A new method for the activation of ethyl benzenesulfenate in electrophilic addition reactions

Article abstract of DOI:10.1007/s11172-008-0370-7

Reactions of unsaturated compounds with the PhSOEt-SOHal₂ and PhSOEt-Me₃SiHal systems (Hal = Cl or Br) were proposed as a new route to haloalkyl phenyl sulfides. With acyclic and mono- and bicyclic alkenes and dienes as examples, the

Full text of DOI:10.1007/s11172-008-0370-7

Russian Chemical Bulletin, International Edition, Vol. 57, No. 12, pp. 2572—2578, December, 2008
2572
A new method for the activation of ethyl benzenesulfenate
in electrophilic addition reactions
N. V. Zyk, A. Yu. Gavrilova, O. A. Mukhina, O. B. Bondarenko, and N. S. Zefirov
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 939 0290. Eꢀmail: gavrilova@org.chem.msu.ru
Reactions of unsaturated compounds with the PhSOEt—SOHal2 and PhSOEt—Me3SiHal
systems (Hal = Cl or Br) were proposed as a new route to haloalkyl phenyl sulfides. With acyclic
and monoꢀ and bicyclic alkenes and dienes as examples, the regioꢀ and stereoselectivity of the
reactions were studied.
Key words: ethyl benzenesulfenate, trimethylsilyl halides, thionyl halides, alkenes, dienes,
sulfenylation, electrophilic addition.
Electrophilic addition of such sulfenic acid derivatives
(Hal = Cl or Br), as in the case of Me3SiHal, proceed
stereospecifically to give transꢀβꢀhaloalkyl phenyl sulfides
in nearly quantitative yields (Table 1).
as sulfenyl chlorides is a wellꢀstudied and convenient route
to sulfurꢀcontaining compounds.1 Sulfenylbromination,2,3
ꢀiodination,4 and ꢀfluorination5 have been studied less
thoroughly because of the low stability of the starting sulfeꢀ
nyl halides. Addition of stable sulfenic acid derivatives
(sulfenamides) to multiple bonds occurs only in the preꢀ
sence of strong protic3 or Lewis acids.2,4—8 It should be
noted that halosulfenylation,2—6 aminosulfenylation,7 or
sulfamatosulfenylation8 are possible when an appropriate
activator is employed. Only a few studies have been devotꢀ
ed to the sulfenylation of unsaturated compounds with
sulfenic acid esters (sulfenates).9—12
Scheme 1
Earlier, we have reported on new methods for haloꢀ
sulfenylation of olefins through their reactions with ethyl
benzenesulfenate in the presence of phosphorus oxohaꢀ
lides13 and trimethylsilyl halides.14 In the present work, we
studied the possibility of sulfenylating alkenes and dienes
with ethyl benzenesulfenate in the presence of trimethylsiꢀ
lyl halides and thionyl halides.
Hal = Cl (2a, 4a), Br (2b, 4b)
These reactions are very easy to implement: a solution
of a coreagent (SOHal2 or Me3SiHal; Hal = Cl or Br) is
slowly added to a solution of an alkene and a sulfenate in
chloroform (or dichloromethane) and the mixture is stirred
at room temperature until the reaction is completed
(15—20 min). Then the mixture is passed through a colꢀ
umn with silica gel and the eluate is concentrated. In most
cases, the resulting product requires no additional purifiꢀ
cation. The structures of the products were determined by
1H and 13C NMR spectroscopy. The compositions of the
novel compounds were confirmed by GCꢀMS or elemenꢀ
tal analysis data.
The transꢀarrangement of the substituents was deterꢀ
mined from H NMR data. For instance, when passing
1
from a nonpolar solvent (C6D6) to a more polar solvent
(CDCl3), the signals for the protons at the substituents in
the spectra of compounds 2a,b become broadened, thus
confirming the transꢀarrangement of the halogen atom and
the phenylthio group.15 The coupling constant in the
1H NMR spectra of compounds 4a,b (J2,3 ≈ 3 Hz) is also
consistent with the transꢀarrangement of the substituents.16
The absence of the products of the Wagner—Meerwein
rearrangement in the case of norbornene is indicative of
the low effective electrophilicity of the sulfenylating sysꢀ
tems. Nevertheless, in the sulfenylation of benzonorborꢀ
The reactions of ethyl benzenesulfenate with cyclohexꢀ
ene and norbornene (Scheme 1) in the presence of SOHal2
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2521—2527, December, 2008.
1066ꢀ5285/08/5712ꢀ2572 © 2008 Springer Science+Business Media, Inc.

Halosulfenylation of alkenes
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 12, December, 2008
2573
Table 1. Yields of the products of the phenylsulfenylhalogenaꢀ
tion of cyclic alkenes 1, 3, 5, 6, and 10
methoxycarbonyl group of the substrate acts as an internal
nucleophile in the final step of the reaction. This pathway
is characteristic of the sulfenylation of such systems.1,8
Alkene
Coreagent
Product
Yield (%)
1
SOCl2
SOBr2
SOCl2
2а
2b
4а
99
99
96
99
95*
47*
96
63
92
97
99
99
Scheme 3
3
5
6
SOBr2
4b
Me3SiCl
Me3SiBr
Me3SiCl
SOCl2
Me3SiBr
SOBr2
7a + 8а
7b + 8b
9a
9a
9b
9b
11
11
10
SOCl2
SOBr2
Hal = Cl, Br
Reactions of ethyl benzenesulfenate with terminal oleꢀ
fins such as hexꢀ1ꢀene (12) and heptꢀ1ꢀene (13) are not
regiospecific (Scheme 4, Table 2). However, in the presꢀ
ence of chlorineꢀcontaining activators, antiꢀMarkowniꢀ
koff adducts (aꢀM) are mainly obtained; i.e., the reaction
is kinetically controlled.1 With bromineꢀcontaining actiꢀ
vators, the reaction yields thermodynamically more stable
Markownikoff adducts (M).
