A sulfoxide version of the Julia-Lythgoe olefination: A new method for the synthesis of olefins from carbonyl compounds and sulfoxides with carbon-carbon coupling

Article abstract of DOI:10.1016/S0040-4020(00)00585-8

Reaction of β-mesyloxy (or acetoxy) sulfoxides, derived from alkyl (or arylmethyl) phenyl sulfoxides and carbonyl compounds in two steps, with alkylmetals (n-BuLi, t-BuLi, or EtMgBr) at low temperature gave olefins in good to excellent yields. When the β-hydroxy sulfoxides derived from arylaldehydes were treated with mesyl chloride in the presence of triethylamine, the sulfoxides directly gave E-olefins in good yields. These reactions offer a sulfoxide version of the Julia-Lythgoe olefination. The reductive vicinal elimination was found to take place through the direct sulfoxide-metal exchange. The stereochemistry of the elimination was investigated and found to be stereospecific; however, the stereospecificity was found to be dependent on the substrates. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4020(00)00585-8

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 6223±6234
A Sulfoxide Version of the Julia±Lythgoe Ole®nation: A New
Method for the Synthesis of Ole®ns from Carbonyl Compounds
and Sulfoxides with Carbon±Carbon Coupling
*
Tsuyoshi Satoh, Noriko Hanaki, Noriko Yamada and Tohru Asano
Department of Chemistry, Faculty of Sciences, Science University of Tokyo, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Received 2 June 2000; accepted 21 June 2000
AbstractÐReaction of b-mesyloxy (or acetoxy) sulfoxides, derived from alkyl (or arylmethyl) phenyl sulfoxides and carbonyl compounds
in two steps, with alkylmetals (n-BuLi, t-BuLi, or EtMgBr) at low temperature gave ole®ns in good to excellent yields. When the b-hydroxy
sulfoxides derived from arylaldehydes were treated with mesyl chloride in the presence of triethylamine, the sulfoxides directly gave
E-ole®ns in good yields. These reactions offer a sulfoxide version of the Julia±Lythgoe ole®nation. The reductive vicinal elimination was
found to take place through the direct sulfoxide±metal exchange. The stereochemistry of the elimination was investigated and found to be
stereospeci®c; however, the stereospeci®city was found to be dependent on the substrates. q 2000 Elsevier Science Ltd. All rights reserved.
Needless to say, the formation of carbon±carbon double
bonds is one of the most important reactions in organic
synthesis.1 Especially, the methods including carbon±
carbon coupling are of high value. The Wittig and related
reactions, Peterson-type reactions, McMurry coupling,
Ramberg±Backlund reaction, and Julia±Lythgoe ole®n-
ation are well-known methods for the formation of ole®nic
compounds with carbon±carbon coupling.2
1-phenyl-1H-tetrazol-5-ylsulfones and aldehydes was
reported.8
The Julia±Lythgoe ole®nation entails some drawbacks in
the step of formation of the carbon±carbon bond with
a-sulfonyl carbanion and carbonyl compounds. Namely,
because the hydrogen on the carbon bearing the sulfonyl
group is highly acidic, in some cases especially when
ketones are used as the carbonyl compounds,5c the addition
reaction of a-sulfonyl carbanion with carbonyl compounds
is reversible with the equilibrium lying towards the starting
material.9 The acidity of the hydrogen is much higher when
R1 is an aromatic group. By this reason, no example of
ole®nation using aryl arylmethyl sulfones (1: R1ˆAryl)
has appeared so far.
The Julia±Lythgoe ole®nation is a method for the formation
of ole®ns 3 from sulfones 1 and carbonyl compounds via
b-hydroxy sulfones and their derivatives 2 in two or three
steps (Scheme 1).3 In the original papers3a,3b the authors
used Na±Hg as a reducing agent in the reductive vicinal
elimination. However, because of the high toxicity of Hg,
this step was improved by replacing Na±Hg with other
reducing agents such as lithium naphthalenide,4 SmI2,5
Mg,6 and electroreductive reaction.7 Recently, one-pot
synthesis of trans-1,2-disubstituted ole®ns using metallated
To overcome the problems described above, we planned to
use sulfoxides instead of the sulfones as shown in Scheme 2.
