Regio- and stereoselective addition of methane- and bromomethanesulfonyl bromides to 1-Phenylthiotricyclo[4.1.0.02,7]heptane

Article abstract of DOI:10.1134/S1070428010050027

1-Phenylthiotricyclo[4.1.0.0^2,7]heptane reacted with MeSO ₂Br and BrCH₂SO₂Br directly at mixing at 20°C in CH₂Cl₂ along a ionic (electrophilic with respect to bromine) mechanism affording a product of an anti-stereoselective addition to the central bicyclobutane C¹-C⁷ bond of the norpinane structure. The reaction product contains the exo-oriented sulfonyl group in the geminal position to the SPh substituent. The structure of the adduct with MeSO₂Br in a single crystal was determined by XRD analysis. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070428010050027

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 5, pp. 624−627. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.A. Vasin, S.G. Kostryukov, V.A. Neverov, V.V. Razin, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46,
No. 5, pp. 636−639.
Regio- and Stereoselective Addition
of Methane- and Bromomethanesulfonyl Bromides
to 1-Phenylthiotricyclo[4.1.0.02,7]heptane
V. A. Vasina, S. G. Kostryukova, V. A. Neverova, and V. V. Razinb
aOgarev Mordovskii State University, Saransk, 430005 Russia
e-mail: vasin@mrsu.ru
bSt. Petersburg State University, St. Petersburg, Russia
Received June 10, 2009
Abstract—1-Phenylthiotricyclo[4.1.0.02,7]heptane reacted with MeSO2Br and BrCH2SO2Br directly at mixing at
20°C in CH2Cl2 along a ionic (electrophilic with respect to bromine) mechanism affording a product of an anti-
stereoselective addition to the central bicyclobutane C1–C7 bond of the norpinane structure. The reaction product
contains the exo-oriented sulfonyl group in the geminal position to the SPh substituent. The structure of the
adduct with MeSO2Br in a single crystal was determined by XRD analysis.
DOI: 10.1134/S1070428010050027
It was shown formerly [1, 2] that 1-phenylthio- and
1-methylthiotricyclo[4.1.0.02,7]heptanes (I) and (II) under
UV irradiation were subject to addition of benzene-
sulfonyl bromide, benzenesulfonyl chloride, S-phenyl-
benzenesulfonothioate, and S-methylbenzenesulfono-
thioate exclusively at the central bicyclobutane C1–C7
bond strictly regio- and stereoselectively with the
formation of norpinane compounds IIIa–IIIc and IVb,
IVd.
The reaction in the dark of compound II with benzene-
sulfonyl bromide and also with Se-phenylbenzene-
sulfonoselenoate resulted in another order and another
stereochemistry of the reagent addition to the C1–C7 bond:
we obtained norpinane compounds Va and Ve [2].
The difference in the behavior of the methylthioether
II with respect to benzenesulfonyl halides was ascribed
to the change in the addition mechanism from the radical
at UV irradiation (benzenesulfonyl chloride) to the ionic
one in the dark (benzenesulfonyl bromide). The
successful reaction in the dark in this case is apparently
favored by lower strength and larger polarity of the SO2–
Br bond compared with the SO2–Cl bond and also by
higher nucleophilicity of compound II than compound I.
Scheme 1.
SR
We investigated in this study the reactions of
phenylthioether I with more active than PhSO2Br sources
of electrophilic bromine, methane- and bromomethane-
sulfonyl bromides, aiming at establishing the regio- and
stereoselectivity of these reagents addition. The reaction
was carried out at 0°C in CH2Cl2 over 6–8 h using
equimolar amounts of the reagents; the reaction did not
require a special initiation. By column chromatography
onAl2O3 we isolated from the reaction mixtures norpin-
ane compounds VI and VII analogous to compounds Va
I, II
PhSO2X,
PhSO2X
hv
SMe
X
X
PhSO2
SR
IIIa_IIIc, IVb, IVd
SO2Ph
Va, Ve
R = Ph (I, III), Me (II, IV); X = Br (a), Cl (b), SPh (c), SMe
(d), SePh (e).
624

REGIO- AND STEREOSELECTIVE ADDITION
625
respectively. In the cyclobutane fragment the dihedral
angle between the planes C1C5C6 and C1C5C7 (140.1°)
and the nonvalence distances C1 C5 (2.149 ) and
YCH2SO_2
YCH2SO2Br
Br
...
I
...
