Investigations into the reaction of the lithium enolate of cyclohexanone and phenyl vinyl sulfoxide: A simple synthesis of a bicyclo[4.2.0]octan-1-ol

Article abstract of DOI:10.1039/b107705h

The enolate generated from cyclohexanone and LDA at -78°C in THF reacts with (±)-phenyl vinyl sulfoxide to give the novel sulfinylbicyclo[4.2.0]octanols 1-3 and monoalkylated sulfoxide 4. The effects of changes in temperature, concentration, and reaction time were studied. By accurate control of temperature, concentration, and reaction time the ratio of bicyclooctanols 1-3 to monoalkylated sulfoxide 4 obtained was 95:5. The bicyclooctanols 1-3 were characterised as the sulfones 5 and 6. The relative stereochemistries of the bicyclooctanols 1-3 were established by X-ray structural determination.

Full text of DOI:10.1039/b107705h

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Investigations into the reaction of the lithium enolate of
cyclohexanone and phenyl vinyl sulfoxide: A simple synthesis
of a bicyclo[4.2.0]octan-1-ol
2
Wendy A. Loughlin,* Catherine C. Rowen and Peter C. Healy
School of Science, Griffith University, Brisbane, Queensland, 4111, Australia.
E-mail: W.Loughlin@sct.gu.edu.au; Fax: ϩϩ(07) 3875 7656; Tel: ϩϩ(07) 3875 7567
Received (in Cambridge, UK) 28th August 2001, Accepted 20th November 2001
First published as an Advance Article on the web 18th December 2001
The enolate generated from cyclohexanone and LDA at Ϫ78 ЊC in THF reacts with ( )-phenyl vinyl sulfoxide to give
the novel sulfinylbicyclo[4.2.0]octanols 1–3 and monoalkylated sulfoxide 4. The effects of changes in temperature,
concentration, and reaction time were studied. By accurate control of temperature, concentration, and reaction
time the ratio of bicyclooctanols 1–3 to monoalkylated sulfoxide 4 obtained was 95 : 5. The bicyclooctanols
1–3 were characterised as the sulfones 5 and 6. The relative stereochemistries of the bicyclooctanols 1–3
were established by X-ray structural determination.
COSY, for the sulfones 5 and 6 respectively. From the HSQC,
signals due to a CH were observed between C6 (δ = 38.9 or 43.1
ppm) and H6, and C8 (δ = 67.1 or 67.1 ppm) and H8 and the
Introduction
During the course of investigations towards the synthesis of
fused-ring natural products we sought to access a fused six- and
four-membered carbocyclic ring bearing a bridgehead hydroxy
group. A review of the literature showed that simple and poly-
signal for a quaternary carbon due to C1 (δ = 76.4 or 73.8 ppm)
was identified in the 13C NMR spectrum, for sulfones 5 and 6
respectively. In the HMBC, 2J and 3J correlations were observed
cyclic fused six- and four-membered carbocyclic rings bearing
between C1 and H7, H7, H8 for sulfone 5 and C1 and H6, H7,
H7, H8 for sulfone 6. For sulfone 5, couplings of (J = 9 and 3.5
a bridgehead hydroxy group can be accessed using [2 ϩ 2]
cycloaddition processes,1,2 samarium diiodide mediated pinacol
Hz) to H7 and a long range coupling (J = 1 Hz) to H6 was
coupling3 and tandem intramolecular Michael–aldol reaction
observed for H8. The latter was confirmed by homonuclear 1H
of α,β-unsaturated esters using TBDMSOTf.4 The construction
decouplings of H8 and H6. Thus the relative stereochemistry
of a substituted cyclobutanol using Diels–Alder methodology
of the carbon ring of bicyclooctanols 1, 2 and 3 was confirmed
and cycloaddition processes with ethylene5 was also reported in
1
by correlation of the H NMR’s of 1, 2 and 3 with those of
the synthesis of a sterpurene. Such routes are reliant on internal
directing groups, controlling reagents and often display non-
stereoselectivity. In the present work we examined whether
fused six-four membered ring systems bearing a bridgehead
sulfones 5 and 6.
The complete relative configuration of bicyclooctanols 1–3
was subsequently established by X-ray structural determination
to be the (1RSC,6SRC,8RSC,RSS)-isomer, (1RSC,6SRC,8SRC,
hydroxy group could be accessed in systems not possessing add-
SRS) and (1RSC,6SRC,8SRC,RSS)-isomer respectively. ORTEP
itional directing groups or in the absence of additives and thus
diagrams of the molecular structures of these compounds are
under mild conditions. We chose cyclohexanone and phenyl
displayed in Fig. 1. These diagrams each clearly show the cis
vinyl sulfoxide as our case study reactants. Described herein are
ring junction with the six-membered ring in a chair conform-
our investigations into the reaction of the lithium enolate of
ation fused to the puckered four-membered ring with the
cyclohexanone and ( )-phenyl vinyl sulfoxide and the explor-
torsion angle C1–C8–C7–C6 ranging between 17 and 23Њ. In
ation of conditions that lead to the controlled formation of
each structure the molecules pack across a crystallographic
8-phenylsulfinylbicyclo[4.2.0]octan-1-ol as the major product.
† Initially, oxidation of the crude sulfoxide product mixture was carried
out with Oxone® (1.0 equivalent) in water–methanol (1 : 1) at room
temperature for 16 hours. One of the compounds isolated after extrac-
tion with ethyl acetate and by column chromatography (ethyl acetate–
hexane 20 : 80 increasing to 50 : 50 in 5% increments) was the ester
arising from over oxidation of the monoalkylated sulfone via a Baeyer–
Villiger type process to give a seven-membered lactone which was
subsequently transesterified with methanol under the conditions of
Oxone® oxidation. 6-Hydroxy-8-phenylsulfonyloctanoic acid, methyl
ester was obtained as a colourless oil (Found: C, 57.25; H, 7.08.
