Adducts of tricyclo[4.1.0.02,7]heptane hydrocarbons with methane- and halomethanesulfonyl thiocyanates and their transformations in the presence of bases (Nucleophiles)

Article abstract of DOI:10.1134/S1070428012040057

1-R-Tricyclo[4.1.0.0^2,7]heptanes (R = H, Me, Ph) take up methane- and halomethanesulfonyl thiocyanates XCH2SO₂SCN (X = H, Cl, Br) at the central C¹-C⁷ bond in benzene at 20°C with high anti-selectivity to give bicyclo[3.1.1]heptane derivatives with the 7-endo-oriented sulfonyl group and the thiocyanato group in the geminal position with respect to the R substituent. The syn-adducts lose HSCN molecule by the action of potassium tert-butoxide in THF at 0°C or on heating in boiling aqueous dioxane containing NaOH with formation of 1-(X-methylsulfonyl) tricyclo[4.1.0.0^2,7]heptanes. Under analogous conditions the anti-adducts (X = Me) are converted into 1,2-bis(7-syn-methylsulfonyl-6-endo-R- bicyclo[3.1.1]hept-6-exo-yl)disulfanes. The anti-adduct derived from unsubstituted tricyclo[4.1.0.0^2,7]heptane and MeSO₂SCN reacted with methyllithium or phenylmagnesium bromide to produce 7-anti-methyl(phenyl)sulfanyl-6-endo-methylsulfonylbicyclo- [3.1.1]heptanes which were also obtained by photochemical addition of MeSO₂SMe(or Ph) to tricyclo- [4.1.0.0^2,7]heptane. Geometric parameters of radical intermediates in the sulfonylation of 1-R-tricyclo- [4.1.0.0^2,7] heptanes were optimized ab initio using 6-31G basis set. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012040057

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 4, pp. 494–504. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.A. Vasin, P.S. Petrov, S.G. Kostryukov, V.V. Razin, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 4,
pp. 496–506.
Adducts of Tricyclo[4.1.0.02,7]heptane Hydrocarbons
with Methane- and Halomethanesulfonyl Thiocyanates and Their
Transformations in the Presence of Bases (Nucleophiles)
V. A. Vasina, P. S. Petrova, S. G. Kostryukova, and V. V. Razinb
a Ogarev Mordovian State University, ul. Bol’shevistskaya 68, Saransk, 430005 Russia
e-mail: vasin@mrsu.ru
b St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
Received June 22, 2011
Abstract—1-R-Tricyclo[4.1.0.02,7]heptanes (R = H, Me, Ph) take up methane- and halomethanesulfonyl thio-
cyanates XCH2SO2SCN (X = H, Cl, Br) at the central C1–C7 bond in benzene at 20°C with high anti-selectivity
to give bicyclo[3.1.1]heptane derivatives with the 7-endo-oriented sulfonyl group and the thiocyanato group in
the geminal position with respect to the R substituent. The syn-adducts lose HSCN molecule by the action of
potassium tert-butoxide in THF at 0°C or on heating in boiling aqueous dioxane containing NaOH with
formation of 1-(X-methylsulfonyl)tricyclo[4.1.0.02,7]heptanes. Under analogous conditions the anti-adducts
(X = Me) are converted into 1,2-bis(7-syn-methylsulfonyl-6-endo-R-bicyclo[3.1.1]hept-6-exo-yl)disulfanes.
The anti-adduct derived from unsubstituted tricyclo[4.1.0.02,7]heptane and MeSO2SCN reacted with methyl-
lithium or phenylmagnesium bromide to produce 7-anti-methyl(phenyl)sulfanyl-6-endo-methylsulfonylbicyclo-
[3.1.1]heptanes which were also obtained by photochemical addition of MeSO2SMe(or Ph) to tricyclo-
[4.1.0.02,7]heptane. Geometric parameters of radical intermediates in the sulfonylation of 1-R-tricyclo-
[4.1.0.02,7]heptanes were optimized ab initio using 6-31G basis set.
DOI: 10.1134/S1070428012040057
We previously reported [1–6] on the addition of
arene- and methanesulfonyl halides at the central bi-
cyclobutane bond in tricyclo[4.1.0.02,7]heptanes I–III.
In keeping with the proposed radical mechanism, the
addition is initiated by strict endo attack by sulfonyl
radical on the unsubstituted position at the C1−C7 bond
to produce a mixture of syn- and anti-adducts having
norpinane structure, the anti-adduct prevailing. We
also showed [7] that sulfur-containing derivatives of
arenesulfonic acids, such as ArSO2SPh and
ArSO2SCN, react with tricycloheptane I in a similar
way with moderate anti-stereoselectivity. In continua-
tion of our studies on regio- and stereoselectivity of
radical sulfonylation of tricycloheptane derivatives, in
the present work we examined reactions of compounds
I–III with methane-, chloromethane-, and bromometh-
anesulfonyl thiocyanates. The expected products, i.e.,
norpinane derivatives having sulfonyl and thiocyanato
groups, attract interest as subjects for subsequent
transformations in reactions with bases (nucleophiles),
and some results of such transformations are reported
here. The radical addition of methanesulfonyl thiocy-
anate at multiple carbon–carbon bonds was described
in [8], whereas there are no published data on analo-
gous reactions with chloro- and bromomethanesulfonyl
thiocyanates.
The initial sulfonyl thiocyanates were synthesized
from methane- and halomethanesulfonyl halides which
were reduced to the corresponding methanesulfinates
with Na2SO3 in the presence of NaHCO3 in aqueous
medium at 20°C. Methanesulfinates thus obtained
were converted into sulfonyl thiocyanates by treatment
of their aqueous solutions with a solution of dirhodan
in benzene according to the procedure described in [9].
As a result, we obtained a solution of the correspond-
ing sulfonyl thiocyanate in benzene which was sub-
jected to further transformations without isolation or
purification. The reactions were performed with equi-
molar amounts of compounds I–III in benzene at 20°C
(reaction time 6−14 h; TLC monitoring) without
resorting to special initiation (Table 1, Scheme 1).
From unsubstituted tricycloheptane I we obtained in
494

ADDUCTS OF TRICYCLO[4.1.0.02,7]HEPTANE HYDROCARBONS
495
Scheme 1.
3
4
5
2
1
XCH2SO2SCN
+
R
SO2CH2X
NCS
SO2CH2X
6
7
R
SCN
R
I–III
IVa–XIIa
IVb–XIIb
I, IV–VI, R = H; II, VII–IX, R = Me; III, X–XII, R = Ph; IV, VII, X, X = H; V, VIII, XI, X = Cl; VI, IX, XII, X = Br.
each case a mixture of norpinane anti- and syn-adducts
IVa/IVb, Va/Vb, or VIa/VIb) (“a”–“b” ratio 2.5:1,
1.8:1, and 1.5:1, respectively, according to the GLC
groups was typical of such groups in model com-
pounds [2, 5, 6]. The configuration of C6 and C7 was
assigned by analysis of multiplicity and position of the
1
1
and H NMR data). We succeeded in isolating com-
6-H and 7-H proton signals in the H NMR spectrum
pounds IVa–VIa and IVb as individual substances by
column chromatography on silica gel and/or crystal-
lization. Compounds Vb and VIb were not isolated
and were characterized as mixtures with isomers Va
and VIa by 1H and 13C NMR spectroscopy. Among the
addition products formed from hydrocarbons II and
III, only major anti-adducts VIIa–XIIa were isolated.
However, their H NMR spectra contained weak
signals some of which could be assigned to syn-
adducts VIIb–XIIb.