The advantages in using sulfoxides 4 are as follows. First, as
Scheme 1. Julia±Lythgoe ole®nation.
Keywords: sulfoxides; elimination; Julia±Lythgoe ole®nation; ole®nes; sulfoxide±metal exchange.
* Corresponding author. Tel.: 181-3-3260-4271; fax: 181-3-3235-2214; e-mail: tsatoh@ch.kagu.sut.ac.jp
0040±4020/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)00585-8

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T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
Scheme 2. Sulfoxide version of the Julia±Lythgoe ole®nation.
the acidity of the hydrogen on the carbon bearing sul®nyl
group is much lower than that of the sulfonyl group,10 the
coupling of a-sul®nyl carbanion with carbonyl compounds
could be expected to proceed smoothly even with ketones.
Second, aryl arylmethyl sulfoxide 4 (R1 or R2ˆAr) may be
used. If this is realized, the Julia±Lythgoe-type ole®nation
could be extended to a synthesis of stylene- and stilbene-
type ole®ns. Third, in the reductive vicinal elimination of 5,
the sulfoxide±metal exchange, which has been extensively
studied by our group,11 would be applied.12 In this case, no
toxic metal or expensive reagent is required.
Sulfoxide 7 (a diastereomeric mixture) was synthesized
from phenyl 3-phenylpropyl sulfoxide 6 and 3-phenyl-
propanal in 85% overall yield.
The b-mesyloxy sulfoxide 7 in THF was treated with
4 equiv.14 of n-BuLi at 2788C for 5 min. Fortunately, the
reaction gave a clean reaction mixture, from which the
desired ole®n 8 was obtained as a mixture of geometrical
isomers (E/Zˆ3:4)15 in 73% yield. tert-Butyllithium
(t-BuLi) was also found to be effective in this reaction.
Even ethylmagnesium bromide (EtMgBr) was effective in
this reaction; however, the yield of 8 was moderate.16 No
improvement of the yield of the ole®n 8 was obtained by
lowering the reaction temperature to 21008C.
In this paper we report in detail the development of a sulf-
oxide version of the Julia±Lythgoe ole®nation based on the
concept described above.13
In this reaction, two different reaction mechanisms would be
expected (Scheme 4). One is the direct b-elimination of the
sul®nyl and mesyloxy groups via the sulfoxide±metal
exchange (path a). The other is a two-step mechanism
(path b). First, the alkyllithium picks up the acidic hydrogen
on the carbon bearing the sul®nyl group to give a-sul®nyl
carbanion, which gives the vinylsulfoxide 9 by elimination
Results and Discussion
At ®rst, we investigated the feasibility for the vicinal elimi-
nation by the sulfoxide±metal exchange using b-mesyloxy
sulfoxide 7 as a representative example (Scheme 3).
Scheme 3.
Scheme 4.

T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
6225
Table 1. Synthesis of aryl-substituted ole®ns from arylmethyl phenyl sulfoxide and 3-phenylpropanal
Entry
11 (Ar)
Ph (11a)
12 (yield/%)
12a (92)
13 (yield/%)
13a (82)
Alkylmetal
14 yield/% (E/Z)
1
2
3
n-BuLi
t-BuLi
EtMgBr
14a 89 (10/7)
14a 92 (10/7)
14a 87 (10/7)
4
(11b)
12b (98)
12c (99)
13b (88)
13c (93)
n-BuLi
14b 90 (3/1)
5
6
7
8
t-BuLi
EtMgBr
n-BuLi
14b 68 (3/1)
14b 66 (3/1)
14c 93 (1/0)a
14c 73 (1/3)
14c 91 (1/0)a
14c 68 (1/3)
14c 75 (1/0)a
14c 98 (1/3)
(11c)
9
t-BuLi
10
11
12
EtMgBr
a The yield from the crystalline of 13c. See text.
of the mesyloxy anion. The vinylsulfoxide 9 is again
attacked by the alkylmetal17 to give vinyllithium 10,
which is protonated by quenching with water.