C15H22O5S requires C 57.30; H, 7.05); νmax(KBr)/cmϪ1 3510 (m), 1734
(s), 1305 (m), 1148 (m); δH(400 MHz) 1.22–1.32 (1H, m, H4), 1.32–1.44
(2H, m, H4, H5), 1.46–1.62 (2H, m, 2 × H3), 1.64–1.75 (1H, m, H7),
1.81–1.92 (1H, m, H7), 2.25 (2H, dd, J2,3 8, J2,3 8, 2 × H2), 2.60 (1H, br
s, Wh/2 28, OH), 3.10–3.20 (1H, m, H8), 3.22–3.33 (1H, m, H8), 3.60
(4H, m, –OCH3, H6), 7.50–7.60 (3H, m, SO2Ph), 7.80–7.90 (2H, m,
SO2Ph); δC(50 MHz) 24.6 (C3), 25.0 (C4), 30.0 (C7), 33.8 (C2), 37.0
(C5), 51.6 (C6), 53.1 (C8), 69.5 (–OCH3), 127.7, 128.0 (o-C6H5), 129.4
Results and discussion
The enolate generated from cyclohexanone and LDA at Ϫ78 ЊC
reacts with ( )-phenyl vinyl sulfoxide to give the novel sulfinyl-
bicyclo[4.2.0]octanols 1–3 with the relative configurations
shown, and the monoalkylated sulfoxide 4 as mixture of dia-
stereoisomers (Scheme 1). The bicyclooctanols 1–3 were char-
acterised as the sulfones 5 and 6 using MCPBA or Oxone®
as the oxidant.† The bicyclooctanols 2 and 3 independently
oxidised to the sulfone 6 confirming that they are epimeric at
sulfur. The sulfones 5 and 6 were characterized by interpret-
ation of spectral data from H and 13C 1D NMR and gCOSY,
1
HMQC or HSQC and HMBC 2D NMR studies. The connect-
ivity of the cyclobutyl ring was apparent from correlations
between the signals due to H8 (δ = 3.43 or 3.52 ppm) and H7 (δ
= 1.76–1.88 or 1.78–1.88 ppm), and H7 (δ = 1.96 or 2.32 ppm),
and H6 to H7 and H7 (δ = 2.14–2.25 or 2.82–2.92 ppm) in the
(m-C6H5), 133.8 (p-C6H5), 139.1 (i-C6H5), 174.2 (C᎐O); (ESMSϩ) 337
᎐
(MNaϩ, 100%).
296
J. Chem. Soc., Perkin Trans. 2, 2002, 296–302
This journal is © The Royal Society of Chemistry 2002
DOI: 10.1039/b107705h

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Table 1 Time course study over 24 hours: % composition of bicyclo-
octanols 1, 2 and 3 or monoalkylated sulfoxide 4 in total reaction
product mixture
Product composition (%)
Time/h
Phenyl vinyl sulfoxide
1
2
3
4
1, 2 and 3
0.25
1.25
5.25
24.0
8
2
0
0
33
33
20
0
43
43
31
0
8
5
2
0
8
17
47
84
81
53
0
100
vinyl sulfoxides to produce ketosulfoxides has been described.6
Cyclobutanol formation has been observed in one instance with
a functionalised ketone.7 In the above reaction, the formation
of bicyclobutanols 1–3 in a combined unoptimized yield of
48% compared to 24% yield of the monoalkylated sulfoxide 4
from simple substrates under mild conditions prompted us to
examine improving the yield of bicyclobutanols 1–3. Due to the
presence of monoalkylated sulfoxide 4 the above reaction was
repeated with an immediate quench using ammonium chloride.
Unreacted phenyl vinyl sulfoxide was recovered and less than
5% of other products were observed. We now studied the effects
of reaction time, temperature and concentration on the product
distribution.
A time course experiment was carried out to determine an
appropriate reaction time for bicyclooctanol formation. Thus
the lithium enolate of cyclohexanone was reacted with phenyl
vinyl sulfoxide in THF under a nitrogen atmosphere at Ϫ10 ЊC
in the dark using a cryogenic unit for temperature control. Over
a 24 hour period, aliquots of the reaction mixture were ana-
lyzed. We carried out this and ensuing reactions in the dark to
exclude competing pathways which may be promoted by light.8
The results are presented in Table 1. A clear trend can be seen
over 24 h. Bicyclooctanol formation was favoured with short
reaction times, of less than 15 minutes. After 24 hours only
monoalkylated sulfoxide 4 was observed. The presumed ring
opening of the bicyclooctanol intermediate to form the
monoalkylated sulfoxide 4 upon quenching was observed to be
relatively slow as the ratio of combined bicyclooctanols 1–3 to
monoalkylated sulfoxide 4 at 5.25 hrs was 55 : 45 respectively.
The exact time of complete conversion to monoalkylated
sulfoxide 4 was not established. A further experiment at the
temperature of Ϫ30 ЊC, combined with rapid addition of phenyl
vinyl sulfoxide, after 5 minutes reaction time gave bicyclo-
octanols 1 (10%), 2 (26%), 3 (5%), monoalkylated sulfoxide 4
(3%) and unreacted phenyl vinyl sulfoxide (27%). The decreased
reaction time of 5 minutes resulted in decreased conversion of
phenyl vinyl sulfoxide and thus a reaction time of 10 minutes
was chosen for the remaining studies. A smaller scale of react-
ants and thus a lower concentration (0.085 M) of enolate was
used.
Fig. 1 Molecular structure of (a) bicyclooctanol 1, (b) bicyclooctanol
2 and (c) bicyclooctanol 3. Displacement ellipsoids are drawn at 30%
probability level.
inversion centre as H-bonded dimers with O1 ؒ ؒ ؒ O2 distances
of the order of 2.7–2.8 Å. The existence of all three structures
as dimers was interesting in that it could be accomodated what-
ever the initial conformational structure of the S᎐O and C–OH
᎐
bonds.
Initially, the lithium enolate of cyclohexanone was reacted
with phenyl vinyl sulfoxide in THF under a nitrogen atmos-
phere at Ϫ30 ЊC for 45 minutes. In the crude mixture, bicyclo-
octanols 1 (13%), 2 (32%), 3 (5%) and monoalkylated sulfoxide
4 (24%) were present. The alkylation of various enolates with
Scheme 1
J. Chem. Soc., Perkin Trans. 2, 2002, 296–302
297

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Fig. 3 Reaction temperature vs. % composition of product in total
Fig. 2 Reaction temperature vs. % composition of product in total
reaction products with 0.085 M of cyclohexanone enolate for the
products, bicyclooctanol 1 (᭹), bicyclooctanol 2 (ꢀ), bicyclooctanol 3
(ᮀ) and monoalkylated sulfoxide 4 (᭺).
reaction products with 0.17 M of cyclohexanone enolate for the
products, bicyclooctanol 1 (᭹), bicyclooctanol 2 (ꢀ), bicyclooctanol 3
(ᮀ) and monoalkylated sulfoxide 4 (᭺).