The structure of compounds IV–XII was deter-
mined on the basis of spectral data. Their IR spectra
contained strong absorption bands at ~1150 and
1300 cm−1, which are typical of symmetric and anti-
symmetric stretching vibrations of sulfonyl group. The
thiocyanato group in IV–XII gave rise to a medium-
intensity IR band at ~2150 cm−1, and the carbon atom
therein resonated in the 13C NMR spectrum at about
δC 110 ppm. The norpinane structure of the adducts
follows from the presence in their 13C NMR spectra of
five signals belonging to the carbon skeleton, whose
intensity and position were typical of structurally relat-
ed compounds. Likewise, the position of signals from
carbon atoms in the methyl- and halomethylsulfonyl
with account taken of Wiberg’s data [10]. The triplet
signal of 7-H indicates its anti orientation. Likewise,
singlet or triplet signal from 6-H corresponds to its
endo or exo orientation in isomers IVa–VIa and IVb–
VIb, respectively. The exo orientation of the SCN
group in VIIa–IXa was assigned on the basis of simi-
larity of the chemical shifts of anti-7-H and analogous
proton in IVa–VIa, δ 4.25–4.49 and 4.07–4.27 ppm,
respectively. In the case of different configuration of
C6, the anti-7-H proton would appear counterposed to
CH3; due to weaker deshielding effect of the latter as
compared to SCN (cf. [7, 11]) the 7-H signal would be
1
1
displaced upfield. In fact, the H NMR spectra of the
reaction mixtures obtained from compound II con-
tained weak triplets at δ 3.70, 3.93, and 3.86 ppm,
which are likely to belong to anti-7-H in the corre-
sponding syn-adducts VIIb–IXb. Finally, the con-
figuration at C6 in Xa–XIIa is confirmed by the pres-
ence of an upfield one-proton multiplet signal from
endo-3-H which is shielded by the endo-phenyl sub-
stituent (cf. [2, 4]).
Thus analysis of the regio- and stereoselectivity of
the addition of sulfonyl thiocyanates to tricyclohep-
tanes I–III led us to conclude that these reactions
Table 1. Reactions of tricycloheptanes I–III with methane- and halomethanesulfonyl thiocyanates
Tricycloheptane no.
Reagent
Reaction time, h
Product
Yield, %
Fraction of the anti-adduct, %
I
MeSO2SCN
12
10
14
11
10
15
06
06
08
IVa, IVb
Va, Vb
VIa, VIb
VIIa
71
49
30
64
44
17
73
44
41
71
I
ClCH2SO2SCN
BrCH2SO2SCN
MeSO2SCN
64
I
60
II
II
II
III
III
III
>93>
>95>
>95>
>98>
>98>
>98>
ClCH2SO2SCN
BrCH2SO2SCN
MeSO2SCN
VIIIa
IXa
Xa
ClCH2SO2SCN
BrCH2SO2SCN
XIa
XIIa
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

VASIN et al.
496
Scheme 2.
H
R
H
H
H
R
IVb–XIIb
IVa–XIIa
syn-Adduct
anti-Adduct
SO2CH2X
SO2CH2X
·
H
A'
A''
follow the same pattern as in the addition of other
sulfonic acid derivatives. The reactions take radical
path involving intermediate norpinan-6-yl radical A
generated by attack of methylsulfonyl radical on the
less substituted bridgehead carbon atom (C7) with
complete inversion of its configuration. The subse-
quent thiocyanato group transfer to the radical center
occurs mainly with retention of configuration, which
eventually determines anti-stereoselectivity of the ad-
dition of sulfonyl thiocyanates at the central C1–C7
bond in I–III.
tivity in the sulfonylation of I–III is determined
mainly by steric factors, namely by considerable
shielding of the reaction center in A′ by the trimeth-
ylene bridge. Fast and reversible transformation of A′
into conformer A″ where the trimethylene bridge
exerts no such effect favors predominant formation of
anti-adducts.
Additional information on the steric and electronic
structure of intermediate radicals A (X = H) was
obtained by optimization of their geometric parameters
ab initio using 6-31G basis set (PC GAMESS 7.1
[13]). The results of calculations showed that the
reaction center in the radical with R = Ph is planar and
is similar to benzyl radical and that unsubstituted (R =
H) and methyl-substituted analogs (R = Me) give rise
to two invertomers A′ and A″ with different angles α
between the C6–R bond and C1C6C5. These inverto-
mers are also characterized by different total energies
and energies of the singly occupied molecular orbitals
(SOMO) (see figure; Table 2).*
In all cases the C3H2 fragment deviates from the
C1C2C4C5 plane toward C6, as follows from the
dihedral angles β between the C1C2C4C5 and C2C3C4
planes (Table 2). Comparison of the interatomic dis-
tances anti-7-H···C6 (l1) and endo-3-H···C6 (l2) in
structures A′ and A″ showed that that steric shielding
of the reaction center by the trimethylene bridge is not
as significant as it may seem at first glance. Never-
theless, its effect cannot be ruled out completely,
especially taking into account participation in the chain
transfer process of such bulky reagents as sulfonic acid
derivatives (which should approach the reaction center
at a definite angle) and differences in the interplanar
angles γ (C1C2C4C5/C1C6C5) and δ (C1C6C5/C1C7C5) in
the intermediates. Presumably, the stereoselectivity of
the addition in the examined reactions (assuming high
rate of invertomer interconversion) is determined by
We previously [12] examined the stereoselectivity
in the addition of sulfonyl halides to tricycloheptane
compounds with different substituents in a bridgehead
position and presumed pyramidal structure of radical
intermediate like A which initially has conformation
A′ and is capable of undergoing reversible inversion to
conformer A″ (Scheme 2). We believed that the stereo-
selectivity should be determined by the relative rates of
the inversion and transfer processes. The rate of the
latter depends not only on the reactivity of reagent as
radical species but also on spatial accessibility of the
reaction center. We also presumed that high anti-selec-
C3
(a)
C4
C2
C1
C6
C5
C7
S
(b)
(c)
R
R
* The calculations revealed energy-degenerate mirror isomers for
each invertomer A′ and A″, which differed by orientation of the
methyl group in the methylsulfonyl fragment with respect to the
C3C6C7 plane.
Calculated structures of 6-R-7-endo-methylsulfonylnor-
pinan-6-yl radicals A: (a) R = Ph, (b) R = H, Me, invertomer
A′, and (c) R = H, Me, invertomer A″.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

ADDUCTS OF TRICYCLO[4.1.0.02,7]HEPTANE HYDROCARBONS
497
Table 2. Calculated geometric parameters, relative energies ΔE (kcal/mol), and energies of singly occupied molecular orbitals
ESOMO (eV) of methylsulfonyl-substituted norpinanyl radicals A
Angle, deg
Interatomic distance, Å
R in A
Conformer
ΔE, kcal/mol
ESOMO, eV
α
β
l1
l2
H
A′
149.7
–157.3–
149.3
151.2
152.5
151.7
157.4
152.1
2.490
2.485
2.491
2.486
2.485
2.815
2.848
2.829
2.962
2.838
0.78
0.00
1.08
0.00
–
–0.3575
–0.3683
–0.3384
–0.3435
–0.3110
A″
Me
Ph
A′
A″
–159.8–
179.4
A′ = A″
conformational factor: axial approach of reagent to
the boat-like conformation of the six-membered
C1C2C3C4C5C6 ring in phenyl-substituted radical A and
invertomers A′ is less favorable than equatorial ap-
proach to the same radical A and invertomers A″ (cf.
[14]). The smaller effective volume of hydrogen atom
(compared to other substituents) at the radical center is
responsible for somewhat lower selectivity in the reac-
tions of tricycloheptane I compared to II and III.
substituted tricycloheptanes XIIIa–XIIIc. The reaction
is likely to involve intermediate formation of α-sul-
fonyl carbanion B, and intramolecular SN2 substitution
in the latter conforms to stereoelectronic requirements
(rear attack) with the SCN group acting as pseudo-
halide ion (Scheme 3; cf. [3]).
Examples of formation of unsaturated sulfones via
E1cb elimination of HSCN from adducts derived from
alkenes and arenesulfonyl thiocyanates were reported
previously [8, 9, 16]. We have synthesized known [17,
18] methyl (E)-2-phenylethenyl sulfones XVa–XVc by
dehydrothiocyanation of the styrene adducts with
methane- and chloro- and bromomethanesulfonyl
thiocyanates XIVa–XIVc prepared under UV initiation
(Scheme 4).
Apart from steric factors, the selectivity of the
addition can also be affected by electronic factors, i.e.,
by different SOMO energies of the invertomers whose
electrophilic nature is determined by the presence of
an electron-withdrawing substituent in norpinanyl
radicals A. The calculated (RHF/6-31G) energies of
the frontier molecular orbitals of MeSO2SCN
(EHOMO = –0.4266, ELUMO = –0.0227 eV) suggest pref-
erential reaction with invertomers A″ whose SOMO
energy is closer to the HOMO energy of methanesul-
fonyl thiocyanate, as compared to A′ [15]. Presumably,
the relations revealed by quantum-chemical calcula-
tions are also inherent to intermediates in the reactions
of I–III with halomethanesulfonyl thiocyanates.
