. Chem., 1998, vol. 63, p. 10060.
57. Gee, N., Shaw, R.A., and Smith, B.C., Inorg. Synth.,
1967, vol. 9, p. 19.
58. Hatani, H. and Baier, J.C., J. Am. Oil Chem. Soc., 1967,
41. Kazankova, M.A., Chirkov, E.A., Kochetkov, A.N.,
Efimova, I.V., and Beletskaya, I.P., Tetrahedron Lett.,
1999, vol. 40, p. 573.
42. Afanasiev, V.V., Beletskaya, I.P., Kazankova, M.A., Efi-
mova, I.V., and Antipin, M.U., Synthesis, 2003, p. 2835.
43. Beletskaya, I.P., Afanasiev, V.V., Kazankova, M.A., and
Efimova, I.V., Org. Lett., 2003, p. 4309.
44. Shulyupin, M.O., Chirkov, E.A., Kazankova, M.A., and
vol. 44, p. 147.
59. Coulson, P.R., Inorg. Chem., 1972, vol. 13, p. 121.
60. Venanzi, L.M., J. Chem. Soc., 1958, p. 719.
61. Lefo, J.R. and Lefo, M.F., J. Am. Chem. Soc., 1961,
Beletskaya, I.P., Synlett, 2005, p. 658.
45. Mann, G., Baranano, D., Hartwig, J.F., Rhengold, A.L.,
and Guzei, I.A., J. Am. Chem. Soc., 1998, vol. 120,
p. 9205.
vol. 83, p. 2948.
62. Lefo, J.R. and Lefo, M.F., J. Am. Chem. Soc., 1961,
vol. 83, p. 2944.
63. Ishii, Y., Ann. N.-Y. Acad. Sci., 1974, vol. 239, p. 114.
46. Doherty, S., Robins, E.G., Nieuwenhuyzen, M., Champ-
kin, P.A., and Clegg, W., Organometallics, 2002,
vol. 21, p. 1383.
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