The scope of the current study on the reaction of the lithium
enolate of cyclohexanone with phenyl vinyl sulfoxide was
restricted to reactions carried out in the dark. Under these con-
ditions we found that the length of reaction time, the temper-
ature and the concentration of the enolate were all critical to
the formation of bicyclooctanol in preference to the mono-
alkylated sulfoxide 4. The bicyclooctanol intermediates are rel-
atively stable under the reaction conditions for periods of hours
(<5 hours) but eventually ring open to form the monoalkylated
sulfoxide 4 upon quenching of the reaction at 24 hours. It was
established that a short reaction time of 10 minutes favoured
the yield of bicyclooctanols 1–3 in conjunction with excellent
conversion of phenyl vinyl sulfoxide.
From the temperature and concentration studies, the ratio of
bicyclooctanols 1–3 to monoalkylated sulfoxide 4 and total
conversion of phenyl vinyl sulfoxide varied significantly. The
general effect of lower temperature was to decrease conversion
of phenyl vinyl sulfoxide and that of higher temperature to
increase formation of monoalkylated sulfoxide 4 in preference
to bicyclooctanols 1–3. At Ϫ10 ЊC, the general effect of con-
centration was at dilute concentration (0.017 M), conversion
of phenyl vinyl sulfoxide was decreased with concominant
decrease in bicyclooctanol formation. However, at the other
concentrations studied (0.085 M and 0.17 M) the ratio of
bicyclooctanols 1–3 to monoalkylated sulfoxide 4 varied
slightly from 95 : 5 to 91 : 9 respectively. This ratio varied sig-
nificantly over the temperature range Ϫ10 ЊC to room temper-
ature and between the enolate concentration of 0.17 M and
0.085 M (Fig. 4). At higher enolate concentration, of 0.17 M
compared to 0.085 M, and higher temperature of above
Ϫ10 ЊC, bicyclooctanol formation was decreased. Thus the
point at which bicyclooctanols 1–3 was preferred over mono-
alkylated sulfoxide 4 formation was dependent on both the
temperature and concentration used. It was established that a
critical temperature of Ϫ10 ЊC and an enolate concentration of
0.085 M was required for formation of bicyclooctanols 1–3. By
accurate control of the temperature and concentration, and
reaction time the bicyclooctanols 1–3 were obtained in a yield
of 75% and in a ratio of 95 : 5 to monoalkylated sulfoxide 4.
The dramatic change in product ratios obtained from the above
studies are suggestive of an ionic process.
Next, the effects of temperature were explored. Six enolate
trapping experiments were carried out at the discreet temper-
atures of Ϫ50 ЊC, Ϫ30 ЊC, Ϫ10 ЊC, 0 ЊC, 10 ЊC and 20 ЊC. The
results are summarised in Fig. 2. At Ϫ30 ЊC bicyclooctanol
formation decreased as a result of incomplete conversion of
phenyl vinyl sulfoxide and at Ϫ50 ЊC bicyclooctanol formation
was less than 6%. Similarly, alkylation of the cyclohexanone
enolate to form monoalkylated sulfoxide 4 at the lower temper-
atures was also reduced. Bicyclooctanol 2 was observed to be
the major bicyclooctanol product between Ϫ30 ЊC and 10 ЊC.
At these temperatures bicyclooctanols 1 and 3 are also
observed. At 20 ЊC bicyclooctanols 1 and 2 are present in
similar yield and bicyclooctanol 3 was not observed. Mono-
alkylated sulfoxide 4 was also formed. The ratio of combined
bicyclooctanol 1–3 to monoalkylated sulfoxide 4 changes from
a 95 : 5 ratio at Ϫ10 ЊC to a 29 : 71 ratio at 20 ЊC.
Next, the effect of concentration was examined. Four enolate
trapping experiments were carried out at the discreet tem-
peratures of Ϫ10 ЊC, 0 ЊC, 10 ЊC and 20 ЊC. This series was
conducted at twice the concentration of the enolate (0.17 M)
compared with the above experiments which were carried at a
0.085 M concentration of the enolate. The results are summar-
ised in Fig. 3.
At 0.17 M bicyclooctanol 2 was observed to be the major
bicyclooctanol product at 0 ЊC and Ϫ10 ЊC. At these temper-
atures bicyclooctanols 1 and 3 are also observed. At 10 ЊC
bicyclooctanols 1 and 2 are present in similar yield and bicyclo-
octanol 3 was not observed. At 20 ЊC the only bicyclooctanol
observed was 1 in 3% yield. Monoalkylated sulfoxide 4 was
also formed. The ratio of combined bicyclooctanols 1–3 to
monoalkylated sulfoxide 4 changes from a 91 : 9 ratio at Ϫ10 ЊC
to 5 : 95 ratio at room temperature. At Ϫ10 ЊC the ratio of the
combined bicyclooctanols 1–3 and monoalkylated sulfoxide 4
was comparable between 0.085 M and 0.17 M. However, the
point at which bicyclooctanol 2 was the major bicyclooctanol
product changed from 10 ЊC at 0.085 M to 0 ЊC at 0.17 M.
Monoalkylated sulfoxide 4 was observed in increased yield of
63% at 0.17 M as compared to a yield of 57% at 0.085 M. A
further experiment conducted at the concentration of 0.017 M
with respect to the enolate was carried out Ϫ10 ЊC, the
temperature at which bicyclooctanol formation was observed
to predominate. At this concentration, bicyclooctanols 1
(11 %), 2 (31%), 3 (3%) and monoalkylated sulfoxide 4 (10%)
were observed in decreased yields in addition to an increase in
unreacted phenyl vinyl sulfoxide (18%).
The ratio of bicyclooctanols 1 : 2 : 3 also was shown to be
dependent on the temperature and concentration used. Note-
worthy is the order of formation of the bicyclooctanols 1–3.
Under higher temperature and concentration only bicyclo-
octanol 1 was observed, albeit in low yield. Bicyclooctanol 3
298
J. Chem. Soc., Perkin Trans. 2, 2002, 296–302

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were recorded on Varian Gemini 200 or Varian Unity 400
spectrometers, with samples dissolved in CDCl3, and referenced
to the solvent peak. Infrared spectra were recorded on a
Perkin–Elmer FTIR 1725X spectrophotometer as KBr discs.