C6 C7 (2.119 ) are close to the corresponding values
SPh
Br
Ph
S
(137.3°, 2.140 and 2.096 ) in an unsubstituted norpinane
in the gas phase [6]. The valence distances C1–C6 and
C5–C6 (average 1.573 Å) are in this compound somewhat
longer than the valence distances C1–C7 and C5–C7
(average 1.542 ) evidently due to the presence of the
electronegative bromine atom in the position 7. The plane
of the phenyl ring is practically orthogonal to the plane
C3C6C7. This ring and the methyl group of the sulfonyl
fragment have the opposite orientation with respect to
the mentioned plane. The atom Br1 deviates from the
plane C3C6C7 by 0.012 in the direction of C4 atom.
+
SO2CH2Y
A
VI, VII
Y = H (VI), BR (VII).
and Ve. The polymeric products of the reaction were
retained in the column.
The use of MeSO2Br and BrCH2SO2Br in the
reaction with methylthioether II under similar conditions
resulted in the formation of tarry polymer products lacking
sulfonyl group in their composition.
To understand the origin of norpinanes VI and VII
we suggest that the addition occurs by the ionic
mechanism where the methane- and bromomethane-
sulfonyl bromides operate as the sources of the
electrophilic bromine. The attack of Br+ is strictly endo-
directed on the unsubstituted nodal carbon atom of the
tricycloheptane I in conformity with the characteristic
feature of the ionic reactions of the bicyclobutane
derivatives [7, 8] and leads to the formation of a norpinanyl
carbocation A stabilized by the mesomeric involvement
of the sulfur atom. The subsequent transfer of the sulfonyl
anion on the carbocation A proceeds highly selectively
into the anti-position. The main reason of the latter we
believe to be in the shielding of the reaction site of the
The structures of compounds VI and VII were
established from the data of H and 13C NMR spectra
1
taking into consideration analogous characteristics of
compound Va. In the 13C NMR spectra five characteristic
peaks were observed of an expected intensity belonging
to the norpinane framework of the molecules, and also
the peak of the methyl (bromomethyl) group. The location
of the bromine atom at the carbon framework of the
molecule is indicated by the relatively large chemical shift
value of the C7 atom in the 13C NMR spectra, and the
syn-orientation of the bromine follows from the triplet
signal of the proton anti-H7, J 5.8 Hz, in the H NMR
spectra [3].
1
The direct proof of adduct VI structure was obtained
by XRD analysis of its single crystal (see the figure).
The studied structure is built of discrete molecules.
Only the van der Waals interaction exists between the
molecules.
Among the features of the spatial arrangement of
norpinane VI the virtually flat trimethylene bridge should
be mentioned: the dihedral angle C1C2C4C5/C2C3C4 is
only 1.27°, atom C3 insignificanly (by 0.018 ) deviates
from the plane C1C2C4C5 in the direction of the phenylthio
group. The similar structure of the trimethylene bridge
was also observed in the known 6,6,7-trisubstituted
norpinanes of the endo,syn-configuration [2, 4]. Our
estimation performed using the calculation program
RICON (method ZP) [5] suggested that both six-
membered rings C6C1C2C3C4C5 and C7C1C2C3C4C5
were in the envelop conformation with the folding
parameters S 1.099, 1.072, θ 36.44, 38.49, ψ2 0.23, 0.86
Perspective view of molecule of syn-7-bromo-exo-6-
(methylsulfonyl)-endo-6-(phenylthio)bicyclo[3.1.1]-heptane
(VI).
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VASIN et al.
626
intermediate A by the fragment C3H2 considerably
deviating from the plane C1C2C4C5 in the direction of
atom C6 because of the repulsion by the bulky bromine
atom attached to C7.
129.1 (2C), 132.17 (Carom). Found, %: C 46.77; H 4.88.
C14H17BrO2S2. Calculated, %: C 46.54; H 4.74.
syn-7-Bromo-exo-6-(bromosulfonyl)-endo-6-
(phenylthio)bicyclo[3.1.1]heptane (VII). Yield 29%,
mp 96°C (CHCl3–hexane). 1H NMR spectrum, δ, ppm:
1.76–1.94 m (2H, H3), 2.15–2.38 m (4H, H2,4), 3.61 d
(2H, H1,5, J 6 Hz), 4.84 s (2H, CH2Br), 5.66 t (1H, H7,
J 6 Hz), 7.30–7.40 m (3Harom), 7.54 d (2Harom, J 7.5 Hz).
13C NMR spectrum, δ, ppm: 12.6 (C3), 26.1 (2C, C2,4),
42.3 (CH2Br), 48.4 (C7), 49.9 (2C, C1,5), 78.4 (C6), 127.7,
129.1 (2C), 129.4 (2C), 131.6 (Carom). Found, %: C 38.38;
H 3.78. C14H16Br2O2S2. Calculated, %: C 38.20; H 3.66.
