Zirconocene Catalysis in Organoaluminum Synthesis of 1-Alkenyl Sulfones and Sulfides

Article abstract of DOI:10.1055/s-0036-1588387

The Cp₂ZrCl₂-catalyzed methylalumination of 1-alkynyl sulfones and 1-alkynyl sulfides with Me₃Al, followed by deuterolysis or hydrolysis, affords the corresponding β,β-disubstituted 1-alkenyl sulfones and 1-alkenyl sulfides in high yields. S-Methyl methanethiosulfonate is shown to be a convenient and efficient sulfanylating agent for 1-alkenylaluminum derivatives.

Full text of DOI:10.1055/s-0036-1588387

SYNTHESIS
0
0
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8
1
1
4
3
7
-
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1
0
X
©
Georg Thieme Verlag Stuttgart · New York
2016, 48, A–I
A
paper
Synthesis
R. N. Kadikova et al.
Paper
Zirconocene Catalysis in Organoaluminum Synthesis of 1-Alkenyl
Sulfones and Sulfides
1
. Me3Al (6 equiv)
Rita N. Kadikova*
Ilfir R. Ramazanov
Alexey V. Vyatkin
Usein M. Dzhemilev
O
S
Cp2ZrCl2 (0.2 equiv)
CH2Cl2
X =
Ph
R
SO2Ph
2. D2O (H2O)
O
R = Bu, Pent, Hex, Ph
79–92%)
(
1
8 h, r.t.
Me
18 h, r.t.
D(H)
SMe
R
X
R
X =
S
Institute of Petrochemistry and Catalysis of Russian
Academy of Sciences, 141 Prospekt Oktyabrya,
Ufa 450075, Russian Federation
R = Hex, Oct, Ph
73–89%)
(
1. Me3Al (3 equiv)
D(H)
Cp2ZrCl2 (0.2 equiv)
CH2Cl2
kadikritan@gmail.com
2
. D2O (H2O)
O
S
1
R
= Oct, Ph, Bu, Pr
R4
S
R4
2
R1
R3
R2
R = H, Bu, Pr
hydro- or
carboaluminaton
R1
R3
R2
al
R3 = Me, H, Et
R1
R2
O
R4 = Me
SR4
20 min, r.t.
69–85%
al = AlMe2, AlEt2
7
Received: 06.10.2016
cohols. Therefore, the exception that we found raised the
question of the scope of applicability of the methylalumina-
tion reaction. Our attention was attracted by acetylenic sul-
fur derivatives. Sulfur has an electronegativity close to that
of phosphorus and, like phosphorus, it is a vital element of
life. Similar to phosphorus, sulfur forms diverse stable or-
ganic compounds in various oxidation states. The known
Accepted after revision: 02.12.2016
Published online: 29.12.2016
DOI: 10.1055/s-0036-1588387; Art ID: ss-2016-t0703-op
Abstract The Cp ZrCl -catalyzed methylalumination of 1-alkynyl sul-
2
2
fones and 1-alkynyl sulfides with Me Al, followed by deuterolysis or hy-
3
drolysis, affords the corresponding β,β-disubstituted 1-alkenyl sulfones
and 1-alkenyl sulfides in high yields. S-Methyl methanethiosulfonate is
shown to be a convenient and efficient sulfanylating agent for 1-alke-
nylaluminum derivatives.
8,9
examples of copper-catalyzed carbomagnesiation
and
10,11
carbozincation
of alkynyl sulfones as well as carbo-
zincation1
2,13
of alkynyl sulfoxides gave hope that carbo-
Key words alkynyl sulfones, alkynyl sulfides, alkenylaluminums,
methylalumination, zirconocene catalysis
alumination of alkynyl sulfur derivatives would also pro-
ceed successfully.
The zirconium-catalyzed carbometalation of acetylenes
The controlled carbometalation of alkynes provides a
powerful tool for the construction of new organometallic
unsaturated species and various ring structures. Previous-
is widely used to prepare substituted olefins that present
practical values for synthetic organic chemistry.1
4–16
In this
1
paper, we report for the first time a Сp ZrCl -catalyzed
2 2
ly, we developed methods for the preparation of 1-alkenyl
phosphines and phosphine oxides based on Zr-catalyzed
carboalumination of 1-alkynyl phosphines and phosphine
oxides. It has been found that the pathway of the reaction
of 1-alkynyl phosphine derivatives with organoaluminum
compounds strongly depends on the nature of the substrate
and the solvent. The ethylalumination takes place under the
methylalumination of substituted 1-alkynyl sulfones, sul-
fides, and sulfoxides on treatment with Me Al. Methylalu-
3
mination of organosulfur acetylenes would open up the
way for a one-pot method transforming acetylenes into
substituted 1-alkenyl sulfones, sulfides, and sulfoxides. Fur-
thermore, we report the development of a new method
suitable for the conversion of a broad range of alkenylalu-
minum derivatives to alkenyl sulfides in one-pot processes.
We found that substituted 1-alkynyl sulfones obtained
from terminal acetylenes (1-hexyne, 1-heptyne, 1-octyne,
2,3
action of Et Al in the case of 1-alkynyl phosphines and
3
phosphine oxides in hexane as the solvent. However, our ef-
forts to carry out Zr-catalyzed methylalumination of 1-
alkynyl phosphines and phosphine oxides by Me Al were
and phenylacetylene) react with 6 equivalents of Me Al in
3
3
unsuccessful. We hypothesized that the acetylene group is
deactivated due to the formation of positive-charged com-
plexes with cationic organoaluminum and/or organozirco-
nium intermediates. It is noteworthy that the Negishi
the presence of 1 equivalent of Cp ZrCl in dichloromethane
2
2
over a period of 18 hours to give, after deuterolysis or hy-
drolysis, β,β-disubstituted 1-alkenyl sulfones in high yields
(Scheme 1). The reaction was stereoselective and gave Z-
isomers of substituted 1-alkenyl sulfones. The structures of
the compounds formed in the reaction were determined by
means of 1D and 2D NMR spectroscopy using the products
of their deuterolysis 2a–d and hydrolysis 3a. The NOESY
spectrum of compound 3а clearly showed coupling be-
4,5
methylalumination holds an important place in alkyne
chemistry owing to a wide variety of compounds that can
be prepared in this way. The reaction was successfully car-
4
ried out with terminal acetylenes, heterosubstituted aryl-
6
ethynes containing O, S, Cl, and Si, and homopropargyl al-
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

B
Synthesis
R. N. Kadikova et al.
Paper
tween the signals of hydrogen at the double bond and
methyl group-hydrogen at the double bond, indicating the
Z-configuration of the 1-alkenyl sulfide formed.
bridized carbon atom located in the β-position relative to
aluminum appeared at 169.32 ppm. The chemical shifts
found for the double bond carbon atoms are close to pub-
lished data for linear alkenylalanes.1
7,18
Besides, the HMBC
Me3Al (6 equiv)
Cp2ZrCl2 (0.2 equiv)
D2O
2
O
S
R
SO2Ph
spectrum of intermediate 4b exhibited cross-peaks be-
tween signals of the double bond carbon atoms and the hy-
drogen atom of the S-methyl group.
R
SO2Ph
X
(H O)
R
Ph
CH2Cl2
r.t., 18 h
Me
AlMe2
O
Me
1
a–d
X = D: 2a: R = Bu (80%), 2b: R = Pent (88%),
c: Hex (81%), 2d: Ph (92%)
X = H: 3a: R = Bu (79%)
The Zr-catalyzed methylalumination of 1-alkynyl sulf-
2
oxides upon treatment with 3 equivalents of Me Al failed.
