Reactions of acylsulfonium salts with unsaturated hydrocarbons

Article abstract of DOI:10.1016/S0040-4020(01)00897-3

The reactions of acylsulfonium salts, obtained from β-(ethylsulfanyl)propionyl fluoride and (ethylsulfanyl)acetyl fluoride, with various unsaturated hydrocarbons proceed through the formation of six- and five-membered cyclic sulfonium salts, respectively. Succeeding cleavage of sulfonium salts by bases affords the corresponding sulfur containing unsaturated ketones.

Full text of DOI:10.1016/S0040-4020(01)00897-3

TETRAHEDRON
Pergamon
Tetrahedron 57 ,2001) 9017±9024
Reactions of acylsulfonium salts with unsaturated hydrocarbons
Valentine G. Nenajdenko,p Mikhail V. Lebedev and Elisabeth S. Balenkova
Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119899, Russian Federation
Received 16 March 2001;revised 13 August 2001;accepted 30 August 2001
AbstractÐThe reactions of acylsulfonium salts, obtained from b-,ethylsulfanyl)propionyl ¯uoride and ,ethylsulfanyl)acetyl ¯uoride, with
various unsaturated hydrocarbons proceed through the formation of six- and ®ve-membered cyclic sulfonium salts, respectively. Succeeding
cleavage of sulfonium salts by bases affords the corresponding sulfur containing unsaturated ketones. q 2001 Elsevier Science Ltd. All rights
reserved.
1. Introduction
2. Results and discussion
2.1. Reactions of EtSCH2CH2COF/BF3 with alkenes
The complexes of acylium salts with different nucleophiles
are in most cases milder reagents than the parent acylium
salts which tend to polymerize ole®ns.1,2 Earlier we have
found that dimethylacylsulfonium salts, obtained from
acylium salts and dimethyl sul®de, are useful for the
functionalization of multiple carbon±carbon bonds.3±8
Their reactions with ole®ns and dienes proceed as conjugate
addition of the acyl group and dimethyl sul®de and give rise
to the corresponding sulfonium salts. Subsequent elimi-
nation of dimethyl sul®de results in unsaturated ketones
,Scheme 1).
The reactions of complex EtSCH2CH2COF/BF3 ,1) with
various alkenes were performed at the temperature range
250 to 08C in dry dichloromethane. The reaction products
isolated after cleavage with base ,KHCO3 aq) were the
products of substitution of hydrogen atom at double bond
of alkene by ,3-ethylsulfanyl)propionyl moiety and ,or) the
products of conjugated addition of ethylsulfanyl and acrylic
groups to the double bond. Use of another Lewis acid
,TiCl4) led to the analogous results, but the yields were
lower.
,b-Alkylsulfanyl)propionyl and ,alkylsulfanyl)acetyl tetra-
¯uoroborates may be considered as an intramolecular model
of acylsulfonium salts mentioned above. Recently, we have
shown that b-alkylthiopropionyl tetra¯uoroborates react
with alkenes and alkynes through the formation of six-
membered sulfonium salts, which upon subsequent cleavage
with base gives rise to the corresponding alkylsulfanyl
substituted unsaturated ketones.9,10 Also acylsulfonium
salts react with various aromatic and heteroaromatic
compounds.11,12
An investigation of the products structure allows us to
propose the following reaction scheme. In the ®rst step the
CvC bond attacks carbonyl atom of the acylsulfonium
salt resulting in the formation of a carbocation which is
stabilized by intramolecular reaction with the sul®de moiety
giving a six-membered sulfonium salt A ,Scheme 2).
However, in most cases we failed to isolate salts A in pure
form, ,in the cases of trans-stilbene and methylenecyclo-
butane the signals of the intermediate sulfonium salt were
observed in the NMR spectra). The stabilization of the
carbocation by formation of the sulfonium salt seems to
proceed both intramoleculary and intermoleculary. The
last path yields non-cyclic oligomeric sulfonium salts
Below we describe our investigations of complexes
b-,ethylsulfanyl)propionyl ¯uoride ,1), ,ethylsulfanyl)-
acetyl ¯uoride ,2) and their reactions with a number of
alkenes and 1,3-dienes.
Scheme 1.
Keywords: acylsulfonium salt;acylation; a,b-unsaturated ketones;polyenones.
Corresponding author. Tel.: 17-095-939-2276;fax: 17-095-932-8846;e-mail: nen@acylium.chem.msu.ru
p
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020,01)00897-3

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V. G. Nenajdenko et al. / Tetrahedron 57 +2001) 9017±9024
that the initially formed sulfonium salt exists in the confor-
mation with equatorial phenyl ring, and anti-elimination of
the sulfonium moiety leads to trans phenyl and carbonyl
groups in the reaction product.
The reactions of a-methylstyrene and 1,1-diphenylethylene
with complex 1 yield a mixture of products: in the case of
a-methylstyrene the ratio of ketone type a/type b was 1:1, in
the case of 1,1-diphenylethyleneÐtype a/type b was 2:1
,Scheme 3). It seems that in these reactions the ratio of
products depends on both the steric size of substituents at
C-2 in the sulfonium salt A and the formation of the double
bond conjugated with aromatic ring. Actually, the presence
of methyl and phenyl or two phenyls at C-2 in the sulfonium
salt A sterically hinders the 3-position and makes the
formation of ketones type a preferable.
Scheme 2.
and makes the cyclic monomer hard to isolate in pure
form.
The reactions of complex 1 with trans-1-phenyl-2-methyl-
ethylene and trans-stilbene proceed chemo- and stereo-
selectively and yields the products of conjugate addition
of acryloyl and ethylsulfanyl groups to double bond of
alkenes ,ketone type a). Only one diastereomer of the
corresponding ketone is formed ,Scheme 4).
The reaction of sulfonium salt A with aqueous KHCO3 leads
to elimination of protons a to the carbonyl group. The ring
cleavage proceeds with cleavage of the C±S bond and gives
rise to a,b-unsaturated ketones. We investigated the
reactions of complex EtSCH2CH2COF/BF3 with a number
of alkenes posessing mono, 1,1-di, 1,2-disubstituted double
bonds, and also alkenes with exo- and endocyclic double
bonds. Depending on the structure of the starting alkene
the formation of two types of unsaturated ketones ,a and
b) is possible. Type a is the product of conjugate addition of
ethylsulfanyl and acryloyl groups to the CvC bond;type b
is the product of substitution of hydrogen atom at the double
bond of the alkene by the ,3-ethylsulfanyl)propionyl
moiety.
To determine the relative con®guration of these ketones we
tried to determine the structure of the initially formed
sulfonium salts, since during base cleavage the chiral
centers at C-2 and C-3 are not affected. However, we failed
to isolate those sulfonium salts in pure form from the
reaction mixture. At the same time, it was found that
treatment of ketones 6a and 7a with perchloric acids led
to six-membered sulfonium salts 8 and 9 ,Scheme 5).