* The ratios of products 7a : 8a and 7b : 8b are 75 : 25 and
60 : 40, respectively.
nadiene 5, we isolated both nonꢀrearranged and rearranged
products (Scheme 2); a reaction with 3,6ꢀdimethoxybenꢀ
zonorbornadiene 6 gives only rearranged halogenꢀcontainꢀ
ing sulfides (see Table 1).
Scheme 4
Scheme 2
R = Bu (12, 14a,b, 16a,b), C5H11 (13, 15a,b, 17a,b);
Hal = Cl (14a, 15a, 16a, 17a, 19a),
Br (14b, 15b, 16b, 17b, 19b)
The sulfenylhalogenation of styrene (18) gives Marꢀ
kownikoff adducts (see Scheme 4), which agrees with the
literature data.17
R = H (5, 7a,b, 8a,b), OMe (6, 9a,b);
Hal = Cl (7a, 8a, 9a), Br (7b, 8b, 9b)
The rearranged character of sulfides 8 and 9 is suggestꢀ
ed by H NMR data for these compounds. Their spectra
show two vicinal coupling constants for the coupling of the
HCHal proton with the H2C(10) protons of the adjacent
A reaction of norbornadiene (20) with PhSOEt yields,
apart from βꢀhalo sulfides 21a,b and 22a,b, nortricyclane
γꢀhalo sulfides 23a,b (Scheme 5, Table 3). Note that we
obtained only one nortricyclane isomer with the exoꢀendoꢀ
arrangement of the substituents (23a,b). This suggests the
formation of a lowꢀpolarity intermediate for which only
endoꢀmigration of the nucleophile is possible. This fact
can be associated with characteristic homoallyl participaꢀ
tion of the second double bond of norbornadiene in the
stabilization of an intermediate carbocation, although its
double bonds are separated.
1
methylene group (J9,10ꢀendo = 7.4—7.9 Hz; J9,10ꢀexo
=
= 3.5—4.0 Hz). The endoꢀposition of the HCHal proton
is confirmed by the longꢀrange Wꢀcoupling constant
J9,11ꢀanti ≈ 1.0 Hz.
Dimethyl norbornꢀ2ꢀeneꢀ5,6ꢀdicarboxylate (10) reacts
with sulfenate in the presence of Me3SiHal to give γꢀlacꢀ
tone (11) as a sole product (Scheme 3). In this case, the

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 12, December, 2008
Zyk et al.
Table 2. Yields of the products of the reactions of ethyl benzeneꢀ
sulfenate activated with Me3SiHal or SOHal2 (Hal = Cl and Br)
with terminal alkenes 12, 13, and 18
21a,b with the endoꢀphenylthio group becomes possible
because an electrophile in an endoꢀattack is coordinated to
both double bonds of norbornadiene.
The structures of the products obtained from ethyl benꢀ
zenesulfenate and such conjugated dienes as cyclopentadiꢀ
ene (24), cyclohexaꢀ1,3ꢀdiene (29), 2,3ꢀdimethylbutaꢀ1,3ꢀ
diene (33), and isoprene (36) (Schemes 6, 7) were deterꢀ
Alkene
Coreagent Product Yield
(%)
C* (%)
аꢀМ
М
Hexꢀ1ꢀene (12) Me3SiCl 14a + 16а 64
SOCl2 14a + 16а 58
Me3SiBr 14b + 16b 60
SOBr2 14b + 16b 56
Heptꢀ1ꢀene (13) Me3SiCl 15a + 17а 65
SOCl2 15a + 17а 58
Me3SiBr 15b + 17b 78
25
22
85
77
23
26
83
84
100
100
100
100
75
78
15
23
77
74
17
16
—
—
—
—
Scheme 6
SOBr2
15b + 17b 70
Styrene (18)
Me3SiCl
SOCl2
Me3SiBr
SOBr2
19a
19a
19b
19b
89
66
97
87
* Hereafter, these are the relative percentages of the products.
Scheme 5
Hal = Cl (21a, 22a, 23a), Br (21b, 22b, 23b)
The ratio of the isomers in the reaction mixture was
determined from the published data.18 The dominant forꢀ
mation of products containing the exoꢀphenylthio group
correlates with a sterically more favorable attack of an
electrophile on the double bond of norbornene derivatives
from the exo side. However, the formation of products
Table 3. Yields of the products of the halosulfenylation
of norbornadiene (20)
Coreagent
Product
Total
C (%)
yield (%)
21
22
23
Me3SiCl
SOCl2
Me3SiBr
SOBr2
21a + 22a + 23a
21a + 22a + 23a
21b + 22b + 23b
21b + 22b + 23b
75
93
99
95
24
18
20
24
56
43
47
45
20
39
33
31

Halosulfenylation of alkenes
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 12, December, 2008
2575
Scheme 7
Hal = Cl (34, Eꢀ35a, 37, 38a, Zꢀ39a, Eꢀ39a), Br (Zꢀ35b, Eꢀ35b, 38b, Zꢀ39b, Eꢀ39b)
mined from the reported19 chemical shifts and coupling
constants.
constant of the HCS proton is not high (3J3,4) and that of
the HCBr proton is high (3J4,5´ = 5.9 Hz), we identified
product 26 as a transꢀ1,2ꢀadduct of cyclopentadiene.