3
After the addition of 3 equivalents of Me Al to 1-(methyl-
3
Scheme 1 syn-Zr-catalyzed methylalumination of substituted 1-alkynyl
sulfones
sulfinyl)dec-1-yne in the presence of 20 mol% Cp ZrCl in
2
2
dichloromethane followed by hydrolysis, dec-1-yn-1-yl
methyl sulfide (7b) was isolated from the reaction mixture
in 79% yield (Scheme 3). Thus, under methylalumination
conditions, 1-alkynyl sulfoxides are reduced to sulfides.
When (hex-1-yn-1-ylsulfonyl)benzene was reacted
with 4 equivalents of Me Al in dichloromethane in the
3
presence of 1 equivalent of Cp ZrCl , the conversion of the
2
2
1
. Me3Al (3 equiv)
starting 1-alkynyl sulfone within 24 hours was 54%. A de-
crease in the amount of Cp ZrCl down to a catalytic
O
S
Cp2ZrCl2 (0.2 equiv)
R
R
S
2
2
CH2Cl2, r.t., 20 min
amount (20 mol%) also favored the reaction to afford sub-
stituted 1-alkenyl sulfones of Z-configuration in high yields.
The use of hexane as the solvent did not hamper the reac-
tion either.
7a: R = Bu (84%)
b: R = Oct (79%)
2
. H2O
7
1
. Me3Al (5 equiv)
O
S
Hex
Me
SMe
Hex
Me
SMe
H
Cp2ZrCl2 (0.2 equiv)
H2O
Hex
As a continuation of our studies on the carbometalation
of sulfur-containing acetylenes in which the sulfur func-
tional group is directly attached to the triple bond, we have
now studied the methylalumination of 1-alkynyl sulfides.
Substituted 1-alkynyl sulfides reacted with 3 equivalents of
Me Al in the presence of 20 mol% Cp ZrCl in dichlorometh-
CH2Cl2, r.t., 18 h
AlMe2
6
b (68%)
Scheme 3 Reaction of 1-alkynyl sulfoxides with Cp ZrCl and Me Al
2
2
3
We have previously described a similar reduction of
sulfoxides to sulfides in the transformation of cyclic orga-
noaluminum compounds into 3-alkyltetrahydrothiophenes
under the action of thionyl chloride.19 The reaction of di-
chloroborane with aliphatic sulfoxides also gives the corre-
sponding sulfides.20 Thus, we propose that the conversion
of 1-alkynyl sulfoxides into 1-alkynyl sulfides 7 under the
reaction conditions of an alkyne methylalumination, pro-
ceeds as follows. According to the Negishi methylalumina-
3
2
2
ane to give, after deuterolysis or hydrolysis, β,β-disubstitut-
ed 1-alkenyl sulfides 5a,c and 6a–c in high yields (Scheme
2). The cross peak between the signals of the hydrogen
atom at the double bond and the methyl group in the
NOESY spectrum indicated a Z-configuration of 6b after hy-
drolysis of a product resulting from the methylalumination
reaction of dec-1-yn-1-yl(methyl)sulfane.
Me3Al (3 equiv)
Cp2ZrCl2 (0.2 equiv)
D2O
2
21
R
SMe
R
SMe
X
tion reaction of alkynes under the reaction conditions,
Cl ZrCp and Me Al undergo a Me–Cl exchange to produce
Me AlCl (A) (Scheme 4). Further, the reaction of Me AlCl
(H O)
R
S
CH3
2
2
3
CH2Cl2, r.t., 18 h
Me
AlMe2
Me
2
2
4a–d
with 1-alkynyl sulfoxides can produce intermediate B,
which generates 1-alkynyl sulfides because of cleavage of
MeOAlMeCl.
X = D: 5a: Hex (85%), 5c: Ph (80%)
X = H: 6a: Hex (73%), 6b: Oct (77%),
6c: Ph (89%)
Scheme 2 Zr-catalyzed methylalumination of substituted 1-alkynyl
sulfides
Me
Me2AlCl + MeClZrCp2
Me3Al + Cl2ZrCp2
Me2Al
R
ZrCp2
Cl Cl
A
In addition, we measured the NMR spectra for orga-
noaluminum intermediate 4b in deuterobenzene solution.
Although the C NMR spectra of the reaction mixture of or-
ganoaluminum compounds are rather complicated for reli-
able assignment of signals, we succeeded in identifying
+
13
R
S
S
O
AlMe2
Cl
O
AlHMe2
Cl
B
27
some of the characteristic signals. Thus, the sole Al NMR
signal is a broadened peak at δAl =168.76. The С NMR sig-
B
R
S
13
MeOAlMeCl
7
nal for the double bond carbon atom attached to aluminum
appeared at 156.78 ppm, while the signal for the sp -hy-
Scheme 4 A plausible mechanism for the reduction of sulfoxides to
2
sulfides in the reaction of 1-alkynyl sulfoxides with Cp ZrCl and Me Al
2
2
3
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

C
Synthesis
R. N. Kadikova et al.
Paper
Note that an increasing amount of Me Al (5 equiv) led to
alkenyl sulfides as the methylalumination products. After
alkenyl(dimethyl)alane 10 with S-methyl methanethiosul-
fonate and 3-chloroperbenzoic acid yielded (E)-2-methyl-
1-(methylsulfonyl)oct-1-ene (11) in 81% yield.
3
the addition of Me Al (5 equiv) to 1-(methylsulfinyl)dec-1-
3
yne in the presence of 20 mol% Cp ZrCl in dichlorometh-
2
2
O
ane followed by hydrolysis, dec-1-yn-1-yl(methyl)sulfane
6b) was isolated from the reaction mixture in 68% yield
R2
S
S
R2
(1 equiv)
Me3Al (2 equiv)
Cp2ZrCl2 (1 equiv)
(
R1
Me
H
R1
Me
H
O
R1
H
within 18 hours (Scheme 3).
CH2Cl2, r.t., 3 h
AlMe2
r.t., 10 min
SR2
In order to develop a new method for the synthesis of
alkenyl sulfides of various structures via organoaluminum
synthesis, we undertook a study aimed at the development
of an efficient sulfanylation reagent for alkenylalanes. De-
velopment of such a sulfanylation reagent would enable the
conversion of a wide range of organoaluminum com-
pounds, in one preparative step, to alkenyl sulfides, which
can be easily oxidized either to sulfoxides or to sulfones.
Earlier, we reported that sulfonic acid derivatives are ef-
ficient for a functionalization of various alkenylalanes. Effi-
cient one-pot methods for alkenylalane halogenation with
8
a,b
9
9
a: R1 = Oct (85%)
1
b: R = Ph (79%)
R2 = Me
Me Al (2 equiv)
Cp2ZrCl2 (1 equiv)
3
Hex
Me
H
Hex
H
CH2Cl2, r.t., 3 h
AlMe2
10
O
Me
(1 equiv)
Hex
Me
S
S
Me
r.t., 10 min
O
mCPBA
(4 equiv)
Hex
H
H
22
Me
SO2Me
sulfonyl halides have been developed, as well as silylation
SMe
1
1 (81%)
23
methods using trialkylsilyl sulfonates. Meanwhile, recent-
ly we have developed a new method for sulfanylation of or-
ganoaluminum compounds on treatment with organic di-
sulfides, which is suitable for the selective preparation of
alkenyl sulfides in high yields in one step under mild condi-
Scheme 5 Reaction of β,β-disubstituted 1-alkenylaluminums with
S-methyl methanethiosulfonate
The discovered reaction is a continuation of our studies
dealing with the development of efficient one-pot methods
24
tions.
