One-Pot Synthesis of 1-Alkenyl Sulfides from Alkynes and Organic Disulfides with the Use of Organoaluminums

Article abstract of DOI:10.1055/s-0034-1380755

Organic disulfides (dipropyl, dihexyl, or diphenyl disulfide) are convenient and efficient agents for the sulfanylation of 1-alkenylaluminum derivatives.

Full text of DOI:10.1055/s-0034-1380755

SYNTHESIS
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
© Georg Thieme Verlag Stuttgart · New York
2015, 47, 2670–2676
paper
2670
I. R. Ramazanov et al.
Paper
Synthesis
One-Pot Synthesis of 1-Alkenyl Sulfides from Alkynes and Organic
Disulfides with the Use of Organoaluminums
Ilfir R. Ramazanov*
hydro- or carbo-
alumination
R1
R3
R2
R1
R2
R4SSR4
Rita N. Kadikova
Tat’yana P. Zosim
Usein M. Dzhemilev
R1
R2
18–24 h, r.t.
R3
al
SR4
R
R
R
1 = alkyl, Ph
2 = H, alkyl
3 = Me, H
81–85%
8 examples
Institute of Petrochemistry and Catalysis of Russian Academy of
Sciences, 141 Prospekt Oktyabrya, Ufa 450075, Russian Federation
ilfir.ramazanov@gmail.com
al = AlMe2, AlEt2
R4 = Pr, (CH2)5Me, Ph
Received: 27.02.2015
Accepted after revision: 16.04.2015
Published online: 19.06.2015
with 1-alkenyl bromides16 and alkynes17 have also been re-
ported; although this reaction permits the preparation of 1-
alkenyl sulfides directly from alkynes, it cannot, unfortu-
nately, be extended to aliphatic terminal or disubstituted
alkynes. Although the reaction of organic disulfides with
organolithium18 or organomagnesium compounds is the
conventional approach to the synthesis of 1-alkenyl and
aryl sulfides, to the best of our knowledge there is no exam-
ple of the preparation of an 1-alkenyl sulfide from an orga-
noaluminum compound. New and efficient methods are
available for the hydro-, carbo-, or cycloalumination of
alkynes to give organoaluminum compounds of various
structures. Here, we describe the development of a one-pot
method for converting a wide range of 1-alkenyl derivatives
of aluminum into the corresponding 1-alkenyl sulfides.
The lack of published reports on the transformation of
1-alkenylaluminum derivatives into 1-alkenyl sulfides sug-
gested that there might be serious obstacles to such trans-
formations. The reaction of diisobutyl[(E)-oct-1-en-1-
yl]aluminum with dipropyl disulfide in hexane solution at
50 °C for 18 hours did not result in the formation of the ex-
pected 1-alkenyl sulfide, and only dipropyl disulfide and
oct-1-ene were detected in the reaction mixture after hy-
drolysis. The inactivity of 1-alkenylaluminum derivatives is
probably due to the low ionicity of the metal–carbon bond
in the organoaluminum compound in comparison with or-
ganic derivatives of magnesium or lithium. However, steric
factors might also play a central role in the reaction. We
surmised that 1-alkenylaluminum compounds containing
methyl or ethyl substituents on the aluminum atom might
be more reactive toward organic disulfides. Negishi methyl-
alumination permits the preparation of 1-alkenyl(dimeth-
yl)aluminum compounds from terminal alkynes with high
yields and high stereoselectivities.19–21 We found that the
reaction of 1-alkenyl(dimethyl)aluminums 1a–f with
dipropyl, dihexyl, or diphenyl disulfide at room tempera-
DOI: 10.1055/s-0034-1380755; Art ID: ss-2015-z0118-op
Abstract Organic disulfides (dipropyl, dihexyl, or diphenyl disulfide)
are convenient and efficient agents for the sulfanylation of 1-alkenylalu-
minum derivatives.
Key words disulfides, alkenes, sulfanylation, organometallic reagents
1-Alkenyl sulfides play important roles in syntheses of
many naturally occurring and biologically active com-
pounds. Because of their ease of transformation, 1-alkenyl
sulfides also serve as versatile building blocks for many
functional molecules. Although there are many approaches
to the preparation of 1-alkenyl sulfides,1,2 the stereoselec-
tive synthesis of E- and Z-isomers remains an important
problem.3,4 1-Alkenyl sulfides are generally prepared by hy-
drosulfurization of alkynes by the action of radical initia-
tors, bases, or metal-complex catalysts. Radical hydrosul-
furization usually leads to mixtures of anti-Markovnikov E-
and Z-isomers. Catalytic hydrosulfurization is usually com-
plicated by the formation of byproducts of the Markovnikov
addition of thiols to alkynes; however, the stereoselectivity
toward the formation of the thermodynamically more sta-
ble E-isomer is greater than in that observed in radical hy-
drosulfurization. Good stereoselectivity has been achieved
by using chloro(triphenylphosphine)rhodium5,6 or gold
complexes7 as catalysts. Markovnikov adducts have been
regioselectively prepared by the use of complexes of nickel,
rhodium, zirconium, lanthanides, or actinides.8–11 In gener-
al, however, only a few stereo- and regioselective methods
give the E- or Z-isomer with more than 95% purity. Another
approach to the selective synthesis of 1-alkenyl sulfides is
cross-coupling of organic halides with thiols catalyzed by
complexes of copper12 or iron,13 or by lanthanum(III) ox-
ide14 or copper(II) oxide.15 Reactions of organic disulfides
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 2670–2676

2671
I. R. Ramazanov et al.
Paper
Synthesis
ture for 18 hours led to the stereoselective formation of the
corresponding 1-alkenyl alkyl sulfides 2a–f in high yields
(Table 1).
proximately estimated as ΔG≠ = RT*ln(10) = 0.593
×
2.303 = 1.37 kcal/mol. The discrepancy between the calcu-
lated and experimental values can be explained by an un-
derestimation of the steric factor in the calculation model.
