Reactions of (phenylethynyl)sulfones with tricyclo[4.1.0.0 2,7]heptanes

Article abstract of DOI:10.1139/cjc-2012-0159

Methyl-, phenyl-, p-chlorophenyl-, and p-tolyl(phenylethynyl)sulfones under photochemical or thermal initiation add to the central bicyclobutane C1-C7 bond of 1-R(H, Me, Ph)-tricyclo[4.1.0.0^2,7]heptanes anti-selectively, and form norpinic adducts containing a phenylethynyl group in a geminal to substituent R position, and an endo-oriented sulfonyl group in position 7. The corresponding ketones were prepared by the hydration of the anti-adducts by the method of Kucherov. The ketone with a methylsulfonyl substituent under reflux in toluene in the presence of KOH powder and the phase-transfer catalyst (TEBA-Cl) afforded the tricyclic sulfone.

Full text of DOI:10.1139/cjc-2012-0159

465
ARTICLE
Reactions of (phenylethynyl)sulfones with tricyclo[4.1.0.02,7]heptanes
V.A. Vasin, Yu.Yu. Masterova, V.V. Razin, and N.V. Somov
Abstract: Methyl-, phenyl-, p-chlorophenyl-, and p-tolyl(phenylethynyl)sulfones under photochemical or thermal initiation add
to the central bicyclobutane C1–C7 bond of 1-R(H, Me, Ph)-tricyclo[4.1.0.02,7]heptanes anti-selectively, and form norpinic adducts
containing a phenylethynyl group in a geminal to substituent R position, and an endo-oriented sulfonyl group in position 7. The
corresponding ketones were prepared by the hydration of the anti-adducts by the method of Kucherov. The ketone with a
methylsulfonyl substituent under reflux in toluene in the presence of KOH powder and the phase-transfer catalyst (TEBA-Cl)
afforded the tricyclic sulfone.
Key words: (phenylethynyl)sulfone, radical addition, sulfonyl-substituted norpinanes, tricyclo[4.1.0.02,7]heptane, cyclization.
Résumé : Sous l'influence d'une initiation photochimique ou thermique les méthyl-, phényl-, p-chlorophényl- et p-tolyl
(phényléthynyl)sulfones s'additionnent sélectivement d'une façon anti a` la liaison centrale C1-C7 du bicyclobutane des 1-R(H, Me,
Ph)-tricyclo[4.1.0.02,7]heptanes, avec formation d'adduits norpiniques contenant un groupe phényléthynyle dans une position
géminale par rapport au substituant R et avec une orientation endo par rapport au goupe sulfonyle en position 7. On a préparé
les cétones correspondantes par hydratation des adduits anti par la méthode de Kucherov. La cétone avec un substituant
méthylsulfonyle, par chauffage au reflux du toluène, en présence de KOH en poudre et d'un catalyseur de transfert de phase, le
chlorure de triéthylbenzylammonium (Cl-TEBA), conduit a` la formation de la sulfone tricyclique. [Traduit par la Rédaction]
Mots-clés : (phényléthynyl)sulfone, addition radicalaire, norpinanes substitués par un groupe sulfonyle, tricyclo[4.1.0.02,7]heptane,
cyclisation.
The analogous photochemical reaction between hydrocarbon 2
and acetylene 1d resulted in the formation of the monoadducts 5d
and 6d in the ratio of 5.5:1. After heating tricycloheptane 2 at
Introduction
Alkynes are useful and versatile intermediates in organic
synthesis.1 The utility of the acetylenic functional group in or-
reflux with acetylenic sulfone 1b in equimolar amounts in toluene
ganic chemistry has been well documented.2 Acetylenic sulfones
for 10 h, the formation of the same monoadducts as those ob-
also have many synthetic applications.3 Thus, for example,
tained in the case of photolysis was observed. However, the con-
phenyl(arylsulfonyl)acetylenes 1a, 1b under thermolysis or pho-
tent of the admixture 7b was slightly increased. Thermolysis of
tolysis add to bicyclic alkenes (norbornene, indene, etc.) forming
sulfones 1b, 1c carried out in sealed glass ampules at 110 °C for
1:1-adducts as a result of the Csp–S bond homolytic scission.4 Tak-
6–8 h in double excess of tricycloheptane 2 afforded compounds
ing into account the known similarity between the structures of a
5b, 5c, 6b, 6c only, in the ratio close to that observed in the case
central C–C bond in bicyclo[1.1.0]butanes and a ␲-bond C=C, the
of photolysis. Propynyl sulfone 1e, in contrast to sulfones 1a–1d,
reaction of acetylenic sulfones 1a, 1b with bicyclobutane compounds
showed no reaction with tricycloheptane 2 under either photoly-
was expected. This assumption seemed to be quite possible inas-
sis or thermal initiation.
much as the hydrocarbons of the tricyclo[4.1.0.02,7]heptane row 2–4
add the sulfonyl derivatives ArSO2X (X = Cl, Br, I, SPh, SMe, SePh,
Photolysis of sulfones 1a–1c in the presence of one and a half
multiple excess of tricycloheptanes 3, 4 in CH2Cl2 (15–20 h, 20 °C)
afforded a unique addition product in each case: the correspond-
ing anti-adducts 8a–8c, 9a–9c in the yield of 50%–55% (Scheme 2).
SCN, N3) because of a homolytic scission of the sulfur–heteroatom
bond in the latter reagents, as we have previously shown.5–12
At the same time, the presence of the respective syn-adducts in the
reaction mixtures in trace amounts is not excluded.
Results and discussion
We investigated the interaction of (phenylethynyl)sulfones
1a–1d and propynyl sulfone 1e with tricycloheptanes 2–4 (Fig. 1).
There is no doubt that the anticipated 1:1-adducts of these reac-
tions are of synthetic interest, owing to the considerable transfor-
mation potential of the acetylenic moiety as well as the sulfonyl
group.
After UV irradiation of equimolar amounts of tricycloheptane 2
with sulfones 1a–1c in CH2Cl2 at 20 °C in quartz tubes for 15–20 h,
the products of the addition to the C1–C7 bond were obtained as a
mixture of anti- and syn-isomers 5a–5c and 6a–6c with an admix-
ture of the sulfonylnorpinanes 7a–7c in the ratio of 4.9:1:0.2, 3.9:
1:0.2, and 4.9:1:0.3, respectively, with 40%–45% total yield (Scheme 1).
The structure of compounds 5a–5d, 6c, 8a–8c, 9a–9c isolated as
individual substances by column chromatography on silica gel
1
and (or) crystallization is confirmed by IR, H and 13C NMR spec-
troscopy data. We did not succeed in isolating syn-adducts 6a, 6b,
6d, so the latter compounds were characterized in the mixtures
with the respective anti-adducts 5a, 5b, 5d by the NMR spectra. To
wit, we have assigned the signals of all the non-aromatic carbon
atoms and the signals of the proton at the C-atom bearing a sul-
fonyl group. The configuration of compounds 5 and 6 at C6 and C7
were determined on the basis of analyzing the positions and mul-
1
tiplicities of the signals from H6 and H7 in the H NMR spectra
taking into account the known structure–spectrum correlations
Received 14 May 2012. Accepted 27 November 2012.