Mass Spectra were recorded on a Fisons VG-Platform II, using
electrospray as the ionization technique, and using Mass Lynx
Version I (IBM) to acquire and process data. Melting points
were recorded on a Gallenkamp Variable Temperature Appar-
atus, and are uncorrected. All chromatographic separations
were carried out by flash chromatography with Merck silica gel
60 (70–230 mesh, ATM). Analytical thin-layer chromatography
(tlc) was carried out with Merck precoated tlc plastic sheets
coated with silica gel 60 F254 (0.2 mm). Lithium diisopropyl
amine was standardized by titration against 2,5-dimeth-
oxybenzyl alcohol prior to use.10 Solvents and commercially
available reagents were purified in the standard manner.
1H NMR product analysis and determination of percentage
composition
Fig. 4 Effects of concentration and reaction temperature on the %
composition of bicyclooctanols 1, 2 and 3 or monoalkylated sulfoxide 4
in total reaction products for cyclohexanone enolate of 0.085 or
0.17 M: monoalkylated sulfoxide 4 at 0.17 M (A), monoalkylated
sulfoxide 4 at 0.085 M (B), bicyclooctanols 1, 2 and 3 at 0.085 M (C),
and bicyclooctanols 1, 2 and 3 at 0.17 M (D).
The crude product mixtures were dried under high vacuum,
freeze dried, and the mass of the crude product determined.
The H NMRs were obtained using CDCl3 as solvent. A D2O
1
exchange was performed on all samples and the 1H 400 (MHz)
spectrum obtained. Integration of the baseline resolved peaks
at δ 3.20, 3.14, 3.05, 2.95 and 6.18 ppm, for bicyclooctanols
1, 2, 3, monoalkylated sulfoxide 4 and unreacted phenyl vinyl
sulfoxide respectively, was used to calculate the percentage
composition of these components from the integral of the total
crude mixture. The crude product mixtures from experiments
Ϫ30 ЊC, 45 minutes, Ϫ10 ЊC 24 hour timecourse and Ϫ30 ЊC,
5 minutes were not freeze dried prior to analysis. Crude yields
greater than the theoretical 100% yield were found to include
water and this was included in calculations.
was the minor isomer and initially formed at lower temper-
atures compared to bicyclooctanols 1 and 2. Formation of
bicyclooctanols 2 as the major isomer was favoured by lower
temperature and lower concentration. Factors such as thermo-
dynamic stability of the products, and steric interactions in the
intermediates leading to the bicyclooctanols 1–3 presumably
influence the ratio of 1 : 2 : 3 observed. The position of the
oxygens, phenyl ring and the bicyclooctanol ring in the X-ray
structures of 1–3 are supportive of this.
Bicyclooctanols 2 and 3 were established to be epimeric at
sulfur. The sulfur epimer of bicyclooctanol 1 was not observed.
The absence of this epimer may be due to unfavourable steric
interactions between the phenyl ring and the six-membered ring
derived form the cyclohexanone.
Enolate trapping
Lithium enolate of cyclohexanone. The lithium enolate of
cyclohexanone was generated using LDA (∼1.5 M, 5.60 mmol,
3.70 ml) and cyclohexanone (0.50 g, 0.53 ml, 5.10 mmol) in
THF (30 ml) at Ϫ78 ЊC (0.17 M) or by using LDA (∼1.7 M, 2.80
mmol, 1.65 ml) and cyclohexanone (0.25 g, 0.26 ml, 2.55 mmol)
in THF (30 ml) at Ϫ78 ЊC (0.085 M) or by using LDA (∼1.6 M,
2.80 mmol, 1.75 ml) and cyclohexanone (0.25 g, 0.26 ml, 2.55
mmol) in THF (150 ml) at Ϫ78 ЊC (0.017 M).
In conclusion, we have established that with control of the
reaction time, temperature, and concentration, the reaction of
the lithium enolate of cyclohexanone with phenyl vinyl sulf-
oxide gave bicyclooctanols 1–3 as the major product(s) in 75%
yield and containing <5% of the monoalkylated sulfoxide 4.
This is the first example of the controlled in situ alkylation of a
lithium enolate and subsequent ring closure to form a fused six
and four-membered ring system bearing a bridgehead hydroxy
group. This occurs to give exclusively the cis ring junction in all
bicyclooctanol products suggesting a selective process for the
C1–C8 bond formation. Noteworthy is that the reaction occurs
in the absence of any additives and can be controlled to give
synthetically useful yields of bicycloaddition adduct in prefer-
ence to the monoalkylated adduct. The formation of bicyclo-
octanols 1–3 in the absence of light indicates their formation is
likely to occur via an ionic process or alternatively a thermally
allowed SET process. Competeing pathways may be involved
in the formation of bicyclooctanols 1–3 and monoalkylated
sulfoxide 4. Although more complex ring systems9 have been
generated using Michael type processes, the direct formation of
a fused six-four membered ring system using simple synthons
under the partially optimised conditions established here
indicates that the reaction may have potential for synthetic
applications. From both preparative and mechanistic view-
points the reaction is important and further investigations are
in progress.
؊30 ؇C, 45 minutes. The lithium enolate of cyclohexanone
(5.10 mmol) was allowed to warm to Ϫ30 ЊC. Phenyl vinyl
sulfoxide (0.78 g, 0.68 ml, 5.10 mmol) added dropwise over
5 minutes at a rate such that the temperature remained at
Ϫ30 ЊC. The reaction stirred for 45 minutes at Ϫ30 5 ЊC. The
reaction was quenched with NH4Cl (saturated aqueous) and
extracted with ethyl acetate (3 × 50 ml). The combined organic
layers were washed with brine (100 ml), dried (MgSO4), filtered
and evaporated to give the crude product mixture as an amber
oil (1.47 g). The percentage composition of the major products,
1
as determined by H NMR (400 MHz) analysis of the crude
product mixture, was: monoalkylated sulfoxide 4, as a mixture
of diastereomers (24%); bicyclooctanol 1 (13%); bicyclooctanol
2 (32 %); bicyclooctanol 3 (5%).
؊10 ؇C, 24 hour timecourse. The lithium enolate of cyclohex-
anone was generated using LDA (∼1.3 M, 17.2 ml, 22.41 mmol)
and cyclohexanone (2.1 ml, 2.0 g, 20.38 mmol) in THF (125 ml)
at Ϫ78 ЊC. After warming to Ϫ12 ЊC, the reaction was placed in
the dark‡ and phenyl vinyl sulfoxide (2.7 ml, 3.1 g, 20.38 mmol)
‡ Reactions done in the dark were carried out with the reaction vessel
thoroughly covered in aluminium foil. Dark conditions were applied
before electrophile addition and were maintained until after the reac-
tion was quenched.