1,3-Elimination of HSCN from norpinane anti-ad-
ducts IVa, VIIa, and Xa is forbidden for stereoelec-
tronic reasons. Therefore, their reactions with hard
nucleophiles, potassium tert-butoxide in THF at 0°C or
NaOH in aqueous dioxane on heating, involved the sp-
carbon atom in the SCN group and resulted in cleavage
of the latter with formation of thiolate ion which was
oxidized with atmospheric oxygen to produce disul-
fanes XVI–XVIII (Scheme 5; cf. [19]). Heating of
anti-adduct XIa with sodium hydroxide in aqueous
dioxane for a longer time afforded 42% of unsaturated
disulfane XIX, which was formed from intermediate
chlorine-containing disulfane analogous to XVIII via
the Ramberg–Bäcklund reaction (cf. [2, 5]). We plan to
optimize the conditions for the tandem process
Some stereoisomeric 7-sulfonylnorpinan-6-yl thio-
cyanates were subjected to the action of various bases
(nucleophiles). Treatment of syn-adducts IVb–VIb
with potassium tert-butoxide in THF at 0°C, as well as
heating in a boiling solution of NaOH in aqueous
dioxane, resulted in elimination of HSCN molecule
with formation of known [5, 6] 1-methylsulfonyl-
Scheme 3.
B–
IVb–VIb
–SCN–
NCS
SO2CH2X
SO2CH2X
XIIIa–XIIIc
B
X = H (a), Cl (b), Br (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

VASIN et al.
498
Scheme 4.
SCN
B–
XCH2SO2SCN, hν
SO2CH2X
XVa–XVc
SO2CH2X
Ph
CH2
Ph
–HSCN
Ph
XIVa–XIVc
X = H (a), Cl (b), Br (c).
Scheme 5.
MeLi or PhMgBr
or CHCl3/NaOH
AgNO3, H2O
IVa
Xa–XIIa
SO2Me
R
SO2CH2X
Ph
SO2CH2X
SR'
SCN
IVa, VIIa–XIIa
OH
XXa–XXIIa
XXa–XXIIa
OH–
R
R
Ph
Ph
IVa, VIIa, Xa
XIa
MeO2S
SO2Me
H2C
CH2
S
S
S
S
XXVI–XXVIII
XIX
IVa, XVI, R = H; VIIa–IXa, XVII, R = Me; Xa–XIIa, XVIII, R = Ph; XXa, R′ = Me; XXIa, R′ = Ph; XXIIa, R′ = CCl3;
IVa, VIIa, Xa, XXIII, X = H; VIIIa, XIa, XXIV, X = Cl; IXa, XIIa, XXV, X = Br.
ensuring the transformation of halogenated norpinanes
VIIIa, IXa, XIa, and XIIa into unsaturated disulfanes
like XIX.
route to substituted norpinane derivatives containing
sulfonyl and thiocyanato groups; subsequent chemical
modification of the latter could extend the series of
preparatively accessible compounds of this type.
Soft carbon-centered nucleophiles, such as methyl-
lithium and phenylmagnesium bromide, also reacted
with anti-adduct IVa at the SCN group, but the reac-
tion center was the sulfur atom, and nucleophilic re-
placement of cyanide ion gave sulfides XXa and
XXIa, respectively [19]. The structure of compounds
XXa and XXIa was proved by their independent syn-
thesis via photochemical reaction of tricycloheptane I
with S-methyl and S-phenyl methanesulfonothioates
(cf. [7]); these reactions were accompanied by forma-
tion of epimeric syn-adducts XXb and XXIb. Like-
wise, anti-adduct IVa reacted with chloroform in the
presence of 40% aqueous NaOH and a phase-transfer
catalyst to produce sulfide XXIIa (cf. [20]).
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded from
solutions in CDCl3 on a Bruker DPX-300 spectrometer
at 300.13 and 75.47 MHz, respectively, using the
residual proton and carbon signals of the solvent as
reference. The IR spectra were measured in KBr on
an InfraLYuM FT-02 spectrometer with Fourier trans-
form (in all cases, frequencies of 10 most intense
absorption bands are given). GLC analyses were
performed on a KristallLyuks-4000 chromatograph
equipped with a flame-ionization detector; carrier gas
nitrogen, flow rate 30 ml/min; A: 1200×3-mm glass
column packed with 3% of OV-225 on Inerton
N-Super (0.125–0.160 mm), oven temperature 210°C,
injector temperature 250°C; B: 1200 ×3-mm glass
column packed with 3% of OV-17 on Inetron N-Super
(0.125–0.160 mm), oven temperature 200°C, injector
temperature 250°C. Components of reaction mixtures
were quantitated by the internal normalization method
(by peak area); the calibration factors for all compo-
nents were assumed to be equal to unity. The chroma-
tograms were processed using NetChrom 1.5 program.
Finally, we have found that compounds Xa–XIIa
are quantitatively converted into tertiary alcohols
XXIII–XXV by the action of AgNO3 in aqueous
dioxane at 20°C. Here, the SCN group is replaced with
retention of configuration. Presumably, the reaction
follows the SN1 mechanism, and high exo-selectivity
of nucleophilic attack on the corresponding benzylic
carbocation is its specific feature, as we noted in [2].
The described sulfonylation of tricycloheptane hy-
drocarbons may be regarded as a convenient synthetic
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

ADDUCTS OF TRICYCLO[4.1.0.02,7]HEPTANE HYDROCARBONS
499
Analytical thin-layer chromatography was performed
on Silufol UV-254 plates using hexane–acetone (2:1;
thiocyanates and disulfanes) and hexane–diethyl ether
(1:1; sulfides) as eluents; spots were visualized by
treatment with iodine vapor. Silicagel L (40–100 μm)
and aluminum oxide of activity grade II were used for
column chromatography; eluent petroleum ether–ace-
tone (6:1). The elemental compositions were deter-
mined on an HP-185B CHN analyzer.
hexane), Rf 0.29, Rt 12.3 min. IR spectrum, ν, cm–1:
2967 w, 2160 m, 1335 m, 1300 m, 1289 s, 1258 m,
1
1134 v.s, 748 m, 556 m, 478 m. H NMR spectrum, δ,
ppm: 1.75–1.93 m (1H, endo-3-H), 1.95–2.13 m (3H,
exo-3-H, endo-2-H, endo-4-H), 2.59–2.73 m (2H, exo-
2-H, exo-4-H), 2.92 s (3H, Me), 2.98 br.d (2H, 1-H,
5-H), 3.77 s (1H, endo-6-H), 4.07 t (1H, anti-7-H,
J = 5.8 Hz). 13C NMR spectrum, δC, ppm: 13.4 (C3),
24.0 (C2, C4), 41.9 (Me), 44.3 (C1, C5), 48.0 (C6), 57.8
(C7), 110.7 (SCN). Found, %: C 47.81; H 5.72; N 5.94.
C9H13NO2S2. Calculated, %: C 46.73; H 5.66; N 6.05.
Tricycloheptanes I [21], II [22], and III** [23],
bromomethanesulfonyl bromide [24], chloromethane-
sulfonyl chloride [25], S-methyl methanethiosulfonate
[26], and S-phenyl methanethiosulfonate [27] were
synthesized by known methods. Commercial methane-
sulfonyl chloride (Merck) contained more than 99% of
the main substance.
7-syn-Methylsulfonylbicyclo[3.1.1]hept-6-endo-yl
thiocyanate (IVb). mp 71–72°C (from acetone–hex-
1
ane), Rf 0.14, Rt 23.8 min. H NMR spectrum, δ, ppm:
1.65–1.77 m and 2.05–2.14 m (1H each, 3-H), 1.90–
2.05 m and 2.44–2.59 m (2H each, 2-H, 4-H), 2.91 s
(3H, SO2Me), 3.20 br.t (2H, 1-H, 5-H, J = 5.7 Hz),
3.43 t (1H, exo-6-H, J = 5.7 Hz), 3.97 t (1H, anti-7-H,
J = 5.7 Hz). 13C NMR spectrum, δC, ppm: 12.4 (C3),
19.9 (C2, C4), 42.0 (SO2Me), 43.2 (C1, C5), (Me), 47.6
(C6), 57.1 (C7), 111.1 (SCN). Found, %: C 46.84;
H 5.73; N 6.11. C9H13NO2S2. Calculated, %: C 46.73;
H 5.66; N 6.05.
Quantum-chemical calculations in terms of RHF
approximation using 6-31G basis set with initial PM3
parameterization were performed using PC GAMESS
7.1 software [13].