V.A. Vasin and Y.Y. Masterova. Department of Chemistry, N.P. Ogarev Mordovian State University, Saransk, 430005, Russian Federation.
V.V. Razin. Department of Chemistry, St. Petersburg State University, St. Petersburg, 198504, Russian Federation.
N.V. Somov. Department of Physics, N.I. Lobachevsky State University, Nizhny Novgorod, 603950, Russian Federation.
Corresponding author: V.A. Vasin (e-mail: orgchem@mrsu.ru).
Can. J. Chem. 91: 465–471 (2013) dx.doi.org/10.1139/cjc-2012-0159
Published at www.nrcresearchpress.com/cjc on 5 December 2012.

466
Can. J. Chem. Vol. 91, 2013
Fig. 1. Starting ethynylsulfones and tricyclo[4.1.0.02,7]heptanes.
Scheme 1. The reaction of compound 2 with ethynylsulfones 1a–1d.
Scheme 2. The reaction of compounds 3, 4 with ethynylsulfones
1a–1c.
substituent R type at this centre and is higher for hydrocarbons 3,
4 than for compound 2.15
Taking into account that a sulfur–carbon bond is stronger
than a sulfur–heteroatom bond, it was initially expected that
(phenylethynyl)sulfones would prove to be ineffective chain
transfer agents in a homolytic process. In particular, this is sug-
gested by the fact that the latter sulfones do not react with open-
chain and monocyclic olefins.4 We suppose that in our case, on
the one hand, the reaction is promoted by higher activity of the
central C1–C7 bond of tricycloheptanes 2–4 in comparison with
an alkene ␲-bond. This bond is readily opened by endo-directed
attack of an aryl sulfonyl radical at the bridgehead C-atom with
the formation of norpinanyl radical A16. On the other hand, it is
also promoted by high activity of the C'C bond in acetylenes
1a–1d with respect to alkyl radicals, caused by the possibility of
the benzyl stabilization of the intermediate, which allows us
to propose Scheme 3 by way of explanation of the obtained
results.
in the row of 6,7-disubstituted norpinanes.13 Thus, a triplet signal
of the proton at the sulfonyl-substituted C-atom indicates its anti
(exo) orientation in both the norpinanes 5 and 6. On the other
hand, the observation of a singlet signal of the proton at the
ethynyl-substituted C-atom attests to the syn (endo) orientation of
this proton in norpinanes 5. It was not possible to determine the
multiplicity of H6 in norpinane 6 because of the signal overlap
with H1,5. The anti (exo) orientation of the proton at the sulfonyl-
substituted C-atom in compound 6 is based on the observed chem-
ical shift value (ϳ3.4 ppm). This value is ϳ0.6 ppm less than the
chemical shift of the analogous proton in norpinane 5 because of
the phenylethynyl group deshielding effect in the latter. The anti
orientation of the geminal to a sulfonyl group proton in com-
pounds 8a–8c and 9a–9c is confirmed by observing its triplet
signal at ϳ4.35 ppm in the 1H NMR spectra. The endo orientation of
the phenyl group in compounds 9a–9c is connected with the
chemical shift value of the endo proton H3 (ϳ0.60–0.75 ppm)
located in the shielding field of the endo oriented phenyl
ring.6,8 The configuration at the tertiary C-atom of compounds
8a–8c and 9a–9c is accepted on the basis of the expected sim-
ilarity between the chemical shifts of the geminal to a sulfonyl
group protons. Compounds 7a–7c were identified in the reac-
tion mixtures by comparing them with authentic samples pre-
pared according to known procedures under oxidation of the
adducts of tricycloheptane 2 with thiophenol,14 p-thiocresol,11
and methanethiol,10 respectively, using hydrogen peroxide in
acetic acid.
In this scheme, radical B, formed by the regioselective attack of
radical A on the ␣-C-atom of acetylene 1a–1d, is proposed as an-
•
other key intermediate. Then, the elimination of RSO2 leads to
the formation of an ethynyl fragment, i.e., the resulting product is
formed by way of addition–elimination.17 A similar radical substi-
tution mechanism of a sulfo group in acetylenic sulfones and
related compounds has been previously reported.18 Apparently,
the preferred formation of the anti-adduct is connected with a
steric factor: the entrance of the reagent to the reaction centre of
radical A from the endo direction is sterically hindered by the
trimethylene bridge. In the case of less sterically hindered hy-
drocarbon 2, this direction is partially realised, and syn-adduct
6a–6d is formed in detectable amounts in the same way.
We propose that the sulfonyl radicals (RSO2•) required for the
initiation of the addition process are generated by the cleavage of
the C–S bond of acetylenic sulfones 1a–1d under thermolysis or
photolysis.19,20 Apparently, propynyl sulfone 1e does not react
with tricycloheptanes 2–4 the same way because of the less effec-
tive stabilization of the reaction centre in intermediate B by the
methyl group, by comparison with a phenyl substituent.
We have carried out the transformations of anti-adducts 5a, 9c
(Scheme 4). The hydration of the adducts by the method of
Kucherov (95% aqueous ethanol, HgSO4, 70 °C, 20 h)21 proceeded
strictly regioselectively and afforded the previously unknown
sulfonylketones of the norpinic row 10a, 11c. The same anti-
adducts 5a, 9c under treatment with KMnO4 in the presence of
the phase-transfer catalyst triethylbenzylammonium chloride
Thus, it can be stated that in the case of the reactions between
tricycloheptanes 2–4 and sulfones 1a–1d the regio- and stereose-
lectivity of the addition are similar to other sulfonylation reac-
tions of the mentioned hydrocarbons, which had been studied by
us earlier.5–12 In all the cases, 6-norpinanyl radical A stands as an
intermediate. Reagent transfer on its reaction centre proceeds
anti-selectively, while the extent of the selectivity depends on the
Published by NRC Research Press

Vasin et al.
467
Scheme 3. The proposed mechanism for the sulfoethynylation reaction of compounds 2–4.
Scheme 4. The transformations of anti-adducts 5a, 9c.
(TEBA-Cl),22 were oxidized to diketones 12a, 13c. As was ex-
pected, these reactions proceeded on the C'C bond only, and the
configurations at C6 and C7 remained the same, as confirmed by
the 1H NMR spectra.
Fig. 2. X-ray molecular structure of the tricyclic sulfone 14 with the
atom numbering system used in the crystallographic analysis. The
non-H atoms are shown with displacement ellipsoids drawn at
the 50% probability level.