1 min the reaction was quenched with deuterated methanol.
No deuterium incorporation was observed in the
produced ole®n 8 by H NMR. From these results, we
1
concluded that the mechanism of the vicinal elimination
is a direct b-elimination via sulfoxide±metal exchange of 7
(path a).
To ascertain which path predominantly takes place, the
reaction was conducted with t-BuLi at 2788C and after
Table 2. Synthesis of aryl-substituted ole®ns from alkyl phenyl sulfoxide or arylmethyl phenyl sulfoxide and arylaldehydes
Entry
1
Sulfoxide (R)
PhCH2CH2 (6)
ArCHO (Ar)
15 (yield/%)a
15a (92)
16 (yield/%)a
16a (76)
2
3
15b (98)
15c (99)
16b (58)
16c (78)
(11b)
4
15d (99)
16d (65)
5
6
(11c)
15e (98)
15f (99)
16e (90)
16f (84)
a Isolated yield after silica gel column chromatography.

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T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
Scheme 5. A presumed mechanism for the elimination of 15 with mesyl chloride.
Synthesis of aryl-substituted 1,2-disubstituted ole®ns
from arylmethyl phenyl sulfoxides and 3-phenyl-
propanal
Addition of the a-sul®nyl carbanion of 6, 11b, and 11c to
piperonal and 1-naphthaldehyde gave the adducts 15a±f in
almost quantitative yields. The adduct 15a was then mesyl-
ated with 2 equiv. of mesyl chloride in CH2Cl2 in the
presence of triethylamine at room temperature. After
30 min, the starting material disappeared and, to our
surprise, the product was found to be not the expected
mesylate but ole®n 16a. The geometry of the ole®n was
As described above, the ole®nation using alkyl phenyl sulf-
oxide giving 1,2-dialkylated ole®n 8 was successful and we
next investigated a synthesis of aryl-substituted ole®ns from
arylmethyl phenyl sulfoxides. It is worth noting that, as
mentioned in the introduction, the Julia±Lythgoe ole®na-
tion with aryl arylmethyl sulfones is dif®cult.
1
determined to be E by H NMR. As shown in Table 2, all
the adducts 15a±f gave E-ole®ns 16a±f in one-operation in
about 60±90% yields.
The ole®nation from arylmethyl phenyl sulfoxide 11 and
3-phenylpropanal was quite successful, and the results are
summarized in Table 1. The ®rst step, addition of the
carbanion of arylmethyl phenyl sulfoxide 11 to 3-phenyl-
propanal gave almost quantitative yields (92±99%) of the
adduct 12. Mesylation of 12 with 2 equiv. of mesyl chloride
in the presence of triethylamine in dichloromethane gave
the mesylate 13 without any problem.
The mechanism of this reaction is presumed as follows
(Scheme 5). First, the hydroxy group of 15 is mesylated to
give the mesylate 17. As the mesyloxy group is placed on
the carbon bearing an aryl group, the mesyloxy group is
readily eliminated to give benzyl-type carbocation 18. A
nucleophile in the reaction mixture attacks the sul®nyl
group to give the ole®n 16. Because the cation 18 is
expected to be the most stable when R and Ar are in
s-trans conformation, the mixture of the diastereomers 15
stereoselectively affords the single E-ole®n. As the nucleo-
phile, we are surmising that the chloro anion from triethyl-
amine hydrochloride is the most likely at present.
The vicinal elimination of 13 with alkylmetals was investi-
gated under similar conditions as described in Scheme 3.