Since cleavage of the latter with base give rise to starting
ketones 6a and 7a, the perchlorates 8 and 9 seems to be of
the same structure as the sulfonium salts A formed in the
acylation reaction. In other words the reaction of sulfonium
ring cleavage is reversible.
The only product in the reaction of styrene with complex
EtSCH2CH2COF/BF3 is the unsaturated ketone of type b
,3b) ,Scheme 3).
The coupling constants H-2 and H-3 in the salts 8 and 9
correspond to axial±axial protons in the six membered ring
,8ÐJˆ12.8 Hz, 9ÐJˆ12.5 Hz). That is in agreement with
formation of threo-isomers of ketones 6a and 7a.
The formation of the double bond conjugated with the
aromatic ring in the reaction with styrene leads to only
one productÐketone of type bÐ,E)-1-phenyl-5-ethyl-
sulfanylpent-1-en-3-one ,3b) ,3Jˆ16.2 Hz). The stereo-
selectivity of this reaction can be explained by the fact
In the reactions of complex 1 with hydrocarbons with
Scheme 3.
Scheme 4.

V. G. Nenajdenko et al. / Tetrahedron 57 +2001) 9017±9024
9019
Scheme 5.
Scheme 6.
exocyclic double bonds the ratio of products type a/type b
seems to depend mostly on steric factors. In the case of
2,2-disubstituted adamantane 10a ,Scheme 6) was obtained.
In the reaction with methylenecyclobutane, protons at C-2
in the intermediate salt A are not so sterically hindered as in
the previous case and after cleavage both possible types of
unsaturated ketones are formed 11a/11b 1:1.
straine in the cyclopentane ring on introducing a double
bond. This facilitates cleavage of intermediate A ,Scheme
1) to ketone of type b ,Scheme 7).
2.2. Reactions of EtSCH2CH2COF/BF3 with 1,3-dienes
Reactions with 1,3-dienes proceed in mild conditions and
almost without polymerization of substrates. The products
in these reaction are ketones of type a and ,or) b ,Scheme 8).
The 1,4-addition of acryloyl and ethylsulfanyl groups to the
1,3-diene system was not observed.
The interaction of complex 1 and cyclic alkenes was studied
using cyclopentene and cyclohexene ,Scheme 7). It was
found that in the case of cyclopentene only one product,
ketone of type b ,12b), was isolated. In contrast, with cyclo-
hexene the ratio of ketones type a/type b was found to be 1:1
,13a/13b). Only one diastereomer of ketone 13a was
formed, but the determination of its con®guration from
coupling constants was not successful due to overlapping
We have studied the reactions of complex 1 with isoprene
and 2,3-dimethylbutadiene. In both cases we isolated the
mixtures of ketones. The formation of ketones of type b
proceeded non-stereoselectively.
1
of signals in the H NMR spectrum.
We suppose that predominant formation of ketone of type b
in the case of cyclopentene is due to the reduction of vicinal
In the reaction of complex 1 with ,E)-1-phenyl-1,3-buta-
diene only ketone type b ,16b) was isolated. This can be
Scheme 7.
Scheme 8.

9020
V. G. Nenajdenko et al. / Tetrahedron 57 +2001) 9017±9024
Scheme 9.
Scheme 10.
explained by the formation of the conjugated phenyl-1,3-
diene-carbonyl group ,Scheme 9).
times the starting materials were not fully converted. When
methyl tri¯ate was used as alkylating reagent the reactions
usually were complete in 1±2 h and no side products were
observed.
The reaction with 1,3-cyclohexadiene leads to the mixture
of ketones type a/type b of 1:1. 1,3-Cyclooctadiene also
gives rise to a mixture of products, but in the last case the
ratio type a/type b is 5:1 ,Scheme 10).
This type of polyenones is synthetically very useful, for
example in Nazarov cyclisations.13 The polyenones might
be obtained by direct acylation of corresponding unsatu-
rated hydrocarbons with acrylic acid derivatives. But, as
was shown, the reactions of methacryloyl tetra¯uoroborate
with alkenes give rise to a,b-b0,g0-unsaturated ketones.14
Complex EtSCH2CH2COF/BF3 1 could be considered in
the reactions with alkenes and 1,3-dienes as a synthetic
equivalent of acryloyl cation, and could be used for intro-
ducing the acryloyl moiety.
2.3. Synthesis of polyconjugated unsaturated ketones
We have found that ketones, obtained in the reactions of 1
with alkenes and 1,3-dienes, after elimination of ethylsulfa-
nyl group, give rise to the corresponding polyenones 19±23
,Scheme 11). Noteworthy, the mixture of ketones type a and
type b can be converted into only one polyenone.
Such transformations have been achieved by S-methylation
and elimination of methyl ethyl sul®de by treatment with
base. Yields for these two steps are almost quantitative and
the work up is very simple.
2.4. Reactions of complex EtSCH2COF/BF3 with alkenes
In the reactions of complex 2 with alkenes the formation of
cyclic sulfonium salts also takes place. In this case the
opening of ®ve-membered sulfonium ring proceeds unam-
biguosly and furnishes substituted ,4-ethylsulfanyl)but-1-
en-3-ones: the reaction of 1,1-diphenylethylene yields the
corresponding unsaturated ketone 24 ,Scheme 12).
We studied S-methylation using several methylating agents,
such as methyl iodide and methyl sulfate. However, in those
cases reactions proceeded very slowly ,2±4 days) and some-
Scheme 11.

V. G. Nenajdenko et al. / Tetrahedron 57 +2001) 9017±9024
9021
Scheme 12.
In the reaction of 2 with trans-stilbene the intermediate
sulfonium salt 25 was isolated as one diastereomer. We
assume pseudo-equatorial±equatorial phenyl groups in
this salt, since the coupling constant between H-2 and H-3
is 13.8 Hz.
Oil, yield 34%, nD ˆ1.5520. IR ,n, cm21): 1670 ,CO),
21
1
1620 ,CvC). NMR H ,400 MHz, CDCl3, d, ppm): 7.59±
3
7.31 ,m, 6H, C6H5, H-1), 6.87 ,d, 1H, H-2, Jˆ16.2 Hz),
3.11±2.97 ,m, 4H, 2CH2), 2.71 ,q, 2H, S-CH2, 3Jˆ7.5 Hz),
1.39 ,t, 3H, CH3, 3Jˆ7.5 Hz). NMR 13C ,100 MHz, CDCl3,
d, ppm): 198.2 ,CO), 142.8 ,C-2), 134.3, 130.5, 128.9,
128.3 ,6C-arom.), 125.7 ,C-1), 40.9, 26.2, 25.8 ,3CH2),
14.8 ,CH3). Found, %: C 70.56, H 7.44. C13H16SO. Calcd,
%: C 70.87, H 7.32.