The formation of transꢀ4ꢀbromoꢀ3ꢀphenylthiocycloꢀ
pentene is attributable to a higher reaction rate under the
conditions we propose (25 °C against –40 °C for sulfeꢀ
nylbromination with sulfenamides in the presence of
POBr319). At the same time, the sulfenylchlorination of
cyclopentadiene does not yield transꢀ4ꢀchloroꢀ3ꢀphenylꢀ
thiocyclopentene. Apparently, this is due to a more rapid
attack of the bromide anion on the carbocationic center
compared to the chloride anion, which is a weaker nucꢀ
leophile.
As with cyclic dienes, reactions of 2,3ꢀdimethylbutadiꢀ
ene (33) and isoprene (36) with sulfenate in the presence of
Me3SiCl or SOCl2 mainly give 1,2ꢀadducts (see Scheme 7;
Table 5, 6). In isoprene, the more substituted double bond
is more reactive (see Table 6). Sulfenylbromination with
ethyl benzenesulfenate—Me3SiBr (or SOBr2) produces
only isomeric 1,4ꢀadducts of 2,3ꢀdimethylbutadiene or
isoprene when its more substituted double bond is atꢀ
tacked (see Table 5 and 6). An attack on the less substitutꢀ
ed double bond of isoprene leads only to a 1,2ꢀadduct
(see Table 6).
Cyclopentadiene (24) and cyclohexaꢀ1,3ꢀdiene (29)
react with the sulfenylchlorinating systems to give only
transꢀ1,2ꢀadducts 25a and 30a (see Scheme 6). However,
the major sulfenylbromination products are stereoisomerꢀ
ic 1,4ꢀadducts, transꢀisomers 27 and 31 being dominant
(Table 4).
It should be noted that the sulfenylbromination of cyꢀ
clopentadiene yields, apart from the earlier19 described
compounds (25b, 27, 28), another product. Based on
1H NMR data, we identified it as transꢀ4ꢀbromoꢀ3ꢀphenylꢀ
thiocyclopentene (26). For instance, the signals for its oleꢀ
finic protons appear as two multiplets at δ 5.89 and 5.96.
The signal for the HC(3) proton is shifted upfield (comꢀ
pared to an analogous signal for compound 25b) and apꢀ
pears as a broadened singlet at δ 4.60, which allowed asꢀ
signment of this signal to the HCS proton. The signal for
the HCBr proton is a doublet with the coupling constant
J = 5.9 Hz (δ 4.54). According to the literature data,20,21
3
substituted cyclopentenes are characterized by Jtrans
=
= 3.0—4.0 Hz and 3Jcis = 6.0—8.0 Hz. Since the coupling
Table 4. Yields of the products of the phenylsulfenylhalogenation
of cyclic dienes 24 and 29
Therefore, the sulfenylchlorination of both cyclic and
linear dienes gives 1,2ꢀadducts, while the major sulfenylꢀ
bromination products are thermodynamically more stable
1,4ꢀadducts.
Diene Coreagent
Total
C* (%)
yield (%)
I
II
27, 31 28, 32
25, 30 26
Table 5. Yields of the products of the phenylsulfenylhalogenaꢀ
tion of 2,3ꢀdimethylbutadiene (33)
24
29
Me3SiCl
SOCl2
Me3SiBr
Me3SiCl
SOCl2
60
60
85
99
99
99
99
100
100
24
100
100
18
—
—
12
—
—
—
—
—
—
42
—
—
56
45
—
—
23
—
—
26
23
Coreagent
Product
Total
C (%)
yield (%)
34
Zꢀ35 Eꢀ35
Me3SiBr
SOBr2
Me3SiCl
SOCl2
Me3SiBr
SOBr2
34 + 35a
34 + 35a
35b
61
24
97
57
88
78
—
—
—
—
50
46
12
22
50
54
32
* The relative percentages of the 1,2ꢀ (I) and 1,4ꢀaddition prodꢀ
ucts (II) are given.
35b

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 12, December, 2008
Zyk et al.