Experimental
1H NMR and 13C NMR spectra were assigned through use of
COSY, HMBC and HMQC experiments. All NMR spectra
J. Chem. Soc., Perkin Trans. 2, 2002, 296–302
299

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was added over 15 minutes at a rate such that the temperature
remained at Ϫ10 ЊC. The reaction stirred for 24 hours at Ϫ10
5 ЊC Aliquots (15 ml) were removed at the end of sulf-
oxide addition (0.25 hours), 1.25, and 5.25 hours. Each aliquot
was quenched and worked up as described above. The crude
product mixture was obtained as a yellow oil. After 24 hours,
the remaining reaction mixture was quenched and extracted in
the same manner as the aliquots to give the crude product as an
amber oil. The crude products from each aliquot were analysed
by 1H NMR (400 MHz) (Table 1).
solid (577 mg). The percentage composition of the major
products, as determined by H NMR (400 MHz) analysis of
the crude product mixture, was: monoalkylated sulfoxide 4,
as a mixture of diastereomers (4 %); bicyclooctanol 1 (23%);
bicyclooctanol 2 (44%); bicyclooctanol 3 (8%).
1
؊30 ؇C and 0.085 M. The lithium enolate of cyclohexanone
(2.55 mmol) was allowed to warm to Ϫ30 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.39 g, 0.34 mL, 2.55 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature was maintained at Ϫ30 ЊC during this
time. The reaction was quenched and worked up as described
above. The crude product mixture was obtained as an amber oil
(528 mg). The percentage composition of the major products,
؊30 ؇C, 5 minutes. The lithium enolate of cyclohexanone
(5.10 mmol) was allowed to warm to Ϫ30 ЊC and phenyl vinyl
sulfoxide (0.78 g, 0.68 ml, 5.10 mmol) added as a bolus. The
reaction was stirred for 5 minutes. The temperature was main-
tained at Ϫ30 ЊC during this time. The reaction was quenched
and worked up as described above. The crude product mix-
ture was obtained as an amber oil (1.34 g). The percentage
composition of the major products, as determined by 1H NMR
(400 MHz) analysis of the crude product mixture, was:
monoalkylated sulfoxide 4, as a mixture of diastereomers (3%);
bicyclooctanol 1 (11%); bicyclooctanol 2 (26%); bicyclooctanol
3 (5%); phenyl vinyl sulfoxide (27 %).
1
as determined by H NMR (400 MHz) analysis of the crude
product mixture, was: monoalkylated sulfoxide 4, as a mixture
of diastereomers (9%); bicyclooctanol 1 (12%); bicyclooctanol
2(30 %); bicyclooctanol 3 (5%); phenyl vinyl sulfoxide (19%).
؊50 ؇C and 0.085 M. The lithium enolate of cyclohexanone
(2.55 mmol) was allowed to warm to Ϫ50 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.39 g, 0.34 mL, 2.55 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature increased to Ϫ40 ЊC during this time. The
reaction was quenched and worked up as described above. The
crude product mixture was obtained as an amber oil (286 mg).
The percentage composition of the major products, as deter-
20 ؇C and 0.085 M. The lithium enolate of cyclohexanone
(2.55 mmol) was allowed to warm to 20 ЊC, placed in the
dark and phenyl vinyl sulfoxide (0.39 g, 0.34 ml, 2.55 mmol)
was added as a bolus and the reaction mixture stirred for 10
minutes. The temperature was maintained at 20 ЊC during this
time. The reaction was quenched and worked up as described
above. The crude product mixture was obtained as an amber oil
(587 mg). The percentage composition of the major products,
1
mined by H NMR (400 MHz) analysis of the crude product
mixture, was: monoalkylated sulfoxide 4, as a mixture of
diastereomers (7%); bicyclooctanol 1 (1%); bicyclooctanol 2
(5%); phenyl vinyl sulfoxide (39%).
1
as determined by H NMR (400 MHz) analysis of the crude
20 ؇C and 0.17 M. The lithium enolate of cyclohexanone
(5.10 mmol) was allowed to warm to 20 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.78 g, 0.68 mL, 5.10 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature was maintained at 20 ЊC during this
time. The reaction was quenched and worked up as described
above. The crude product mixture was obtained as an amber oil
(1.28 g). The percentage composition of the major products, as
determined by 1H NMR (400 MHz) analysis of the crude prod-
uct mixture, was: monoalkylated sulfoxide 4, as a mixture of
diastereomers (63%); bicyclooctanol 1 (3%).
product mixture, was: monoalkylated sulfoxide 4, as a mixture
of diastereomers (57%); bicyclooctanol 1 (13%); bicyclooctanol
2 (10 %).
10 ؇C and 0.085 M. The lithium enolate of cyclohexanone
(2.55 mmol) was allowed to warm to 10 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.39 g, 0.34 mL, 2.55 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature was maintained at 10 ЊC during this time.
The reaction was quenched and worked up as described above.
The crude product mixture was obtained as an amber oil,
which later solidified (610 mg). The percentage composition of
1
10 ؇C and 0.17 M. The lithium enolate of cyclohexanone
(5.10 mmol) was allowed to warm to 10 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.78 g, 0.68 ml, 5.10 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature was maintained at 10 ЊC during this time.
The reaction was quenched and worked up as described above.
The crude product mixture was obtained as an amber oil (1.28
g). The percentage composition of the major products, as
determined by 1H NMR (400 MHz) analysis of the crude prod-
uct mixture, was: monoalkylated sulfoxide 4, as a mixture of
diastereomers (44%); bicyclooctanol 1 (11 %); bicyclooctanol 2
(11 %).
the major products, as determined by H NMR (400 MHz)
analysis of the crude product, was: monoalkylated sulfoxide 4,
as a mixture of diastereomers (39%); bicyclooctanol 1 (16%);
bicyclooctanol 2 (23%); bicyclooctanol 3 (1 %).
0 ؇C and 0.085 M. The lithium enolate of cyclohexanone
(2.55 mmol) was allowed to warm to 0 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.39 g, 0.34 mL, 2.55 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature was maintained at 0 ЊC during this time.
The reaction was quenched and worked up as described above.
The crude product mixture was obtained as a dark amber solid
(584 mg). The percentage composition of the major products,
1
as determined by H NMR (400 MHz) analysis of the crude
0 ؇C and 0.17 M. The lithium enolate of cyclohexanone
(5.10 mmol) was allowed to warm to 0 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.78 g, 0.68 mL, 5.10 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature was maintained at 0 ЊC during this time.