3. Conclusion
Thus, the reaction of alkenes and dienes with ,b-ethyl-
sulfanyl)propionyl ¯uoride/BF3 and ,ethylsulfanyl)acetyl
¯uoride/BF3 complexes proceeds as addition of acyl moiety
to a double bond followed by the intramolecular conjugate
addition of sul®de which results in six- or ®ve-membered
sulfonium salts, respectively. Subsequent cleavage of these
salts by base gives rise to ethylsulfanyl substituted unsatu-
rated ketones, which can be converted into synthetically
useful polyenones by S-methylation and elimination of
methyl ethyl sul®de.
4.2.2. 2-Phenyl-2-ethylsulfanylhex-5-en-4-one 24a), 2E)-
2-phenyl-6-ethylsulfanyl-hex-2-en-4-one 24b2E)), 2Z)-2-
phenyl-6-ethylsulfanylhex-2-en-4-one 24b2Z)). 2:1:1, oil,
yield 68%. IR ,n, cm21): 1695 ,CO), 1610 ,CvC). NMR 1H
,400 MHz, CDCl3, d, ppm): 4b ,E1Z): 7.46±7.15 ,m, 5H,
C6H5), 6.43 ,m, 1H, vCHCO ,Z)), 6.09 ,m, 1H, vCHCO
,E)), 2.52±2.05 ,m, 12H, 6CH2), 2.45 ,br.s, 3H, CH3Cv,
,E) or ,Z)), 2.09 ,br.s, 3H, CH3Cv, ,E) or ,Z)), 1.19 ,t, 3H,
3
CH3, ,E) or ,Z), Jˆ7.4 Hz), 1.08 ,t, 3H, CH3, ,E) or ,Z),
3Jˆ7.4 Hz), 4a: 7.46±7.15 ,m, 5H, C6H5), 6.12 ,dd, 1H,
3
3
H-5, Jˆ17.4, 10.1 Hz), 6.01 ,dd, 1H, H-6, Jˆ17.4 Hz,
2Jˆ1.6 Hz), 5.53 ,dd, 1H, H-6, Jˆ10.1 Hz, Jˆ1.6 Hz),
3.32 ,d, 1H, H-3, 2Jˆ5.3 Hz), 3.02 ,d, 1H, H-3, 2Jˆ
5.3 Hz), 2.22 ,q, 2H, S-CH2, 3Jˆ7.6 Hz), 1.84 ,s, 3H,
3
2
4. Experimental
4.1. General
CH3), 0.96 ,t, 3H, CH3, Jˆ7.6 Hz). NMR 13C ,100 MHz,
3
Reagents and solvents were handled by using standard
techniques. NMR spectra were recorded on Bruker AMX
400 and Varian VXR-300 spectrometers with TMS as an
internal standard. IR spectra were obtained with UR-20
spectrometer as ®lms. Silica gel Merck 60 and Merck
60F254 plates were used for conventional and analytical
,TLC) chromatography, respectively.
CDCl3, d, ppm): 4b ,E1Z): 198.4 and 198.4 ,CO),
153.6 and 152.1 ,C-2), 141.9 and 140.3 ,C-q arom.),
128.8, 127.9, 127.6, 126.7, 126.2, 126.0, 123.3 ,5C-arom.,
C-3), 44.4, 42.5, 26.7, 25.9, 25.4, 25.4, 25.3, 18.0 ,3CH3,
C-1), 14.4 and 14.3 ,CH3). 4a 196.4 ,CO), 143.5 ,C-q
arom.), 136.4 ,C-5), 128.1, 127.6, 126.3 ,5C arom.), 127.3
,C-6), 51.4, 48.9, 25.8, 22.4 ,2CH2, C-1, C-2), 13.4 ,CH3).
Found, %: C 71.57, H 7.79. C14H18SO. Calcd, %: C 71.75, H
7.74.
4.2. General procedure for ethylsulfanyl substituted
unsaturated ketones 3±7, 10±18, 24
4.2.3. 1,1-Diphenyl-1-ethylsulfanylpent-4-en-3-one 25a),
1,1-diphenyl-5-ethylsulfanylpent-1-en-3-one 25b). 2:1,
oil, yield 87%. IR ,n, cm21): 1700, 1680 ,CO), 1610
A well-stirred solution of ethylsulfanyl substituted acyl
¯uoride ,0.02 mole) in dichloromethane ,40 mL) was
saturated by gaseous BF3 at 2608C. A solution of alkene
,0.02 mole) dichloromethane ,in 10 mL) was added. The
reaction mixture was stirred for 15 min at 2408C and the
temperature was raised to 08C. The reaction mixture was
stirred for 1 h and then was added to a mixture of ether and
aqueous KHCO3 and stirred for an additional 1 h. The
organic layer was separated, the aqueous layer was
extracted with ether ,2£50 mL). The organic solvents
were removed in vacuo. The products were puri®ed by
column chromatography ,silica gel, hexane/EtOAc 9/1).
1
,CvC). NMR H ,200 MHz, CDCl3, d, ppm): 5a: 7.51±
7.16 ,m, 10H, 2C6H5), 5.95 ,m, 2H, H-5, H-4), 5.36 ,m,
3
1H, H-4), 3.61 ,s, 2H, CH2CO), 2.11 ,q, 2H, S-CH2, Jˆ
3
7.5 Hz), 0.98 ,t, 3H, CH3, Jˆ7.5 Hz), 5b: 7.51±7.16 ,m,
10H, 2C6H5), 6.54 ,s, 1H, H-2), 2.67±2.40 ,m, 4H, CH2±
3
CH2), 2.32 ,q, 2H, S-CH2, Jˆ7.5 Hz), 1.12 ,t, 3H, CH3,
3Jˆ7.5 Hz). NMR 13C ,50 MHz, CDCl3, d, ppm): 5a:
196.5 ,CO), 143.7 ,C-4), 136.0±125.6 ,C6H5, C-5), 114.0
,C-l), 51.3 ,C-2), 23.7 ,S-CH2), 13.1 ,CH3). 5b: 199.8 ,CO),
136.0±125.6 ,C6H5, C-l, C-2), 57.5, 44.4 ,C-4, C-5), 25.7
,S-CH2), 14.5 ,CH3). Found, %: C 77.24, H 7.21. C19H20SO.
Calcd, %: C 76.99, H 6.80.
4.2.1. 2E)-1-Phenyl-5-ethylsulfanylpent-1-en-3-one 23b).