Table 6. Yields of the products of the phenylsulfenylhalogenation
of isoprene 36
antiꢀH(7)); 1.72 (m, 1 H, exoꢀH(5)); 1.86 (d, 1 H, synꢀH(7),
2J7,7 = 10.5 Hz); 2.05 (m, 1 H, exoꢀH(6)); 2.33 (br.s, 1 H, H(4));
2.52 (br.s, 1 H, H(1)); 3.12 (dd, 1 H, HCS, J3,2 = 3.5 Hz, J3,7ꢀanti
=
= 2.9 Hz); 4.08 (m, 1 H, HCCl); 7.25 (tm, 1 H, pꢀH(Ar), J = 7.3 Hz);
7.33 (t, 2 H, mꢀH(Ar), J = 7.3 Hz); 7.44 (d, 2 H, oꢀH(Ar),
J = 7.3 Hz). The spectrum agrees with the literature data.17
endoꢀ2ꢀBromoꢀexoꢀ3ꢀphenylthiobicyclo[2.2.1]heptane (4b),
Rf 0.73. 1H NMR, δ: 1.40 (m, 1 H, endoꢀH(5)); 1.45 (d, 1 H,
Coreagent
Product
Total
C (%)
yield (%)
37 38 Zꢀ39 Eꢀ39
Me3SiCl 37 + 38a + 39a
SOCl2
Me3SiBr
SOBr2
98
97
97
96
66 20
64 23
7
7
7
6
19
26
2
37 + 38a + 39a
38b + 39b
antiꢀH(7), J7,7 = 10.6 Hz); 1.58 (m, 1 H, endoꢀH(6)); 1.72
2
—
—
13 68
18 56
(m, 1 H, exoꢀH(5)); 1.85 (d, 1 H, synꢀH(7), J7,7 = 10.6 Hz);
38b + 39b
2.04 (m, 1 H, exoꢀH(6)); 2.30 (br.s, 1 H, H(4)); 2.53 (br.s, 1 H,
H(1)); 3.22 (dd, 1 H, HCS, J3,2 = 3.9 Hz, J3,7ꢀanti = 2.7 Hz); 4.11
(m, 1 H, HCBr); 7.25 (tm, 1 H, pꢀH(Ar), J = 7.4 Hz); 7.33 (t, 2 H,
mꢀH(Ar), J = 7.4 Hz); 7.44 (d, 2 H, oꢀH(Ar), J = 7.4 Hz). The
spectrum agrees with the literature data.2
To sum up, the sulfenylation of alkenes and dienes with
sulfenic acid esters in the presence of trimethylsilyl halides
or thionyl halides as coreagents can be regarded as a new
and promising method for functionalization of unsaturatꢀ
ed compounds.
A mixture of endoꢀ9ꢀchloroꢀexoꢀ10ꢀphenylthiotricycloꢀ
[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (7a) and exoꢀ9ꢀchloroꢀsynꢀ11ꢀ
phenylthiotricyclo[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene
(8a),
Rf 0.71. Compound 7a. 1H NMR, δ: 2.10 (dm, 1 H, antiꢀH(11),
2J11,11 = 9.9 Hz); 2.28 (d, 1 H, synꢀH(11), 2J11,11 = 9.9 Hz); 3.12
(t, 1 H, HCS, J = 2.9 Hz); 3.37 (s, 1 H, H(1)); 3.57 (m, 1 H,
H(8)); 4.38 (t, 1 H, HCCl, J = 3.6 Hz); 7.10—7.35 (m, 7 H, Ar);
7.42 (d, 2 H, Ar, J = 7.0 Hz). MS, m/z (Irel (%)): 288 (12), 286
[M]+ (33); 250 [M – HCl]+ (17); 177 [M – SPh]+ (12); 141
[M – HCl – SPh]+ (72); 128 (7); 116 (100); 91 (3). Compound
Experimental
1
H NMR spectra were recorded on a Bruker Avance specꢀ
trometer (400 MHz) in CDCl3 at 28 °C. Chemical shifts are
given on the δ scale with reference to Me4Si as the internal
standard. IR spectra were recorded on a URꢀ20 instrument (thin
film). Mass spectra were measured on a Finnigan MIAT TSQ
7000 instrument (70 eV). The course of the reactions was moniꢀ
tored, and the purity of the products was checked, by TLC on
Silufol UVꢀ254 plates with AcOEt—light petroleum (1 : 3 v/v) as
an eluent.
Solvents were purified according to standard procedures.16
Ethyl benzenesulfenate was prepared as described earlier.22
Sulfenylhalogenation of alkenes and dienes with ethyl benzeneꢀ
sulfenate in the presence of trimethylsilyl halides or thionyl halides
(general procedure). A solution of trimethylsilyl halide or thionyl
halide in anhydrous CHCl3 (or CH2Cl2) was slowly added dropꢀ
wise under dry argon at room temperature to a vigorously stirred
solution of an approximately equimolar mixture of an alkene
(or a diene) and ethyl benzenesulfenate in the corresponding
solvent. The alkene (diene) : Me3SiHal (or SOHal2) ratio was
1 : 1. The reaction mixture was stirred until the reaction was comꢀ
pleted (monitoring by TLC), passed through a column (h = 5 cm),
and concentrated in vacuo.
The yields of the products are given in Tables 1—6. The
1H NMR spectra of compounds 14b, 16b, 21—23, 25a, 30—32,
and 34—39 are identical with the literature data.6,18,19
transꢀ1ꢀChloroꢀ2ꢀphenylthiocyclohexane (2a), Rf 0.75.
1H NMR, δ: 1.44, 1.66, 1.80 (all m, 2 H each, CH of cyclohexꢀ
ane); 2.27, 2.39 (both m, 1 H each, CH of cyclohexane); 3.36
(m, 1 H, HCS); 4.06 (m, 1 H, HCCl); 7.27—7.38 (m, 3 H, Ar);
7.50 (d, 2 H, Ar, J = 7.0 Hz). The spectrum agrees with
the literature data.17
transꢀ1ꢀBromoꢀ2ꢀphenylthiocyclohexane (2b), Rf 0.73.