Hence the studied new reactions of sulfobromination
of 1-phenylthiotricycloheptane I like the formerly reported
[2] addition of PhSO2Br and PhSO2SePh to
tricycloheptane II with respect to the regio- and
stereoselectrivity of the addition are completely resembling
the addition reactions to 1-phenyltricyclo[4.1.0.02,7]-
heptane initialed by the electrophilic bromine, namely the
bromomethoxy(hydroxy)lation [9, 10] and N-halo-
succinimides addition in the aprotic solvent [11].
XRD analysis of compound VI. Experimental set
of intensities of 3141 reflections was obtained from
a colorless prismatic single crystal of the size 1.0 × 0.4 ×
0.3 mm on an automatic four-circle diffractometer
Siemens P3/PC at 293 K (graphite monochromator,
MoKa-radiation, λ 0.71073 , θ-5/3θ scanning, 2θmax
55.76°, spherical segment –9 ≤ h ≤ 25, 0 ≤ k ≤ 8, –27 ≤
l ≤ 27).After the averaging of equivalent reflections 2846
(Rint 0.0180) independent reflections were obtained that
were used in solving and refining the structure. Crystals
EXPERIMENTAL
Elemental analysis was carried out on a CHN-analyzer
HP-185Β. 1H and 13C NMR spectra of compounds were
registered on a spectrometer Bruker AC-300 (300.130
and 75.468 MHz respectively) in CDCl3. The conditions
of analytical TLC were as follows: adsorbent Silufol UV-
254, eluent hexane–ethyl ether, 1 : 1. Development in
iodine chamber. The column chromatography was
performed onAl2O3 of II activity grade, eluent low-boiling
petroleum ether–ethyl ether, 3 : 1.
monoclinic, a 20.423(11), b 6.783(6), c 22.176(8)
,
β108.29(4)°, V 2917(9) 3, Μ 361.31, Z 8, dcalc
1.646 g/cm3, μ 3.099 mm–1, F(000) 1472, space group C
2/c. The structure was solved by the direct method. All
atoms were localized by successive syntheses of the
Tricycloheptane I [12], MeSO2Br [13], and
BrCH2SO2Br [14] were obtained by published
procedures.
electron density. The refinement was performed by F2
hkl
in the anisotropic approximation for all nonhydrogen
atoms and in the isotropic approximation for hydrogen
atoms. The final divergence factors are as follows: R1
0.0519 [calculated by Fhkl for 2336 reflections with I >
2σ(I)], wR2 0.1443 (calculated by F2hkl for 3141 reflec-
tions used in the refining). The number of independent
refined parameters 172, GOOF 1.070. The residual
electron density from the difference Fourier series was
1.718 and –1.1.474 e/ –3. The correcton for extinc-tion
was not done. All calculations were performed using the
software SHELXTL ver.5.1 [15]. Weight scheme w–1=
Reaction of tricycloheptane I with methane-
sulfonyl bromides.At cooling with an ice bath a solution
of 0.708 g (3.5 mmol) of tricycloheptane I in 5 ml of
anhydrous CH2Cl2 was mixed with 3.5 mmol of
MeSO2Br or BrCH2SO2Br in 5 ml of the same solvent,
and 100 mg of anhydrous Na2CO3 was added. The
mixture was kept in a tightly stoppered flask for 30 h at
20°C, then the reaction mixture was filtered, the solvent
was evaporated in a vacuum of the water-jet pump. The
oily residue was subjected to column chromatography on
Al2O3.
2
σ (FO2) + (0.1066P)2 + 2.6728P where P = 1/3(FO2 + 2FO2).
syn-7-Bromo-exo-6-(sulfonyl)-endo-6-(phenyl-
thio)bicyclo[3.1.1]heptane (VI). Yield 30%, mp 110–
The XRD data for compound VI are deposited in the
Cambridge Crystallographic Data Center (no. CCDC
733628) and can be obtained free at the address
www.ccdc.cam.ac.uk/conts/retrieving.html or by post at
The Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge CB2 1EZ, UK; fax: (+44)-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk.
1
111°C (CH2Cl2–hexane). H NMR spectrum, δ, ppm:
1.72–1.90 m (2H, H3), 2.13–2.43 m (4H, H2,4), 3.12 s
(3H, CH3), 3.48 br.s (2H, H1,5), 5.67 t (1H, H7, J 6 Hz),
7.24–7.38 m (3Harom), 7.48–7.52 m (2Harom). 13C NMR
spectrum, δ, ppm: 12.5 (C3), 26.3 (2C, C2,4), 38.4 (CH3),
49.3 (C1,5), 49.8 (2C, C7), 79.1 (C6); 127.2, 128.7 (2C),
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REGIO- AND STEREOSELECTIVE ADDITION
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