When the solution of ketone 11c in toluene was heated at reflux
in the presence of powdered KOH and a catalytical amount of
TEBA-Cl for 5 h,23 this led to the formation of the cyclic sulfone 14.
This transformation includes base-catalyzed epimerization at the
C7 atom, with the formation of intermediate product C and cycl-
ization of the latter by intramolecular aldol condensation pro-
ceeding with strictly regioselective dehydration.23
We have carried out the desulfonylation of anti-adduct 5a by
treatment with 6% sodium amalgam in methanol in the presence
of NaH2PO4.4 The structure of the resultant 6-(phenylethynyl)
1
norpinane 15 is confirmed by IR, H, and 13C NMR spectroscopy
data and mass spectrum analysis.
The structure of the tricyclic unsaturated sulfone 14 was as-
signed unequivocally by X-ray crystallography (Fig. 2, Table 1) and
confirmed by IR, 1H, and 13C NMR spectroscopy data.
Conclusions
The method presented herein for acetylenyl norpinanyl sul-
fones, and the methods of refunctionalization and desulfonation
demonstrate the considerable potentialities for further transfor-
mation of the products from reaction between quite available
tricyclo[4.1.0.02,7]heptanes and (phenylethynyl)sulfones.
KAP5, 15 m × 9.25 mm × 0.25 ␮m; carrier gas helium, flow rate 1 mL
min−1;temperature was programmed from 50 to 250 °C; ionization
by electronic impact, Uion at 70 eV. Analytical TLC was performed
by Sorbfil plates: eluent, low-boiling petroleum ether–acetone,
10–6:1; developer, iodine. Column chromatography was per-
formed on silica gel Merck 60 (0.040–0.063 mm−1); eluent, low-
boiling petroleum ether –acetone, 6:1. A mercury-discharge high
pressure lamp DRT-400 (400 W, ␭ = 240–320 nm) and halogen
filament lamp KGLN-500 were used for the photochemical reac-
tions. Suitable crystals for X-ray crystallographic study of 14 were
Experimental section
General
All melting points reported are uncorrected. H and 13C NMR
1
spectra were recorded in CDCl3 on a Bruker AMX-400 spectrome-
ter (400 and 100 MHz, respectively). IR spectra were measured on
a Fourier Spectrometer InfraLum FT-02 (KBr pellets). Elemental
analyses were carried out by a CHNS analyzer VarioMICRO. Mass
spectra were recorded using a KONIK RBK-HRGC5000B-MSQ12 sys-
tem (KONIXBERT HI-TECH, S.A., Spain) equipped with a column
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468
Can. J. Chem. Vol. 91, 2013
Table 1. Crystallographic data and selected data collection parame-
ters for the sulfone 14.
(2.65 g, 6.55 mmol) in dry benzene (30 mL), NEt3 (0.86 g, 1.2 mL,
8.52 mmol) was added. The mixture was stirred at 20 °C for 80 h.
Precipitated triethylammonium iodide was filtered and washed
with dry benzene (10 mL). The solvent was removed under reduced
pressure, and the residue was recrystallized (ethanol – low-boiling
petroleum ether, 2:1) to afford 1d as a colourless solid. Yield: 1.50 g
(82.8%); mp 103–104 °C; lit. value32 mp 104–105 °C. 1H NMR ␦ (ppm):
7.50 (t, J = 7.6 Hz, 2H, H-Ar), 7.58–7.67 (m, 3H, H-Ar), 7.69, (d, J =
8.8 Hz, 2H, H-Ar), 8.13 (d, J = 8.8 Hz, 2H, H-Ar). 13C NMR ␦ (ppm):
85.0, 94.0 (C'C); 117.6, 128.7, 128.9, 129.7, 131.7, 132.8, 140.2, 141.0
(C-Ar). IR (KBr, cm−1): 540 (m), 663 (s), 756 (s), 852 (s), 1011 (m), 1084
(s), 1157 (vs), 1331 (s), 1443 (m), 2183 (s). Anal. calcd. for C14H9ClO2S
(%): C 60.76, H 3.28, S 11.58; found: C 60.69, H 3.34, S 11.48.
Parameter
Value
Empirical formula
C22H22O2S
Formula weight
350.46
Colour, habit
Colourless, block
Crystal dimensions (mm)
0.50 × 0.31 × 0.28
Crystal system
Monoclinic
Space group
P 21/c
Z
4
a (Å)
8.9080 (4)
b (Å)
17.3582 (7)
c (Å)
12.1245 (6)
␣ (°)
␤ (°)
␥ (°)
90
General procedure for photochemical reaction of tricycloheptane
(2) with (phenylethynyl)sulfones (1a–1d)
101.415 (5)
90
A solution of tricycloheptane 2 (0.28 g, 3 mmol) and (phenylethynyl)
sulfone 1 (3 mmol) in dry CH2Cl2 (12 mL) in a hermetically closed
quartz test tube was irradiated by mercury lamp at 20 °C for 15–20 h.
After evaporation of the solvent the residue was analyzed by TLC
and 1H NMR methods and chromatographed on silica gel.
Collection ranges
−7 ≤ h ≤ 8; −13 ≤ k ≤ 13; −15 ≤ l ≤ 15
1837.69 (14)
1.267
Mo K␣ (␭ = 0.71073 Å)
0.188
744
Volume (Å3)
D
calcd (Mg/m3)
Radiation
Absorption coefficient (␮) (mm−1)
F(000)
␪ range for data collection (°)
Observed reflections
Independent reflections
Rint
3.51–26.37
8282
3684
0.0386
3684/0/227
1.074
7-syn-Benzenesulfonyl-6-exo-(phenylethynyl)bicyclo[3.1.1]heptane
(5a)
Colourless solid. Yield: 0.51 g (43.6%); mp 129–130 °C; Rf = 0.38.
1H NMR ␦ (ppm): 1.78–1.93 (m, 1H, endo-H3), 1.95–2.14 (m, 3H,
exo-H3 and endo-H2,4), 2.62–2.75 (m, 2H, exo-H2,4), 2.84–2.92 (m,
2H, H1,5), 2.89 (s, 1H, H6), 4.04 (t, J = 5.7 Hz, 1H, H7), 7.25–7.32 (m,
3H, H-Ar), 7.33–7.40 (m, 2H, H-Ar), 7.58 (t, J = 7.5 Hz, 2H, H-Ar), 7.65
(t, J = 7.3 Hz, 1H, H-Ar), 7.92 (d, J = 7.6 Hz, 2H, H-Ar). 13C NMR ␦
(ppm): 13.9 (C3), 23.3 (C2,4), 32.0 (C7), 45.3(C1,5), 61.1 (C6); 82.6, 90.0
(C'C); 123.0, 127.5, 128.0, 128.2, 129.3, 131.5, 133.4, 140.2 (C-Ar). IR
(KBr, cm−1): 621 (s), 691 (s), 729 (s), 756 (m), 1150 (vs), 1285 (s), 1316 (s),
1447 (m), 1489 (m), 2222 (w), 2951 (m). Anal. calcd. for C21H20O2S
(%): C 74.97, H 5.99, S 9.53; found: C 74.86, H 6.12, S 9.31.