1H NMR, δ: 1.50 (m, 2 H, CH of cyclohexane); 1.73 (m, 3 H,
CH of cyclohexane); 1.92, 2.34, 2.47 (all m, 1 H each, CH of
cyclohexane); 3.52 (m, 1 H, HCS); 4.30 (m, 1 H, HCBr); 7.24—7.37
(m, 3 H, Ar); 7.47 (d, 2 H, Ar, J = 7.0 Hz). The spectrum agrees
with the literature data.2
2
8a. 1H NMR, δ: 2.19 (dd, 1 H, endoꢀH(10), J10,10 = 13.3 Hz,
J10,9 = 7.4 Hz); 2.80 (dt, 1 H, exoꢀH(10), 2J10,10 = 13.3 Hz, J10,9
= 3.7 Hz, J10,1 = 3.7 Hz); 3.49 (m, 1 H, H(1)); 3.64 (br.s, 1 H,
H(8) or HCS); 3.68 (br.s, 1 H, HCS or H(8)); 3.88 (dd, 1 H,
HCCl, J9,10ꢀendo = 7.4 Hz, J9,10ꢀexo = 3.7 Hz); the signals for the
aromatic protons overlap those of compound 7a. MS, m/z
(Irel (%)): 288 (12), 286 [M]+ (33); 250 [M – HCl]+ (11); 177
[M – SPh]+ (8); 141 [M – HCl – SPh]+ (95); 129 (100); 128 (89);
116 (53); 115 (60); 91 (3).
A mixture of endoꢀ9ꢀbromoꢀexoꢀ10ꢀphenylthiotricycloꢀ
[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (7b) and exoꢀ9ꢀbromoꢀsynꢀ11ꢀ
phenylthiotricyclo[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (8b), Rf 0.77.
Compound 7b. 1H NMR, δ: 2.09 (ddt, 1 H, antiꢀH(11), 2J11,11
=
= 9.8 Hz, J11,10 = 3.3 Hz, J11,1 = J11,8 = 1.7 Hz); 2.27 (dt, 1 H,
synꢀH(11), 2J11,11 = 9.9 Hz, J11,1 = J11,8 = 1.3 Hz); 3.24 (t, 1 H,
HCS, J = 3.3 Hz); 3.37 (br.s, 1 H, H(1)); 3.57 (m, 1 H, H(8));
4.38 (t, 1 H, HCBr, J = 3.5 Hz); 7.10—7.40 (m, 7 H, Ar); 7.50
(d, 2 H, Ar, J = 7.0 Hz). MS, m/z (Irel (%)): 332 (8), 330 [M]+
(7); 251 [M – Br]+ (100); 142 [M – Br – SPh]+ (12); 141
[M – HBr – SPh]+ (91); 116 (28); 115 (36); 91 (3). Compound
8b. 1H NMR, δ: 2.20 (ddd, 1 H, endoꢀH(10), 2J10,10 = 13.6 Hz,
J10,9 = 7.9 Hz, J10,11 = 1.3 Hz); 2.94 (dt, 1 H, exoꢀH(10), 2J10,10
=
= 13.6 Hz, J10,9 = J10,1 = 4.0 Hz); 3.48 (m, 1 H, H(1)); 3.67
(t, 1 H, HCS, J11,9 = J11,10ꢀendo = 1.3 Hz); 3.78 (br.s, 1 H, H(8));
3.84 (ddd, 1 H, HCBr, J9,10ꢀendo = 7.9 Hz, J9,10ꢀexo = 4.0 Hz,
J9,11 = 1.3 Hz); the signals for the aromatic protons overlap those
of compound 7b. MS, m/z (Irel (%)): 332 (8); 330 [M]+ (8);
251 [M – Br]+ (25); 142 (19); 141 [M – HBr – SPh]+ (100);
129 (18); 128 (16); 123 (80); 115 (34); 91 (3).
exoꢀ9ꢀChloroꢀ3,6ꢀdimethoxyꢀsynꢀ11ꢀphenylthiotricycloꢀ
[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (9a), Rf 0.63. Found (%):
C, 65.43; H, 5.87. C19H19ClO2S. Calculated (%): C, 65.80;
H, 5.48. 1H NMR, δ: 2.19 (dd, 1 H, endoꢀH(10), 2J10,10 = 13.2 Hz,
2
J10,9 = 7.6 Hz); 2.77 (dt, 1 H, exoꢀH(10), J10,10 = 13.2 Hz,
endoꢀ2ꢀChloroꢀexoꢀ3ꢀphenylthiobicyclo[2.2.1]heptane (4a),
Rf 0.75. 1H NMR, δ: 1.38—1.57 (m, 3 H, endoꢀH(5), endoꢀH(6),
J10,9 = 3.8 Hz, J10,1 = 3.8 Hz); 3.62 (br.s, 1 H, HCS); 3.71
(m, 1 H, H(1)); 3.77, 3.81 (both s, 3 H each, OMe); 3.88 (dd, 1 H,

Halosulfenylation of alkenes
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 12, December, 2008
2577
HCCl, J9,10ꢀendo = 7.6 Hz, J9,10ꢀexo = 3.8 Hz); 3.92 (br.s, 1 H,
H(8)); 6.61 (d, 1 H, H(4) or H(5), J = 9.0 Hz); 6.65 (d, 1 H, H(5)
or H(4), J = 9.0 Hz); 7.23 (t, 1 H, Ar, J = 7.2 Hz); 7.31 (t, 2 H,
Ar, J = 7.2 Hz); 7.47 (d, 2 H, Ar, J = 7.2 Hz).
exoꢀ9ꢀBromoꢀ3,6ꢀdimethoxyꢀsynꢀ11ꢀphenylthiotricycloꢀ
[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (9b), Rf 0.69. Found (%):
(t, 3 H, Me, J = 7.2 Hz); 2.06 (m, 1 H, H(3)); 3.43 (t, 1 H, HCBr,
2J1,1 = J1,2 = 9.8 Hz); 3.66 (dd, 1 H, HCBr, 2J1,1 = 9.8 Hz, J1,2
= 3.3 Hz); the signal for the HCS proton overlaps that for comꢀ
pound 15b (δ 3.31); the signals for the H2C(3), H2C(4), H2C(5),
H2C(6), and aromatic protons overlap those for compound 15b.