The reaction was quenched and worked up as described above.
The crude product mixture was obtained as an amber oil
(1.26 g). The percentage composition of the major products, as
determined by 1H NMR (400 MHz) analysis of the crude prod-
uct mixture, was: monoalkylated sulfoxide 4, as a mixture of
diastereomers (39%); bicyclooctanol 1 (17%); bicyclooctanol 2
(19%); bicyclooctanol 3 (2%).
product mixture, was: monoalkylated sulfoxide 4, as a mixture
of diastereomers (29%); bicyclooctanol 1 (17%); bicyclooctanol
2 (26 %); bicyclooctanol 3 (1 %).
؊10 ؇C and 0.085 M. The lithium enolate of cyclohexanone
(2.55 mmol) was allowed to warm to Ϫ10 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.39 g, 0.34 mL, 2.55 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature was maintained at Ϫ10 ЊC during this
time. The reaction was quenched and worked up as described
above. The crude product mixture was obtained as an amber
300
J. Chem. Soc., Perkin Trans. 2, 2002, 296–302

View Online
؊10 ؇C and 0.17 M. The lithium enolate of cyclohexanone
(5.10 mmol) was allowed to warm to Ϫ10 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.78 g, 0.68 mL, 5.10 mmol) was
added as a bolus and the reaction mixture stirred for 10 min-
utes. The temperature was maintained at Ϫ10 ЊC during this
time. The reaction was quenched and worked up as described
above. The crude product mixture was obtained as a dark
amber solid (1.24 g). The percentage composition of the major
3420 (s), 2916 (m), 1010 (m); δH(400 MHz) 1.21–1.70, 2.04–2.32
(11H, m, 2 × H2, 2 × H3, 2 × H4, 2 × H5, H6β, 2 × H7), 3.20
(1H, s, OH), 3.29 (1H, dd, J8β,7 8, J8β,7 10, H8β), 7.44–7.51 (3H,
m, m- and p-C6H5C6H5), 7.57–7.62 (2H, m, o-C6H5); δC(100
MHz) 18.7, 20.1, 21.2, 23.2 (C3, C4, C5 & C7), 31.6 (C2), 38.6
(C6), 69.3 (C8), 74.5 (C1), 124.2 (o-C6H5), 129.2 (m-C6H5),
131.1 (p-C6H5), 142.2 (i-C6H5); (ESMSϩ) 257 (MLiϩ, 100%);
(LSIMS) (Found: 251.10956. C14H19O2S requires 251.11058).
1
products, as determined by H NMR (400 MHz) analysis of
the crude product mixture, was: monoalkylated sulfoxide 4,
as a mixture of diastereomers (7%); bicyclooctanol 1 (23%);
bicyclooctanol 2 (43%); bicyclooctanol 3 (7%).
Bicyclooctanol 3. The crude reaction mixture from the reac-
tion between the lithium enolate of cyclohexanone and phenyl
vinyl sulfoxide at Ϫ10 ЊC in the dark (5.10 mmol scale) was
separated be silica column chromatography (100% ether) and
two major fractions were obtained.
؊10 ؇C and 0.017 M. The lithium enolate of cyclohexanone
(2.55 mmol) was allowed to warm to Ϫ10 ЊC, placed in the dark
and phenyl vinyl sulfoxide (0.39 g, 0.34 ml, 2.55 mmol) was
added as a bolus and the reaction mixture stirred for 10 minutes.
The temperature was maintained at Ϫ10 ЊC during this time.
The reaction was quenched and worked up as described above.
The crude product mixture was obtained as an amber oil (512
mg). The percentage composition of the major products, as
determined by 1H NMR (400 MHz) analysis of the crude prod-
uct mixture, was: monoalkylated sulfoxide 4, as a mixture of
diastereomers (10%); bicyclooctanol 1 (11 %); bicyclooctanol 2
(31 %); bicyclooctanol 3 (3%); phenyl vinyl sulfoxide (18%).
Fraction 1 (74 mg, 6%) contained (1RSC,6SRC,8SRC,RSS)-
8-phenylsulfinyl bicyclo[4.2.0]octan-1-ol 3 as a white solid,
mp 134–135 ЊC (ether) (Found: C, 67.49; H, 7.34; S, 12.73.
C14H18O2S requires C, 67.16; H, 7.25; S, 12.81); νmax(KBr)/cmϪ1
3318 (s), 2934 (s), 1017 (s); ); δH(400 MHz) 1.20–1.70 (8H, m,
H2, 2 × H3, 2 × H4, 2 × H5, H7), 1.86–1.98 (1H, m, H2), 2.21
(1H, ddd, J7,8α 3.5, J7,6β 10, J7,7 12.5, H7), 2.58–2.69 (1H, m,
H6β); 3.05 (1H, ddd, J8α,6β 1, J8α,7 3.5, J8α,7 8, H8α), 3.36 (1H, s,
OH), 7.41–7.50 (3H, m, m- and p-C6H5), 7.52–7.56 (2H, m,
o-C6H5); δC(100 MHz) 17.4 (C7), 20.7 (C3 & C4), 24.5 (C5),
35.6 (C2), 43.3 (C6), 67.4 (C8), 74.6 (C1), 124.2 (o-C6H5),
129.0 (m-C6H5), 130.5 (p-C6H5), 141.4 (i-C6H5); (ESMSϩ) 257
(MLiϩ, 100%).
Isolation of bicyclooctanols 1–3
Fraction 2 (851 mg, 66%) contained monoalkylated sulf-
oxide, 4 as a mixture of diastereomers, bicyclooctanol 1 and 2.
Bicyclooctanols 1, 2 and monoalkylated sulfoxide 4. The crude
product mixture from the reaction between the lithium enolate
of cyclohexanone and phenyl vinyl sulfoxide at 20 ЊC in the
dark (2.55 mmol scale) was separated by silica column chroma-
tography (4% isopropanol in DCM) and three major fractions
were obtained.