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2␴(I)]
R indices (all data)
R(F) = 0.0412, wR(F2) = 0.104
R(F) = 0.0459, wR(F2) = 0.107
0.293 and −0.303
Largest diff. peak and hole (e Å−3
)
obtained by crystallization from acetone – low-boiling petroleum
ether (1:7). A single crystal was measured with an Oxford Diffrac-
tion Xcalibur XGemini S diffractometer equipped with a CCD-
detector SAPPHIRE III at a temperature of 298(2) K. An analytical
absorption correction with the program CrysAlisPro (Agilent
Technologies, 2011)24 gave a correction factor between 0.362 and
0.577. Analytical numeric absorption correction using a multifac-
eted crystal model was based on expressions derived by R. C. Clark
and J. S. Reid.25 The structure was determined by direct methods
using the program SHELXS.26 Refinement was performed with
the program SHELXL-97.26 Positions of hydrogen atoms were
inferred from neighbouring sites and refined in the “riding
model” (Uiso(H) = 1.2Uequiv(carbon) Å2). Crystallographic data
and selected data collection parameters are reported in Table 1.
7-syn-Benzenesulfonyl-6-endo-(phenylethynyl)bicyclo[3.1.1]hep-
tane (6a)
Fragment of 1H NMR ␦ (ppm): 3.37 (t, J = 5.6 Hz, H7). Fragment of
13C NMR ␦ (ppm): 13.9 (C3), 21.2 (C2,4), 31.6 (C6), 43.5 (C1,5), 61.5
(C7); 84.5, 86.2 (C'C).
6-exo-(Phenylethynyl)-7-syn-p-toluenesulfonylbicyclo[3.1.1]hep-
tane (5b)
Colourless solid. Yield: 0.51 g (41.6%); mp 139–140 °C; Rf = 0.40.
1H NMR ␦ (ppm): 1.79–1.92 (m, 1H, endo-H3),1.94–2.12 (m, 3H, exo-H3
and endo-H2,4), 2.46 (s, 3H, CH3), 2.63–2.74 (m, 2H, exo-H2,4), 2.85–
2.89 (m, 2H, H1,5), 2.89 (s, 1H, H6), 4.02 (t, J = 5.9 Hz, 1H, H7),
7.27–7.31 (m, 3H, H-Ar), 7.34–7.39 (m, 4H, H-Ar), 7.79 (d, J = 8.3 Hz,
2H, H-Ar). 13C NMR ␦ (ppm): 13.9 (C3), 21.5 (CH3), 23.3 (C2,4), 31.9
(C6), 45.2 (C1,5), 61.1 (C7); 82.5, 90.1 (C'C); 123.1, 127.5, 127.9, 128.2,
129.9, 131.5, 137.3, 144.3 (C-Ar). IR (KBr, cm−1): 602 (m), 679 (s), 756 (m),
814 (m), 1150 (s), 1285 (vs), 1316 (s), 1489 (w), 1597 (w), 2222 (vw),
2951 (w). Anal. calcd. for C22H22O2S (%): C 75.40, H 6.33, S 9.15; found:
C 75.35, H 6.34, S 8.82.
Materials and reagents
Solvents (acetone, ether, benzene, methanol, low-boiling pe-
troleum ether) were purified by known methods. Tricyclohep-
tanes 2,27 328, and 429,30 as well as phenyl-,31 p-tolyl- and methyl
(phenylethynyl)sulfones19 were prepared according to procedures
in the literature.
1-Chloro-4-(phenylethynylsulfonyl)benzene (1d)
To a solution of Na2SO3 (2.75 g, 21.8 mmol) and NaHCO3 (3.66 g,
43.6 mmol) in water (40 mL), 4-chlorobenzenesulfonylchloride (4.60
g, 21.8 mmol) was added at 20 °C under stirring. The reaction
mixture was stirred at 70 °C for 5 h and then extracted with ether
(3 × 55 mL). Then I2 (3.65 g, 14.4 mmol) in benzene (55 mL) was
added to the prepared water solution. The organic layer was sep-
arated, dried with MgSO4 for 1 h, and then filtered. To the filtered
solution, phenylacetylene (1.76 g, 1.9 mL, 17.2 mmol) was added
and the reaction mixture was irradiated by halogen lamp at 20 °C
for 3.5 h. The solvent was removed under reduced pressure, and
the residue was washed with ethanol – low-boiling petroleum
ether (1:1) to afford 1-chloro-4-(2-iodo-2-phenylvinylsulfonyl)benzene
(2.8 g, 31.8%) as a colourless solid. To a solution of the latter product
6-endo-(Phenylethynyl)-7-syn-p-toluenesulfonylbicyclo[3.1.1]heptane
(6b)
Fragment of 1H NMR ␦ (ppm): 3.34 (t, J = 5.3 Hz, H7). Fragment of
13C NMR ␦ (ppm): 13.9 (C3), 21.2 (CH3), 23.4 (C2,4), 31.6 (C6), 43.4
(C1,5), 61.5 (C7); 84.5, 88.2 (C'C).
7-syn-Methylsulfonyl–6-exo-(phenylethynyl)bicyclo[3.1.1]heptane
(5c)
Colourless solid. Yield: 0.39 g (40.9%); mp 125–126 °C; Rf = 0.23.
1H NMR ␦ (ppm): 1.75–1.87 (m, 1H, endo-H3), 1.89–2.01 (m, 3H,
exo-H3 and endo-H2,4), 2.48–2.59 (m, 2H, exo-H2,4), 2.86 (s, 3H,
CH3), 2.89 (s, 1H, H6), 2.98–3.04 (m, 2H, H1,5), 4.08 (t, J = 5.8 Hz, 1H,
H7), 7.30–7.31 (m, 3H, H-Ar), 7.40–7.43 (m, 2H, H-Ar). 13C NMR ␦
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Vasin et al.
469
(ppm): 13.7 (C3), 23.0 (C2,4), 32.3 (C7), 41.6 (CH3), 45.2 (C1,5), 59.3
(C6); 82.8, 89.9 (C'C); 123.0, 128.0, 128.3, 131.5 (C-Ar). IR (KBr, cm−1):
694 (m), 764 (vs), 960 (w), 1157 (m), 1281 (vs), 1315 (m), 1489 (w), 2222
(vw), 2870 (w), 2955 (w). Anal. calcd. for C16H18O2S (%): C 70.04, H 6.61,
S 11.68; found: C 69.91, H 6.49, S 11.69.