Reaction of tricycloheptanes I–III with methane-
sulfonyl thiocyanates (general procedure). Sul-
fonyl halide MeSO2Cl, ClCH2SO2Cl, or BrCH2SO2Br,
15.6 mmol, was added under vigorous stirring over
a period of 10–20 min to a mixture of 1.96 g
(15.6 mmol) of Na2SO3 and 2.62 g (31.2 mol) of
NaHCO3 in 64 ml of water. The mixture was stirred for
2 h at 20°C, and unreacted sulfonyl halide was
removed by extraction with benzene (3 × 15 ml).
A freshly prepared solution of dirhodan [obtained by
treatment of a suspension of 4.52 g (14 mmol) of
thoroughly dried Pb(SCN)2 in 20 ml of anhydrous
benzene with a solution of 0.65 ml (2.0 g, 12.5 mmol)
of bromine in 20 ml of benzene] was added to the
aqueous phase, and the mixture was vigorously shaken
in a separatory funnel. The organic phase was
separated, dried for 5 min by stirring with anhydrous
CaCl2, and immediately added (without additional
purification) to a solution of 10 mmol of tricyclohep-
tane I–III in 10 ml of anhydrous benzene. The mixture
was kept for 6–14 h at 20°C in a tightly capped flask,
the progress of the reaction being monitored by TLC.
The solvent was removed under reduced pressure
(water-jet pump), and the solid residue was analyzed
7-syn-Chloromethylsulfonylbicyclo[3.1.1]hept-6-
endo-yl thiocyanate (Va). mp 104–105°C (from
CHCl3–hexane), Rf 0.14, Rt 16.9 min. IR spectrum, ν,
cm–1: 2157 m, 1339 m, 1308 s, 1289 m, 1262 m,
1142 v.s, 1127 m, 606 s, 490 m. 1H NMR spectrum, δ,
ppm: 1.75–1.94 m (1H, endo-3-H), 1.95–2.13 m (3H,
exo-3-H, endo-2-H, endo-4-H), 2.56–2.72 m (2H, exo-
2-H, exo-4-H), 2.99 br.d (2H, 1-H, 5-H, J = 5.6 Hz),
3.74 s (1H, endo-6-H), 4.26 t (1H, anti-7-H, J =
5.8 Hz), 4.46 s (2H, CH2Cl). 13C NMR spectrum, δC,
ppm: 13.4 (C3), 24.4 (C2, C4), 45.2 (C1, C5), 48.9 (C6),
55.6 (CH2Cl), 57.4 (C7), 110.5 (SCN). Found, %:
C 40.52; H 4.59; N 5.32. C9H12ClNO2S2. Calculated,
%: C 40.67; H 4.55; N 5.27.
7-syn-Chloromethylsulfonylbicyclo[3.1.1]hept-6-
endo-yl thiocyanate (Vb) was isolated by fractional
crystallization; stereochemical purity 80%, Rt 29.5 min.
1H NMR spectrum, δ, ppm: 1.70–2.13 m (4H, 3-H,
endo-2-H, endo-4-H; overlapped by the signal of Va),
2.42–2.56 m (2H, exo-2-H, exo-4-H), 3.19 br.t (2H,
1-H, 5-H, J = 5.4 Hz), 3.64 t (1H, exo-6-H, J =
5.4 Hz), 4.00 t (1H, anti-7-H, J = 5.4 Hz), 4.44 s (2H,
CH2Cl). 13C NMR spectrum, δC, ppm: 12.5 (C3), 20.2
(C2, C4), 44.2 (C1, C5), 47.9 (C6), 54.7 (CH2Cl), 57.4
(C7), 110.9 (SCN). Found, %: C 40.77; H 4.52; N 5.7.
C9H12ClNO2S2. Calculated, %: C 40.67; H 4.55; N 5.27.
1
by GLC, column A) and/or H NMR and subjected to
column chromatography on silica gel or crystallization.
7-syn-Methylsulfonylbicyclo[3.1.1]hept-6-exo-yl
thiocyanate (IVa). mp 152–153°C (from acetone–
7-syn-Bromomethylsulfonylbicyclo[3.1.1]hept-6-
exo-yl thiocyanate (VIa). mp 91–92°C (from ace-
** Compound II contained ~8% of octane, and compound III,
~13% of 1-phenyltricyclo[4.1.0.03,7]heptane.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

VASIN et al.
500
tone–hexane), Rf 0.60, Rt 5.5 min. IR spectrum, ν,
60.9 (C6), 110.6 (SCN). Found, %: C 43.01; H 5.07;
N 5.11. C10H14ClNO2S2. Calculated, %: C 42.93;
H 5.04; N 5.01.
cm–1: 2951 m, 2944 m, 2157 s, 1335 m, 1308 s,
1
1289 m, 1138 v.s, 1100 m, 756 m, 536 s. H NMR
spectrum, δ, ppm: 1.80–1.94 m (1H, syn-3-H), 2.00–
2.16 m (3H, endo-3-H, endo-2-H, endo-4-H), 2.61–
2.74 m (2H, exo-2-H, exo-4-H), 3.04 br.s (2H, 1-H,
5-H), 3.77 s (1H, endo-6-H), 4.33 t (1H, anti-7-H, J =
5.5 Hz), 4.39 s (2H, CH2Br). 13C NMR spectrum, δC,
ppm: 13.4 (C3), 24.3 (C2, C4), 43.0 (CH2Br), 45.4 (C1,
C5), 48.8 (C6), 55.9 (C7), 110.6 (SCN). Found, %:
C 34.94; H 4.02; N 4.45. C9H12BrNO2S2. Calculated,
%: C 34.85; H 3.90; N 4.52.
7-syn-Bromomethylsulfonyl-6-endo-methylbicy-
clo[3.1.1]hept-6-exo-yl thiocyanate (IXa). mp 114–
115°C (from CHCl3–hexane), Rf 0.42. IR spectrum, ν,
cm–1: 2970 w, 2149 s, 1331 m, 1316 s, 1142 v.s,
1
1096 m, 621 m, 575 m, 552 m, 478 m. H NMR spec-
trum, δ, ppm: 1.62–1.75 m (1H, endo-3-H), 1.76 s
(3H, Me), 1.97–2.12 m (2H, exo-2-H, exo-4-H), 2.13–
2.27 m (1H, exo-3-H), 2.48–2.61 m (2H, exo-2-H, exo-
4-H), 2.96 br.d (2H, 1-H, 5-H, J = 5.8 Hz), 4.38 s (2H,
CH2Br), 4.49 t (1H, anti-7-H, J = 5.8 Hz). 13C NMR
spectrum, δC, ppm: 12.7 (C3), 19.7 (Me), 22.1 (C2, C4),
43.4 (CH2Br), 48.5 (C1, C5), 57.3 (C7), 110.5 (SCN).
Found, %: C 36.90; H 4.42; N 4.21. C10H14BrNO2S2.
Calculated, %: C 37.04; H 4.35; N 4.32.
7-syn-Bromomethylsulfonylbicyclo[3.1.1]hept-6-
endo-yl thiocyanate (VIb) was isolated by fractional
crystallization. Stereochemical purity 67%, Rf 0.35,
1
Rt 9.3 min. H NMR spectrum (a fragment), δ, ppm:
1.65–2.10 m (4H, 3-H, endo-2-H, endo-4-H; over-
lapped by the signal of VIa), 2.40–2.55 m (2H, exo-
2-H, 4-H), 3.18 br.t (2H, 1-H, 5-H, J = 5.5 Hz), 3.60 t
(1H, exo-6-H, J = 5.4 Hz), 3.97 t (1H, anti-7-H, J =
5.4 Hz), 4.34 s (2H, CH2Br). 13C NMR spectrum, δC,
ppm: 12.7 (C3), 20.3 (C2, C4), 42.0 (CH2Br), 43.2 (C1,
C5), 45.0 (C6), 55.7 (C7), 110.9 (SCN). Found, %:
C 34.88; H 3.93; N 4.41. C9H12BrNO2S2. Calculated,
%: C 34.85; H 3.90; N 4.52.