We obtained much better results compared with those from
the vicinal elimination of 7 (see Scheme 3). As shown in
Table 1, in the step for vicinal elimination with n-BuLi,
t-BuLi, even EtMgBr gave good to excellent yields. It is
noted that the mesylates 13a and 13b are a mixture of
diastereomers with respect to the three chiral centers. The
elimination of these mixtures gave predominantly E-ole®ns.
Synthesis of tri-substituted ole®ns from cyclohexanone
In order to investigate if this method can be extended to a
synthesis of tri-substituted ole®ns, we next examined the
reaction using cyclohexanone as a representative example
of ketones. The results are summarized in Table 3.
The results in entries 7, 9, and 11 are quite interesting. The
adduct of 11c with 3-phenylpropanal gave a mixture of the
diastereomers. In this case one of the isomers could be
isolated as a crystal (the relative stereochemistry is not
known yet). The crystalline isomer was mesylated and
then treated with alkylmetals to give a single geometrical
isomer, which was determined to be E-con®guration. This
result implies that the stereochemistry of the elimination
must be stereospeci®c, not stereoselective. The details of
The reaction of the a-sul®nyl carbanion of 6, 11b, and 11c
with cyclohexanone again gave the adduct 17 in almost
quantitative yields. However, we came across a problem
in the next step. Namely, mesylation of the a-hydroxy sulf-
oxide 17 with mesyl chloride under similar conditions as
described above gave only a complex mixture. One cause of
this dif®culty is the easily eliminative nature of the tertiary
mesylate.
the stereochemistry of this elimination are discussed later.
Synthesis of stylene- and stilbene-type ole®ns from
arylaldehydes
We next changed the mesylate to acetate, and this worked
well to afford the stable acetate 18 in good yields. The next
step was somewhat subtle. If the rate of the reaction of an
alkylmetal with the acetoxy group is faster than that with the
sul®nyl group, the elimination reaction of 18 would be
impossible. At any rate, 18b was treated with n-BuLi in
THF at 2788C for 5 min. Fortunately, this reaction also
We next extended the above-mentioned chemistry to use
arylaldehydes. If arylaldehydes can be used in the presented
method, we would obtain stylene- and stilbene-type ole®ns.
The results are summarized in Table 2.

T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
6227
Table 3. Synthesis of tri-substituted ole®ns from alkyl phenyl sulfoxide or arylmethyl phenyl sulfoxide and cyclohexanone
Entry
Sulfoxide (R)
PhCH2CH2 (6)
17 (yield/%)
17a (87)
18 (yield/%)
18aa (84)
Alkylmetal
19 (yield/%)
1
2
3
n-BuLi
t-BuLi
EtMgBr
19a (83)
19a (93)
19a (±)b
4
(11b)
17b (98)
17c (95)
18ba (70)
18c (81)
n-BuLi
19b (78)
5
6
t-BuLi
EtMgBr
19b (81)
19b (41)c
7
8
9
(11c)
n-BuLi
t-BuLi
EtMgBr
19c (84)
19c (80)
19c (23)c
a Although the acetates 18a and 18b are a mixture of separable diastereomers, the next reaction was carried out without sepatrtion of the diastereomers.
b No reaction.
c Considerable amount of the starting material 18 remained.
worked to give tri-substituted ole®n 19b in 78% yield. In
this reaction a small amount of the starting material was
recovered; however, no hydroxy compound 17b (the
product from the reaction of the acetoxy group with
n-BuLi) was observed. As shown in Table 3, t-BuLi was
found to be as effective as n-BuLi. However, the reaction
with EtMgBr was rather slow and after 5 min a considerable
amount of the acetate 18 remained in the reaction mixture.
Especially, EtMgBr did not work at all with the acetate 18a
(entry 3).
propanal and piperonal. The results are summarized in
Table 4.