9022
V. G. Nenajdenko et al. / Tetrahedron 57 +2001) 9017±9024
3
4.2.4. 1,2-Diphenyl-1-ethylsulfanylpent-4-en-3-one 26a).
Yield 30%, pale yellow crystals, mp 72±748C. IR ,n,
cm21): 1680 ,CO), 1610 ,CvC). NMR 1H ,200 MHz,
CDCl3, d, ppm): 7.12±6.90 ,m, 10H, 2C6H5), 6.41 ,dd,
1H, H-4, 3Jˆ17.5, 9.3 Hz), 6.14 ,dd, 1H, H-5, 3Jˆ
,m, 2H, CH adamantyl), 2.41 ,q, 2H, SCH2, Jˆ7.5 Hz),
3
2.24±1.40 ,m, 12H, adamantyl), 1.15 ,t, 3H, CH3, Jˆ
7.5 Hz). NMR 13C ,50 MHz, CDCl3, d, ppm): 199.1 ,CO),
137.7 ,CHv), 126.4 ,CH2v), 54.5 ,S-C-q), 45.6, 42.0,
39.0, 34.5, 33.0, 32.6, 27.4, 27.3, 20.5 ,adamantyl, SCH2),
13.6 ,CH3). Found, %: C 72.35, H 9.20, S 12.20. C16H24SO.
Calcd, %: C 72.68, H 9.15, S 12.12.
2
3
2
17.5 Hz, Jˆ2.1 Hz), 5.65 ,dd, 1H, H-5, Jˆ9.3 Hz, Jˆ
3
2.1 Hz), 4.60 ,d, 1H, H-1 or H-2, Jˆ11.2 Hz), 4.39 ,d,
3
3
1H, H-1 or H-2, Jˆ11.2 Hz), 2.32 ,q, 2H, SCH2, Jˆ
7.4 Hz), 1.11 ,t, 3H, CH3, 3Jˆ7.4 Hz). NMR 13C
,50 MHz, CDCl3, d, ppm): 197.5 ,CO), 140.1, 135.9
,C-4), 135.5, 129.5, 129.3, 128.6, 128.2, 127.8, 126.9,
126.6 ,10C-arom., C-5), 61.1, 50.7 ,C-l, C-2), 25.9
,SCH2), 14.1 ,CH3). Found, %: C 77.46, H 6.89.
C19H20SO. Calcd, %: C 76.99, H 6.80.
4.3.4. 1-21-Ethylsulfanylcyclobut-1-yl)but-3-en-2-one
211a), 1-cyclobutyliden-4-ethylsulfanylbutan-2-one 211b).
1:1, oil, yield 54%. IR ,n, cm21): 1700 ,CO), 1640 ,CvC).
NMR H ,200 MHz, CDCl3, d, ppm): 11a: 6.50±6.10 ,m,
1
2H, H-4, H-5), 5.85±5.65 ,m, 1H, H-5), 3.80±1.80 ,m, 12H,
6CH2), 1.40±1.11 ,m, 3H, CH3); 11b: 6.00±5.86 ,m, 1H,
H-2), 3.80±1.80 ,m, 12H, 6CH2), 1.40±1.11 ,m, 3H, CH3).
NMR 13C ,50 MHz, CDCl3, d, ppm): 198.0, 197.5 ,CO, 11a
and 11b), 166.5 ,C q 11b), 136.7 ,vCH 11a), 127.5 ,vCH
11b), 120.4 ,vCH2 11a), 49.0, 42.5 ,CH2CO 11a and 11b),
47.7 ,C q 11a), 33.7 ,C-2 and C-4 cyclobut. 11a), 34.2, 32.4
,C-2 and C-4 cyclobut. 11b), 25.8, 25.2, 22.7 ,3CH2 11a and
11b) 17.6, 16.1 ,C-3 cyclobut. 11a and 11b), 14.3, 14.1
,2CH3, 11a and 11b). Found, %: C 65.35, H 8.70.
C10H16SO. Calcd, %: C 65.17, H 8.75.
4.2.5. 4-Methyl-5-phenyl-5-ethylsulfanylpent-1-en-3-one
27a). Yield 67%, oil. IR ,n, cm21): 1680 ,CO), 1620
,CvC). NMR H ,400 MHz, CDCl3, d, ppm): 7.40±7.15
1
3
,m, 5H, C6H53), 6.49 ,dd, 1H, H-2, Jˆ18.8, 11.2 Hz), 6.32
3
,d, 1H, H-1, Jˆ18.8 Hz), 5.85 ,d, 1H, H-1, Jˆ11.2 Hz),
3
3.96 ,d, 1H, H-5, Jˆ10.8 Hz), 3.27 ,m, 1H, H-2), 2.3±2.1
3
,m, 2H, SCH2), 1.06 ,t, 3H, CH3, Jˆ7.6 Hz). NMR 13C
,100 MHz, CDCl3, d, ppm): 202.3 ,CO), 148.6, 136.1
,C-2), 128.6, 128.4, 128.4, 127.2 ,5C-arom., C-1), 51.4,
48.0 ,C-4, C-5), 25.7 ,SCH2), 16.6, 14.1 ,2CH3). Found,
%: C 71.46, H 7.87. C14H18SO. Calcd, %: C 71.75, H 7.74.
4.3.5.
1-21-Cyclopentenyl)-3-2ethylsulfanyl)-1-propa-
none 212b). Oil, yield 62%. IR ,n, cm21): 1680 ,CO),
1620 ,CvC). NMR H ,200 MHz, CDCl3, d, ppm): 6.79±
1
6.77 ,m, 1H, vCH), 2.98±2.70 ,m, 4H, COCH2CH2), 2.61±
2.45 ,m, 6H, 2CH2-allyl., CH2-ethyl.), 1.98±1.86 ,m, 2H,
4.3. Preparation of sulfonium salts 8 and 9
3
CH2-cyclopent.), 1.25 ,t, 3H, CH3, Jˆ7.6 Hz). NMR 13C
To corresponding unsaturated ketone ,0.005 mole) dis-
solved in dichloromethane ,10 mL) was added 70% aqueous
solution of perchloric acid ,4.5 mL). After 0.5 h of stirring
sulfonium salt was precipitated by addition of ether
,20 mL). The crude product was puri®ed by reprecipitation
from methanol.
,50 MHz, CDCl3, d, ppm): 196.1 ,CO), 144.8 ,C-1 cyclo-
pent.), 143.1 ,C-2 cyclopent.), 38.6, 33.4, 30.0, 25.5, 25.3,
22.1 ,6CH2), 14.1 ,CH3). Found, %: C 64.84, H 9.32.
C10H16SO. Calcd, %: C 65.17, H 8.75.