7-syn-Methylsulfonyl-6-endo-phenylbicyclo-
[3.1.1]hept-6-exo-yl thiocyanate (Xa). mp 177–
178°C (from CHCl3–hexane). IR spectrum, ν, cm–1:
2965 w, 2153 s, 1455 m, 1337 s, 1287 s, 1140 v.s,
1
946 w, 754 m, 737 m, 561 m, 530 m. H NMR spec-
trum, δ, ppm: 0.60–0.79 m (1H, endo-3-H), 1.51–
1.68 m (1H, exo-3-H), 2.09–2.22 m (2H, endo-2-H,
endo-4-H), 2.57–2.71 m (2H, exo-2-H, exo-4-H),
2.99 s (3H, MeSO2), 3.47 br.d (2H, 1-H, 5-H, J =
5.6 Hz), 4.38 t (1H, anti-7-H, J = 5.6 Hz), 7.27 d (2H,
Harom, J = 5.6 Hz), 7.37–7.51 (3H, Harom). 13C NMR
spectrum, δC, ppm: 12.7 (C3), 22.2 (C2, C4), 42.2 (Me),
46.9 (C1, C5), 58.0 (C7), 63.7 (C6), 110.4 (SCN); 125.3
(2C), 128.5, 129.0 (2C), 137.8 (Carom). Found, %:
C 58.57; H 5.66; N 4.46. C15H17NO2S2. Calculated, %:
C 58.60; H 5.57; N 4.56.
6-endo-Methyl-7-syn-methylsulfonylbicyclo-
[3.1.1]hept-6-exo-yl thiocyanate (VIIa). mp 119–
120°C (from CHCl3–hexane), Rf 0.40. IR spectrum, ν,
cm–1: 2150 s, 1291 s, 1283 s, 1267 m, 1208 w, 1140
1
v.s, 1094 w, 978 w, 750 w, 544 m. H NMR spectrum,
δ, ppm: 1.63–1.75 m (1H, endo-3-H), 1.77 s (3H, Me),
1.97–2.11 m (2H, endo-2-H, endo-4-H), 2.13–2.30 m
(1H, exo-3-H), 2.45–2.59 m (2H, exo-2-H, exo-4-H),
2.92 br.d (2H, 1-H, 5-H, J = 5.5 Hz), 2.96 s (3H,
MeSO2), 4.25 t (1H, anti-7-H, J = 5.5 Hz). 13C NMR
spectrum, δC, ppm: 12.8 (C3), 19.8 (Me), 22.0 (C2, C4),
42.6 (MeSO2), 47.3 (C1, C5), 59.5 (C7), 60.5 (C6),
110.7 (SCN). Found, %: C 49.03; H 6.27; N 5.67.
C10H15NO2S2. Calculated, %: C 48.95; H 6.16; N 5.71.
7-syn-Chloromethylsulfonyl-6-endo-phenylbicy-
clo[3.1.1]hept-6-exo-yl thiocyanate (XIa). mp 181–
182°C (from CHCl3–hexane). IR spectrum, ν, cm–1:
3011 m, 2149 m, 1456 w, 1337 m, 1304 m, 1156 s,
1
1115 v.s, 735 m, 704 w, 515 w. H NMR spectrum
(DMSO-d6), δ, ppm: 0.46–0.66 m (1H, endo-3-H),
1.36–1.55 m (1H, exo-3-H), 2.04–2.21 m (2H, endo-
2-H, endo-4-H), 2.44–2.57 m (2H, exo-2-H, exo-4-H),
3.61 br.d (2H, 1-H, 5-H, J = 5.4 Hz), 4.77 t (1H, anti-
7-H, J = 5.4 Hz), 5.36 s (2H, CH2Cl), 7.41–7.61 m
(5H, Harom). 13C NMR spectrum (DMSO-d6), δC, ppm:
12.7 (C3), 22.1 (C2, C4), 47.1 (C1, C5), 55.5 (CH2Cl),
57.5 (C7), 64.1 (C6), 111.5 (SCN); 125.7 (2C), 128.3,
128.8 (2C), 138.5 (Carom). Found, %: C 52.58; H 4.63;
N 4.18. C15H16ClNO2S2. Calculated, %: C 52.70;
H 4.72; N 4.10.
7-syn-Chloromethylsulfonyl-6-endo-methylbicy-
clo[3.1.1]hept-6-exo-yl thiocyanate (VIIIa). mp 126–
127°C (from CHCl3–hexane), Rf 0.44. IR spectrum, ν,
cm–1: 3002 w, 2936 m, 2145 m, 1335 m, 1304 s,
1154 s, 1119 v.s, 1092 m, 733 s, 532 s, 498 m. 1H NMR
spectrum, δ, ppm: 1.65–1.76 m (1H, endo-3-H), 1.77 s
(3H, Me), 1.99–2.14 m (2H, endo-2-H, endo-4-H),
2.14–2.29 m (1H, exo-3-H), 2.47–2.62 m (2H, exo-
2-H, exo-4-H), 2.96 br.d (2H, 1-H, 5-H, J = 5.7 Hz),
4.47 t (1H, anti-7-H, J = 5.7 Hz), 4.48 s (2H, CH2Cl).
13C NMR spectrum, δC, ppm: 12.6 (C3), 19.7 (Me),
22.1 (C2, C4), 48.1 (C1, C5), 56.8 (CH2Cl), 57.8 (C7),
7-syn-Bromomethylsulfonyl-6-endo-phenylbicy-
clo[3.1.1]hept-6-exo-yl thiocyanate (XIIa). mp 189–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

ADDUCTS OF TRICYCLO[4.1.0.02,7]HEPTANE HYDROCARBONS
501
190°C (from CHCl3–hexane). IR spectrum, ν, cm–1:
2-Bromomethylsulfonyl-1-phenylethyl thiocy-
anate (XIVc). Yield 26%, mp 95–96°C (from CHCl3–
hexane), Rf 0.18. IR spectrum, ν, cm–1: 2944 m,
2149 m, 1316 s, 1308 s, 1274 m, 1138 v.s, 1096 m,
849 m, 702 m, 502 m. 1H NMR spectrum, δ, ppm: 3.53 d
(1H, J = 12.3 Hz), 4.11 d (1H, CH2Br, J = 12.3 Hz);
3.90 d.d (1H, CH2, J = 4.8, 14.9 Hz), 4.33 d.d (1H,
CH2, J = 9.8, 14.9 Hz); 4.96 d.d (1H, CH, J = 4.8,
9.8 Hz), 7.50 br.s (5H, Harom). 13C NMR spectrum, δC,
ppm: 42.3 (CH2Br), 46.3 (CH2), 54.1 (CH), 109.6
(SCN); 127.7 (2C), 129.8 (2C), 130.6, 134.2 (Carom).
Found, %: C 37.62; H 3.24; N 4.42. C10H10BrNO2S2.
Calculated, %: C 37.51; H 3.15; N 4.37.
3017 m, 2944 m, 2149 m, 1335 m, 1298 s, 1138 v.s,
1
1096 m, 737 m, 702 m, 675 m, 513 m. H NMR spec-
trum, δ, ppm: 0.62–0.82 m (1H, endo-3-H), 1.53–
1.71 m (1H, exo-3-H), 2.09–2.28 m (2H, endo-2-H,
endo-4-H), 2.57–2.73 m (2H, exo-2-H, exo-4-H),
3.53 br.d (2H, 1-H, 5-H, J = 5.4 Hz), 4.41 s (2H,
CH2Br), 4.61 t (1H, anti-7-H, J 5.4 Hz), 7.26 d (2H,
Harom, J = 5.4 Hz), 7.38–7.53 m (3H, Harom). 13C NMR
spectrum, δC, ppm: 12.6 (C3), 22.3 (C2, C4), 43.2
(CH2Br), 48.2 (C1, C5), 56.5 (C7), 64.3 (C6), 110.4
(SCN); 125.3 (2C), 128.5, 129.0 (2C), 137.8 (Carom).
Found, %: C 46.71; H 3.99; N 3.52. C15H16BrNO2S2.
Calculated, %: C 46.64; H 4.17; N 3.63.
Elimination of HSCN from syn-adducts IVb–
VIb (general procedure). a. A mixture of 0.72 g
(18 mmol) of NaOH, 20 ml of aqueous dioxane (1:1),
and 3 mmol of adduct IVb, Vb, or VIb (compounds
Vb and VIb contained, respectively, 10 and 15% of
isomer Va or VIa) was heated for 3 h under reflux. The
mixture was cooled, diluted with five volumes of water,
and extracted with CH2Cl2 (3×10 ml). The combined
extracts were washed with water until neutral reaction,
dried over MgSO4, and evaporated, and the residue
was purified by flash chromatography on silica gel and
crystallization. The yield of tricycloheptanes XVa–
XVc was 69, 52, and 44%, respectively, calculated on
the initial syn-adduct IVb–VIb; the properties of the
products were consistent with the data of [5, 6].