7-syn-Benzenesulfonyl-6-endo-methyl-6-exo-
(phenylethynyl)bicyclo[3.1.1]heptane (8a)
Colourless solid. Yield: 0.68 g (53.6%); mp 88–89 °C; Rf = 0.41.
1H NMR ␦ (ppm): 1.41 (s, 3H, CH3), 1.62–1.76 (m, 1H, endo-H3), 1.91–
2.04 (m, 2H, endo-H2,4), 2.23–2.38 (m, 1H, exo-H3), 2.43–2.54 (m, 2H,
exo-H2,4), 2.81 (br.d, 2H, H1,5), 4.23 (t, J = 5.7 Hz, 1H, H7), 7.25–7.31
(m, 3H, H-Ar), 7.31–7.37 (m, 2H, H-Ar), 7.58 (t, J = 7.3 Hz, 2H, H-Ar),
7.65 (t, J = 7.5 Hz, 1H, H-Ar), 7.94 (d, J = 7.6 Hz, 2H, H-Ar). 13C NMR
␦ (ppm): 13.2 (C3), 16.6 (CH3 C6), 20.7 (C2,4), 37.1 (C6), 48.0 (C1,5),
61.9 (C7); 80.4, 95.6 (C'C); 123.2, 127.3, 127.8, 128.2, 129.3, 131.5,
133.3, 140.7 (C-Ar). IR (KBr, cm−1): 606 (vs), 691 (s), 721 (s), 764 (s),
1088 (m), 1150 (vs), 1281 (s), 1304 (s), 1485 (m), 1447 (m), 2215 (vw),
2967 (m). Anal. calcd. for C22H22O2S (%): C 75.40, H 6.33, S 9.15;
found: C 75.40, H 6.32, S 9.36.
7-syn-Methylsulfonyl-6-endo-(phenylethynyl)bicyclo[3.1.1]heptane
(6c)
Colourless solid. Yield: 75.0 mg (7.8%); mp 161–162 °C; Rf = 0.17.
1H NMR ␦ (ppm): 1.97–2.07 (m, 2H, H3), 2.12–2.22 (m, 2H, endo-H2,4),
2.35–2.45 (m, 2H, exo-H2,4), 2.89 (s, 3H, CH3), 3.06–3.10 (m, 3H, H1,5
and H6), 3.42 (t, J = 5.3 Hz, 1H, H7), 7.30–7.33 (m, 3H, H-Ar), 7.41–
7.44 (m, 2H, H-Ar). 13C NMR ␦ (ppm): 13.6 (C3), 20.7 (C2,4), 31.6 (C6),
41.9 (CH3), 43.1 (C1,5), 59.5 (C7); 84.5, 85.9 (C'C); 123.1, 128.1, 128.3,
131.6 (C-Ar). IR (KBr, cm−1): 544 (m), 691 (m), 756 (vs), 961 (m), 1096 (m), 1142
(s), 1254 (m), 1293 (m), 1323 (s), 1443 (m), 1489 (vs), 2218 (vw), 2959 (w).
Anal. calcd. for C16H18O2S (%): C 70.04, H 6.61, S 11.68; found: C 69.92,
H 6.70, S 11.59.
6-endo-Methyl-6-exo-(phenylethynyl)-7-syn-
p-toluentsulfonylbicyclo[3.1.1]heptane (8b)
Colourless solid. Yield: 0.58 g (52.9%); mp 118–119 °C; Rf = 0.53.
1H NMR ␦ (ppm): 1.45 (s, 3H, CH3C6), 1.66–1.79 (m, 1H, endo-H3),
1.97–2.07 (m, 2H, endo-H2,4), 2.28–2.41 (m, 1H, exo-H3), 2.50 (s, 3H,
CH3C6H4), 2.47–2.58 (m, 2H, exo-H2,4), 2.84 (br.d, J = 5.6 Hz, 2H,
H1,5), 4.25 (t, J = 5.7 Hz, 1H, H7), 7.30–7.36 (m, 3H, H-Ar), 7.37–7.44
(m, 4H, H-Ar), 7.86 (d, J = 8.3 Hz, 2H, H-Ar). 13C NMR ␦ (ppm): 13.2
(C3), 16.6 (CH3C6), 20.7 (C2,4), 21.5 (CH3C6H4), 37.1 (C6), 47.9 (C1,5),
62.0 (C7); 80.4, 95.8 (C'C); 123.2, 127.4, 127.8, 128.2, 129.9, 131.5,
137.8, 144.1 (C-Ar). IR (KBr, cm−1): 671 (s), 760 (s), 1088 (m), 1146 (vs),
1281 (m), 1439 (w), 1311 (m), 1489 (w), 1597 (w), 2218 (vw), 2874 (w).
Anal. calcd. for C23H24O2S (%): C 75.79, H 6.64, S 8.80; found: C
75.71, H 6.62, S 8.97.
7-syn-(p-Chlorobenzenesulfonyl)-6-exo-
(phenylethynyl)bicyclo[3.1.1]heptane (5d)
Colourless solid. Yield: 0.42 g (37.8%); mp 160–161 °C; Rf = 0.59.
1H NMR ␦ (ppm): 1.80–1.90 (m, 1H, endo-H3), 1.96–2.09 (m, 3H,
exo-H3 and endo-H2,4), 2.61–2.65 (m, 2H, exo-H2,4), 2.86–2.89 (m,
3H, H1,5 and H6), 3.99 (t, J = 6.0 Hz, 1H, H7), 7.27–7.29 (m, 3H, H-Ar),
7.34–7.35 (m, 2H, H-Ar), 7.54 (d, J = 8.9 Hz, 2H, H-Ar), 7.84 (d, J = 8.9
Hz, 2H, H-Ar). 13C NMR ␦ (ppm): 14.0 (C3), 23.5 (C2,4), 32.2 (C6), 45.5
(C1,5), 61.6 (C7); 82.8, 90.0 (C'C); 123.1, 128.2, 128.4, 129.2, 129.9,
131.7, 138.8, 140.4 (C-Ar). IR (KBr, cm−1): 644 (m), 756 (s), 1088 (m),
1149 (vs), 1277 (m), 1319 (m), 1473 (w), 1574 (w), 2226 (vw), 2951 (w).
Anal. calcd. for C21H19ClO2S (%): C 68.01, H 5.16, S 8.64; found: C 68.11,
H 5.26, S 8.53.
6-endo-Methyl-7-syn-methylsulfonyl-6-exo-
(phenylethynyl)bicyclo[3.1.1]heptane (8c)
Colourless solid. Yield: 0.44 g (50.5%); mp 122–123 °C; Rf = 0.37.