The spectrum agrees with the literature data.2
=
C, 58.56; H, 5.04. C19H19BrO2S. Calculated (%): C, 58.31;
1ꢀChloroꢀ1ꢀphenylꢀ2ꢀphenylthioethane (19a), Rf 0.58.
1H NMR, δ: 3.54 (dd, 1 H, HCS, 2J2,2 = 13.8 Hz, J2,1 = 8.7 Hz);
3.68 (dd, 1 H, HCS, 2J2,2 = 13.8 Hz, J2,1 = 6.3 Hz); 4.94 (dd, 1 H,
HCCl, J1,2 = 8.7 Hz, J1,2 = 6.3 Hz); 7.20—7.40 (m, 10 H, Ar).
The spectrum agrees with the literature data.17
2
H, 4.86. 1H NMR, δ: 2.20 (dd, 1 H, endoꢀH(10), J10,10
=
=
2
= 13.4 Hz, J10,9 = 7.8 Hz); 2.90 (dt, 1 H, exoꢀH(10), J10,10
= 13.4 Hz, J10,9 = J10,1 = 4.0 Hz); 3.62 (br.s, 1 H, HCS); 3.69
(br.s, 1 H, H(1)); 3.77, 3.81 (both s, 3 H each, OMe); 3.83 (dd, 1 H,
HCBr, J9,10ꢀendo = 7.8 Hz, J9,10ꢀexo = 4.0 Hz); 3.98 (br.s, 1 H,
H(8)); 6.62 (d, 1 H, H(4) or H(5), J = 8.8 Hz); 6.65 (d, 1 H, H(5)
or H(4), J = 8.8 Hz); 7.24 (t, 1 H, Ar, J = 7.2 Hz); 7.32 (t, 2 H,
Ar, J = 7.2 Hz); 7.48 (d, 2 H, Ar, J = 7.2 Hz).
Methyl 3ꢀoxoꢀexoꢀ9ꢀphenylthioꢀ2ꢀoxatricyclo[4.2.1.04,8]ꢀ
nonaneꢀendoꢀ5ꢀcarboxylate (11), Rf 0.63. 1H NMR, δ: 1.69 (d, 1 H,
antiꢀH(7), 2J7,7 = 11.6 Hz); 2.33 (d, 1 H, synꢀH(7), 2J = 11.6 Hz);
2.73 (br.s, 1 H, HC(6)); 2.87 (dd, 1 H, H(4), J4,5 = 10.8 Hz,
1ꢀBromoꢀ1ꢀphenylꢀ2ꢀphenylthioethane (19b), Rf 0.64. 1H
2
NMR, δ: 3.72 (dd, 1 H, HCS, J2,2 = 13.8 Hz, J2,1 = 10.0 Hz);
3.84 (dd, 1 H, HCS, 2J2,2 = 13.8 Hz, J2,1 = 5.7 Hz); 5.04 (dd, 1 H,
HCBr, J1,2 = 10.0 Hz, J1,2 = 5.7 Hz); 7.20—7.40 (m, 10 H, Ar).
A mixture of transꢀ3ꢀbromoꢀ4ꢀphenylthiocyclopentene (25b),
transꢀ4ꢀbromoꢀ3ꢀphenylthiocyclopentene (26), transꢀ3ꢀbromoꢀ5ꢀ
phenylthiocyclopentene (27), and cisꢀ3ꢀbromoꢀ5ꢀphenylthiocycloꢀ
pentene (28), Rf 0.62. Compound 25b. 1H NMR, δ: 2.44 (ddt,
2
J4,8 = 4.8 Hz); 3.16 (dd, 1 H, HC(5), J5,4 = 10.8 Hz, J5,6
=
1 H, H(5), J5,5 = 18.6 Hz, J = 2.7 Hz, J = 1.4 Hz); 3.19 (ddq,
2
= 3.3 Hz); 3.36 (td, 1 H, H(8), J8,1 = J8,4 = 4.8 Hz, J = 1.3 Hz);
3.75 (s, 3 H, OMe); 4.08 (d, 1 H, HCS, J9,7 = 2.1 Hz); 4.68 (d, 1 H,
HCO, J1,8 = 4.8 Hz); 7.23 (t, 1 H, Ar, J = 7.0 Hz); 7.27—7.40
(m, 2 H, Ar); 7.51 (d, 2 H, Ar, J = 7.5 Hz). IR, ν/cm–1: 1785
(C=O, γꢀlactone ring), 1735 (C=O, COOMe). The spectrum
agrees with the literature data.8
1 H, H(5´), J5,5 = 18.6 Hz, J5´,4 = 7.0 Hz, J = 1.7 Hz); 4.28
(d, HCS, J4,5´ = 7.0 Hz); 5.00 (br.s, HCBr). Compound 26.
2
1H NMR, δ: 2.78 (ddt, 1 H, H(5), J5,5 = 18.9 Hz, J = 2.7 Hz,
J = 1.4 Hz); 3.16 (m, 1 H, H(5´)); 4.54 (d, HCBr, J4,5´ = 5.9 Hz);
4.59 (br.s, HCS); 5.89 (m, 1 H, H(1)); 5.96 (m, 1 H, H(2)).