Oxidation of 8-phenylsulfinylbicyclo[4.2.0]octanol 1
(1RSC,6SRC,8RSC,RSS)-8-Phenylsulfinylbicyclo[4.2.0]octan-1-
ol 1 (28 mg, 0.11 mmol) in methanol (1 ml) and Oxone®
(138 mg, 0.22 mmol) in water (1 ml) were stirred at room
temperature for 24 hours. The reaction mixture was extracted
with ethyl acetate (3 × 20 ml), the combined organic layers were
washed with brine (20 ml), dried (MgSO4), filtered and evapor-
ated. Recrsytallisation of the solid residue yielded (1RS, 6SR,
8RS)-8-phenylsulfonyl bicyclo[4.2.0]octan-1-ol 5 (26mg, 89%)
as a white solid, mp 132–134 ЊC (ether) (Found: C, 63.07, H,
6.79. C14H18O3S requires C, 63.13, H, 6.81); νmax(KBr)/cmϪ1
3494 (s), 1304 (s), 1148 (s); δH(400 MHz) 1.16–1.40 (2H, m,
H3, H4), 1.41–1.50 (1 H, m, H5), 1.50–1.65 (3H, m, H3, H4,
H5),1.76–1.88 (2H, m, H2, H7), 1.96 (1H, ddd, J7,8β 10.5,
J7,6β 11, J7,7 11, H7), 2.14–2.25 (1H m, H6β), 2.52–2.64 (2H, m,
H2, OH), 3.43 (1H, dd, J8β,7 10.5 and 11, H8β), 7.48–7.55 (2H,
m, m-C6H5, 7.57–7.64 (1H, m, p-C6H5), 7.81–7.86 (o-C6H5);
δC(100 MHz) 19.9 (C3/C4), 20.3 (C7), 21.1 (C3/C4), 23.1
(C5), 30.7 (C2), 38.9 (C6), 67.1 (C8), 76.4 (C1), 127.5(o-C6H5),
129.1 (m-C6H5),133.4 (p-C6H5),140.5 (i-C6H5); (ESMSϩ) 289
(MNaϩ, 100%).
Fraction 1 (303 mg, 47%) contained a 1 : 1 diastereomeric
mixture of 2-[2Ј-(phenylsulfinyl)ethyl]cyclohexanone 4 as a pale
yellow solid, mp 88–89 ЊC§ (ether), (lit.,7 83–84 ЊC), νmax(KBr)/
cmϪ1 1699 (s), 1032 (m); δH(400 MHz) (* denotes second
isomer) 1.32–1.48 (1H, m, H3), 1.50–1.80 (3H, m, H1Ј, H4, H5),
1.80–2.20 (4H, m, H1Ј, H3, H4, H5), 2.20–2.42 (3H, m, H2,
2 × H6), 2.46–2.58 (1H, m, H2), 2.70* (1H, ddd, J2Ј,1Ј 5, J2Ј,1Ј 10,
J2Ј,2Ј 13, H2Ј), 2.84–2.91 (2H, m, 2 × H2Ј), 2.95* (1H, ddd,
J2Ј,1Ј 5, J2Ј,1Ј 10, J2Ј,2Ј 13, H2Ј), 7.40–7.65 (5H, m, C6H5); δC(100
MHz) (* denotes second isomer) 22.0, 23.0* (C1Ј), 25.0 (C4),
27.9 (C5), 34.3 or 34.4 (C3), 42.1 (C6), 49.2 or 49.8 (C2), 54.3,
55.1* (C2Ј), 123.9 or 124.0 (o-C6H5), 129.1 (m-C6H5), 130.8
(p-C6H5), 143.5 or 144.0 (i-C6H5 ipso), 212.1 (C1); (ESMSϩ)
251 (MHϩ, 100%); (LSIMS) (Found: 251. 11161. C14H19O2S
requires 251.11058).
Fraction 2 (64 mg, 10%) contained (1RSC,6SRC,8SRC,SRS)-
8-phenylsulfinylbicyclo[4.2.0]octan-1-ol 2, as a white solid, mp
121–123 ЊC (ether) (Found: C, 67.30; H, 7.35; S, 13.06.
C14H18O2S requires C, 67.16; H, 7.25; S, 12.81); νmax(KBr)/cmϪ1
3338 (s), 2930 (s) 2912 (s), 1031 (s); δH(400 MHz) 1.20–1.38 (2H,
m, H4, H5), 1.38–1.52 (3H, m, H4, H3), 1.52–1.61 (1H, m, H2),
1.66–1.80 (3H, m, H2, H5, H7), 2.00 (1H, ddd, J7,8α 4, J7,6β 10,
J7,7 13, H7), 2.69–2.79 (1H, m, H6β), 3.14 (1H, ddd, J8α,6β 1,
J8α,7 4, J8α,7 8, H8α), 4.15 (1H, s, OH), 7.42–7.52 (3H, m, m- and
p-C6H5), 7.63–7.70 (2H, m, o-C6H5); δC(100 MHz) 20.8 (C3),
21.1 (C4), 21.4 (C7), 25.0 (C5), 36.5 (C2), 40.9 (C6), 67.0 (C8),
75.8 (C1), 125.0 (o-C6H5), 129.0 (m-C6H5),130.9 (p-C6H5),
142.7 (i-C6H5); (ESMSϩ) 257 (MLiϩ, 100%); (LSIMS) (Found:
251.11134. C14H19O2S requires 251.11058).
Oxidation of 8-phenylsulfinylbicyclo[4.2.0]octanol 2
3-Chloroperoxybenzoic acid (77%, 50 mg, 0.22 mmol) was
added to a solution of (1RSC,6SRC,8SRC,SRS)-8-phenylsulfinyl
bicyclo[4.2.0]octan-1-ol 2 (49 mg, 0.20 mmol) in chloroform
(2 ml). The solution was stirred at room temperature for
21 hours. The chloroform was removed in vacuo and the residue
taken up in ethyl acetate (25 ml). The ethyl acetate was washed
with NaHCO3 (saturated aqueous) (3 × 50 ml), brine (50 ml),
dried (MgSO4), filtered and evaporated to give a colourless oil
(33 mg, 62%). Recrystallisation yielded (1RS,6SR,8SR)-8-
phenylsulfonylbicyclo[4.2.0]octan-1-ol 6 as a white solid, mp
90–92 ЊC (ether) (Found: C, 63.30; H, 6.65. C14H18O3S requires
C, 63.13, H, 6.81); νmax(KBr)/cmϪ1 3475 (s), 2934 (m), 1304 (s),
1138 (s); δH(400 MHz) 1.21–1.34 (1H, m, H4), 1.34–1.56
(5H, m, H2, H3, H3, H4, H5), 1.59–1.73 (1H, m, H5), 1.78–1.88
(2H, m, H2, H7), 2.32 (1H, ddd, J7,8α 3.5, J7,6β 10, J7,7 13, H7),
2.82–2.92 (1H, m, H6β), 3.52 (1H, ddd, J8α,6β 1, J8α,7 3.5, J8α,7 9,
Fraction 3 (70 mg, 11%) contained (1RSC,6SRC,8RSC,RSS)-
8-phenylsulfinylbicyclo[4.2.0]octan-1-ol 1, as an off-white solid,
mp 146–147 ЊC (ether) (Found: C, 67.00; H, 7.24; S, 12.78.