The observed reaction is a rare example of the selective
conversion of organoaluminum compounds into organic
sulfides. It is known that trialkylaluminums react nonselec-
tively with sulfur, disulfur dichloride, or sulfur dichloride to
give mixtures of organic sulfides, disulfides, and trisul-
fides.22 Because of the simplicity and the high efficiency of
our new procedure, we examined the possibility of apply-
ing this method to the functionalization of 1-alkenylalumi-
nums of various structures.
Table 1 Preparation of 1-Alkenyl Alkyl Sulfides 2 from Terminal
Alkynes 1
Me3Al
(2 equiv)
Cp2ZrCl2
(1 equiv)
R2SSR2
R1
Me
H
R1
Me
H
(3 equiv)
R1
H
SR2
CH2Cl2
r.t., 3 h
AlMe2
r.t., 18 h
1a–f
2a–f
We found that zirconium-catalyzed hydroalumination23
or methylalumination of dec-5-yne followed by treatment
with three equivalents of dipropyl disulfide gave the alke-
nyl sulfides 4 and 6, respectively, in high yields (Scheme 1).
The zirconium-catalyzed reaction of disubstituted
alkynes with triethylaluminum gives aluminacyclopent-2-
enes, a particular type of 1-alkenylaluminum compound.24
The reaction of aluminacyclopent-2-ene 7 with organic di-
sulfides (dipropyl or dihexyl disulfide) gave sulfides 9a and
9b in high yield (Scheme 2). Increasing the amount of or-
ganic disulfide did not result in the formation of the ex-
pected products of disulfanylation. We assume that the re-
action stopped at the stage of the formation of the stable in-
tramolecular six-membered cyclic complex 8, in which the
sulfur atom is coordinated to the aluminum atom, thereby
reducing the the reactivity of the Al–C bonds. The free en-
ergies of activation for the reactions of 1,2,3-trimethylalu-
minacyclopent-2-ene with dimethyl disulfide, as estimated
by the B3LYP/6-31G(d) method, are 45.8, 53.8, and 62.7
kcal/mol for the reactions with the Al–C(sp2) bond, the Al–
CH2 bond, and the Al–Me bond, respectively. The greater ac-
tivity of the Al–CH2 bond can be explained by taking into
account the steric factors and the calculated activation en-
ergy for the reaction with dimethyl(2-methylprop-1-en-1-
yl)aluminum.
Entry
2
R1
R2
Yield (%)
1
2
3
4
5
6
2a
(CH2)5Me
(CH2)5Me
(CH2)5Me
Ph
(CH2)5Me
71
76
85
79
84
77
2b
2c
2d
2e
2f
Pr
Ph
(CH2)5Me
Ph
Pr
Ph
Ph
Although all the Al–C bonds might be involved in the re-
action, three molar equivalents of the organic disulfide
were sufficient to ensure the complete conversion of the 1-
alkenylaluminum into the corresponding 1-alkenyl sulfide.
This appears to be due to the higher reactivity of the Al–
C(sp2) bond in comparison with that of the Al–C(sp3) bonds.
The free energies of activation for the reactions of dimeth-
yl(2-methylprop-1-en-1-yl)aluminum and trimethylalumi-
num with dimethyl disulfide at 298 K were estimated to be
46.1 and 60.2 kcal/mol, respectively by the B3LYP/6-31G(d)
method. However, the use of one equivalent of dihexyl di-
sulfide in the reaction with 1-alkenylaluminum 1a resulted
in the formation of a mixture of alkenyl sulfides and hexyl
methyl sulfide in a 2:1 ratio. Because one Al–C(sp2) bond
and five Al–C(sp3) bonds take part in the reaction, the dif-
ference in the free energies of activation at 298 K can be ap-
9
2
10
1
Et3Al (2 equiv)
Cp2TiCl2 (0.05 equiv)
PrSSPr
(3 equiv)
7
4
Bu
H
Bu
3
8
6
5
13
r.t., 18 h
hexane, r.t., 6 h
12
AlEt2
H
S
11
3
4 (71%)
Bu
Bu
2
9
1
10
14
Me3Al (2 equiv)
Cp2ZrCl2 (1 equiv)
PrSSPr
(3 equiv)
4
7
Bu
Me
Bu
AlMe2
8
3
6
5
13
r.t., 18 h
CH2Cl2, 50 °C, 6 h
S
11
12
5
6 (80%)
Scheme 1 Preparation of alkenyl sulfides 4 and 6 from dec-4-yne
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 2670–2676