The carbanion of 20 was added to the aldehydes to give the
adduct 21; however, the yields were found to be somewhat
lower than the yield of the reaction of the carbanions of
sulfoxides 6 and 11 with aldehydes. In these cases, the
adducts 21 are mixtures of two diastereomers, which were
separated easily by silica gel column chromatography. The
next step was conducted with these separated diastereomers
(expressed as L and P). The adduct 21a was acetylated as
above to give the acetate 22 in almost quantitative yield.
The elimination reaction of 22 was conducted with alkyl-
metals (entries 1±6). As shown in Table 4, EtMgBr was not
a good reagent for this reaction (entries 5 and 6). Both
n-BuLi and t-BuLi worked; however, the yields were
Synthesis of tri-substituted ole®ns from cyclohexyl p-
tolyl sulfoxide and aldehydes
Next, we investigated the reaction starting from a-branched
sulfoxide, cyclohexyl p-tolyl sulfoxide 20, with 3-phenyl-
Table 4. Synthesis of tri-substituted ole®ns from cyclohexyl p-tolyl sulfoxide and aldehydes
Entry
RCHO (R)
PhCH2CH2
21 (yield/%)
22 (yield/%)
22 (96)
Alkylmetal
Ole®n (yield/%)
1
2
3
4
5
6
21a (78) (L:Pˆ66:34)a
n-BuLi (from 22-L)
n-BuLi (from 22-P)
t-BuLi (from 22-L)
t-BuLi (from 22-P)
EtMgBr (from 22-L)
EtMgBr (from 22-P)
19a (43)
19a (90)
19a (63)
19a (79)
19a (17)
19a (±)b
c
7
8
21b (64) (L:Pˆ35:65)a
±
from 21b-L
from 21b-P
23 (54)
23 (71)
a The ratio of the less polar isomer (L) and the more polar isomer (P) on silica gel TLC.
b No reaction.
c The alcohol 21b was treated with mesyl chloride in the presence of triethylamine. Refer to the Table 2.

6228
T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
Scheme 6. Treatment of b-mesyloxy sulfoxide 25 with alkylmetals.
found to be variable with the isomers. Usually, the P-isomer
gave better yields than the L-isomer (entries 1±4). Mesyl-
ation of the adduct derived from aryl aldehyde 21b directly
gave the ole®n 23 in moderate to good yields (entries 7 and
8). Here again, the yields were found to be variable
depending on the diastereomers.
out with the Wittig reaction. However, we investigated the
feasibility for the methylenation of aldehydes by the
presented method starting from methyl phenyl sulfoxide
as a one-carbon unit. The results are shown in Scheme 6.
The reaction of the aldehyde 24 with the carbanion of methyl
phenyl sulfoxide gave a quantitative yield of the adduct,
which was mesylated in the usual way to give the mesylate
25. The results of the reaction of 25 with alkylmetals are
summarized in Scheme 6. The reaction with n-BuLi gave
the desired ole®n 26 in 33% yield; however, the main
product was vinylsulfoxide 27. In this case, n-BuLi reacted
with both the sul®nyl group and the acidic hydrogen on the
carbon bearing the sul®nyl group. The hydrogen on the
carbon bearing sul®nyl group of 25 is less sterically
hindered compared with other b-mesyloxy (or acetoxy)
sulfoxides, for example, 7, 13, 18, and 22. This is thought
to be the reason why the alkylmetals attack the acidic hydro-
gen to give vinylsulfoxides 27, 28, and 29.
An attempt to synthesize tetra-substituted ole®ns by using
cyclohexyl p-tolyl sulfoxide 20 with a ketone was exam-
ined. However, the reaction of lithium carbanion of 20 with
1,4-cyclohexanedione mono-ethylene ketal gave not the
desired adduct but a complex mixture. The synthesis of
tetra-substituted ole®ns by the presented method could not
be realized.
Trial to synthesize mono-substituted ole®ns and stereo-
speci®city of the presented procedure
Methylenation of aldehydes is most conveniently carried
Scheme 7.