1H NMR ␦ (ppm): 1.41 (s, 3H, CH3 C6), 1.57–1.73 (m, 1H, endo-H3),
1.89–2.00 (m, 2H, endo-H2,4), 2.05–2.19 (m, 1H, exo-H3), 2.30–2.42
(m, 2H, exo-H2,4), 2.91 (s, 3H, CH3SO2), 2.91–2.96 (m, 2H, H1,5), 4.22
(t, J = 5.6 Hz, 1H, H7), 7.29–7.34 (m, 3H, H-Ar), 7.40–7.44 (m, 2H,
H-Ar). 13C NMR ␦ (ppm): 13.0 (C3), 16.5 (CH3C6), 20.4 (C2,4), 37.2
(C6), 42.0 (CH3SO2), 47.9 (C1,5), 60.2 (C7); 80.7, 95.6 (C'C); 123.2,
128.0, 128.3, 131.6 (C-Ar). IR (KBr, cm−1): 559 (m), 694 (m), 760 (s),
1142 (s), 1284 (vs), 1304 (m), 1447 (w), 1447 (w), 1489 (w), 2230 (vw),
2948 (m). Anal. calcd. for C17H20O2S (%): C 70.80, H 6.99, S 11.12;
found: C 70.71, H 7.07, S 11.02.
7-syn-(p-Chlorobenzenesulfonyl)-6-endo-
(phenylethynyl)bicyclo[3.1.1]heptane (6d)
1
Fragment of H NMR ␦ (ppm): 3.30 (t, J = 5.7 Hz, 1H, H7) ppm.
Fragment of 13C NMR ␦ (ppm): 13.9 (C3), 21.2 (C2,4), 31.7 (C7), 43.5
(C1,5), 61.5 (C6); 85.1, 86.1 (C'C).
General procedure for thermal reaction of tricycloheptane (2)
with (phenylethynyl)sulfones (1b, 1c)
Method A
A mixture of tricycloheptane 2 (0.564 g, 6 mmol) and
(phenylethynyl)sulfone 1b, 1c (3 mmol) in a heat-resistant glass
ampule was purged with argon, fused, and heated at 110 °C for
6–8 h. Then an ampule was opened, and the content was analyzed
by TLC and H NMR methods. The products 5, 6, and 7 were ob-
tained in the ratio of 5.0:1:0.2 and 5.2:1:0.2, respectively.
7-syn-Benzenesulfonyl-6-endo-phenyl-6-exo-
(phenylethynyl)bicyclo[3.1.1]heptane (9a)
Colourless solid. Yield: 0.63 g (51.0%); mp 182–183 °C; Rf = 0.38.
1H NMR ␦ (ppm): 0.66–0.80 (m, 1H, endo-H3), 1.61–1.74 (m, 1H, exo-
H3), 2.04–2.16 (m, 2H, endo-H2,4), 2.64–2.77 (m, 2H, exo-H2,4), 3.36–
3.42 (m, 2H, H1,5), 4.36 (t, J = 5.7 Hz, 1H, H7), 7.21–7.34 (m, 8H, H-Ar),
7.40 (t, J = 7.4 Hz, 2H, H-Ar), 7.63 (t, J = 7.4 Hz, 2H, H-Ar), 7.70 (t, J =
7.3 Hz, 1H, H-Ar), 8.00 (d, J = 7.2 Hz, 2H, H-Ar). 13C NMR ␦ (ppm): 13.0
(C3), 21.0 (C2,4), 43.5 (C6), 48.3 (C1,5), 60.4 (C7); 82.8, 94.2 (C'C);
123.0, 125.8, 126.7, 127.5, 127.9, 128.1, 128.6, 129.4, 131.5, 133.5, 139.2,
140.4 (C-Ar). IR (KBr, cm−1): 617 (s), 721 (s), 764 (s), 1088 (m), 1150 (vs),
1285 (m), 1312 (m), 1447 (m), 1489 (w), 2223 (vw), 2955 (w). Anal.
calcd. for C27H24O2S (%): C 78.61, H 5.86, S 7.77; found: C 78.65, H
5.80, S 7.79.
1
Method B
A solution of tricycloheptane 2 (0.282 g, 3 mmol) and
(phenylethynyl)sulfone 1c (3 mmol) in toluene (25 mL), under ar-
gon, was heated at reflux for 10 h in round-bottomed flask
equipped with backflow condenser. After removing of the solvent
by a water-jet air pump, the residue was analyzed by TLC and
1H NMR methods. The products 5c, 6c, and 7c were obtained in the
ratio of 3.6:1:0.2.
6-endo-Phenyl-6-exo-(phenylethynyl)-7-syn-
p-toluenesulfonylbicyclo[3.1.1]heptane (9b)
General procedure for photochemical reaction of tricycloheptanes
(3, 4) with (phenylethynyl)sulfones (1a–1c)
Colourless solid. Yield: 0.64 g (50.3%); mp 162–163 °C; Rf = 0.34.
1H NMR ␦ (ppm): 0.63–0.77 (m, 1H, endo-H3), 1.59–1.70 (m, 1H, exo-
H3), 2.01–2.13 (m, 2H, endo-H2,4), 2.47 (s, 3H, CH3), 2.61–2.72 (m,
2H, exo-H2,4), 3.32–3.38 (m, 2H, H1,5), 4.31 (t, J = 5.7 Hz, 1H, H7),
7.20–7.33 (m, 8H, H-Ar), 7.35–7.43 (m, 4H, H-Ar), 7.86 (d, J = 8.3 Hz,
2H, H-Ar). 13C NMR ␦ (ppm): 13.1 (C3), 21.0 (C2,4), 21.6 (CH3), 43.5
(C6), 48.3 (C1,5), 60.5 (C7); 82.7, 94.3 (C'C); 123.1, 125.8, 126.7, 127.6,
A solution of tricycloheptanes 3, 4 (4.5 mmol) and (phenylethynyl)
sulfones 2a–2c (3 mmol) in dry CH2Cl2 (12 mL) in a hermetically
closed quartz test tube was irradiated by mercury lamp at 20 °C for
15–20 h. Then the solvent was removed by a water-jet air pump.
The products were isolated from the residue by column chroma-
tography on silica gel and crystallization from ether.
Published by NRC Research Press

470
Can. J. Chem. Vol. 91, 2013
127.9, 128.1, 128.6, 130.0, 131.5, 137.6, 139.3, 144.4 (C-Ar). IR (KBr,
cm−1): 602 (m), 671 (vs), 760 (m), 1088 (m), 1150 (vs), 1285 (s), 1312 (m),
1447 (w), 1493 (w), 1597 (m), 2222 (vw), 2955 (m). Anal. calcd. for
C28H26O2S (%): C 78.84, H 6.14, S 7.52; found: C 78.75, H 6.19, S 7.59.
70.8 (C2), 125.1 (C-Ar), 126.1 (C=C), 126.3, 127.6 (C-Ar), 128.4 (C=C);
128.5, 128.9, 141.6, 142.6, 145.4 (C-Ar). IR (KBr, cm−1): 702 (s), 756 (m),
1119 (vs), 1246 (w), 1296 (s), 1311 (w), 1446 (m), 1493 (w), 2862 (w),
2939 (w). Anal. calcd. for C22H22O2S (%): C 75.40, H 6.33, S 9.15.