2672
I. R. Ramazanov et al.
Paper
Synthesis
Bu
Bu
Bu
Et3Al (1 equiv)
Cp2ZrCl2 (0.1 equiv)
RSSR (3 equiv)
r.t., 24 h
Bu
SR
Bu
Bu
hexanes, 40 °C, 2 h
Al
Et
S
Al
R
Et
8a,b
7
H2O
RS
9a: R = Pr (68%)
9b: R = (CH2)5Me (73%)
Scheme 2 Preparation of alkenyl sulfides 9a and 9b from dec-5-yne
Because the functionalization of aluminacyclopent-2-
enes involved only the Al–C(sp3) bond of the metallacycle,
we were interested in examining the reactions of alumina-
cyclopentanes with disulfides. Zirconium-catalyzed cy-
cloalumination of oct-1-ene,25 followed by treatment with
dipropyl disulfide, gave a mixture of the two monosulfa-
nylation products 12a and 12b (Scheme 3). The use of ten
molar equivalents of the disulfide did not lead to the forma-
tion of the product of double sulfanylation. The reaction ap-
pears to stop at the stage of formation of the stable intra-
molecular six-membered cyclic complex 11. Quantum
chemical calculations showed that the Al–C bond of the
aluminacycle 10 has a higher activity than the Al–Et bond.
We have therefore developed an efficient method for
the preparation of 1-alkenyl sulfides from 1-alkenylalumi-
nums by the action of organic disulfides. This is a useful ex-
tension of existing approaches to the formation of C–S
bonds, and is an analogue of the alkyne carbosulfurization
reaction. The advantages of our new method are its one-pot
character and the elimination of the need to isolate the in-
termediate 1-alkenylaluminums. For example, the 1-alke-
nyl sulfide 2a can be prepared in two steps by a zirconium-
catalyzed methylalumation of oct-1-yne followed by io-
dinolysis of the reaction mixture. In the next step, the iso-
lated 1-iodoalkene is converted into sulfide 2a by treatment
with hexane-1-thiol in the presence of bis(triphe-
nyl)(phenanthroline)copper(I) nitrate.12 Our method is
therefore convenient for the synthesis of β,β- and α,β,β-
substituted vinyl sulfides. The high regio- and stereoselec-
tivity of the reaction arises from the well-proven method of
zirconium-catalyzed carboalumination of alkynes.
The reagents were obtained from Sigma-Aldrich or Acros. CH2Cl2 and
hexane were distilled over P2O5. The diphenyl and dialkyl disulfides
were prepared by oxidation of the corresponding thiols with a
KMnO4–CuSO4·5 H2O system.26 NMR spectra were recorded on Bruker
Avance 400 and 500 spectrometers. Chemical shifts are referenced to
TMS as the internal standard. The numbering of the atoms in the 13
C
and 1H NMR spectra of the compounds 2a–f and 5a,b is shown in Fig-
ure 1. Elemental analysis was performed by using a Carlo-Erba CHN
1106 elemental analyzer. Mass spectra were recorded on a Finnigan
4021 instrument. The yields were calculated from the isolated
amounts of the 1-alkenyl sulfides obtained from the starting alkynes.
All quantum chemical calculations were performed by using Gaussian
09 software.27
(CH2)5Me
Me(CH2)5
(CH2)5Me
Et3Al (1 equiv)
PrSSPr (3 equiv)
r.t., 24 h
Cp2ZrCl2 (0.1 equiv)
+
Me(CH2)5
Al
Et
hexanes, 40 °C
2 h
Al
Et
S
Al
S
SPr
SPr
Pr
Pr
Et
10
11a
11b
H2O
5
7
2
13
5
9
10
7
12
8
6
1
11
8
3
4
4
1
S
+
12
3
10
6
S
13
9
11
2
12a
~ 1:1 (77%)
12b
Scheme 3 Preparation of dialkyl sulfides 12 from oct-1-ene
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 2670–2676

2673
I. R. Ramazanov et al.
Paper
Synthesis
14
13
7
7
15
8
12
11
8
5
5
10
6
3
6
3
2
H
H
1
H
1
4
4
1
2
11
10
13
12
2
12
3
9
9
S
S
9
S
14
5
15
11
2b
2c
2a
4
10
7
6
14
15
8
10
1
14
12
15
13
12
8
12
11
13
H
2
H
2
H
2
10
3
11
9
7
6
10
11
7
5
6
1
1
4
3
3
S
9
S
S
2d
9
2e
5
2f
5
8
4
4
7
6
8
2
1
2
4
1
13
5
4
5
3
8
17
10
15
12
3
13
11
14
15
10
9
8
S
18
6
11
14
12
7
16
9
6
S
7
9a
9b
Figure 1 Numbering of atoms in the 13C NMR and 1H NMR spectra of the compounds 2a–f and 5a,b
(1E)-1-(Hexylsulfanyl)-2-methyloct-1-ene (2a); Typical Procedure
1H NMR (400 MHz, CDCl3): δ = 0.90 [t, J = 6.8 Hz, 3 H, C(8)H3], 1.02 [t,
J = 7.6 Hz, 3 H, C(11)H3], 1.20–1.38 [m, 6 H, C(5–7)H2], 1.37–1.47 [m, 2
H, C(4)H2], 1.60–1.71 [m, 2 H, C(10)H2], 1.74 [s, 3 H, C(12)H3], 2.06 [t,
J = 7.2 Hz, 2 H, C(3)H2], 2.62 [t, J = 8.0 Hz, 2 H, C(9)H2], 5.63 [s, 1 H,
C(1)H].