T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
6229
EtMgBr was found to be the best reagent of the three. In this
case 26 was obtained in 61% yield with a mixture of vinyl-
sulfoxides 27 and 28 (10% yield). The reaction of 25 with
t-BuLi is very interesting. In this case, the desired 26 was
obtained in 39% yield; however, the main product was
ole®n having tert-butylsul®nyl group 29. The formation of
29 was presumed to take place through the ligand exchange
reaction18 of the produced vinyl sulfoxide 27 with t-BuLi.
(diastereomeric mixture; 1.85 g; 98%) as colorless crystals.
To a CH2Cl2 solution of 30 (1.41 g; 3.7 mmol) in a dried
¯ask was added Et3N (1.0 ml; 7.4 mmol) followed by MsCl
(0.6 ml; 7.4 mmol) at room temperature, and the stirring
was continued for 30 min. The reaction was quenched
with sat. aq. NH4Cl, and the mixture was extracted with
CH2Cl2. The organic layer was washed successively with
7% HCl, sat. aq. NaHCO3, and sat. aq. NH4Cl, and dried
over MgSO4. After removal of the solvent, the product was
puri®ed by silica gel column chromatography to give 7
(1.5 g; 87%) as a colorless oil (about 4:6:17:13 diastereo-
meric mixture). IR (neat) 3061, 3026, 2933, 2863, 1603,
1496, 1454, 1354, 1173, 1086 (SO), 1047 (SO), 750,
Finally, we studied the stereochemistry of the elimination.
As mentioned above (Table 1; entries 7±12), the elimination
of the b-mesyloxy sulfoxides with alkylmetals is thought to
proceed in a stereospeci®c manner. To elucidate the stereo-
chemical correlation between the b-mesyloxy sulfoxide and
the product, and ascertain whether the stereospeci®city is
high or low, we carried out the experiment shown in Scheme
7. First, the two main isomers of the adduct of 6 and
3-phenylpropanal were separated and the relative stereo-
chemistry (syn and anti) of the hydroxyl and the sul®nyl
1
700 cm21; H NMR d 1.68±1.94 (1H, m), 2.00±2.40 (4H,
m), 2.40±2.73 (2H, m), 2.80±3.02 (2H, m), 2.60 (0.36H, s),
3.00 (1.02H, s), 3.04 (1.38H, s), 3.23 (0.24H, s), 4.65
(0.12H, dt, Jˆ11.0, 2.5 Hz), 5.04 (0.46H, dt, Jˆ9.75,
3.05 Hz), 5.06 (0.34H, dt, Jˆ9.2, 3.5 Hz), 5.12 (0.08H, td,
Jˆ6.7, 1.5 Hz), 6.81±7.63 (15H, m).
1
groups was determined from H NMR by comparison of
the data with those of Bravo's report.19
1,6-Diphenyl-3-hexene (8). In a ¯ame-dried ¯ask, to a THF
solution of n-BuLi (0.72 mmol) at 2788C under argon
atmosphere was added a THF solution of 7 (80 mg;
0.18 mmol) dropwise with stirring, and the stirring was
continued for 5 min. The reaction was quenched with sat.
aq. NH4Cl, and the mixture was extracted with AcOEt. The
organic layer was washed with sat. aq. NH4Cl, and dried
over MgSO4. After removal of the solvent, the product was
puri®ed by silica gel column chromatography to give 8
(31 mg; 73%) as a colorless oil (about E/Zˆ3:4 mixture).