Thus, heteroatomic sulfonic acid derivatives
24
demonstrated high performance in functionalization of or-
ganoaluminum compounds, providing introduction of a he-
teroatomic function into an acetylene molecule in one pre-
parative step. In this connection, we assumed that S-methyl
methanethiosulfonate would also be reactive toward orga-
noaluminum compounds. The Negishi methylalumination
results in the formation of 1-alkenyl(dimethyl)alanes from
terminal acetylenes in high yield and with high stereoselec-
for the synthesis of alkenyl sulfides from alkenylalanes.
The reactions of trialkylalane with S, S Cl , or SCl reported
2
2
2
in the literature are nonselective and often produce mix-
25
tures of organic sulfides, disulfides, and trisulfides.
Owing to the simplicity of the procedure described
above and to the high efficiency of S-methyl methanethio-
sulfonate for the preparation of alkenyl sulfides, an attempt
was made to apply this strategy for the functionalization of
alkenylalanes of various structures containing an ethyl
group at aluminum. Previously, we reported the Ti-cata-
lyzed hydroalumination of disubstituted acetylenes with
4,21
tivity.
Our assumption was confirmed, as we found for
the first time that 1-alkenyl(dimethyl)alanes 8a,b reacted
with S-methyl methanethiosulfonate at room temperature
over a period of 10 minutes to give 1-alkenyl alkyl sulfides
26
Et Al. The reaction of α,β-disubstituted vinylalane 12 ob-
3
9
a,b in high yields with high regio- and stereoselectivity
tained in this reaction with 1 equivalent of S-methyl meth-
anethiosulfonate furnished alkenyl sulfide 13 in high yield
(Scheme 6).
(Scheme 5). Upon sulfide group addition, the stereochemi-
cal configuration of the double bond was retained. This was
confirmed by the NOESY spectrum of compound 9a, exhib-
iting coupling between hydrogen at the double bond and
the α-hydrogen atoms of n-C H group. It is worth noting
that one mole equivalent of the S-methyl methanesul-
fonothioate is sufficient for complete conversion of alkenyl-
alane. This indicates that the transformation involves only
the Al–C(sp ) bond in alkenylalane. Apparently, this is at-
tributable to a higher reactivity of the Al–C(sp ) bond com-
pared with the Al–C(sp ) bond due to higher nucleophilicity
of the carbon center at the double bond. Thus, 1-alkenyl(di-
methyl)alanes reacted with S-methyl methanethiosulfonate
to give 1-alkenyl alkyl sulfides with high regio- and stereo-
selectivity, that allowed the further oxidation of the sul-
fides to sulfones. For example, sequential treatment of 1-
O
R2
S
S
R2
8
17
Et3Al (2 equiv)
O
R1
R1
S
R1
H
R1
Cp TiCl (0.05 equiv)
2
2
(1 equiv)
R1
R1
r.t., 10 min
R2
hexane, r.t., 6 h
H
AlEt2
1
12
13 a: R = Bu (80%)
1
2
1
3 b: R = Pr (76%)
2
R2 = Me
3
Scheme 6 Reaction of α,β-disubstituted 1-alkenylaluminums with
S-methyl methanethiosulfonate
Aluminacyclopent-2-enes represent an interesting ex-
ample of cyclic α,β,β-trisubstituted vinylalanes obtained
by the Zr-catalyzed reaction of disubstituted acetylenes
17
with Et Al. The reaction of aluminacyclopentene 14 with
3
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

D
Synthesis
R. N. Kadikova et al.
Paper
S-methyl methanethiosulfonate involves only the Al–C(sp2)
bond of the metallacycle and gives sulfides 15a,b in a high
yield (Scheme 7). An increase in the amount of the disulfide
does not favor the formation of a disulfide product. Mean-
while, the sulfanylation of aluminacyclopent-2-enes with
organic disulfides, which we proposed previously, fur-
Finnigan 4021 instrument. The yields were calculated from the isolat-
ed amounts of 1-alkenyl sulfides and 1-alkenyl sulfones obtained
from starting alkynes.
1-Alkenyl Sulfones 2a–d and 3a via Zr-Catalyzed Methylalumina-
tion of 1-Alkynyl Sulfones (Figure 1)
3
nished sulfanylation products only at the Al–C(sp ) bond of
10
8
11
23
11
9
12
the metallacycle. The silylation of 2,3-dialkyl-substituted
aluminacyclopent-2-enes on treatment with organosilicon
9
7
5
10
6
5
3
O
3
S
6
3
O
esters of sulfonic acids also involves the Al–C(sp ) bond of
4
O
S
2
1
4
O
22
the ring. Thus, methyl thiosulfonate provided a chemose-
2
1
D
2
7
D
lective functionalization of the Al–C(sp ) bond of cyclic
8
2a
2
b
α,β,β-trisubstituted vinylalanes.
12
13
10
11
R1
R1
7
6
Et3Al (1 equiv)
Np2ZrCl2 (0.1 equiv)
8
11
5
9
5
1
0
4
O
R1
R1
6
3
O
8
S
1
S
1
3
hexane, 40 °C, 2 h
Al
Et
4
O
2
O
2
D
D
9
1
4
7
O
2c
2d
1
0
11
R2
S
S
R2
1
.
R1
R1
S
(
1 equiv)
9
O
5a: R1 = Pr (73%)
1
5
4
14
1
6
8
r.t., 10 min
. H2O
15b: R = Bu (69%)
3
O
R2 = Me
S
1
O
2
2
H
Scheme 7 Reaction of aluminacyclopent-2-enes with S-methyl meth-
anethiosulfonate
7
3a
Figure 1 Numbering of atoms in the 13С and H NMR spectra of the
1
compounds 2a–d and 3a
In summary, we have accomplished for the first time
the selective Cp ZrCl -catalyzed methylalumination of sub-
2
2
(Z)-[(2-Methylhex-1-en-1-yl-1-d)sulfonyl]benzene (2a); Typical
stituted 1-alkynyl sulfones and 1-alkynyl sulfides by reac-
Procedure
tions with Me Al providing 1-alkenyl sulfones and 1-alke-
To a 25 mL, argon-swept flask, equipped with a magnetic stirrer and
3
nyl sulfides, respectively, in high yields. Also, we have de-
veloped a new sulfanylation method for 1-alkenylalanes
with S-methyl methanethiosulfonate, which gives substi-
tuted 1-alkenyl sulfides in high yields and with high selec-
tivity in one step under mild conditions.
rubber septa, were added Cp
2 2
ZrCl (117 mg, 0.40 mmol) suspended in
CH Cl (5 mL) and Me Al (1.14 mL, 12 mmol) (Caution: organoalumi-
2
2
3
nums are pyrophoric and can ignite on contact with air, H O, or any
oxidizer) at r.t. To the solution was added 1-(phenylsulfonyl)-1-
hexyne (444 mg, 2 mmol) at r.t. and stirred for 18 h. Then, the reac-
2
tion mixture was diluted with hexane (5 mL) and D O (3 mL) was add-
2
ed dropwise while cooling the reaction flask in an ice bath. The pre-
cipitate was filtered on a filter paper and the aqueous layer was ex-
All reagents were obtained from Sigma-Aldrich or Acros. The use of n-
hexane as solvent is represented by – hexane – consistently through-
out. CH Cl and hexane were distilled over P O . S-Methyl methaneth-
tracted with Et
washed with brine (10 mL) and dried (anhyd CaCl
solvent and purification of the residue by column chromatography
2
O (3 × 5 mL). The combined organic layers were
). Evaporation of
2
2
2
2
5
iosulfonate was prepared by reduction of sulfonyl halides with Zn
(PE/EtOAc, 9:1 to 4:1) gave a colorless oil; yield: 380 mg (80%); R =
0.81 (PE/EtOAc, 4:1).
f
27
powder.