13C NMR (100 MHz, CDCl3): δ = 13.23 [C(11)], 14.06 [C(8)], 17.78
[C(12)], 22.62 [C(7)], 23.55 [C(10)], 27.80 [C(4)], 28.87 and 31.72
[C(5,6)], 36.04 [C(9)], 39.30 [C(3)], 118.07 [C(1)], 137.47 [C(2)].
A 25-mL argon-swept flask, equipped with a magnetic stirrer and a
rubber septum, was charged with a suspension of Cp2ZrCl2 (0.58 g, 2
mmol) in CH2Cl2 (5 mL) and with Me3Al (0.38 mL, 4 mmol) at room
temperature. (CAUTION: Organoaluminum compounds are pyrophoric
and can ignite on contact with air, water, or any oxidizer). Oct-1-yne
(0.30 mL, 2 mmol) was added, and the mixture was stirred at r.t. for 3
h. The mixture was cooled to 0 °C, dihexyl disulfide (1.41 g, 6 mmol)
was added, and the resulting mixture was stirred at r.t. for 18 h. The
mixture was then diluted with hexane (5 mL), and H2O (3 mL) was
added dropwise while the flask was cooled in an ice bath. The precip-
itate that formed was removed by filtration on a filter paper, and the
aqueous layer was extracted with Et2O (3 × 5 mL). The organic layers
were combined, washed with brine (10 mL), dried (CaCl2), and con-
centrated. The residue was purified by column chromatography (sili-
ca gel, hexane) to give a colorless oil; yield: 0.34 g (71%); Rf = 0.79
(hexane).
MS (EI): m/z (%) = 200 (49) [M]+, 157 (17) [M – Pr]+, 129 (100) [M –
Am]+, 95 (34), 87 (75), 55 (29).
Anal. Calcd for C12H24S: C, 71.93; H, 12.07. Found: C, 72.14; H, 12.11.
{[(1E)-2-Methyloct-1-en-1-yl]sulfanyl}benzene (2c)
Prepared by the typical procedure from oct-1-yne (0.22 g, 2 mmol)
and PhSSPh (1.31 g, 6 mmol) as a colorless oil; yield: 0.40 g (85%); Rf =
0.81 (hexane).
1H NMR (400 MHz, CDCl3): δ = 0.85–0.95 [m, 6 H, C(8,15)H3], 1.20–
1.36 [m, 10 H, C(6,7,12,13,14)H2], 1.36–1.50 [m, 4 H, C(5,11)H2], 1.55–
1.68 [m, 2 H, C(4)H2], 1.73 [s, 3 H, C(9)H3], 2.04 [t, J = 10.0 Hz, 2 H,
C(10)H2], 2.64 [t, J = 7.5, 2 H, C(3)H2], 5.63 [s, 1 H, C(2)H].
1H NMR (400 MHz, CDCl3): δ = 0. 94 [t, J = 6.8 Hz, 3 H, C(8)H3], 1.28–
1.43 [m, 6 H, C(5–7)H2], 1.48–1.58 [m, 2 H, C(4)H2], 1.89 [s, 3 H,
C(15)H3], 2.21 [t, J = 8.0 Hz, 2 H, C(3)H2], 5.97 [s, 1 H, C(1)H], 7.15–
7.38 (m, 5 H, Ph).
13C NMR (100 MHz, CDCl3): δ = 14.17 and 14.23 [C(8,15)], 17.96
[C(9)], 22.70 and 22.77 [C(7,14)], 27.79 [C(11)], 28.36 [C(5)], 28.87
[C(12)], 30.26 [C(4)], 31.43 [C(6)], 31.72 [C(13)], 34.03 [C(3)], 39.30
[C(10)], 118.22 [C(2)], 137.63 [C(1)].
13C NMR (100 MHz, CDCl3): δ = 14.11 [C(8)], 18.02 [C(15)], 22.66
[C(7)], 27.76 [C(4)], 28.91 [C(6)], 31.71 [C(5)], 39.41 [C(3)], 115.13
[C(1)], 123.53 [C(14)], 127.85 and 128.86 [2 C and 2 C, C(10–13)],
137.52 [C(9)], 143.70 [C(2)].
MS (EI): m/z (%) = 242 (22) [M+], 213 (15) [M – Et]+, 157 (41), 123 (9),
MS (EI): m/z (%) = 234 (100) [М]+, 163 (75) [M – Am]+, 135 (52), 110
115 (24), 87 (41), 81 (41), 55 (78), 41 (100).
(17), 91 (21), 69 (33), 55 (17), 41 (24).
Anal. Calcd for C15H30S: C, 74.31; H, 12.47. Found: C, 74.60; H, 12.53.
Anal. Calcd for C15H22S: C, 76.86; H, 9.46. Found: C, 77.21; H, 9.45.
(1E)-2-Methyl-1-(propylsulfanyl)oct-1-ene (2b)
[(E)-2-(Hexylsulfanyl)-1-methylvinyl]benzene (2d)
Prepared by the typical procedure from oct-1-yne (0.22 g, 2 mmol)
and PrSSPr (0.90 g, 6 mmol) as a colorless oil; yield: 0.30 g (76%); Rf =
0.87 (hexane).