Reaction of styrene with methanesulfonyl thio-
cyanates (general procedure). A solution of the corre-
sponding sulfonyl thiocyanate in benzene, prepared
as described above from 15.6 mmol of MeSO2Cl,
ClCH2SO2Cl, or BrCH2SO2Br, was immediately mixed
with a solution of 10 mmol of freshly distilled styrene
in benzene. The mixture was kept for 48–72 h at 20°C,
the solvent was removed under reduced pressure, and
the solid residue was purified by crystallization to
isolate compounds XIVa–XIVc.
2-Methylsulfonyl-1-phenylethyl thiocyanate
(XIVa). Yield 32%, mp 83–84°C (from CHCl3–hex-
ane), Rf 0.18. IR spectrum, ν, cm–1: 2157 m, 1420 s,
1412 m, 1323 s, 1312 s, 1285 v.s, 1146 s, 1138 s,
1
976 s, 810 m, 748 v.s, 706 s, 498 m, 448 m. H NMR
b. A solution of 0.23 g (1 mmol) of syn-adduct IVb
in 10 ml of anhydrous THF was cooled to 0°C, 0.225 g
(2 mmol) of powdered potassium tert-butoxide was
added under stirring in a stream of argon, the mixture
was stirred for 2 h at 0°C and filtered through a 1-cm
layer of Al2O3, and the precipitate was washed on
a filter with 10 ml of anhydrous diethyl ether. The sol-
vent was evaporated, and the residue was recrystallized
from CHCl3–hexane (1:3). Yield of tricycloheptane
XVa 0.126 g (73%).
spectrum, δ, ppm: 2.60 s (3H, Me), 3.86 d.d (1H, CH2,
J = 5.1, 14.5 Hz), 3.94 d.d (1H, CH2, J = 8.7, 14.5 Hz),
4.96 d.d (1H, CH, J = 5.1, 8.7 Hz), 7.48 br.s (5H,
Harom). 13C NMR spectrum, δC, ppm: 42.5 (Me), 46.3
(CH2), 59.4 (CH), 109.9 (SCN); 127.6 (2C), 129.7
(2C), 130.2, 135.2 (Carom). Found, %: C 49.86; H 5.66;
N 5.73. C10H11NO2S2. Calculated, %: C 49.77; H 4.59;
N 5.80.
2-Chloromethylsulfonyl-1-phenylethyl thiocy-
anate (XIVb). Yield 21%, mp 87–88°C (from CHCl3–
hexane), Rf 0.23. IR spectrum, ν, cm–1: 2149 m,
1319 v.s, 1308 m, 1277 m, 1239 m, 1150 v.s, 1119 s,
Elimination of HSCN from adducts XIVa–XIVc
(general procedure). A solution of 2 mmol of XIVa–
XIVc in 20 ml of THF was treated with 0.3 g
(2.7 mmol) of powdered t-BuOK as described above in
b to isolate (E)-[(2-methylsulfonyl)-, (E)-[(2-chloro-
methylsulfonyl)-, and (E)-[(2-bromomethylsulfonyl)-
vinyl]benzenes XVa–XVc in 67, 54, and 51% yield,
respectively. The physical constants and spectral
parameters of sulfones XVa–XVc coincided with those
reported in [17, 18].
1
748 m, 698 m, 502 s. H NMR spectrum, δ, ppm:
3.61 d (1H, J = 13.1 Hz), 4.21 d (1H, CH2Cl, J =
13.1 Hz), 3.86 d.d (1H, CH2, J = 5.1, 14.9 Hz),
4.27 d.d (1H, CH2, J = 10.2, 14.9 Hz), 4.96 d.d (1H,
13
CH, J = 5.1, 10.2 Hz), 7.49 br.s (5H, Harom). C NMR
spectrum, δC, ppm: 46.1 (CH2), 53.7 (CH2Cl), 56.6
(CH), 109.6 (SCN); 127.6 (2C), 129.8 (2C), 130.5,
134.2 (Carom). Found, %: C 43.44; H 3.69; N 5.16.
C10H10ClNO2S2. Calculated, %: C 43.55; H 3.66;
N 5.08.
6-anti-Methylsulfanyl-7-endo-methylsulfonylbi-
cyclo[3.1.1]heptane (XXa). A solution of 0.23 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

VASIN et al.
502
(1 mmol) of compound IVa in 15 ml of anhydrous
diethyl ether was cooled to –20°C, 3 ml of a 1 M
solution of methyllithium in diethyl ether was slowly
added under vigorous stirring in an argon atmosphere,
and the mixture was stirred for 30 min at –20°C and
for 5 h at 20°C, cooled with an ice bath, treated with
10 ml of water, and extracted with diethyl ether (3×
10 ml). The extract was dried over MgSO4, the solvent
was removed under reduced pressure, the oily residue
was subjected to column chromatography on Al2O3,
and the eluate was distilled under reduced pressure.
Yield 0.19 g (86%), bp 109–110°C (1 mm), Rt 3.6 min
(column B), Rf 0.20. IR spectrum, ν, cm–1: 2957 w,
2927 w, 2971 w, 2855 v.w, 1292 m, 1135 m, 730 m,
pressure, and the residue was recrystallized from
CHCl3–hexane (1:3). Yield 0.20 g (62%), mp 176–
177°C (from CHCl3–hexane). IR spectrum, ν, cm–1:
2955 w, 2936 w, 2870 w, 1285 m (SO2), 1142 m (SO2),
1
864 m, 756 m, 559 m. H NMR spectrum, δ, ppm:
1.87–2.17 m (3H, endo-3-H, endo-2-H, endo-4-H),
2.58–2.71 m (2H, exo-2-H, exo-4-H), 2.88 s (3H,
SO2Me), 3.16 br.d (2H, 1-H, 5-H, J 5.8 Hz), 3.74 s
(1H, 7-H), 3.86 t (1H, 6-H, J = 5.8 Hz). 13C NMR
spectrum, δC, ppm: 13.7 (C3), 23.9 (C2, C4), 41.9 (Me),
44.1 (C1, C5), 51.5 (C7), 59.7 (C6), 96.2 (CCl3). Found,
%: C 33.44; H 4.19. C9H13Cl3O2S2. Calculated, %:
C 33.40; H 4.05.
Reaction of tricycloheptane I with S-methyl
methanesulfonothioate. A quartz test tube was
charged with a solution of 0.94 g (10 mmol) of com-
pound I and 1.26 g (10 mmol) of MeSO2SMe in 8 ml
of anhydrous CH2Cl2. The test tube was tightly capped,
and the mixture was irradiated over a period of 14 h at
20°C with a DRT-400 high-pressure mercury discharge
lamp at a distance of ~20 cm. The progress of the
reaction was monitored by TLC and GLC. By column
chromatography on Al2O3 we isolated 1.32 g (60%) of
XXa and 0.26 g (12%) of XXb.
1
570 m, 479 w. H NMR spectrum, δ, ppm: 1.73–
2.01 m (4H, 3-H, endo-2-H, endo-4-H), 2.10 s (3H,
SMe), 2.42–2.62 m (2H, exo-2-H, exo-4-H), 2.75 br.d
(2H, 1-H, 5-H, J = 5.7 Hz), 2.84 s (3H, SO2Me), 3.07 s
(1H, 7-H), 4.07 t (1H, 6-H, J = 5.7 Hz). 13C NMR
spectrum, δC, ppm: 13.8 (C3), 14.8 (SMe), 24.1 (C2,
C4), 41.7 (SO2Me), 43.4 (C1, C5), 47.8 (C7), 59.3 (C6).
Found, %: C 48.97; H 7.21. C9H16O2S2. Calculated, %:
C 49.06; H 7.32.
6-endo-Methylsulfonyl-7-anti-phenylsulfanylbi-
cyclo[3.1.1]heptane (XXIa) was synthesized in a sim-
ilar way from 0.23 g (1 mmol) of IVa in 15 ml of
diethyl ether and 4 ml of a 0.8 M solution of PhMgBr
in diethyl ether. Crystallization of the crude product
from diethyl ether–hexane (1:4) gave 0.25 g (89%) of
XXIa, mp 136–137°C, Rt 8.0 min (column B), Rf 0.26.