4.3.6. 1-[2-2Ethylsulfanyl)cyclohexyl]-2-propen-1-one
213a), 1-21-cyclohexenyl)-3-2ethylsulfanyl)-1-propanone
4.3.1. Rel-22R,3R)-4-oxo-2,3-diphenyl-1-ethyltetrahydro-
2H-thiopyranium perchlorate 28). Yield 99%, oil. IR ,n,
213b). Oil, 1:1, yield 23%. IR ,n, cm21): 1695 ,CO), 1630
,CvC). NMR H ,200 MHz, CDCl3, d, ppm): 13a: 6.44
1
1
cm21): 1700 ,CO). NMR H ,400 MHz, CD3CN, d, ppm):
3
7.49±7.02 ,m, 10H, 2C6H5), 5.39 ,d, 1H, H-2, 3Jˆ12.8 Hz),
,dd, 1H, CH acryl., Jˆ15.3, 10.4 Hz,), 6.26 ,dd, 1H, CH2
3
2
3
acryl., Jˆ15.3 Hz, Jˆ1.3 Hz), 5.82 ,dd, 1H, CH2 acryl.,
3Jˆ10.4 Hz, 2Jˆ1.3 Hz), 13b: 6.58 ,m, 1H, CH vinyl.), 13a
and 13b: 2.95±1.30 ,m, 26H, 5CH2, 2CH 13a;7CH 2 13b),
1.30±1.18 ,m, 6H, 2CH3 13a and 13b). NMR 13C ,50 MHz,
CDCl3, d, ppm): 202.6, 199.3 ,CO, 13a and 13b), 140.1,
138.0, 136.2, 128.2 ,Cv, 13a and 13b), 52.1, 43.8, 37.2,
34.1, 30.5, 26.2, 26.2, 25.7, 25.3, 25.0, 23.6, 23.2, 21.8, 21.4
,5CH2, 2CH 13a;7CH 2 13b), 14.8, 14.6 ,CH3 13a and 13b).
Found, %: C 66.85, H 8.98. C11H18SO. Calcd, %: C 66.62, H
9.15.
4.80 ,d, 1H, H-3, Jˆ12.8 Hz), 4.11±3.76 ,m, 2H, CH2),
3
3.49±3.12 ,m, 4H, 2CH2), 1.19 ,t, 3H, CH3, Jˆ7.5 Hz).
13C NMR ,100 MHz, CD3CN, d, ppm): 199.8 ,CO),
132.5, 130.6, ,2C-q), 129.8, 129.5, 129.2, 128.7, 127.9,
127.4 ,10CH-arom.), 60.1, 58.7 ,2CH), 36.6, 36.0, 34.6
,3CH2), 8.1 ,CH3).
4.3.2. Rel-22R,3R)-3-Methyl-4-oxo-2-phenyl-1-ethyltetra-
hydro-2H-thiopyranium perchlorate 29). Yield 99%, oil.
1
IR ,n, cm21): 1700 ,CO). NMR H ,400 MHz, CD3CN, d,
3
ppm): 7.55 ,m, 5H, C6H5), 4.85 ,d, 1H, H-2, Jˆ12.5 Hz),
3.99±3.03 ,m, 7H, CH, 3CH2) 1.17 ,t, 3H, CH3, 3Jˆ7.4 Hz),
0.87 ,d, 3H, CH3, 3Jˆ7.2 Hz). 13C NMR ,100 MHz,
CD3CN, d, ppm): 203.8 ,CO), 130.8, 129.9, 129.3, 128.2
,6C-arom.), 61.9, 53.9 ,2CH), 35.7, 35.4, 34.3 ,3CH2), 11.2,
8.8 ,2CH3).
4.3.7. 5-Ethylsulfanyl-5-methyl-1,6 heptadien-3-one
214a) 242E1Z))-1-ethylsulfanyl-5-methyl-4,6-heptadien-
3-one 214b). 7:1, yield 47%, oil. IR ,n, cm21): 1680, 1640
1
,CO, CvC). 14a. NMR H ,400 MHz, CDCl3, d, ppm):
3
6.37 ,dd, 1H, H-2, Jˆ17.5, 10.5 Hz), 6.19 ,d, 1H, H-1,
3
3Jˆ17.5 Hz), 5.86 ,dd, 1H, H-6, Jˆ17.3, 10.5 Hz), 5.78
3
3
,d, 1H, H-1, Jˆ10.5 Hz), 5.07 ,d, 1H, H-7, Jˆ10.5 Hz),
4.95 ,d, 1H, H-7, 3Jˆ17.3 Hz), 2.87 ,s, 2H, CH2CO), 2.42±
2.35 ,m, 2H, SCH2), 1.55 ,br.s, 3H, CH3), 1.17 ,t, 3H, CH3,
3Jˆ7.4 Hz). NMR 13C ,100 MHz, CDCl3, d, ppm): 197.2
,CO), 142.1, 137.2, 128.1, 112.4 ,2CHv, 2CH2v), 51.1
,C-q), 49.3 ,COCH2), 25.0 ,SCH2), 20.6 ,CH3), 14.0
4.3.3. 1-22-Ethylsulfanyladamant-2-yl)but-3-en-2-one
210a). Yield 92%, pale yellow crystals, mp 51±528C. IR
1
,n, cm21): 1700 ,CO), 1620 ,CvC). NMR H ,200 MHz,
CDCl3, d, ppm): 6.46 ,dd, 1H, H-3, 3Jˆ17.4, 10.4 Hz), 6.15
3
2
,dd, 1H, H-4, Jˆ17.4 Hz, Jˆ1.4 Hz), 5.68 ,dd, 1H, H-4,
2
3Jˆ10.4 Hz, Jˆ1.4 Hz), 3.19 ,s, 2H, CH2-1), 2.65±2.51

V. G. Nenajdenko et al. / Tetrahedron 57 +2001) 9017±9024
9023
1
,CH3). 14b. NMR H ,400 MHz, CDCl3, d, ppm): 5.3±5.2
134.8, 134.5, 133.0, 127.8, 127.3, 127.3, 123.8 ,8Cv), 49.2
,CHCO), 41.9 ,CHS), 37.1 ,CH2CO), 26.1, 25.9, 24.9, 23.7,
19.4, 19.3 ,7CH2), 14.8, 14.6 ,2CH3). Found, %: C 67.29, H
8.37. C11H16SO. Calcd, %: C 67.30, H 8.21.
,m, 1H, H-4,E1Z)), 3.12±2.65 ,m, 4H, SCH2CH2,E1Z)),
1.99 ,br.s, 3H, CH3,E)), 1.69 ,br.s, 3H, CH3,Z)), 1.28±1.19
,m, 3H, CH3,E1Z)). NMR 13C ,100 MHz, CDCl3, d, ppm):
198.7, 198.6 ,CO,E1Z)), 140.3, 135.4, 129.2, 120.6
,Cv,E1Z)), 26.4, 25.9, 25.3, 24.8 ,SCH2CH2,E1Z)),
14.5, 14.5 ,CH3,E1Z)). Other signals of 14b are overlapped
with those of 14a. Found, %: C 65.63, H 8.77. C10H16OS.