Prepared by the typical procedure from PhC≡CH (0.20 g, 2 mmol) and
dihexyl disulfide (1.41 g, 6 mmol) as a colorless oil; yield: 0.37 g
(79%); Rf = 0.89 (hexane).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 2670–2676

2674
I. R. Ramazanov et al.
Paper
Synthesis
1H NMR (500 MHz, CDCl3): δ = 0.96 [t, J = 6.8 Hz, 3 H, C(8)H3], 1.30–
1.44 [m, 4 H, C(6,7)H2], 1.44–1.53 [m, 2 H, C(5)H2], 1.69–1.79 [m, 2 H,
C(4)H2], 2.18 [s, 3 H, C(9)H], 2.83 [t, J = 7.6 Hz, 2 H, C(3)H2], 6.37 [s, 1
H, C(2)H], 7.23–7.50 (m, 5 H, Ph).
MS (EI): m/z (%) = 228 (66) [М]+, 185 (100) [M – Pr]+, 143 (23), 129
(18), 109 (32), 101 (35), 67 (40), 55 (43), 41 (47).
Anal. Calcd for C14H28S: C, 73.61; H, 12.36. Found: C, 73.73; H, 12.44.
13C NMR (125 MHz, CDCl3): δ = 14.09 [C(8)], 17.63 [C(9)], 22.61 [C(7)],
28.39 [C(5)], 30.55 [C(4)], 31.46 [C(6)], 34.31 [C(3)], 123.99 [C(2)],
125.12 and 128.35 [2 C and 2 C, C(11–14)], 126.59 [C(15)], 133.22
[C(10)], 142.16 [C(1)].
MS (EI): m/z (%) = 234 (100) [М]+, 149 (62) [M – Am]+, 135 (53), 115
(30), 105 (20), 77 (9), 55 (7), 43 (35).
(5E)-5-(Propylsulfanyl)dec-5-ene (4)
Dec-5-yne (0.28 g, 2 mmol) and Et3Al (0.3 mL, 2 mmol) were added to
a suspension of Cp2TiCl2 (0.025 g, 0.1 mmol) in hexane (5 mL) under
argon at r.t. After 6 h, PrSSPr (0.90 g, 6 mmol) was added at 0 °C, and
the mixture was stirred for 18 h at r.t. The mixture was diluted with
hexane (5 mL), and H2O (3 mL) was added dropwise while the flask
was cooled in an ice bath. The precipitate was removed by filtration
on a filter paper and the aqueous layer was extracted with Et2O (3 × 5
mL). The organic layers were combined, washed with brine (10 mL),
dried (CaCl2), and concentrated. The residue was purified by column
chromatography (hexane) to give a colorless oil; yield: 0.36 g (83%);
Rf = 0.71 (hexane).
1H NMR (400 MHz, CDCl3): δ = 0.85–0.97 [m, 6 H, C(1,10)H3], 1.00 [t,
J = 7.2 Hz, 3 H, C(13)H3], 1.25–1.44 [m, 6 H, C(2,3,9)H2], 1.44–1.55 [m,
2 H, C(8)H2], 1.65–1.77 [m, 2 H, C(12)H2], 2.05–2.20 [m, 2 H, C(4)H2],
2.37 [t, J = 7.6 Hz, 2 H, C(7)H2], 2.64 [t, J = 7.0 Hz, 2 H, C(11)H2], 5.84 [t,
J = 7.5 Hz, 1 H, C(6)H].
Anal. Calcd for C15H22S: C, 76.86; H, 9.46. Found: C, 76.63; H, 9.42.
[(E)-1-Methyl-2-(propylsulfanyl)vinyl]benzene (2e)
Prepared by the typical procedure from PhC≡CH (0.20 g, 2 mmol) and
PrSSPr (0.90 g, 6 mmol); yield: 0.32 g (84%); Rf = 0.73 (hexane).
1H NMR (400 MHz, CDCl3): δ = 1.07 [t, J = 7.6 Hz, 3 H, C(5)H3], 1.71–
1.82 [m, 2 H, C(4)H2], 2.17 [s, 3 H, C(6)H3], 2.80 [t, J = 7.2 Hz, 2 H,
C(3)H2], 6.35 [s, 1 H, C(1)H], 7.23–7.44 (m, 5 H, Ph).
13C NMR (100 MHz, CDCl3): δ = 13.31 [C(5)], 17.61 [C(6)], 23.81 [C(4)],
36.28 [C(3)], 123.94 [C(2)], 125.11 and 128.33 [2 C and 2 C, C(8–11)],
126.58 [C(12)], 133.26 [C(7)], 142.15 [C(1)].
13C NMR (100 MHz, CDCl3): δ = 13.29 [C(13)], 14.07 and 14.11
[C(1,10)], 22.27 [C(11)], 22.47 and 22.57 [C(2,9)], 28.78 [C(4)], 29.50
[C(7)], 30.78 [C(8)], 31.87 [C(3)], 40.48 [C(11)], 130.82 [C(6)], 134.87
[C(5)].