IR spectrum, ν, cm–1: 2924 w, 2867 w, 1586 m, 1485 m,
1285 m, 1258 m, 1134 m, 965 w, 745 m, 559 m.
1H NMR spectrum, δ, ppm: 1.80–2.17 m (4H, 3-H,
endo-2-H, endo-4-H), 2.70 br.d (2H, 1-H, 5-H, J =
5.7 Hz), 2.72 s (3H, SO2Me), 3.58 s (1H, 7-H), 4.16 t
(1H, 6-H, J = 5.7 Hz), 7.13–7.37 m (5H, Harom).
13C NMR spectrum, δC, ppm: 13.6 (C3), 23.8 (C2, C4),
41.6 (SO2Me), 43.3 (C1, C5), 46.8 (C7), 58.7 (C6);
126.0, 128.4 (2C), 128.8 (2C), 135.2 (Carom). Found,
%: C 59.62; H 6.55. C14H18O2S2. Calculated, %:
C 59.54; H 6.42.
6-syn-Methylsulfanyl-7-endo-methylsulfonylbi-
cyclo[3.1.1]heptane (XXb). bp 105–108°C (1 mm),
1
Rt 4.5 min (column B), Rf 0.09. H NMR spectrum, δ,
ppm: 1.72–2.03 m (4H, 3-H, endo-2-H, endo-4-H),
2.07 s (3H, SMe), 2.09–2.37 m (2H, exo-2-H, exo-4-
H), 2.83 s (3H, SO2Me), 2.96 br.t (2H, 1-H, 5-H, J =
5.7 Hz), 3.14 t (1H, anti-7-H, J = 5.7 Hz), 3.36 t (1H,
exo-6-H, J = 5.7 Hz). 13C NMR spectrum, δC, ppm:
13.3 (C3), 15.1 (SMe), 20.1 (C2, C4), 41.8 (SO2Me),
42.6 (C1, C5), 47.7 (C7), 58.9 (C6). Found, %: C 49.15;
H 6.99. C9H16O2S2. Calculated, %: C 49.06; H 7.32.
Reaction of tricycloheptane I with S-phenyl
methanesulfonothioate. As described above, irradia-
tion of a solution of 0.94 g (10 mmol) of I and 1.88 g
(10 mmol) of MeSO2SPh in 10 ml of anhydrous
CH2Cl2 over a period of 12 h gave a mixture of sul-
fones XXIa and XXIb at a ratio of 65:35 (column B,
oven temperature 240°C, Rt 8.0 and 13.5 min, respec-
tively). By column chromatography on Al2O3 we
isolated 1.69 g (60%) of XXIa and 0.42 g (15%) of
XXIb.
6-endo-Methylsulfonyl-7-anti-trichloromethyl-
sulfanylbicyclo[3.1.1]heptane (XXIIa). A 1 M solu-
tion of sodium hydroxide, 2 ml, was added dropwise
under vigorous stirring to a mixture of 0.23 g (1 mmol)
of IVa, 3 ml of CHCl3, 3 ml of dioxane, and 60 mg of
benzyltriethylammonium chloride. The mixture was
stirred for 1 h, following disappearance of IVa by
TLC. The product was extracted into diethyl ether
(3×5 ml), the extract was washed with water and dried
over MgSO4, the solvent was removed under reduced
6-endo-Methylsulfonyl-7-syn-phenylsulfanylbi-
cyclo[3.1.1]heptane (XXIb). Viscous oily substance,
1
Rf 0.09. H NMR spectrum, δ, ppm: 1.75–2.23 m (4H,
3-H, endo-2-H, endo-4-H), 2.41–2.59 m (2H, exo-2-H,
exo-4-H), 2.70 s (3H, SO2Me), 2.92 br.s (2H, 1-H,
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ADDUCTS OF TRICYCLO[4.1.0.02,7]HEPTANE HYDROCARBONS
503
5-H), 3.36 t (1H, anti-7-H, J = 5.8 Hz), 3.55 t (1H,
exo-6-H, J = 5.8 Hz), 7.12–7.25 m (5H, Harom).
13C NMR spectrum, δC, ppm: 13.3 (C3), 20.2 (C2, C4),
41.8 (SO2Me), 43.5 (C1, C5), 48.1 (C7), 59.8 (C6);
126.3, 128.8 (2C), 129.8 (2C), 136.0 (Carom). Found,
%: C 59.71; H 6.29. C14H18O2S2. Calculated, %:
C 59.54; H 6.42.
1,2-Bis(7-syn-methylsulfonyl-6-endo-phenylbi-
cyclo[3.1.1]hept-6-exo-yl)disulfane (XVIII). Yield
62%, mp 210°C (decomp., from CHCl3–hexane),
Rf 0.32. IR spectrum, ν, cm–1: 3067 w, 2926 s, 1456 w,
1318 s, 1287 v.s, 1140 v.s, 754 s, 704 s, 563 s. 1H NMR
spectrum, δ, ppm: 0.47–0.63 m (2H, endo-3-H), 1.37–
1.51 m (2H, exo-3-H), 1.85–1.98 m (4H, endo-2-H,
endo-4-H), 2.31–2.48 m (4H, exo-2-H, exo-4-H),
2.82 br.d (4H, 1-H, 5-H, J = 5.6 Hz), 2.87 s (6H,
MeSO2), 4.29 t (2H, anti-7-H, J = 5.6 Hz), 7.01 d (4H,
1,2-Bis(7-syn-methylsulfonylbicyclo[3.1.1]hept-
6-exo-yl)disulfane (XVI). a. Powdered potassium tert-
butoxide, 2 mmol, was quickly added under stirring in
an argon atmosphere to a solution of 1 mmol of anti-
adduct IVa in 15 ml of anhydrous THF, and the
mixture was stirred for 2 h at 0°C under argon, the
progress of the reaction being monitored by TLC. The
mixture was then filtered through a 1-cm layer of
Al2O3, the filtrate was evaporated to dryness under
reduced pressure (water-jet pump), and the residue was
H
arom, J = 7.6 Hz), 7.24–7.49 m (6H, Harom). 13C NMR
spectrum, δC, ppm: 13.2 (C3), 22.1 (C2, C4), 42.1
(MeSO2), 47.2 (C1, C5), 57.9 (C7), 61.6 (C6); 126.5
(4C), 127.2 (2C), 128.3 (4C), 139.1 (2C) (Carom).
Found, %: C 59.62; H 5.97. C28H34O4S4. Calculated,
%: C 59.75; H 6.09.
1,2-Bis(7-methylidene-6-endo-phenylbicyclo-
[3.1.1]hept-6-exo-yl)disulfane (XIX). anti-Adduct
XIa, 342 mg, was added to a solution of 0.4 g of
NaOH in 5 ml of aqueous dioxane (1:1). The mixture
was heated for 5 h under reflux, cooled, and extracted
with diethyl ether (5×5 ml). The extract was washed
with water, dried over MgSO4, and evaporated, and the
residue was purified by recrystallization. Yield 91 mg
(42%), mp 153–154°C (from CHCl3–hexane). IR spec-
trum, ν, cm–1: 2948 w, 1628 s, 1314 v.s, 1159 s, 1127 s,
1
analyzed by H NMR and purified by crystallization.
Yield 72%, mp 189–190°C (from CHCl3–hexane),
Rf 0.28. IR spectrum, ν, cm–1: 2951 s, 1321 s, 1306 s,
1281 s, 1256 s, 1136 v.s, 965 s, 754 s, 559 s, 478 s.
1H NMR spectrum, δ, ppm: 1.73–1.88 m (2H, endo-
3-H), 1.90–2.05 m (6H, exo-3-H, endo-2-H, endo-
4-H), 2.53–2.68 m (4H, exo-2-H, exo-4-H), 2.83 br.d
(4H, 1-H, 5-H, J = 5.7 Hz), 2.87 s (6H, MeSO2), 3.30 s
(2H, endo-6-H), 4.03 t (2H, anti-7-H, J = 5.7 Hz).
13C NMR spectrum, δC, ppm: 13.9 (C3), 24.2 (C2, C4),
41.9 (MeSO2), 43.8 (C1, C5), 50.4 (C6), 58.5 (C7).
Found, %: C 46.89; H 6.44. C16H26O4S4. Calculated,
%: C 46.80; H 6.38.