(Methylthio)acetylenes were prepared from terminal
28
alkynes and S-methyl methanethiosulfonate. Substituted 1-alkynyl
sulfones were prepared by electrophilic substitution reaction
trimethylsilyl-1-alkynes under the influence benzenesulfonyl chlo-
ride and powdered aluminum chloride. IR spectra were recorded on
Bruker VE Vertex 70v spectrometer as liquid films or in Nujol and are
reported in wavenumbers (cm ). NMR spectra were recorded on a
Bruker Avance 400 spectrometer. The H NMR spectra were recorded
at 400 MHz and C NMR spectra at 100 MHz in CDCl . The chemical
IR (film): 2958, 2933, 2872, 1612, 1447, 1304, 1290, 1151, 1085, 751,
–1
723, 690 cm
.
1
H NMR (400 MHz, CDCl ): δ = 0.90 (t, J = 7.1 Hz, 3 Н, 6-СН ), 1.25–
29
3
3
1
3
.40 (m, 4 Н, 4,5-СН ), 1.88 (s, 3 Н, 7-СН ), 2.59 (t, J = 7.5 Hz, 2 Н,
2
3
-СН ), 7.50–7.95 (m, 5 Н, C H ).
–1
2
6
5
13
1
C NMR (100 MHz, CDCl ): δ = 13.9 (C-6), 22.8 (C-5), 24.5 (C-7), 29.1
3
13
(C-4), 32.3 (C-3), 127.1 (2 C, С-9), 129.1 (2 C, C-10), 132.1 (С-11),
42.6 (С-8), 158.3 (C-2).
3
1
shifts are reported in ppm relative to TMS as the internal standard.
13
1
+
The numbering of atoms for С and H NMR assignments of the com-
pounds 2a–d, 3a, 5a,c, 6a–c, 7b, 9a,b, 11, 13a,b, and 15a,b is shown
in Figures 1–4. Elemental analysis was performed using a Carlo-Erba
CHN 1106 elemental analyzer. Mass spectra were obtained on a
MS (EI): m/z (%) = 239 (27, [M ]), 210 (47), 204 (7), 173 (11), 144 (32),
125 (68), 97 (92), 82 (100), 56 (79), 41 (57).
Anal. Calcd for C13H17DO S: C, 69.91. Found: C, 69.94.
2
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E
Synthesis
R. N. Kadikova et al.
Paper
(
Z)-[(2-Methylhept-1-en-1-yl-1-d)sulfonyl]benzene (2b)
Using the procedure described above, 1-(phenylsulfonyl)-1-heptyne
472 mg, 2 mmol) gave a crude product that was purified by flash
IR (film): 2958, 2933, 2872, 1611, 1446, 1323, 1290, 1151, 1085, 751,
–1
723, 690 cm .
1
(
H NMR (400 MHz, CDCl ): δ = 0.91 (t, J = 6.7 Hz, 3 Н, 6-СН ), 1.25–
3 3
chromatography (silica gel, PE/EtOAc, 9:1 to 4:1) to afford a colorless
1.45 (m, 4 Н, 4,5-СН ), 1.88 (s, 3 Н, 7-СН ), 2.60 (t, J = 7.5 Hz, 2 Н, 3-
2
3
oil; yield: 445 mg (88%); R = 0.80 (PE/EtOAc, 4:1).
СН ), 6.18 (s, 1-СН), 7.50–7.95 (m, 5 Н, C H ).
2 6 5
f
1
3
IR (film): 2957, 2931, 2861, 1612, 1447, 1313, 1305, 1151, 1086, 753,
C NMR (100 MHz, CDCl ): δ = 13.9 (C-6), 22.8 (C-5), 24.5 (C-7), 30.1
3
–1
723, 690 cm
.
(C-4), 32.3 (C-3), 126.2 (С-1), 127.1 (2 C, C-9), 129.1 (2 С, С-10), 132.1
(С-11), 142.6 (C-8), 158.3 (C-2).
1
H NMR (400 MHz, CDCl ): δ = 0.89 (t, J = 6.7 Hz, 3 Н, 7-СН ), 1.20–
3
3
+
1
.35 (m, 4 Н, 4,6-СН ), 1.35–1.50 (m, 2 Н, 5-СН ), 1.89 (s, 3 Н, 8-СН ),
MS (EI): m/z (%) = 238 (23, [M ]), 209 (39), 143 (36), 125 (52), 96 (67),
2
2
3
2
.59 (t, J = 7.5 Hz, 2 Н, 3-СН ), 7.50–7.95 (m, 5 Н, C H ).
81 (100), 55 (92), 41 (73).
2
6
5
13
C NMR (100 MHz, CDCl ): δ = 13.9 (C-7), 22.4 (C-6), 24.5 (C-8), 27.5
Anal. Calcd for C13H18O S: C, 65.51; H, 7.61. Found: C, 65.54; Н, 7.67.
3
2
(C-5), 31.8 (C-4), 32.3 (C-3) 127.1 (2 C, С-9), 129.1 (2 C, C-10), 132.1
(
С-11), 142.7 (С-8), 158.3 (C-1).
1
-Alkenyl Sulfides 5a,c and 6a–c via Zr-Catalyzed Methylalumina-
+
MS (EI): m/z (%) = 253 (30, [M ]), 236 (3), 210 (52), 198 (7), 162 (10),
tion of 1-Alkynyl Sulfides (Figure 2)
1
30 (36), 125 (88), 96 (89), 82 (54), 69 (100), 56 (81), 41 (97).
7
6
5
6
5
Anal. Calcd for C14H19DO S: C, 70.84. Found: C, 70.87.
8
2
5
4
4
6
3
S
1
10
S
1
8
S
1
8
(
Z)-[(2-Methyloct-1-en-1-yl-1-d)sulfonyl]benzene (2с)
Using the procedure described above, (oct-1-yn-1-ylsulfonyl)benzene
500 mg, 2 mmol) gave a crude product that was purified by flash
4
3
3
2
2
2
D
D
H
9
7
7
(
5a
5c
6c
chromatography (silica gel, PE/EtOAc, 9:1 to 4:1) to afford a colorless
oil; yield: 433 mg (81%); R = 0.79 (PE/EtOAc, 4:1).
7
6
f
8
9
5
10
IR (film): 2955, 2930, 2858, 1612, 1545, 1447, 1312, 1305, 1150,
7
6
3
–1
1085, 754, 725, 690 cm
.
S
1
10
8
5
4
2
3
1
H NMR (400 MHz, CDCl ): δ = 0.89 (t, J = 6.7 Hz, 3 Н, 8-СН ), 1.22–
S
1
12
3
3
H
4
1
.35 (m, 6 Н, 5,6,7-СН ), 1.35–1.48 (m, 2 Н, 4-СН ), 1.89 (s, 3 Н, 9-
9
2
2
2
H
СН ), 2.59 (t, J = 10.0, 2 Н, 3-СН ), 7.50–8.05 (m, 5 Н, C H ).
6a
6b
3
2
6
5
11
1
3
C NMR (100 MHz, CDCl ): δ = 14.1 (C-8), 22.5 (C-7), 24.5 (C-9), 27.9
Figure 2 Numbering of atoms in the 13С and H NMR spectra of the
compounds 5a,c and 6a–c
1
3
(C-4), 29.4 and 31.6 (C-5,6), 32.5 (C-3) 127.2 (2 C, С-11), 129.1 (2 C, C-
1
2), 132.9 (С-13), 142.7 (С-10), 158.3 (C-2).