Compound 27. 1H NMR, δ: 2.52 (ddd, 1 H, H(4), 2J4,4 = 15.3 Hz,
2ꢀChloroꢀ1ꢀphenylthiohexane (14a), Rf 0.69. 1H NMR, δ:
0.94 (t, 3 H, Me, J = 6.7 Hz); 1.35 (m, 3 H, H(4), H2(5)); 1.55
(m, 1 H, H(4)); 1.70, 2.02 (both m, 1 H each, H(3)); 3.19 (dd, 1
J4,3 = 7.1 Hz, J4,5 = 5.7 Hz); 2.85 (ddd, 1 H, H(4´), J4,4
=
2
= 15.3 Hz, J4´,5 = 7.3 Hz, J4´,3 = 2.3 Hz); 4.47 (ddq, 1 H, HCS,
J5,4´ = 7.3 Hz, J5,4 = 5.7 Hz, J = 1.8 Hz); 5.02 (dq, 1H, HCBr,
J3,4 = 7.1 Hz, J3,4´ = J = J = 2.3 Hz). Compound 28. 1H NMR, δ:
2.52 (dt, 1 H, H(4), 2J4,4 = 15.5 Hz, J = 2.0 Hz); 3.04 (dt, 1 H,
2
H, HCS, J1,1 = 13.7 Hz, J1,2 = 8.2 Hz); 3.40 (dd, 1 H, HCS,
2J1,1 = 13.7 Hz, J1,2 = 5.7 Hz); 4.00 (tdd, 1 H, HCCl, J2,3 = J2,1
= 8.2 Hz, J2,1 = 5.7 Hz, J2,3 = 3.8 Hz); 7.2—7.6 (m, 5 H, Ar).
=
2
H(4´), J4,4 = 15.5 Hz, J4´,3 = J4´,5 = 7.5 Hz); 4.36 (dm,
1ꢀChloroꢀ2ꢀphenylthiohexane (16a), Rf 0.69. 1H NMR, δ:
0.97 (t, 3 H, Me, J =7.2 Hz); 1.35—1.69 (m, 5 H, H(3), H2C(4),
H2C(5)); 2.02 (m, 1 H, H(3)); 3.28 (m, 1 H, HCS); 3.52 (dd, 1 H,
1 H, HCS, J5,4´ = 7.5 Hz); 5.05 (dt, 1 H, HCBr, J3,4´ = 7.5 Hz,
J = 2.1 Hz). The signals for the H(1) and H(2) protons in comꢀ
pounds 25b, 27, and 28 appear at δ 5.98—6.09; the signals for the
aromatic protons appear at δ 7.24—7.48. A mixture of compounds
25b, 26, 27, and 28. MS, m/z (Irel (%)): 174 [M – HBr]+ (100);
147 (23); 141 (37); 97 (23).
2
HCCl, J1,1 = 10.9 Hz, J1,2 = 9.3 Hz); 3.72 (dd, 1 H, HCCl,
2J1,1 = 10.9 Hz, J1,2 = 4.1 Hz); 7.20—7.60 (m, 5 H, Ar). Product
16a was not isolated in the individual state. The spectrum reꢀ
corded for the mixture 14a+16a (with the latter being a domiꢀ
nant component) agrees with the literature data.6
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 08ꢀ03ꢀ00707ꢀa)
and the Russian Academy of Sciences (Program "Theoꢀ
retical and Experimental Investigations of the Nature
of Chemical Bonding and Chemical Processes").
A mixture of 2ꢀchloroꢀ1ꢀphenylthioheptane (15a) and 1ꢀchloꢀ
roꢀ2ꢀphenylthioheptane (17a), Rf 0.65. Compound 15a. 1H NMR,
δ: 0.92 (t, 3 H, Me, J = 6.5 Hz); 1.33 (m, 5 H, H(4), H2C(5),
H2C(6)); 1.55 (m, 1 H, H(4)); 1.70, 2.02 (both m, 1 H each,
H(3)); 3.19 (dd, 1 H, HCS, 2J1,1 = 13.7 Hz, J1,2 = 8.2 Hz); 3.40
2
(dd, 1 H, HCS, J1,1 = 13.7 Hz, J1,2 = 5.5 Hz); 4.00 (tdd, 1 H,
References
HCCl, J2,3 = J2,1 = 8.2 Hz, J2,1 = 5.5 Hz, J2,3 = 3.4 Hz);
7.20—7.60 (m, 5 H, Ar). Compound 17a. 1H NMR, δ: 0.95
(t, 3 H, Me, J = 7.2 Hz); 3.28 (m, 1 H, HCS); 3.52 (dd, 1 H,
1. I. V. Koval´, Usp. Khim., 1995, 64, 781 [Russ. Chem. Rev.,
1995, 64 (Engl. Transl.)].
2
HCCl, J1,1 = 10.9 Hz, J1,2 = 9.2 Hz); 3.73 (dd, 1 H, HCCl,
2J1,1 = 10.9 Hz, J1,2 = 3.9 Hz); the signals for the H2C(3), H2C(4),
H2C(5), H2C(6), and aromatic protons overlap those for comꢀ
pound 15a. The spectrum agrees with the literature data.23
A mixture of 2ꢀbromoꢀ1ꢀphenylthioheptane (15b) and 1ꢀbroꢀ
moꢀ2ꢀphenylthioheptane (17b), Rf 0.65. Compound 15b.