IR (neat) 3026, 2924, 1604, 1496, 1454, 747, 698 cm21; 1H
NMR d 2.28±2.32 (4H, m), 2.57 (2.3H, t, Jˆ7.8 Hz), 2.65
(1.7H, t, Jˆ7.8 Hz), 5.42 (1.14H, ddd, Jˆ5.5, 5.0, 0.8 Hz),
5.48 (0.86H, ddd, Jˆ5.0, 3.5, 1.5 Hz), 7.14±7.28 (10H, m);
13C NMR d 29.15 (Z: vinyl-C), 34.37 (E: vinyl-C), 35.82,
35.04, 125.68, 125.74, 128.22, 128.44, 129.43, 130.07,
142.03, 142.06. MS m/z (%) 236 (M1, 18), 145 (14), 91
(100). Calcd for C18H20: M, 236.1563. Found: m/z 236.1559.
anti-30 and syn-30 were mesylated to give anti-7 and syn-7,
respectively. These mesylates were treated with n-BuLi at
2788C. From anti-7 the produced ole®n 8 was found to be a
mixture of E and Z (E/Zˆ4:1). In contrast to this, the elimi-
nation of syn-7 gave an E/Z-mixture of 8, and the main
product was Z (E/Zˆ3:8). From these results it is concluded
that the elimination takes place mainly via trans-elimination
and that the stereospeci®city is dependent on the substrates;
the speci®city is in some cases high (see Table 1) and in
some cases not.
Experimental
1
All melting points are uncorrected. H NMR spectra were
measured in a CDCl3 solution with JEOL JNM-LA 400 and
500 spectrometer. Electron-impact mass spectra (MS) were
obtained at 70 eV by direct insertion. Silical gel 60
(MERCK) containing 0.5% ¯uorescence reagent 254 and
quartz column were used for column chromatography and
the products having UV absorption were detected by UV
irradiation. In experiments requiring a dry reagent and
solvent, diisopropylamine and triethylamine were distilled
from CaH2 and THF was distilled from diphenylketyl.
Methanol and liquid N2 were used for the cooling bath at
21008C.
1,4-Diphenyl-1-phenylsul®nyl-2-butanol (12a). Above-
mentioned reaction was carried out with benzyl phenyl sulf-
oxide to give 12a as colorless crystals (diastereomeric
mixture) in 92% yield. IR (neat) 3384, 3059, 3026, 2911,
2859, 1600, 1493, 1454, 1442, 1085(SO), 1040(SO), 749,
1
700 cm21; H NMR d 1.71±2.16 (2H, m), 2.67±2.81 (2H,
m), 3.39±3.8 (1H, m), 4.48±4.86 (1H, m), 5.44 (1H, bs,
OH), 6.81±7.38 (15H, m).MS m/z (%) 351 (M1, 0.7), 225
(10), 207 (30), 126 (13), 91 (100), 77 (10). Calcd for
C22H23O2S: M, 351.1419. Found: m/z 351.1406.
3-Mesyloxy-1,6-diphenyl-4-phenylsul®nylhexane (7). To
a THF solution (25 ml) of diisopropylamine (0.9 ml;
6.5 mmol) in a ¯ame-dried ¯ask was added n-BuLi
(6.5 mmol) at 08C under argon atmosphere. After 15 min,
the solution was cooled to 2558C and 3-phenylpropyl
phenyl sulfoxide 6 (1.12 g; 5 mmol) in THF was added
dropwise with stirring. After 15 min, 3-phenylpropanal
(0.86 ml; 6.5 mmol) in THF was added to the reaction
mixture at 2558C, and the stirring was continued for
30 min. The reaction was quenched with sat. aq. NH4Cl,
and the mixture was extracted with AcOEt. The organic
layer was washed with sat. aq. NH4Cl and dried over
MgSO4. After removal of the solvent, the product was
puri®ed by silica gel column chromatography to give 30
3-Mesyloxy-1,4-diphenyl-4-phenylsul®nylbutane (13a).
Colorless oil; IR (neat) 3031, 2934, 2863, 1602, 1496,
1454, 1354, 1173, 1086(SO), 1047(SO), 748, 700 cm21
;
1H NMR d 1.81±2.17 (2H, m), 2.70±3.01 (2H, m), 3.13,
3.16, 3.37, 3.41 (each s, CH3), 3.55±3.80 (1H, m), 5.46±
5.56 (1H, m), 6.94±7.34 (15H, m).