1
1032 m, 721 m, 696 m, 527 m, 507 w. H NMR spec-
trum, δ, ppm: 1.41–1.53 m (2H), 1.62–1.78 m (2H,
3-H), 1.98–2.17 m (4H), 2.29–2.45 m (4H, 2-H, 4-H),
3.83 br.s (4H, 1-H, 5-H), 5.28 s (4H, CH2=), 7.21–
7.30 m (4H) and 7.38–7.54 (6H) (Harom). Found, %:
C 78.11; H 7.19. C28H30S2. Calculated, %: C 78.09;
H 7.02.
b. anti-Adduct IVa, VIIa, or Xa, 2 mmol, was dis-
solved in 10 ml of dioxane, 10 ml of a 1.2 M solution
of NaOH was added under argon, and the mixture was
heated for 3.5 h under reflux, cooled to room tempera-
ture, and diluted with 100 ml of water. The precipitate
of XVI–XVIII was filtered off, dried in air, and
purified by recrystallization. Yield of XVI 65%.
Disulfane XIX was synthesized in a similar way
from compound XIIa; yield 53%.
Reaction of anti-adducts Xa–XIIa with AgNO3 in
aqueous dioxane (general procedure). A flask protect-
ed from light was charged with 1 mmol of sulfone Xa–
XIIa and 15 ml of dioxane, a solution of 0.255 g
(1.5 mmol) of AgNO3 in 15 ml of water was added,
and the mixture was stirred for 5–10 h at 20°C. The
resulting colorless suspension was treated with 8 ml of
a 0.2 M solution of KCl, the precipitate was filtered off
and washed with 10 ml of chloroform on a filter, and
the filtrate was extracted with chloroform (3×10 ml).
The combined extracts were dried over MgSO4 and
evaporated under reduced pressure, and the solid
residue was analyzed by NMR. Alcohols XXIII–XXV
were purified by recrystallization.
1,2-Bis(6-endo-methyl-7-syn-methylsulfonylbi-
cyclo[3.1.1]hept-6-exo-yl)disulfane (XVII). Yield
80%, mp 122–123°C (from CHCl3–hexane), Rf 0.34.
IR spectrum, ν, cm–1: 2967 m, 2924 m, 1296 v.s,
1285 v.s, 1246 m, 1091 m, 927 m, 752 m, 544 s.
1H NMR spectrum, δ, ppm: 1.45 s (6H, CH3), 1.54–
1.67 m (2H, endo-3-H), 1.86–1.98 m (4H, endo-2-H,
endo-4-H), 2.04–2.18 m (2H, exo-3-H), 2.34–2.45 m
(4H, exo-2-H, exo-4-H), 2.78 br.d (4H, 1-H, 5-H, J =
5.5 Hz), 2.87 s (6H, MeSO2), 4.25 t (2H, 7-H, J =
5.5 Hz). 13C NMR spectrum, δC, ppm: 13.1 (C3), 19.0
(CH3), 21.8 (C2, C4), 42.1 (MeSO2), 46.8 (C1, C5), 56.4
(C6), 59.2 (C7). Found, %: C 49.09; H 6.74.
C18H30O4S4. Calculated, %: C 49.28; H 6.89.
7-syn-Methylsulfonyl-6-endo-phenylbicyclo-
[3.1.1]heptan-6-exo-ol (XXIII). Yield 91%, mp 185–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

VASIN et al.
504
186°C (from acetone–CH2Cl2). IR spectrum, ν, cm–1:
556 m, 706 s, 760 m, 1084 m, 1134 s (νsSO21), 1238 s,
1289 v.s (νasSO2), 2951 m, 3441 s (OH). H NMR
spectrum, δ, ppm: 0.62–0.92 m (1H, endo-3-H), 1.39–
1.65 m (1H, exo-3-H), 1.70 br.s (1H, OH), 1.87–
2.09 m (2H, endo-2-H, endo-4-H), 2.43–2.65 m (2H,
exo-2-H, exo-4-H), 2.92 s (3H, SO2Me), 3.29 br.d (2H,
1-H, 5-H, J = 5.7 Hz), 4.31 t (1H, anti-7-H, J =
5.7 Hz), 7.27 d (2H, Harom, J = 7.5 Hz), 7.37–7.49 m
(3H, Harom). 13C NMR spectrum, δC, ppm: 12.9 (C3),
22.5 (C2, C4), 42.1 (SO2Me), 48.0 (C1, C5), 57.5 (C7),
79.6 (C6); 125.3 (2C), 128.2, 129.0 (2C), 139.6 (Carom).
Found, %: C 63.01; H 6.97. C14H18O3S. Calculated, %:
C 63.13; H 6.81.
8. Wolf, G.C., J. Org. Chem., 1974, vol. 39, p. 3454.
9. Tanaskov, M.M., Starodub, P.E., Stadnichuk, M.D., and
Tanaskova, E.A., Zh. Org. Khim., 1981, vol. 17, p. 1800.
10. Wiberg, K.B. and Hess, B.A., J. Org. Chem., 1966,
vol. 31, p. 2250.
11. Razin, V.V., Vasin, V.A., and Blinkov, I.E., Zh. Org.
Khim., 1993, vol. 29, p. 916.
12. Vasin, V.A., Kostryukov, S.G., and Razin, V.V., Russ. J.
Org. Chem., 1998, vol. 34, p. 1136.
13. Schmidt, M.W., Baldridge, K.K., Boatz, J.A.,
Elbert, S.T., Gordon, M.S., Jensen, J.J., Koseki, S.,
Matsunaga, N., Nguyen, K.A., Su, S., Windus, T.L.,
Dupuis, M., and Montgomery, J.A., J. Comput. Chem.,
1993, vol. 14, p. 1347; Granovsky, A.A., PC GAMESS/
Firefly version 7.1.F; http://classic.chem.msu.su/gran/
gamess/index.html
7-syn-Chloromethylsulfonyl-6-endo-phenylbi-
cyclo[3.1.1]heptan-6-exo-ol (XXIV). Yield 88%,
mp 176–177°C (from CHCl3). IR spectrum, ν, cm–1:
3511 m (OH), 3010 m, 2940 m, 1339 m, 1304 s
(νasSO2), 1157 s (νsSO2), 1115 s, 737 s, 540 w.
1H NMR spectrum, δ, ppm: 0.70–0.92 m (1H, endo-
3-H), 1.47–1.63 m (1H, exo-3-H), 1.93 br.s (1H, OH),
1.95–2.10 m (2H, endo-2-H, endo-4-H), 2.49–2.67 m
(2H, exo-2-H, exo-4-H), 3.35 br.d (2H, 1-H, 5-H),
4.45 s (2H, CH2Cl), 4.50 t (1H, 7-H, J = 5.5 Hz); 7.27–
7.32 m (2H) and 7.40–7.49 m (3H) (Harom). 13C NMR
spectrum, δC, ppm: 12.8 (C3), 22.7 (C2, C4), 49.0 (C1,
C5), 55.5 (CH2Cl); 57.5 (C7), 80.2 (C6); 125.1 (2C),
128.0, 128.8 (2C), 139.4. Found, %: C 55.81; H 5.67.
C14H17ClO3S. Calculated, %: C 55.90; H 5.70.
14. Nicolaou, K.C. and Smith, A.L., Acc. Chem. Res., 1992,
vol. 25, p. 497.
15. Tedder, J.M. and Nechvatal, A., Pictorial Orbital
Theory, London: Pitman, 1985. Translated under the
title Orbital’naya teoriya v konturnykh diagrammakh,
Moscow: Mir, 1988, p. 41; Fleming, I., Frontier
Orbitals and Chemical Reactions, Chichester: Wiley,
1976, chap. 5.
16. Olsen, S.C. and Christophersen, C., Acta Chem. Scand.,
Ser. B, 1975, vol. 29, p. 891.
17. Vasin, V.A., Bolusheva, I.Yu., and Razin, V.V., Sulfur
Lett., 2003, vol. 26, p. 101.
18. Vasin, V.A., Bolusheva, I.Yu., and Razin, V.V., J. Sulfur
Chem., 2005, vol. 26, p. 139.
19. Hogg, D.R., Comprehensive Organic Chemistry,
Barton, D. and Ollis, W.D., Eds., Oxford: Pergamon,
1979, vol. 3. Translated under the title Obshchaya
organicheskaya khimiya, Moscow: Khimiya, 1983,
vol. 5, p. 418.
7-syn-Bromomethylsulfonyl-6-endo-phenylbicy-
clo[3.1.1]heptan-6-exo-ol (XXV). Yield 79% [2].
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