Calcd, %: C 65.17, H 8.75.
4.3.11. 1-[2-2Ethylsulfanyl)-3-cyclooctenyl]-2-propen-1-
one 218a), 1-21,3-cyclooctadienyl)-3-2ethylsulfanyl)-1-
propanone 218b). 5:1, yield 55%. IR ,n, cm21): 1690,
1
1630 ,CO, CvC). NMR H ,400 MHz, CDCl3, d, ppm):
3
18a: 6.32 ,dd, 1H, CH-acryl., Jˆ17.6, 10.4 Hz), 6.15 ,dd,
2
1H, CH2-acryl., 3Jˆ17.6 Hz, Jˆ1.2 Hz), 5.82±5.74 ,m,
4.3.8. 5-Ethylsulfanyl-5,6-dimethyl-1,6-heptadien-3-one
215a), 242E1Z))-1-ethylsulfanyl-5,6-dimethyl-4,6-hepta-
dien-3-one 215b). 3:1, yield 55%, oil. IR ,n, cm21): 1690,
1H, vCH-cyclocten.), 5.66 ,dd, 1H, CH2-acryl., 3Jˆ
10.4 Hz, 2Jˆ1.2 Hz), 5.58 ,d.t, 1H, vCH, 3Jˆ9.8 Hz),
3
1
3.93 ,dd, 1H, SCH, Jˆ9.8, 4.8 Hz), 3.93 ,dd, 1H, COCH,
1640 ,CO, CvC). 15a. NMR H ,400 MHz, CDCl3, d,
3
3Jˆ11.2 Hz, Jˆ4.8 Hz), 2.50±1.20 ,m, 10H, 5CH2), 1.13
3
ppm): 6.36 ,dd, 1H, H-2, Jˆ17.5, 10.4 Hz), 6.21 ,dd, 1H,
3
H-1, 3Jˆ17.5 Hz, 2Jˆ1.2 Hz), 5.76 ,dd, 1H, H-1, 3Jˆ
,t, 3H, CH3, Jˆ7.2 Hz), 18b: 6.95 ,br.s, 1H, vCH-2-
2
cyclocten.), 5.82±5.74 ,m, 2H, CHvCH), 2.90 ,t, 2H,
10.4 Hz, Jˆ1.2 Hz), 4.95 ,br.s, 1H, H-7), 4.79 ,br.s, 1H,
3
3
2
COCH2, Jˆ7.2 Hz), 2.72 ,t, 2H, SCH2CH2, Jˆ7.2 Hz),
H-7), 3.06 ,d, 1H, H-4, Jˆ15.8 Hz), 2.87 ,d, 1H, H-4,
3
2Jˆ15.8 Hz), 2.38±2.27 ,m, 2H, SCH2), 1.92 ,br.s, 3H,
2.50±1.20 ,m, 10H, 5CH2), 1.15 ,t, 3H, CH3, Jˆ7.2 Hz).
NMR 13C ,100 MHz, CDCl3, d, ppm): 18a: 200.7 ,CO),
136.1, 131.5, 131.1, 127.8 ,4Cv), 54.8 ,CHCO), 41.1
,CHS), 30.2, 29.3, 27.1, 26.3 ,5CH2), 14.6 ,CH3), 18b:
198.9 ,CO), 140.2 ,C-q), 136.8, 136.6, 123.8 ,3CHv),
37.5 ,CH2CO), 29.9, 26.0, 25.8, 24.6, 23.9, 21.5 ,6CH2),
14.6 ,CH3). Found, %: C 69.29, H 8.77. C13H20SO. Calcd,
%: C 69.59, H 8.98.
3
CH3), 1.58 ,s, 3H, CH3), 1.18 ,t, 3H, CH3, Jˆ7.4 Hz).
NMR 13C ,100 MHz, CDCl3, d, ppm): 197.0 ,CO), 145.5,
136.8, 127.8, 112.3 ,4Cv), 51.0 ,C-q), 48.3 ,COCH2), 25.0
,SCH2), 22.4, 19.4 ,2CH3), 13.9 ,CH3). 15b. NMR 1H
,400 MHz, CDCl3, d, ppm): 6.23 ,br.s, 2H, H-4,E1Z)),
5.17±5.12 ,m, 4H, H-7,E1Z)), 3.02±2.45 ,m, 12H,
CH2SCH2CH2,E1Z)), 1.94 ,br.s, 3H, CH3,E or Z)), 1.90
,br.s, 3H, CH3,E or Z)), 1.89 ,br.s, 3H, CH3,E or Z)), 1.71
,br.s, 3H, CH3,E or Z)), 1.25±1.15 ,m, 6H, CH3,E1Z)).
NMR 13C ,100 MHz, CDCl3, d, ppm): 198.6 ,CO,E1Z)),
147.6, 141.2, 140.2, 123.5, 117.8, 115.9 ,8Cv,E1Z)), 40.5,
28.9, 28.9 ,SCH2CH2,E1Z)), 23.1, 22.7, 22.6, 19.3,
,4CH3,E1Z)), 15.0, 14.8 ,CH3,E1Z)). Found, %: C
66.64, H 9.47. C11H18OS. Calcd, %: C 66.62, H 9.15.
4.4. General procedure for polyeneones preparation 19±
23
To a solution of ethylsulfanyl substituted ketone ,or to a
mixture of ketones) in dichloromethane at 08C solution
of methyltri¯uoromethanesulfonate in dichloromethane
,1 equiv.) was added dropwise. The reaction mixture was
stirred at rt until the starting material disappears ,controlled
by TLC). Then an excess of saturated aqueous KHCO3 was
added and the reaction mixture was stirred 2 h. The organic
layer was separated, the aqueous layer was extracted with
ether ,2£20 mL). The combined organic phases were dried
,Na2SO4) and concentrated at reduced pressure. The crude
product was puri®ed by colomn chromatography.