Found: C 75.38, H 6.37, S 9.11.
7-syn-Methylsulfonyl-6-endo-phenyl-6-exo-
(phenylethynyl)bicyclo[3.1.1]heptane (9c)
General procedure for oxidation of anti-adducts (5a, 9c)
Colourless solid. Yield: 0.57 g (54.2%); mp 160–161 °C; Rf = 0.22.
1H NMR ␦ (ppm): 0.61–0.74 (m, 1H, endo-H3), 1.46–1.60 (m, 1H, exo-
H3), 2.00–2.12 (m, 2H, endo-H2,4), 2.46–2.58 (m, 2H, exo-H2,4), 2.95
(s, 3H, CH3), 3.48–3.54 (m, 2H, H1,5), 4.37 (t, J = 5.6 Hz, 1H, H7),
7.24–7.36 (m, 8H, H-Ar), 7.41 (t, J = 7.4 Hz, 2H, H-Ar). 13C NMR ␦
(ppm): 12.8 (C3), 20.6 (C2,4), 41.9 (C1,5), 43.5 (C6), 48.2 (CH3), 58.5
(C7); 83.0, 94.1 (C'C); 122.9, 125.7, 126.7, 128.0, 128.1, 128.6, 131.5,
138.9 (C-Ar). IR (KBr, cm−1): 548 (m), 710 (m), 764 (m), 957 (m), 1142
(vs), 1285 (s), 1304 (m), 1455 (w), 1489 (w), 2226 (vw), 2948 (w). Anal.
calcd. for C22H22O2S (%): C 75.40, H 6.33, S 9.15; found: C 75.12, H
6.27, S 8.93.
To a solution containing anti-adducts 5a, 9c (3 mmol), CH3COOH (7.4
mL) and TEBA-Cl (0.34 g, 1.5 mmol) in CH2Cl2 (25 mL), a solution of
KMnO4 (1.90 g, 12 mmol) in H2O (40 mL) was added. The reaction
mixture was heated at reflux and stirred for 12 h, then the excess
of KMnO4 and formed MnO2 were removed by the addition of
small portions of Na2SO3. The organic layer was separated and
washed with water, the water layer was extracted by CH2Cl2 (2 × 15
mL). The combined extract was dried with MgSO4. Then the sol-
vent was removed under reduced pressure, and the aimed products
were purified by crystallization (n-pentane–CHCl3).
7-syn-Benzenesulfonyl-6-exo-(1=,2=-dioxo-2=-
General procedure for hydration of anti-adducts (5a, 9b)
A solution of anti-adducts 5a, 9b (3 mmol) in 95% aqueous eth-
anol (60 mL) in the presence of catalytic amounts of HgSO4 and
H2SO4 was heated at reflux at 70 °C for 20 h. The solvent was
removed under reduced pressure, the aimed products were puri-
fied by crystallization from ethanol.
phenylethyl)bicyclo[3.1.1]heptane (12a)
Pale-yellow solid. Yield: 0.96 g (86.7%); mp 117–118 °C. 1H NMR ␦
(ppm): 1.84–1.98 (m, 1H, endo-H3), 2.10–2.21 (m, 1H, exo-H3), 1.99–
2.10 (m, 2H, endo-H2,4), 2.68–2.80 (m, 2H, exo-H2,4), 3.14 (br.s, 2H,
H1,5), 3.46 (s, 1H, H6), 3.86 (t, J = 5.7 Hz, 1H, H7), 7.50 (t, J = 7.6 Hz,
2H, H-Ar), 7.58 (d, J = 7.5 Hz, 2H, H-Ar), 7.62–7.70 (m, 2H, H-Ar), 7.89
(d, J = 7.3 Hz, 2H, H-Ar), 7.95 (d, J = 7.3 Hz, 2H, H-Ar). 13C NMR ␦
(ppm): 14.2 (C3), 23.9 (C2,4), 41. 7 (C1,5), 48.1 (C6), 59.5 (C7); 127.5,
128.9, 129.4, 130.2, 131.9, 133.6, 134.9, 140.1 (C-Ar), 191.3, 202.1 (C=O).
IR (KBr, cm−1): 610 (s), 691 (m), 725 (m), 1150 (vs), 1281 (m), 1447 (m),
1678 (s), 1694 (m), 2959 (w). Anal. calcd. for C21H20O4S (%): C 68.47,
H 5.47, S 8.70; found: C 68.39, H 5.40, S 8.67.
7-syn-Benzenesulfonyl-6-exo-(benzoylmethyl)bicyclo[3.1.1]heptane
(10a)
Colourless solid. Yield: 0.72 g (67.9%); mp 149–150 °C. 1H NMR ␦
(ppm): 1.89–2.12 (m, 5H, H3 and endo-H2,4), 2.48 (t, J = 7.5 Hz, 1H,
H6), 2.57 (br.d, J = 5.9 Hz, 2H, H1,5), 2.61–2.72 (m, 2H, exo-H2,4), 3.18
(d, J = 7.5 Hz, 2H, CH2C=O), 3.60 (t, J = 5.9 Hz, 1H, H7), 7.46 (t, J =
7.6 Hz, 2H, H-Ar), 7.53–7.60 (m, 3H, H-Ar), 7.61–7.67 (m, 1H, H-Ar),
7.86–7.94 (m, 4H, H-Ar). 13C NMR ␦ (ppm): 14.1 (C3), 24.3 (C2,4), 36.8
(C6), 38.9 (C1,5), 42.2 (CH2C=O), 60.5 (C7); 127.3, 127.8, 128.6, 129.2,
133.2, 136.5, 140.5 (C-Ar), 198.4 (C = O). IR (KBr, cm−1): 617 (m), 691
(m), 722 (m), 1088 (m), 1146 (vs), 1280 (m), 1316 (m), 1447 (m), 1678 (s),
2948 (m). Anal. calcd. for C21H22O3S (%): C 71.16, H 6.26, S 9.04;
found C 71.08, H 6.20, S 9.00.