+
MS (EI): m/z (%) = 267 (2, [M ]), 257 (81), 229 (52), 217 (64), 189 (17),
1
(Z)-Methyl(2-methyloct-1-en-1-yl-1-d)sulfane (5a); Typical Proce-
dure
87 (13), 157 (15), 133 (14), 115 (8), 73 (10), 57 (100), 41 (33).
Anal. Calcd for C15H21DO S: C, 67.37. Found: C, 67.39.
To a 25 mL, argon-swept flask, equipped with a magnetic stirrer and
rubber septa, were added Cp ZrCl (117 mg, 0.40 mmol) suspended in
2
2
2
CH Cl (5 mL) and Me Al (0.57 mL, 6 mmol) (Caution: organoalumi-
(
Z)-[(2-Phenylprop-1-en-1-yl-1-d)sulfonyl]benzene (2d)
2
2
3
nums are pyrophoric and can ignite on contact with air, H O, or any
2
Using the procedure described above, [(phenylethynyl)sulfonyl]ben-
zene (484 mg, 2 mmol) gave a crude product that was purified by
flash chromatography (silica gel, PE/EtOAc, 9:1 to 4:1) to afford color-
oxidizer) at r.t. To the solution was added methyl(oct-1-yn-1-yl)sul-
fane (312 mg, 2 mmol) of at r.t. and stirred for 18 h. Then, the reaction
mixture was diluted with hexane (5 mL), and D O (3 mL) was added
2
less crystals; yield: 456 mg (92%); R = 0.63 (PE/EtOAc, 4:1).
f
dropwise while cooling the reaction flask in an ice bath. The precipi-
tate was filtered on a filter paper and the aqueous layer was extracted
IR (film): 3043, 3029, 2959, 2928, 1612, 1483, 1445, 1411, 1392,
1
–1
316, 1029, 984, 750, 697 cm .
with Et O (3 × 5 mL). The combined organic layers were washed with
2
1
H NMR (400 MHz, CDCl ): δ = 2.56 (s, 3 Н, 7-СН ), 7.20–8.00 (m, 10
brine (10 mL) and dried (anhyd CaCl ). Evaporation of solvent and pu-
3
3
2
Н, C H ).
rification of the residue by column chromatography (silica gel, hex-
6
5
13
ane) gave a colorless oil; yield: 294 mg (85%); R = 0.43 (hexane).
C NMR (100 MHz, CDCl ): δ = 17.2 (C-7), 126.3 (2 C, C-5), 127.3 (2 C,
f
3
C-9), 128.8 (2 C, C-10), 129.3 (2 C, C-4), 129.9 (C-6), 133.2 (С-11),
IR (film): 2958, 2933, 2859, 2200, 1730, 1698, 1467, 1457, 1377,
1307, 1099, 1041, 1009, 804, 780, 750, 698 cm .
–1
153.4 (C-1), 140.1 (С-8), 142.2 (С-3).
+
1
MS (EI): m/z (%) = 259 (24, [М ]), 224 (11), 116 (100), 106 (65), 92 (3),
H NMR (400 MHz, CDCl ): δ = 0.91 (t, J = 7.5 Hz, 3 Н, 8-СН ), 1.24–
3 3
77 (37), 51 (33).
1.36 (m, 6 Н, 5,6,7-СН ), 1.36–1.46 (m, 2 Н, 4-СН ), 1.76 (s, 3 Н, 9-СН ),
2
2
3
2
.15 (t, J = 7.5 Hz, 2 Н, 3-СН ), 2.24 (s, 3 Н, 10- СН ).
Anal. Calcd for C15H13DO S: C, 74.04. Found: C, 74.07.
2
3
2
13
C NMR (100 MHz, CDCl ): δ = 14.1 (C-8), 17.3 (C-10), 22.6 (C-7), 22.8
3
1
(C-9), 27.3 (C-4), 29.1 and 31.8 (2 C, С-5,6), 33.6 (C-3), 119.70 (t, J
=
(
Z)-[(2-Methylhex-1-en-1-yl)sulfonyl]benzene (3a)
Using the procedure described above, reaction of 1-(phenylsulfonyl)-
-heptyne (444 mg, 2 mmol) and H O (instead of D O) gave a crude
C,D
21.0, C-1), 137.4 (С-2).
+
1
MS (EI): m/z (%) = 173 (2, [M ]), 157 (3), 124 (2), 115 (4), 101 (100), 67
2
2
product that was purified by column chromatography on silica gel
PE/EtOAc, 9:1 to 4:1) to afford a colorless oil; yield: 376 mg (79%); Rf
0.83 (PE/EtOAc, 4:1).
(21), 59 (23), 41 (21).
(
=
Anal. Calcd for C10H19DS: C, 69.29. Found: C, 69.32.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

F
Synthesis
R. N. Kadikova et al.
Paper
1
3
(
Z)-Methyl(2-phenylprop-1-en-1-yl-1-d)sulfane (5c)
Using the procedure described above, methyl(phenylethynyl)sulfane
296 mg, 2 mmol) gave a crude product that was purified by flash
chromatography (silica gel, hexane) to afford a colorless oil; yield:
61 mg (80%); R = 0.50 (hexane).
C NMR (100 MHz, CDCl ): δ = 14.1 (C-10), 17.4 (C-12), 22.7 (C-9),
3
2
3
2.9 (C-11), 27.4 (C-4), 29.3 and 29.5, 30.1 and 31.9 (4 C, С-5,6,7,8),
3.6 (C-3), 120.1 (С-1), 137.5 (С-2).
(
+
MS (EI): m/z (%) = 200 (21, [M ]), 185 (3), 101 (100), 81 (12), 67 (17),
41 (27).
2
f
IR (film): 3019, 2986, 2962, 2923, 2200, 1600, 1495, 1437, 1316,
Anal. Calcd for C12H24S: C, 71.93; H, 12.07. Found: C, 71.97; Н, 12.11.
–1
1300, 1027, 1013, 803, 762, 750, 725, 697 cm .
1
H NMR (400 MHz, CDCl ): δ = 2.19 (d, J = 3.4 Hz, 3 Н, 8-СН ), 2.29 (d,
(Z)-Methyl(2-phenylprop-1-en-1-yl)sulfane (6c)
3
3
J = 3.4 Hz, 3 Н, 7-СН ), 7.10–7.65 (m, 5 Н, C H ).
3
6
5
Using the procedure described above, methyl(phenylethynyl)sulfane
(296 mg, 2 mmol) gave a crude product that was purified by flash
chromatography (silica gel, hexane) to afford a colorless oil; yield:
13
1
C NMR (100 MHz, CDCl ): δ = 18.1 (C-7), 24.8 (C-8), 123.6 (t, J
=
3
C,D
2
1.0 Hz, C-1), 127.1 (C-6), 127.5 (C-5), 128.1 (C-4) 133.6 (С-2), 140.5
C-3).
MS (EI): m/z (%) = 165 (100, [M ]), 150 (68), 135 (82), 116 (67), 106
18), 91 (15), 77 (20), 63 (11), 51 (22), 40 (8).
Anal. Calcd for C10H11DS: C, 72.67. Found: C, 72.61.
(
292 mg (89%); R
f
= 0.41 (hexane).
+
IR (film): 3019, 2980, 2962, 2919, 1599, 1490, 1437, 1316, 1027,
–1
(
1013, 803, 762, 725, 697 cm
1H NMR (400 MHz, CDCl
): δ = 2.20 (s, 3 Н, 8-СН
СН ), 6.03 (s, 1-СН), 7.15–7.65 (m, 5 Н, C H ).