4.3.9. 24E,6E)-1-2Ethylsulfanyl)-7-phenyl-4,6-heptadien-
3-one 216). Yield 64%, oil. IR ,n, cm21): 1660, 1640 ,CO,
CvC). NMR 1H ,400 MHz, CDCl3, d, ppm): 7.50±7.26 ,m,
3
6H, C6H5, H-6), 6.95 ,d, 1H, H-7, Jˆ15.6 Hz), 6.88 ,dd,
1H, H-5, 3Jˆ15.6, 10.2 Hz), 6.29 ,d, 1H, H-4, 3Jˆ15.6 Hz),
2.95±2.81 ,m, 4H, 2CH2), 2.55 ,q, 2H, S-CH2, 3Jˆ7.4 Hz),
1.25 ,t, 3H, CH3, 3Jˆ7.4 Hz). NMR 13C ,100 MHz, CDCl3,
d, ppm): 198.3 ,CO), 143.8, 142.9, ,2CHv), 135.8 ,C-q),
129.2, 129.1, 128.8, 127.2, 126.5 ,5CH-arom., 2CHv),
40.7, 26.2, 25.8 ,3CH2), 14.7 ,CH3). Found, %: C 73.55,
H 7.36. C15H18SO. Calcd, %: C 73.13, H 7.36.
4.4.1. 21E)-1-Phenyl-1,4-pentadien-3-one 219). Yield
1
73%, oil. IR ,n, cm21): 1670, 1640 ,CO, CvC). NMR H
,400 MHz, CDCl3, d, ppm): 7.67 ,d, 1H, H-2, 3Jˆ15.8 Hz),
3
7.60±7.30 ,m, 5H, C6H5), 7.01 ,d, 1H, H-1, Jˆ15.8 Hz),
3
4.3.10. 1-[2-2Ethylsulfanyl)-3-cyclohexenyl]-2-propen-1-
one 217a), 1-21,3-cyclohexadienyl)-3-2ethylsulfanyl)-1-
propanone 217b). 1:1, oil, yield 40%. IR ,n, cm21): 1690,
6.73 ,dd, 1H, H-4, Jˆ17.4, 10.6 Hz), 6.39 ,dd, 1H, H-4,
2
3
3Jˆ17.4 Hz, Jˆ1.2 Hz), 5.87 ,dd, 1H, H-4, Jˆ10.6 Hz,
2Jˆ1.2 Hz). NMR 13C ,100 MHz, CDCl3, d, ppm): 189.4
,CO), 143.9, 135.4 ,2CH), 134.5 ,C-q), 130.6, 128.9 ,2CH),
128.5 ,CH2), 128.4, 124.1 ,2CH). Found, %: C 83.08;H
9.99;C 11H10O. Calcd, %: C 83.51;H 10.11.
1
1630 ,CO, CvC). NMR H ,400 MHz, CDCl3, d, ppm):
3
17a: 6.56 ,dd, 1H, CH-acryl., Jˆ17.5, 10.6 Hz), 6.26 ,dd,
3
2
1H, CH2-acryl., Jˆ17.5 Hz, Jˆ1.4 Hz), 5.90±5.68 ,m,
3
2H, 2vCH-cyclohexen.), 5.76 ,dd, 1H, CH2-acryl., Jˆ
2
10.6 Hz, Jˆ1.4 Hz), 3.72 ,br.s, 1H, SCH), 3.17±3.10 ,m,
4.4.2. 1,1-Diphenyl-1,4-pentadien-3-one 220). Yield 91%,
oil. IR ,n, cm21): 1680, 1630 ,CO, CvC). NMR 1H
,400 MHz, CDCl3, d, ppm): 7.45±7.13 ,m, 10H, 2C6H5),
6.68 ,s, 1H, H-2), 6.12±6.07 ,m, 2H, H-4, H-5), 5.50±
5.40 ,m, 1H, H-5). NMR 13C ,100 MHz, CDCl3, d, ppm):
191.7 ,CO), 141.0, 138.9, 136.2, 130.0, 129.5, 128.9, 128.6,
128.4, 128.3, 127.4, 125.9 ,12C-arom., 2CvC). Found, %:
C 87.51;H 6.12;C 17H14O. Calcd, %: C 87.15;H 6.02.
3
1H, COCH), 2.55 ,q, 2H, SCH2-ethyl., Jˆ7.2 Hz), 2.15±
3
1.80 ,m, 4H, 2CH2-cyclohexen.), 1.24 ,t, 3H, CH3, Jˆ
7.2 Hz), 17b: 6.93 ,d, 1H, vCH-2-cyclohexen., 3Jˆ
5.6 Hz), 6.30±6.10 ,m, 2H, CHvCH), 2.95 ,t, 2H,
3
3
COCH2, Jˆ7.8 Hz), 2.80 ,t, 2H, SCH2CH2, Jˆ7.8 Hz),
3
2.55 ,q, 2H, SCH2-ethyl., Jˆ7.2 Hz), 2.41 ,t, 2H, CH2-6-
3
cyclohexen., Jˆ9.6 Hz), 2.29±2.18 ,m, 2H, CH2-5-cyclo-
hexen.), 1.24 ,t, 3H, CH3, 3Jˆ7.2 Hz). NMR 13C ,100 MHz,
CDCl3, d, ppm): 17a and 17b: 199.3, 198.1 ,CO), 135.2,
4.4.3. 1-22-Adamantyliden)-3-buten-2-one 221). Yield

9024
V. G. Nenajdenko et al. / Tetrahedron 57 +2001) 9017±9024
1
98%, oil. IR ,n, cm21): 1670, 1640 ,CO, CvC). NMR H
dichloromethane ,50 mL) was saturated with BF3 at
2608C. After stirring 10 min at 2608C trans-stylbene
,0.02 mole) in dichloromethane ,30 mL) was added. The
reaction mixture was allowed to warm up to the rt and
than poured into dry ether ,100 mL). The precipitate was
®ltered off, washed with cold methanol, dry ether and dried
in vacuo. Yield 59%, mp 109±1118C. IR ,n, cm21): 1760
,CO). NMR 1H ,400 MHz, CD3CN, d, ppm): 7.61±7.00 ,m,
3
,400 MHz, CDCl3, d, ppm): 6.38 ,dd, 1H, H-4, Jˆ17.6,
3
10.4 Hz), 6.17 ,d, 1H, H-5, Jˆ17.6), 6.10 ,s, 1H, H-2),
3
5.67 ,d, 1H, H-5, Jˆ10.4 Hz), 3.99 ,br.s, 1H, CH-allyl.),
2.39 ,br.s, 1H, CH-allyl.), 2.14±1.55 ,m, 12H, adamantyl).
NMR 13C ,100 MHz, CDCl3, d, ppm): 191.0 ,CO), 172.5
,C-q), 138.3 ,vCH2), 126.7, 115.2 ,2CHv), 41.6, 40.3,
39.2, 36.7, 33.3, 33.2, 27.8 ,adamantyl). Found, %: C
83.44;H 9.14;C 14H18O. Calcd, %: C 83.12;H 8.97.