MS (EI): m/z (%) = 192 (100) [M]+, 163 (4) [M – Et]+, 149 (80) [M – Pr]+,
134 (47), 115 (34), 105 (18), 77 (16), 65 (7), 51 (11).
Anal. Calcd for C12H16S: C, 74.94; H, 8.39. Found: C, 74.79; H, 8.31.
MS (EI): m/z (%) = 214 (56) [М]+, 192 (5), 185 (4) [M – Et]+, 171 (100)
[M – Pr]+, 129 (69), 116 (40), 95 (58), 74 (49), 67 (79), 55 (83).
[(E)-1-Methyl-2-(phenylsulfanyl)vinyl]benzene (2f)28
Prepared by the typical procedure from PhC≡CH (0.20 g, 2 mmol) and
PhSSPh (1.31 g, 6 mmol) as a colorless oil; yield: 0.35 g (77%); Rf = 0.65
(hexane).
Anal. Calcd for C13H26S: C, 72.82; H, 12.22. Found: C, 72.93; H, 12.20.
(5E)-5-[2-(Propylsulfanyl)ethyl]dec-5-ene (9a)
1H NMR (400 MHz, CDCl3): δ = 2.34 [s, 3 H, C(3)H3], 6.66 [s, 1 H,
C(2)H], 7.26–7.36 [m, 2 H, C(9,15)H], 7.36–7.52 [m, 8 H, C(5–8,11–
14)H].
13C NMR (100 MHz, CDCl3): δ = 17.86 [C(3)], 121.45 [C(2)], 125.50
[C(13,14)], 126.52 and 127.27 [C(9,15)], 128.49 [C(5,6)], 129.15 and
129.18 [2 C and 2 C, C(7,8,11,12)], 136.48 [C(10)], 137.29 [C(4)],
141.78 [C(1)].
Dec-5-yne (0.28 g, 2 mmol) and Et3Al (0.3 mL, 2 mmol) were added to
a suspension of Cp2TiCl2 (0.025 g, 0.1 mmol) in hexane (5 mL) under
argon at 40 °C. After 2 h, PrSSPr (0.90 g, 6 mmol) was added at 0 °C,
and the mixture was stirred for 24 h at r.t. The mixture was then di-
luted with hexane (5 mL), and H2O (3 mL) was added dropwise while
the flask was cooled in an ice bath. The precipitate was removed by
filtration on a filter paper. The aqueous layer was extracted with Et2O
(3 × 5 mL). The organic layers were combined, washed with brine (10
mL), dried (CaCl2), and concentrated. The residue was purified by col-
umn chromatography (silica gel, hexane) to give a colorless oil; yield:
0.33 g (68%); Rf = 0.49 (hexane).
1H NMR (400 MHz, CDCl3): δ = 0.86–0.97 [m, 6 H, C(1,10)H3], 1.01 [t,
J = 7.4 Hz, 3 H, C(13)H3], 1.25–1.40 [m, 8 H, C(2,3,8,9)H2], 1.58–1.69
[m, 2 H, C(12)H2], 1.95–2.06 [m, 4 H, C(4,7)H2], 2.26 [t, J = 8.2 Hz, 2 H,
C(14)H2], 2.53 [t, J = 7.2 Hz, 2 H, C(11)H2], 2.58 [t, J = 8.2 Hz, 2 H,
C(15)H2], 5.18 [t, J = 7.6 Hz, 1 H, C(6)H].
(5E)-5-Methyl-6-(propylsulfanyl)dec-5-ene (6)
Me3Al (0.38 mL, 4 mmol) and dec-5-yne (0.28 g, 2 mmol) were added
to a suspension of Cp2ZrCl2 (0.58 g, 2 mmol) in CH2Cl2 (5 mL) under
argon at r.t., and the mixture was stirred for 6 h at 60 °C. PrSSPr (0.90
g, 6 mmol) was added, and the mixture was stirred for 18 h at r.t.
Workup as described above gave a crude product that was purified by
flash chromatography (silica gel, hexane) to give a colorless oil; yield:
0.37 g (80%); Rf = 0.68 (hexane).
13C NMR (100 MHz, CDCl3): δ = 13.53 [C(13)], 14.02 [2C, C(1,10)],
22.79 and 27.41 [C(2,9)], 23.02 [C(12)], 27.41 [C(7)], 29.70 [C(4)],
30.73 [C(3)], 31.16 and 34.27 [C(11,15)], 32.22 [C(8)], 37.26 [C(14)],
126.33 [C(6)], 137.86 [C(5)].
MS (EI): m/z (%) = 242 (3) [М]+, 213 (4) [M – Et]+, 200 (35), 199 (100)
[M – Pr]+, 185 (15) [M – Bu]+, 157 (12), 143 (16), 123 (78), 109 (45), 89
(78), 81 (61), 55 (76).
1H NMR (400 MHz, CDCl3): δ = 0.86–0.95 [m, 6 H, C(1,10)H3], 0.99 [t, J
= 7.4 Hz, 3 H, C(14)H3], 1.26–1.44 [m, 6 H, C(2,3,9)H2], 1.44–1.59 [m, 4
H, C(8,13)H2], 1.93 [s, 3 H, C(11)H3], 2.12 [t, J = 7.6 Hz, 2 H, C(4)H2],
2.25 [t, J = 7.8 Hz, 2 H, C(7)H2], 2.54 [t, J = 7.2 Hz, 2 H, C(12)H2].