C14H18O2S requires C, 67.16; H, 7.25; S, 12.81); νmax(KBr)/cmϪ1
§ It was assumed that the difference in melting point was due to a
different diastereomeric ratio in the product.
J. Chem. Soc., Perkin Trans. 2, 2002, 296–302
301

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H8α), 7.49–7.56 (2H, m, m-C6H5), 7.58–7.64 (1H, m, p-C6H5),
7.89–7.94 (2H, m, o-C6H5); δC(100 MHz) 19.8 (C7), 20.6 & 20.7
(C3 & C4), 24.1 (C5), 35.5 (C2), 43.1 (C6), 67.1 (C8), 73.8 (C1),
127.9 (o-C6H5), 129.1 (m-C6H5), 133.5 (p-C6H5), 139.9 (i-C6H5);
(ESMSϩ) 289 (MNaϩ, 100%).
0.15 × 0.05 mm, N = 2699, No [I > 2σ(I )] = 1015; R = 0.052,
Rw = 0.038.
(1RSC,6SRC,8SRC,SRS)-8-Phenylsulfinylbicyclo[4.2.0]octan-
1-ol 2. Recrystallized from ether. C14H18O2S1 M = 250.4, mono-
clinic, space group P21/a (C25h No. 14 variant), a = 12.719(6), b =
19.14(1), c = 11.106(7) Å, β = 102.55(5)Њ, U = 2639 Å3, Z = 8,
Dc = 1.26g cmϪ3, F(000) = 1072, µ (Mo-Kα) = 2.33 cmϪ1, Crystal
size: 0.25 × 0.20 × 0.15 mm, N = 4807, No [I > 2σ (I )] = 1474;
R = 0.072, Rw = 0.073.
(1RSC,6SRC,8SRC,RSS)-8-Phenylsulfinylbicyclo[4.2.0]octan-
1-ol 3. Recrystallized from ether. C14H18O2S1 M = 250.4,
monoclinic, space group P21/a, a = 12.774(2), b = 9.135(2),
c = 11.388(2) Å, β = 104.79(1)Њ, U = 1285 Å3, Z = 4, Dc =
1.29 g cmϪ3, µ(Mo-Kα) = 2.39 cmϪ1, Crystal size: 0.40 × 0.30 ×
0.25 mm, N = 2430, No [I > 2σ(I )] = 1726; R = 0.046, Rw = 0.055.
Oxidation of 8-phenylsulfinylbicyclo[4.2.0]octanol 3
3-Chloroperoxybenzoic acid (57%, 7 mg, 0.023 mmol) was
added to a solution of (1RSC,6SRC,8SRC,RSS)-8-phenylsulfinyl-
bicyclo[4.2.0]octan-1-ol 3 (6 mg, 0.024 mmol) in chloroform
(1 ml). The solution was stirred at room temperature for
16 hours. The chloroform was removed in vacuo and the residue
taken up in ethyl acetate (20 ml). The ethyl acetate was washed
with NaHCO3 (saturated aqueous) (3 × 50 ml), brine (50 ml),
dried (MgSO4), filtered and evaporated to give (1RS,6SR,8SR)-
8-phenylsulfonylbicyclo[4.2.0] octan-1-ol 6 as a white solid
(6 mg, 94%) with identical 1H NMR (400 MHz) and 13C NMR
(100 MHz) data as the sulfone obtained from the oxidation of
bicyclooctanol 2.
Acknowledgements
We gratefully acknowledge support for this work from the
Australian Research Council and Griffith University and the
award of an APAWS to C. Rowen.
Crystal structure determination of 8-phenylsulfinylbicyclo-
[4.2.0]octanols 1–3
References
Data collection, structure solution and refinement.¶ Unique
data sets were measured at 295 K within 2 θmax = 50Њ using a
Rigaku AFC7R four circle diffractometer (ω-2 θ scan mode,
monochromated Mo-Kα radiation λ = 0.71069 Å) yielding N
independent reflections, No with I > 2σ(I ) being considered
‘observed’. The structures were solved by direct methods and
refined by full matrix least squares refinement on |F|. Aniso-
tropic thermal parameters were refined for non-hydrogen
atoms; (x, y, z, Uiso)H were located by difference methods and
constrained at estimated values with the exception of the
hydroxyl protons on 1 and 2 which were not located. Weights
derivative of w = 1/[σ2(F)] were employed. Conventional
residuals R, Rw on |F| at convergence are quoted; statistical
weights were employed. Neutral atom complex scattering
factors were employed, computation used the teXsan crys-
tallographic software package, version 1.8 of the Molecular
Structure Corporation.11
1 For example H. Suginome, T. Takeda, M. Itoh, Y. Nakayama and
K. Kobayashi, J. Chem. Soc., Perkin Trans. 1, 1995, 49; P. Galatsis,
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6 K. Seki, T. Ohnuma, T. Oishi and Y. Ban, Tetrahedron Lett., 1975,
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Crystal data for (1RSC,6SRC,8RSC,RSS)-8-phenylsulfinyl-
bicyclo[4.2.0]octan-1-ol 1. Recrystallized from ether. C14H18-
15
O S M = 250.4, orthorhombic, space group Pbca (D No.61),
2h
2
1
a = 11.296(3), b = 22.296(3), c = 10.547(4) Å, U = 2656 Å3, Z = 8,
Dc = 1.37 g cmϪ3, µ (Mo-Kα) = 2.38 cmϪ1, Crystal size: 0.60 ×
9 J. Montgomery and L. Overman, J. Org. Chem., 1993, 58, 6476.
10 M. Winkle, J. Lansinger and R. Ronald, J. Chem. Soc., Chem.
Comm., 1980, 87.
11 TeXsan, ‘Single Crystal Structure Analysis Software’, Version 1.8,
Molecular Structure Coporation, Woodlands, TX, 1997.
¶ Crystallographic data for the structural analyses have been deposited
with the Cambridge Crystallographic Data Centre (CCDC reference
numbers 170562–170564). See http://www.rsc.org/suppdata/p2/b1/
b107705h/ for crystallographic files in cif or other electronic format.
302
J. Chem. Soc., Perkin Trans. 2, 2002, 296–302