3
10H, 2C6H5), 6.05 ,d, 1H, H-2, Jˆ13.8 Hz), 4.90 ,d, 1H,
3
2
H-3, Jˆ13.8 Hz), 4.42 ,d, 1H, Jˆ18.1 Hz, CH2CO), 4.25
,d, 1H, 2Jˆ18.1 Hz, CH2CO), 3.40±2.78 ,m, 2H, S1-CH2±
4.4.4. 1-21,3-Cyclohexadienyl)-2-propen-1-one 222).
Yield 88%. IR ,n, cm21): 1680, 1640 ,CO, CvC). NMR
1H ,400 MHz, CDCl3, d, ppm): 6.89 ,dd, 1H, COCHv,
3Jˆ17.0, 10.5 Hz), 6.88 ,d, 1H, H-2 cyclohexyl., 3Jˆ
3
CH3), 0.91 ,t, 3H, Jˆ7.2 Hz, S1-CH2±CH3). 13C NMR
,100 MHz, CD3CN, d, ppm): 200.0 ,CO), 132.7, 131.5,
130.4, 129.9, 129.6, 129.5, 129.0, 126.7 ,12C arom.),
59.5, 53.0 ,2CH), 43.7 ,CH2CO), 32.6 ,CH2CH3), 10.0
,CH2CH3). Found, %: C 58.38, H 5.26. C18H19BF4OS.
Calcd, %: C 58.40, H 5.17.
3
4.5 Hz), 6.19 ,dd, 1H, H-3 cyclohexyl., Jˆ4.5, 4.5 Hz),
3
2
6.19 ,dd, 1H, vCH2, Jˆ17.0 Hz, Jˆ2.0 Hz), 6.07±6.03
,m, 1H, H-4 cyclohexyl.), 5.62 ,dd, 1H, vCH2, 3Jˆ
2
10.5 Hz, Jˆ2.0 Hz), 2.44±2.40 ,m, 2H, COCCH2), 2.25±
2.17 ,m, 2H, CH2-5 cyclohexyl.). NMR 13C ,100 MHz,
CDCl3, d, ppm): 190.5 ,CO), 136.3 ,C-q), 135.4, 134.2,
131.1, 127.5, 124.0 ,4CHv, CH2v), 22.8, 19.8
,CH2CH2). Found, %: C 80.85;H 7.98;C 9H10O. Calcd,
%: C 80.56;H 7.51.
References
1. Shastin, A. V.;Balenkova, E. S. Zh. Org. Khim. 1983, 19,
659±660.
2. Gridnev, I. D.;Balenkova, E. S. Zh. Org. Khim. 1990, 26, 46±
53.
4.4.5. 1-21,3-Cyclooctadienyl)-2-propen-1-one 223). Yield
1
76%. IR ,n, cm21): 1680, 1650 ,CO, CvC). NMR H
,400 MHz, CDCl3, d, ppm): 7.00 ,br.s, H-2 cyclooctyl.),
3. Vertelezkij, P. V.;Balenkova, E. S. Zh. Org. Khim. 1990, 26,
2446±2447.
3
4. Nenajdenko, V. G.;Vertelezkij, P. V.;Balenkova, E. S.
Vestnik MGU Ser. 2. Khim. 1996, 37, 540±543.
5. Nenajdenko, V. G.;Balenkova, E. S. Zh. Org. Khim. 1993, 29,
687±688.
6.94 ,dd, 1H, COCHv, Jˆ17.2, 10.8 Hz), 6.21 ,dd, 1H,
3
2
vCH2, Jˆ17.2 Hz, Jˆ2.0 Hz), 5.90±5.87 ,m, 2H, H-3,
3
2
H-4 cyclooctyl.), 5.68 ,dd, 1H, vCH2, Jˆ10.8 Hz, Jˆ
2.0 Hz), 2.60±2.40 ,m, 2H, CH2-8 cyclooctyl), 2.25±2.10
,m, 2H, CH2-5 cyclooctyl.), 1.60±1.40 ,m, 4H, CH2-6,
CH2-7 cyclooctyl.). NMR 13C ,100 MHz, CDCl3, d, ppm):
191.6 ,CO), 140.8 ,C-q), 137.9, 136.8, 131.9, 127.8, 124.0
,4CHv, CH2v), 30.0, 25.1, 24.1, 21.7 ,4CH2-cyclooctyl.).
Found, %: C 81.65, H 8.91. C11H14O. Calcd, %: C 81.44, H
8.70.
6. Nenajdenko, V. G.;Leshcheva, I. F.;Balenkova, E. S.
Tetrahedron 1994, 50, 775±782.
7. Nenajdenko, V. G.;Gridnev, I. D.;Balenkova, E. S.
Tetrahedron 1994, 50, 11023±11038.
8. Nenajdenko, V. G.;Balenkova, E. S. Tetrahedron 1994, 50,
12407±12414.
9. Nenajdenko, V. G.;Lebedev, M. V.;Balenkova, E. S.
Tetrahedron Lett. 1995, 36, 6317±6320.
4.4.6. 1,1-Diphenyl-4-ethylsulfanylbut-1-en-3-one 224).
Yield 87%, oil. IR ,n, cm21): 1690 ,CO), 1620 ,CvC).
NMR H ,400 MHz, CDCl3, d, ppm): 7.42±7.20 ,m, 10H,
10. Nenajdenko, V. G.;Lebedev, M. V.;Balenkova, E. S. Synlett
1995, 11, 1133±1134.
1
11. Lebedev, M. V.;Nenajdenko, V. G.;Balenkova, E. S.
Tetrahedron 1998, 21, 5599±5606.
2C6H5), 6.77 ,s, 1H, vCH), 3.08 ,s, 2H, CH2), 2.32 ,q, 2H,
C
S-CH2, 3Jˆ7.6 Hz), 1.20 ,t, 3H, CH3, 3Jˆ7.6 Hz). NMR 13
12. Lebedev, M. V.;Nenajdenko, V. G.;Balenkova, E. S.
Synthesis 1998, 1, 89±93.
,100 MHz, CDCl3, d, ppm): 195.3 ,CO), 154.7 ,C-1), 140.7,
138.7, 129.5, 129.3, 128.6, 128.4, 128.3, 128.2, 124.4
,2C6H5, C-2), 40.8 ,C-4), 25.8 ,S-CH2-ethyl.), 14.1 ,CH3).
Found, %: C 76.71, H 6.09. C18H18SO. Calcd, %: C 76.56, H
6.42.
13. Nazarov, I. I. Uspehi Khim. 1951, 20, 71±122.
14. Kanischev, M. I.;Smith, W. A.;Schegolev, A. A.;Caple, R.
Bull. Russ. Acad. Sci. 1978, 1, 243±246.
4.4.7. Rel-22R,3R)-4-oxo-2,3-diphenyl-1-ethyltetrahydro-
thiophenium tetra¯uoroborate 225). A well stirred
solution of ethylsulfanylacetyl ¯uoride ,0.02 mole) in