13C NMR (100 MHz, CDCl3): δ = 13.43 [C(14)], 14.00 [2 C, C(1,10)],
20.76 [C(11)], 22.63 and 22.76 [C(2,9)], 23.14 [C(13)], 30.71 [C(3)],
31.39 [C(8)], 31.78 [C(7)], 34.41 [C(12)], 34.56 [C(4)], 127.80 [C(6)],
139.33 [C(5)].
Anal. Calcd for C15H30S: C, 74.31; H, 12.47. Found: C, 74.12; H, 12.40.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 2670–2676

2675
I. R. Ramazanov et al.
Paper
Synthesis
(5E)-5-[2-(Hexylsulfanyl)ethyl]dec-5-ene (9b)
Acknowledgment
Prepared by the same procedure as above from dec-5-yne (0.28 g, 2
mmol) and dihexyl disulfide (1.41 g, 6 mmol) as a colorless oil; yield:
0.42 g (73%); Rf = 0.50 (hexane).
1H NMR (400 MHz, CDCl3): δ = 0.83–1.00 [m, 9 H, C(1,10,16)H3], 1.23–
1.39 [m, 10 H, C(2,8,9,14,15)H2], 1.39–1.46 [m, 4 H, C(3,13)H2], 1.56–
1.66 [m, 2 H, C(12)H2], 1.97–2.06 [m, 2 H, C(7)H2], 2.26 [t, J = 7.6 Hz, 2
H, C(17)H2], 2.39–2.45 [m, 2 H, C(4)H2], 2.54 [t, J = 7.2 Hz, 2 H,
C(11)H2], 2.58 [t, J = 7.6 Hz, 2 H, C(18)H2], 5.18 [t, J = 7.2 Hz, 1 H,
C(6)H2].
This work was supported by the Department of Chemistry and Mate-
rial Sciences of the Russian Academy of Sciences (Program No. 1-
OKhNM), which is gratefully acknowledged.
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0034-1380755.
S
u
p
p
o
nrtIo
g
f
rmoaitn
S
u
p
p
ortiInfogrmoaitn
13C NMR (100 MHz, CDCl3): δ = 14.03 [3 C, C(1,10,16)], 22.40 and
22.57 and 22.79 [C(2,9,15)], 27.41 [C(7)], 28.64 [2 C, C(3,13)], 29.70
[C(12)], 30.73 and 31.47 [C(8,14)], 31.25 [C(18)], 32.21 [2 C, C(4,11)],
37.25 [C(17)], 126.34 [C(6)], 137.87 [C(5)].
MS (EI): m/z (%) = 284 (<1) [М]+, 255 (<1) [M – Et]+, 241 (3) [M – Pr]+,
227 (4), 199 (19), 157 (3), 137 (14), 123 (33), 95 (36), 81 (35), 55 (95),
41 (100).
References
(1) Zyk, N. V.; Beloglazkina, E. K.; Belova, M. A.; Dubinina, N. S. Russ.
Chem. Rev. 2003, 72, 769.
(2) Kondo, T.; Mitsudo, T.-a. Chem. Rev. 2000, 100, 3205.
(3) Palani, T.; Park, K.; Song, K. H.; Lee, S. Adv. Synth. Catal. 2013,
355, 1160.
Anal. Calcd for C18H36S: C, 75.98; H, 12.75. Found: C, 76.24; H, 12.71.
(4) Downey, C. W.; Craciun, S.; Neferu, A. M.; Vivelo, C. A.; Mueller,
C. J.; Southall, B. C.; Corsi, S.; Etchill, E. W.; Sault, R. J. Tetrahe-
dron Lett. 2012, 53, 5763.
(5) Shoai, S.; Bichler, P.; Kang, B.; Buckley, H.; Love, J. A. Organome-
tallics 2007, 26, 5778.
(6) Yang, Y.; Rioux, R. M. Chem. Commun. 2011, 47, 6557.
(7) Corma, A.; González-Arellano, C.; Iglesias, M.; Sánchez, F. Appl.
Catal., A. 2010, 375, 49.
(8) Weiss, C. J.; Wobser, S. D.; Marks, T. J. Organometallics 2010, 29,
6308.
(9) Cao, C.; Fraser, L. R.; Love, J. A. J. Am. Chem. Soc. 2005, 127,
17614.
(10) Weiss, C. J.; Marks, T. J. J. Am. Chem. Soc. 2010, 132, 10533.
(11) Malyshev, D. A.; Scott, N. M.; Marion, N.; Stevens, E. D.;
Ananikov, V. P.; Beletskaya, I. P.; Nolan, S. P. Organometallics
2006, 25, 4462.
(12) Bates, C. G.; Saejueng, P.; Doherty, M. Q.; Venkataraman, D. Org.
Lett. 2004, 6, 5005.
(13) Lin, Y.-Y.; Wang, Y.-J.; Lin, C.-H.; Cheng, J.-H.; Lee, C.-F. J. Org.
Chem. 2012, 77, 6100.