1H NMR, δ: 0.92 (t, 3 H, Me, J = 6.5 Hz); 1.35 (m, 5 H, H(4),
H2C(5), H2C(6)); 1.59 (m, 1 H, H(4)); 1.84, 2.14 (both m, 1 H
each, H(3)); 3.31 (dd, 1 H, HCS, 2J1,1 = 13.8 Hz, J1,2 = 9.0 Hz);
3.40 (dd, 1 H, HCS, 2J1,1 = 13.8 Hz, J1,2 = 5.1 Hz); 4.00 (tdd, 1 H,
HCBr, J2,3 = J2,1 = 9.0 Hz, J2,1 = 5.1 Hz, J2,3 = 3.5 Hz);
7.20—7.60 (m, 5 H, Ar). Compound 17b. 1H NMR, δ: 0.96
2. N. V. Zyk, E. K. Beloglazkina, R. Gazzaeva, V. S. Tyurin,
I. D. Titanyuk, Phosphorus, Sulfur, Silicon, Relat. Elem., 1999,
155, 33.
3. L. Benati, P. C. Montevecchi, P. Spagnolo, Tetrahedron,
1993, 49, 5365.
4. N. V. Zyk, E. K. Beloglazkina, S. E. Sosonyuk, M. N. Bulꢀ
anov, Yu. B. Chudinov, Izv. Akad. Nauk, Ser. Khim., 2000,
1569 [Russ. Chem. Bull., Int. Ed., 2000, 49, 1557].
5. V. D. Sorokin, I. G. Plokhikh, M. Yu. Berlin, Yu. K. Grishin,
K. A. Potekhin, A. S. Koz´min, N. S. Zefirov, Dokl. Akad.
Nauk, 1993, 332, 730 [Dokl. Chem., 1993, 332 (Engl. Transl.)].

2578
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 12, December, 2008
Zyk et al.
6. L. Benati, L. Capella, P. C. Montevecchi, P. Spagnolo, Tetꢀ
rahedron, 1994, 50, 12395.
7. L. Benati, P. C. Montevecchi, P. Spagnolo, Tetrahedron
Lett., 1984, 25, 2039.
8. N. S. Zefirov, N. V. Zyk, A. G. Kutateladze, Yu. A. Lapin,
Zh. Org. Khim., 1987, 23, 392 [Russ. J. Org. Chem., 1987, 23
(Engl. Transl.)].
9. N. S. Zefirov, N. V. Zyk, Yu. A. Lapin, A. G. Kutateladze,
B. I. Ugrak, Zh. Org. Khim., 1992, 28, 1126 [Russ. J. Org.
Chem., 1992, 28 (Engl. Transl.)].
16. A. J. Gordon, R. A. Ford, The Chemist´s Companion, A Wileyꢀ
Interscience Publication—John Wiley and Sons, New
York—London—Sydney—Toronto, 1972.
17. G. A. Jones, C. J. M. Stirling, N. G. Bromby, J. Chem. Soc.,
Perkin Trans. 2, 1983, 385.
18. N. V. Zyk, E. K. Beloglazkina, M. A. Belova, I. F. Leshcheꢀ
va, N. S. Zefirov, Izv. Akad. Nauk, Ser. Khim., 2002, 1356
[Russ. Chem. Bull., Int. Ed., 2002, 51, 1468].
19. E. K. Beloglazkina, M. A. Belova, R. L. Antipin, N. V. Zyk,
A. K. Buryak, Zh. Org. Khim., 2003, 39, 549 [Russ. J. Org.
Chem., 2003, 39 (Engl. Transl.)].
10. Y. Ito, T. Ogawa, Tetrahedron Lett., 1978, 34, 2953.
11. D. R. Hogg, J. H. Smith, P. W. Vipond, J. Chem. Soc., C,
1968, 2713.
20. F. G. Cocu, G. Wolczunowicz, L. Bors, Th. Posternak, Helv.
Chim. Acta, 1970, 53, 739.
12. E. D. Edstrom, T. Livinghouse, J. Am. Chem. Soc., 1986,
108, 1334.
13. N. V. Zyk, A. Yu. Gavrilova, O. A. Mukhina, O. B. Bondꢀ
arenko, N. S. Zefirov, Zh. Org. Khim., 2006, 42, 1865 [Russ.
J. Org. Chem., 2006, 42 (Engl. Transl.)].
14. N. V. Zyk, A. Yu. Gavrilova, O. A. Mukhina, O. B. Bondꢀ
arenko, N. S. Zefirov, Izv. Akad. Nauk, Ser. Khim., 2006,
1798 [Russ. Chem. Bull., Int. Ed., 2006, 55, 1865].
15. N. S. Zefirov, V. V. Samoshin, O. A. Subbotin, V. I. Baranenꢀ
kov, S. Wolfe, Tetrahedron, 1978, 34, 2953.
21. K. Hartke, H.ꢀU. Gleim, Liebigs Ann. Chem., 1976, 716.
22. L. Chang, D. B. Denney, D. Z. Denney, K. J. Kazior, J. Am.
Chem. Soc., 1977, 99, 2293.
23. N. S. Zefirov, A. S. Koz´min, V. D. Sorokin, A. V. Shastin,
E. S. Balenkova, Dokl. Akad. Nauk, 1984, 276, 1139 [Dokl.
Chem. USSR, 1984 (Engl. Transl.)].
Received June 27, 2008;
in revised form October 30, 2008