.
), 2.30 (s, 3 Н, 7-
3
3
3
6
5
13
(Z)-Methyl(2-methyloct-1-en-1-yl)sulfane (6a)
C NMR (100 MHz, CDCl ): δ = 18.2 (C-7), 24.9 (C-8), 124.1 (C-1),
3
1
27.2 (C-6), 127.6 (2 C, C-5), 128.1 (2 C, C-4) 131.5 (С-2), 140.7 (C-3).
Using the procedure described above, reaction of methyl(oct-1-yn-1-
yl)sulfane (368 mg, 2 mmol) and H O (instead of D O) gave a crude
+
2
2
MS (EI): m/z (%) = 164 (100, [M ]), 149 (73), 134 (85), 115 (74), 105
product that was purified by column chromatography on silica gel
hexane) to afford a colorless oil; yield: 292 mg (73%); R = 0.45 (hex-
ane).
(20), 91 (20), 77 (21), 51 (21).
(
f
Anal. Calcd for C10H12S: C, 73.12; H, 7.36. Found: C, 73.15; Н, 7.40.
IR (film): 2955, 2930, 2858, 1612, 1545, 1447, 1377, 1307, 1099,
Reaction of 1-Alkynyl Sulfoxides with Cp ZrCl and Me Al (Figure
2
2
3
–1
1041, 1009, 804, 780, 750, 698 cm .
3)
1
H NMR (400 MHz, CDCl ): δ = 0.91 (t, J = 6.3 Hz, 3 Н, 8-СН ), 1.26–
3
3
9
7
5
3
1
.36 (m, 6 Н, 5,6,7-СН ), 1.36–1.48 (m, 2 Н, 4-СН ), 1.76 (s, 3 Н, 9-
2
2
S
11
СН ), 2.16 (t, J = 8.0 Hz, 2 Н, 3-СН ), 2.24 (s, 3 Н, 10-СН ), 5.60 (s, 1 H,
10
3
2
3
8
6
4
1-СН).
7b
13
Figure 3 Numbering of atoms in the H and 13С NMR spectra of 7b
1
C NMR (100 MHz, CDCl ): δ = 14.1 (C-8), 17.3 (C-10), 22.6 (C-7), 22.9
3
(C-9), 27.3 (C-4), 29.1 and 31.8 (2 C, С-5,6), 33.7 (C-3), 120.1 (C-1),
1
37.5 (С-2).
MS (EI): m/z (%) = 172 (21, [M ]), 157 (3), 115 (4), 101 (100), 81 (12),
7 (22), 59 (23), 41 (21).
Anal. Calcd for C10H20S: C, 69.70; H, 11.70. Found: C, 69.68; Н, 11.66.
Dec-1-yn-1-yl(methyl)sulfane (7b); Typical Procedure
+
To a 25 mL, argon-swept flask, equipped with a magnetic stirrer and
rubber septa, were added Cp ZrCl (117 mg, 0.40 mmol) suspended in
6
2
2
CH Cl (5 mL) and Me Al (0.57 mL, 6 mmol) (Caution: organoalumi-
2 2 3
nums are pyrophoric and can ignite on contact with air, H O, or any
2
oxidizer) at 0 °C. To the solution was added 1-(methylsulfinyl)dec-1-
yne (400 mg, 2 mmol) of at r.t. and stirred for 20 min. Then, the reac-
(
Z)-Methyl(2-methyldec-1-en-1-yl)sulfane (6b)
To a 25 mL, argon-swept flask, equipped with a magnetic stirrer and
rubber septa, were added Cp ZrCl (117 mg, 0.40 mmol) suspended in
CH Cl (5 mL) and Me Al (0.57 mL, 6 mmol) (Caution: organoalumi-
nums are pyrophoric and can ignite on contact with air, H O, or any
oxidizer) at r.t. To the solution was added dec-1-yn-1-yl(methyl)sul-
fane (424 mg, 2 mmol) of at r.t. and stirred for 18 h. Then, the reaction
mixture was diluted with hexane (5 mL), and H O (3 mL) was added
dropwise while cooling the reaction flask in an ice bath. The precipi-
tate was filtered on a filter paper and the aqueous layer was extracted
with Et O (3 × 5 mL). The combined organic layers were washed with
brine (10 mL) and dried (anhyd CaCl ). Evaporation of solvent and pu-
tion mixture was diluted with hexane (5 mL), and H O (3 mL) was
2
2
2
added dropwise while cooling the reaction flask in an ice bath. The
precipitate was filtered on a filter paper and the aqueous layer was
2
2
3
2
extracted with Et O (3 × 5 mL). The combined organic layers were
2
washed with brine (10 mL) and dried (anhyd CaCl ). Evaporation of
2
solvent and purification of the residue by column chromatography
2
(
eluent: hexane) gave a colorless oil; yield: 291 mg (79%); R = 0.48
f
(hexane).
IR (film): 3260, 3323, 2957, 2923, 2871, 2855, 2260, 2200, 1698,
2
–1
1468, 1457, 1377, 1096, 1041, 1009, 806, 720, 695, 680 cm
.
2
rification of the residue by column chromatography (silica gel, hex-
ane) gave a colorless oil; yield: 308 mg (77%); R = 0.47 (hexane).
1
H NMR (400 MHz, CDCl ): δ = 0.90 (t, J = 6.7 Hz, 3 Н, 10-СН ), 1.20–
3
3
f
1.45 (m, 10 Н, 5,6,7,8,9-СН ), 1.45–1.58 (m, 2 Н, 4-СН ), 2.29 (t, J = 8.0
2 2
Hz, 2 Н, 3-СН ), 2.37 (s, 3 Н, 11-СН ).
IR (film): 2957, 2923, 2871, 2855, 1730, 1696, 1465, 1457, 1377,
2
3
–1
13
1307, 1099, 1041, 1005, 801, 777, 722, 698 cm
.
C NMR (100 MHz, CDCl ): δ = 14.1 (C-10), 19.3 (C-11), 20.1, 28.8,
3
1
28.9, 29.1, and 29.2 (C-5,6,7,8,9), 22.7 (C-4), 31.8 (C-3), 69.8 (С-1),
3.3 (С-2).
MS (EI): m/z (%) = 184 (2, [M
H NMR (400 MHz, CDCl ): δ = 0.90 (t, J = 6.8 Hz, 3 Н, 10-СН ), 1.15–
3
3
9
1
.35 (m, 8 Н, 5,6,7,8-СН ), 1.35–1.50 (m, 2 Н, 4-СН ), 1.76 (s, 3 Н, 11-
2
2
СН ), 2.16 (t, J = 7.5 Hz, 2 Н, 3-СН ), 2.24 (s, 3 Н, 12-СН ), 5.60 (s, 1 H,
1
+
]), 183 (14), 155 (7), 141 (26), 127 (33),
3
2
3
-СН).
93 (53), 79 (67), 55 (57), 41 (100).
Anal. Calcd for C11H20S: C, 71.67; H, 10.94. Found: C, 71.69; Н, 10.91.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

G
Synthesis
R. N. Kadikova et al.
Paper
1-Alkenyl Sulfides 9a,b via Zr-Catalyzed Methylalumination of
(E)-Methyl(2-phenylprop-1-en-1-yl)sulfane (9b)
Terminal Alkynes Followed by Treatment with S-Methyl Methane-
thiosulfonate (Figure 4)
Using the procedure described above, phenylacetylene (204 mg, 2
mmol) and S-methyl methanethiosulfonate (252 mg, 2 mmol) gave a
crude product that was purified by flash chromatography (silica gel,
7
8
hexane) to afford a colorless oil; yield: 177 mg (79%); R = 0.89 (hex-
f
9
5
10
ane).