3-Methyl-1-(propylsulfanyl)nonane (12a) and 3-[(propylsulfa-
nyl)methyl]nonane (12b)
Oct-1-ene (0.22 g, 2 mmol) and Et3Al (0.3 mL, 2 mmol) were added to
a suspension of Cp2ZrCl2 (0.058 g, 0.2 mmol) in hexane (5 mL) under
argon at 40 °C. After 2 h, dihexyl disulfide (1.41 g, 6 mmol) was added
at 0 °C, and the mixture was stirred for 24 h at r.t. The mixture was
then diluted with hexane (5 mL), and D2O (3 mL) was added dropwise
while the flask was cooled in an ice bath. The precipitate was re-
moved by filtration on a filter paper. The aqueous layer was extracted
with Et2O (3 × 5 mL). The organic layers were combined, washed with
brine (10 mL), dried (CaCl2), and concentrated. The residue was puri-
fied by column chromatography (hexane) to give a mixture of the two
regioisomers 12a and 12b as a colorless oil; yield: 0.33 g (77%); Rf =
0.67 (hexane).
1H NMR (400 MHz, CDCl3): δ = 0.85–0.95 [m, 6 H, 0.5 × C(9,13)H3, 0.5
× C(1′,9′)H3], 1.0 [t, J = 7.4 Hz, 3 H, 0.5 × C(12)H3, 0.5 × C(12′)H3], 1.20–
1.56 [m, 13 H, 0.5 × C(2–8)H2, 0.5 × C(2′-8′)H2], 1.56–1.68 [m, 2 H, 0.5
× C(11)H2, 0.5 × C(11′)H2], 2.44–2.60 [m, 4 H, 0.5 × C(1,10)H2, 0.5 ×
C(10′,13′)H2].
(14) Reddy, V. P.; Swapna, K.; Kumar, A. V.; Rao, K. R. Tetrahedron
Lett. 2010, 51, 293.
Anal. Calcd for C13H28S: C, 72.15; H, 13.04.
(15) Ranu, B. C.; Dey, R.; Chatterjee, T.; Ahammed, S. ChemSusChem
2012, 5, 22.
(16) Ogawa, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1989, 18, 769.
(17) Wang, Z.-L.; Tang, R.-Y.; Luo, P.-S.; Deng, C.-L.; Zhong, P.; Li, J.-H.
Tetrahedron 2008, 64, 10670.
(18) Neumann, H.; Seebach, D. Tetrahedron Lett. 1976, 17, 4839.
(19) Van Horn, D. E.; Negishi, E. J. Am. Chem. Soc. 1978, 100, 2252.
(20) Negishi, E.; Van Horn, D. E.; Yoshida, T. J. Am. Chem. Soc. 1985,
107, 6639.
(21) Van Horn, D. E.; Negishi, E. J. Am. Chem. Soc. 1978, 100, 2252.
(22) Zakharkin, L. I.; Gavrilenko, V. V. Bull. Acad. Sci. USSR, Div. Chem.
Sci. (Engl. Transl.) 1960, 9, 1294.
13C NMR (100 MHz, CDCl3): δ (12a) = 13.52 [C(12)], 14.08 [C(9)], 19.37
[C(13)], 22.66 [C(8)], 23.06 [C(11)], 25.56 [C(2)], 26.89 [C(7)], 29.59
and 31.90 and 32.74 [C(4–6)], 34.21 [C(1)], 36.91 [C(10)], 39.41 [C(3)].
MS (EI): m/z (%) (12a) = 216 (40) [М]+, 173 (45) [M – Pr]+, 140 (9), 111
(44), 89 (47), 83 (31), 70 (100), 55 (85).
13C NMR (100 MHz, CDCl3): δ (12b) = 10.80 [C(1′)], 13.52 [C(12′)],
14.08 [C(9′)], 22.66 [C(8′)], 23.00 [C(11′)], 25.56 [C(2′)], 26.63 [C(7′)],
29.87 and 31.94 and 32.26 [C(4′-6′)], 39.94 [C(13′)], 36.76 [C(10′)],
39.41 [C(3′)].
MS (EI): m/z (%) (12b) = 216 (20) [М]+, 173 (17) [M – Pr]+, 111 (27), 89
(10), 83 (14), 70 (100), 56 (51), 55 (40).
(23) Ibragimov, A. G.; Ramazanov, I. R.; Khalilov, L. M.; Sultanov, R.
M.; Dzhemilev, U. M. Mendeleev Commun. 1996, 6, 231.
(24) Dzhemilev, U. M.; Ibragimov, A. G.; Zolotarev, A. P. Mendeleev
Commun. 1992, 2, 135.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 2670–2676

2676
I. R. Ramazanov et al.
Paper
Synthesis
(25) Dzhemilev, U. M.; Ibragimov, A. G.; Zolotarev, A. P.; Muslukhov,
R. R.; Tolstikov, G. A. Bull. Acad. Sci. USSR. Div. Chem. Sci. (Engl.
Transl.) 1989, 38, 194.
Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.;
Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.;
Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam,
N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin,
A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.;
Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.;
Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09,
Revision A.1; Gaussian, Inc: Wallingford, 2009.
(26) Patnode, W. I.; Schmidt, F. C. J. Am. Chem. Soc. 1945, 67, 2272.
(27) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.;
Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada,
M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.;
Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Montgomery, J. A. J.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.;
(28) Ager, D. J. J. Chem. Soc., Perkin Trans. 1 1986, 183.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 2670–2676