6-exo-(1=,2=-Dioxo-2=-phenylethyl)-7-syn-methylsulfonyl-6-endo-
phenylbicyclo[3.1.1]heptane (13c)
Pale-yellow solid. Yield: 1.04 g (86.7%); mp 189–190 °C. 1H NMR ␦
(ppm): 0.64–0.79 (m, 1H, endo-H3), 1.50–1.65 (m, 1H, exo-H3), 2.02–
2.17 (m, 2H, endo-H2,4), 2.55–2.69 (m, 2H, exo-H2,4), 2.94 (s, 3H,
CH3), 3.70 (t, J = 5.7 Hz, 1H, H7), 4.08 (br.d, 2H, H1,5), 7.14–7.32 m
(9H, H-Ar), 7.45 (d, J = 7.2 Hz, 1H, H-Ar). 13C NMR ␦ (ppm): 13.3 (C3),
20.6 (C2,4), 41.9 (CH3), 43.8 (C1,5), 57.1 (C7), 60.8 w (C6); 128.1, 128.15,
128.3, 129.1, 132.0, 132.2, 134.2 (C-Ar), 194.7, 200.3 (C=O). IR (KBr,
cm−1): 648 (m), 706 (m), 752 (m), 1142 (vs), 1285 (m), 1304 (m), 1451
(m), 1663 (s), 1694 (m), 2963 (w). Anal. calcd. for C22H22O4S (%):
C 69.09, H 5.80, S 8.38; found: C 68.27, H 5.83, S 8.62.
6-exo-(Benzoylmethyl)-7-syn-methylsulfonyl-6-endo-
phenylbicyclo[3.1.1]heptane (11c)
Colourless solid. Yield: 0.66 g (62.6%); mp 208–209 °C. 1H NMR ␦
(ppm): 0.54–0.66 (m, 1H, endo-H3), 1.45–1.54 (m, 1H, exo-H3), 2.07 (t,
J = 12.1 Hz, 2H, endo-H2,4), 2.45–2.53 (m, 2H, exo-H2,4), 2.94 (s, 3H,
CH3), 3.41 (s, 2H, CH2C=O), 3.47 (br.d, 2H, H1,5), 3.98 (t, J = 5.7 Hz,
1H, H7), 7.13 (t, J = 6.7 Hz, 3H, H-Ar), 7.20 (t, J = 7.4 Hz, 2H, H-Ar), 7.27
(t, J = 7.8 Hz, 2H, H-Ar), 7.43 (t, J = 7.4 Hz, 1H, H-Ar), 7.51–7.53 (m,
2H, H-Ar). 13C NMR ␦ (ppm): 13.3 (C3), 21.4 (C2,4), 41.8 (CH3), 44.5
(C1,5), 46.4 (CH2C=O), 48.0 (C6), 57.8 (C7); 126.1, 126.5, 127.8, 128.0,
128.2, 132.8, 137.4, 141.5 (C-Ar), 199.0 (C=O). IR (KBr, cm−1): 706 (m),
760 (s), 1134 (vs), 1269 (m), 1289 (s), 1319 (m), 1455 (m), 1655 (vs), 2951
(m), 2971 (m). Anal. calcd. for C22H24O3S (%): C 71.71, H 6.57, S 8.69;
found: C 71.69, H 6.37, S 8.42.
Desulfonylation of anti-adduct (5a)
6-exo-(Phenylethynyl)bicyclo[3.1.1]heptane (15)
A mixture of 5a (0.84 g, 2.5 mmol) and NaH2PO4 (5.2 g,
43.3 mmol) in dry methanol (30 mL) was stirred under argon for 15
min. While efficiently stirred, 6% sodium amalgam (7.66 g) was
added in portions. The reaction mixture was kept stirring for 10 h,
and NaH2PO4 (5.2 g, 43.3 mmol) was added. Then 6% sodium amal-
gam (7.66 g) was added in portions, and the reaction mixture was
kept stirring for 8 h. Then the reaction mixture was filtered and
the solvent was removed under reduced pressure. The residue was
dissolved in CH2Cl2 (15 mL), washed to neutrality with water, and
dried with MgSO4. The solvent was removed under reduced pres-
sure, and distillation of the residue afforded 15 as a colourless oil.
Yield: 0.38 g (77.6%); bp 117 °C (1 mm Hg). 1H NMR ␦ (ppm): 1.48 (dd,
1H, J4 = 5.9 and J2 = 9.2 Hz, syn-H7), 1.72–1.82 (m, 1 H, exo-H3),
1.82–2.00 (m, 5H, endo-H3 and H2,4), 2.49–2.55 (m, 2H, H1,5), 2.56
(d, J4 = 5.9 Hz, 1H, endo-H6), 2.66 (dt, J3 = 6.3 and J2 = 9.2 Hz, 1H,
anti-H7), 7.26–7.35 (m, 3H, H-Ar), 7.42–7.49 (m, 2 H, H-Ar). 13C NMR
␦ (ppm): 15.4 (C3), 29.2 (C2,4), 29.7 (C6), 37.9 (C7), 40.5 (C1,5); 81.3,
94.0 (C'C); 124.2, 127.3, 128.1, 131.5 (C-Ar). MS (EI+) m/z (%): 196 (8)
[M+], 168 (40), 167 (58), 155 (19), 154 (30), 153 (36), 152 (18), 141 (35),
128 (72), 115 (100), 77 (18). IR (film, cm−1): 536 (w), 690 (s), 756 (vs),
Intramolecular cyclization reaction of (11c)
3,3-Dioxo-5,7-diphenyl-3-thiatricyclo[5.4.0.02,8]undec-5-ene (14)
A solution of 11c (0.74 g, 2 mmol) in toluene (35 mL) in the
presence of powdered KOH (0.79 g, 14 mmol) and TEBA-Cl (70 mg,
0.31 mmol) was heated at reflux for 25 h. The solvent was removed
under reduced pressure, the residue was chromatographed on
silica gel, and the tricyclic compound 14 was obtained as a colour-
less solid. Yield: 210 mg (27.2%); mp 213–214 °C; Rf = 0.28. 1H NMR ␦
(ppm): 0.74–0.87 (m, 1H, endo-H10), 1.37–1.50 (m, 3H, exo-H10), 2.06–
2.19 (m, 2H, endo-H9,11), 2.24–2.36 (m, 2H, exo-H9,11), 3.24 (s, 1H,
H2), 3.64 (br.s, 2H, H1,8), 4.50 (s, 2H, H4), 5.95 (s, 1H, H6), 7.15 (d, J =
7.6 Hz, 2H, H-Ar), 7.24–7.33 (m, 6H, H-Ar), 7.40 (t, J=7.5Hz,2H, H-Ar). 13
NMR ␦ (ppm): 12.8 (C10), 28.9 (C9,11), 46.0 (C1,8), 52.2 (C7), 53.6 (C4),
C
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Vasin et al.
471
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1443 (w), 1489 (m), 1597 (w), 2222 (w), 2858 (m), 2943 (s). Anal. calcd.
for C15H16 (%): C 91.78, H 8.22; found: C 91.70, H 8.30.
Supplementary data
Supplementary data are available with the article through the
journal Web site at http://nrcresearchpress.com/doi/suppl/10.1139/
cjc-2012-0159. CCDC 873094 contains the X-ray data in CIF format
for this manuscript. These data can be obtained, free of charge,
via http://www.ccdc.cam.ac.uk/products/csd/request (or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
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