7
6
6
5
6
3
H
8
5
4
IR (film): 3056, 3027, 2956, 2922, 1730, 1685, 1595, 1493, 1443,
2
1 O
S
4
3
H
1377, 1313, 1028, 984, 810, 750, 695 cm
–1
.
H
10
4
3
2
9
O
1
2
1
1
H NMR (400 MHz, CDCl ): δ = 2.15 (s, 3 Н, 8-СН ), 2.42 (s, 3 Н, 7-
3 3
S
12
S
8
СН ), 6.30 (s, 1 H, 1-СН), 7.20–7.40 (m, 5 Н, C H ).
9a
11
7
9b
11
3
6
5
13
C NMR (100 MHz, CDCl ): δ = 17.3 (C-7), 17.5 (C-8), 125.1 (2 C, C-5),
3
5
4
9
5
8
125.3 (C-1), 125.9 (C-6), 128.3 (2 C, C-4) 133.1 (С-2), 141.9 (C-3).
6
10
3
7
3
6
+
MS (EI): m/z (%) = 164 (100, [M ]), 149 (74), 134 (84), 115 (73), 105
4
7
8
2
1
2
1
(19), 91 (19), 77 (20), 63 (12), 51 (21).
11
H
S
9
H
S
Anal. Calcd for C10H12S: C, 73.12; H, 7.36. Found: C, 73.09; Н, 7.41.
1
3a
13b
5
1
8
5
9
(E)-2-Methyl-1-(methylsulfonyl)oct-1-ene (11)
6
10
3
6
3
7
1
Using the procedure described above, oct-1-yne (220 mg, 2 mmol)
and S-methyl methanethiosulfonate (252 mg, 2 mmol) gave a crude
product that was used without further purification. To a solution of
methyl(2-methyloct-1-en-1-yl)sulfane (400 mg, 2 mmol) in anhyd
4
7
4
8
2
1
2
0
S
11
12
S
13
9
11
1
5a
15b
Figure 4 Numbering of atoms in the H and 13С NMR spectra of the
compounds 9a,b, 11, 13a,b and 15a,b
1
CH
2 2
Cl (20 mL/mmol sulfide) was added 3-chloroperbenzoic acid
(692 mg, 4.0 equiv) in one portion at 0 °C and the reaction mixture
was stirred at 0 °C for 2 h. The reaction was quenched with 30% aq
Na SO and extracted with CH Cl . The combined organic extracts
2
3
2
2
(
E)-Methyl(2-methyldec-1-en-1-yl)sulfane (9a); Typical Procedure
were washed with sat. aq NaHCO and brine, and dried (MgSO ). The
solvent was removed under reduced pressure and the residue was pu-
rified by flash column chromatography (PE/EtOAc, 9:1) to give a col-
3
4
To a 25 mL, argon-swept flask, equipped with a magnetic stirrer and
rubber septa, were added Cp ZrCl (580 mg, 2 mmol) suspended in
2
2
CH Cl (5 mL) and Me Al (0.38 mL, 4 mmol) (Caution: organoalumi-
2
2
3
orless oil; yield: 330 mg (81%); R = 0.84.
f
nums are pyrophoric and can ignite on contact with air, H O, or any
2
IR (film): 2956, 2930, 2859, 1631, 1465, 1413, 1379, 1300, 1132, 963,
oxidizer) at 0 °C. To the solution was added 1-octyne (220 mg, 2
mmol) at r.t. and stirred for 3 h. S-Methyl methanethiosulfonate (252
mg, 2 mmol) was added to the reaction mixture at 0 °C and stirred at
r.t. for 10 min. Then, the mixture was diluted with hexane (5 mL), and
–1
8
13, 771, 752 cm
1H NMR (400 MHz, CDCl
1.40 (m, 6 Н, 5,6,7-СН ), 1.40–1.56 (m, 2 Н, 4-СН
), 2.17 (s, 3 H, 9-CH ), 2.95 (s, 3 Н, 10-СН ), 6.12 (s, 1 H, 1-СН).
.
): δ = 0.90 (t, J = 5.9 Hz, 3 Н, 8-СН
), 1.22–
3
3
), 2.12–2.21 (m, 2 Н,
2
2
H O (3 mL) was added dropwise while cooling the reaction flask in an
3-СН
2
3
3
2
ice bath. The precipitate was filtered on a filter paper and the aqueous
13
C NMR (100 MHz, CDCl ): δ = 14.1 (C-8), 17.8 (C-9), 22.5 (C-7), 27.1
3
layer was extracted with Et O (3 × 5 mL). The combined organic layers
2
(C-4), 28.7 and 31.5 (C-5,6), 40.3 (C-3), 43.8 (C-10), 125.1 (С-1), 158.9
(С-2).
were washed with brine (10 mL) and dried (anhyd CaCl ). Evaporation
2
of solvent and purification of the residue by column chromatography
+
MS (EI): m/z (%) = 204 (<1, [M ]), 147 (14), 134 (22), 124 (15), 109 (9),
(
eluent: hexane) gave a colorless oil; yield: 284 mg (85%); R = 0.49
f
95 (40), 81 (48), 69 (60), 55 (97), 41 (100).
(hexane).
Anal. Calcd for C12H24S: C, 58.78; H, 9.87. Found: C, 59.98; Н, 9.91.
IR (film): 2958, 2923, 2871, 2858, 2845, 1730, 1696, 1465, 1377,
–1
1
310, 1099, 1041, 1008, 801, 777, 750, 722, 698 cm .
1-Alkenyl Sulfides 13a,b via Ti-Catalyzed Hydrolalumination of
1
H NMR (400 MHz, CDCl ): δ = 0.90 (t, J = 6.7 Hz, 3 Н, 10-СН ), 1.15–
3
3
Alkynes Followed by Treatment with S-Methyl Methanethiosul-
fonate
1
.35 (m, 10 Н, 5,6,7,8,9-СН ), 1.35–1.50 (m, 2 Н, 4-СН ), 1.73 (s, 3 Н,
2
2
1
1-СН ), 2.05 (t, J = 8.0 Hz, 2 Н, 3-СН ), 2.26 (s, 3 Н, 12-СН ), 5.60 (s, 1
3
2
3
H, 1-СН).
(
E)-Dec-5-en-5-yl(methyl)sulfane (13a); Typical Procedure
13
C NMR (100 MHz, CDCl ): δ = 14.1 (C-10), 17.2 (C-12), 17.8 (C-11),
3
To Cp TiCl (250 mg, 0.10 mmol) suspended in hexane (5 mL) were
added 5-decyne (276 mg, 2 mmol) and Et Al (0.30 mL, 2 mmol) at r.t.
under an argon atmosphere. After 6 h, to the reaction mixture was
added S-methyl methanethiosulfonate (250 mg, 2 mmol) at 0 °C and
stirred for 10 min at r.t. Then, the mixture was diluted with hexane (5
2
2
22.7, 29.3, 29.4, 29.5, and 31.9 (C-5,6,7,8,9), 27.8 (C-4), 39.2 (C-3),
3
119.7 (С-1), 136.9 (С-2).
+
MS (EI): m/z (%) = 200 (23, [M ]), 185 (3), 115 (3), 101 (100), 67 (17),
55 (16), 41 (23).
Anal. Calcd for C12H24S: C, 71.93; H, 12.07. Found: C, 71.98; Н, 12.15.
mL), and H O (3 mL) was added dropwise while cooling the reaction
flask in an ice bath. The precipitate was filtered on a filter paper and
2
the aqueous layer was extracted with Et O (3 × 5 mL). The combined
2
organic layers were washed with brine (10 mL) and dried (anhyd
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I

H
Synthesis
R. N. Kadikova et al.
Paper
13
CaCl ). Evaporation of solvent and purification of the residue by col-
C NMR (100 MHz, CDCl ): δ = 13.3 (C-12), 14.1 and 14.2 (C-6,10),
2
3
umn chromatography (eluent: hexane) gave a colorless oil; yield: 298
15.9 (C-13), 22.5 (C-4), 23.1 (C-8), 27.1 (C-11), 30.7 (С-7), 31.1 and
31.4 (C-5,9), 32.0 (С-3), 128.7 (C-1), 143.4 (C-2).
mg (80%); R = 0.53 (hexane).
f
+
IR (film): 2958, 2933, 2873, 2862, 1716, 1466, 1457, 1411, 1379,
MS (EI): m/z (%) = 214 (7, [М ]), 200 (42), 185 (4), 172 (90), 158 (19),
–1
1261, 1097, 1088, 1047, 1020, 805, 731 cm
.
124 (20), 117 (37), 95 (24), 82 (63), 55 (48).
1
H NMR (400 MHz, CDCl ): δ = 0.80–1.05 (m, 6 Н, 6,10-СН ), 1.25–
Anal. Calcd for C13H26S: C, 72.82; H, 12.22. Found: C, 72.79; Н, 12.19.
3
3
1
2
7
.45 (m, 6 Н, 4,5,9-СН ), 1.45–1.55 (m, 2 Н, 8-СН ), 2.11 (q, J = 7.1 Hz,
2
2
Н, 3-СН ), 2.15–2.30 (m, 2 Н, 7-СН ), 2.21 (s, 3 Н, 11-СН ), 5.12 (t, J =
2
2
3
(E)-(5-Ethyloct-4-en-4-yl)(methyl)sulfane (15b)
.3 Hz, 2-СН).
Using the procedure described above, 4-octyne (220 mg, 2 mmol) and
S-methyl methanethiosulfonate (250 mg, 2 mmol) gave a crude prod-
uct that was purified by flash chromatography (silica gel, hexane) to
13
C NMR (100 MHz, CDCl ): δ = 13.9 and 14.1 (C-6,10), 14.8 (C-11),
3
22.3 (C-4), 22.5 (С-8), 28.2 (C-7), 31.3 and 31.6 (C-5,9), 32.2 (С-3),
122.5 (С-2), 135.7 (C-1).
afford a colorless oil; yield: 295 mg (69%); R = 0.51 (hexane).
f
+
MS (EI): m/z (%) = 186 (2, [М ]), 157 (<1), 131 (8), 117 (17), 97 (28), 83
(
IR (film): 2957, 2930, 2873, 2861, 1711, 1458, 1378, 1336, 1309,
1140, 956, 745 cm .
–1
57), 69 (52), 61 (63), 55 (72), 41 (57).
1
Anal. Calcd for C11H22S: C, 70.89; H, 11.90. Found: C, 70.91; Н, 11.88.
H NMR (400 MHz, CDCl ): δ = 0.80–0.95 (m, 6 Н, 5,8-СН ), 1.00 (t, J =
3
3
6
.0 Hz, 3 Н, 10-СН ), 1.25–1.45 (m, 2 Н, 4-СН ), 1.45–1.60 (m, 2 Н, 7-
3
2
(E)-Methyl(oct-4-en-4-yl)sulfane (13b)
СН
2
), 2.09 (t, J = 6.0 Hz, 2 Н, 6-СН
2
), 2.16 (s, 3 Н, 11-СН ), 2.26 (t, J =
3
8
.0 Hz, 2 Н, 3-СН ), 2.37 (q, J = 8.0 Hz, 2 Н, 9-СН ).
Using the procedure described above, 4-octyne (220 mg, 2 mmol) and
S-methyl methanethiosulfonate (250 mg, 2 mmol) gave a crude prod-
uct that was purified by flash chromatography (silica gel, hexane) to
2
2
13
C NMR (100 MHz, CDCl ): δ = 13.4 (C-10), 13.8 and 14.3 (C-5,8), 15.9
3
(C-11), 22.1 (C-4), 22.3 (C-7), 27.1 (C-9), 32.9 (С-3), 34.4 (С-6), 128.7
afford a colorless oi; yield: 250 mg (76%); R = 0.46 (hexane).
(C-1), 143.5 (C-2).
f
+
IR (film): 2958, 2933, 2873, 1730, 1715, 1465, 1457, 1437, 1378,
MS (EI): m/z (%) = 186 (73, [М ]), 171 (41), 144 (23), 129 (49), 1116
–1
1140, 1119, 755, 735 cm
.
(11), 101 (23), 95 (46), 87 (28), 81 (63), 79 (30), 67 (100), 55 (87), 41
(99).
1
H NMR (400 MHz, CDCl ): δ = 0.85–1.06 (m, 6 Н, 5,8-СН ), 1.35–1.47
3
3
(
m, 2 Н, 4-СН ), 1.47–1.60 (m, 2 Н, 7-СН ), 2.09 (q, J = 7.6 Hz, 2 Н, 3-
Anal. Calcd for C11H22S: C, 70.89; H, 11.90. Found: C, 70.87; Н, 11.93.
2
2
СН ), 2.16–2.26 (m, 2 Н, 6-СН ), 2.21 (s, 3 Н, 9-СН ), 5.14 (t, J = 7.2 Hz,
2
2
3
1
H, 2-СН).
1
3
C NMR (100 MHz, CDCl ): δ = 13.8 (2 C, C-5,8), 14.8 (C-9), 22.2 (C-4),
Acknowledgment
3
2
3.2 (С-7), 30.6 (C-3), 33.8 (С-6), 122.5 (С-2), 135.6 (C-1).
This work was supported by the Russian Foundation for Basic Re-
search under Grant No. 16-33-60167 and 16-33-00403, which are
gratefully acknowledged. We thank Dr. T. V. Tyumkina and Dr. L. M.
Khalilov for help in the interpretation of spectral data. We also ac-
knowledge the Center of collective use of the unique equipment
«Agidel» at the Institute of Petrochemistry and Catalysis of the Rus-
sian Academy of Sciences.
+
MS (EI): m/z (%) = 158 (44, [М ]), 143 (21), 129 (100), 115 (11), 88
(
18), 81 (60), 67 (27), 55 (29), 41 (49).
Anal. Calcd for C H18S: C, 68.28; H, 11.46. Found: C, 68.31; Н, 11.48.
9
1
-Alkenyl Sulfides 15a,b via Zr-Catalyzed Cyclic Carboalumination
of Alkynes Followed by Treatment with S-Methyl Methanethiosul-
fonate
Supporting Information
(E)-(6-Ethyldec-5-en-5-yl)(methyl)sulfane (15a); Typical Procedure
To Cp ZrCl (580 mg, 0.20 mmol) suspended in hexane (5 mL) were
2
2
Supporting information for this article is available online at
added 5-decyne (276 mg, 2 mmol) and Et Al (0.30 mL, 2 mmol) at 40
3
http://dx.doi.org/10.1055/s-0036-1588387.
S
u
p
p
ortioIgnfmr oaitn
S
u
p
p
o
nrtogI
i
f
rm oaitn
°C under an atmosphere of argon. After 2 h, to the reaction mixture
was added S-methyl methanethiosulfonate (250 mg, 2 mmol) at 0 °C
and stirred for 24 h at r.t. Then, the mixture was diluted with hexane
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©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–I