1,4-Diphenyl-1-butene (14a). Colorless oil (about E/Zˆ
10:7 mixture); IR (neat) 3060, 3025, 2924, 2853, 1601,
1
1495, 1453, 741, 698 cm21; H NMR d 2.50±2.55 (1H, m),
2.63±2.68 (1H, m), 2.74±2.80 (2H, m), 5.75 (0.41H, dt,
Jˆ11.3, 7.5 Hz), 6.25 (0.59H, dt, Jˆ16.0, 6.5 Hz), 6.44
(0.59H, d, Jˆ16,0 Hz), 6.46 (0.41H, d, Jˆ11.3 Hz), 7.17±

6230
T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
7.33 (10H, m). MS m/z (%) 208 (M1, 26), 117 (100), 91 (24).
Calcd for C16H16: M, 208.1252. Found: m/z 208.1257.
m), 3.79 (0.75H, s), 3.80 (2.25H, s), 5.61 (0.75H, dt,
Jˆ11.6, 5.8 Hz), 6.11 (0.25H, dt, Jˆ15.8, 6.0 Hz), 6.36
(1H, m), 6.82±6.87 (2H, m), 7.17±7.32 (7H, m). MS m/z
(%) 238 (M1, 13), 147 (100), 91 (21). Calcd for C17H18O:
M, 238.1357. Found: m/z 238.1363. (E)-isomer: Colorless
oil; IR (neat) 2999, 2923, 2834, 1605, 1510, 1249, 1029,
1-(1-Naphthyl)-4-phenyl-1-phenylsul®nyl-2-butanol (12b).
Colorless crystals (diastereomeric mixture); IR (KBr) 3366,
3058, 2922, 1596, 1509, 1444, 1086 (SO), 1029 (SO), 802,
1
1
780, 746, 699 cm21; H NMR d 1.23±2.05 (2H, m), 2.60±
718, 695 cm21; H NMR d 2.50 (2H, dd, Jˆ15.2, 7.2 Hz),
3.02 (2H, m), 4.34±4.69 (1H, m), 4.70±4.90 (1H, m), 6.91±
8.00 (17H, m).
2.78 (2H, t, Jˆ7.9 Hz), 3.79 (3H, s), 6.11 (1H, dt, Jˆ15.8,
6.8 Hz), 6.36 (1H, d, Jˆ15.8 Hz), 6.83 (2H, d, Jˆ8.8 Hz),
7.17±7.32 (7H, m). MS m/z (%) 238 (M1, 15), 147 (100),
115 (9), 91 (18). Calcd for C17H18O: M, 238.1357. Found:
m/z 238.1360.
2-Mesyloxy-1-(1-naphthyl)-4-phenyl-1-phenylsul®nylbu-
tane (13b). Colorless crystals (about 1:3:3:13.5 diastereo-
meric mixture); IR (KBr) 3024, 2930, 1596, 1496, 1444,
1355, 1173, 1087 (SO), 1046 (SO), 781, 746, 699 cm21
;
1-(3,4-Methylenedioxyphenyl)-4-phenyl-2-phenysul®nyl-
1-butanol (15a). Colorless oil (diastereomeric mixture); IR
(neat) 3320, 3061, 3026, 2897, 2779, 1604, 1504, 1486,
1H NMR d 1.62±2.47 (2H, m), 2.57±3.10 (2H, m), 3.21
(0.44H, s), 3.32 (0.15H, s), 3.39 (0.44H, s), 3.46 (1.97H,
s), 4.30±4.90 (1H, m), 5.56±5.72 (1H, m), 6.77±8.00 (17H,
m).
1
1445, 1248, 1085(SO), 1036(SO), 932, 746, 700 cm21; H
NMR d 1.82±2.04 (4H, m), 2.67±2.70 (1H, m), 3.27 (1H, d,
Jˆ1.5 Hz), 5.44 (1H, bs), 5.97 (2H, s), 6.57±7.72 (13H, m).
MS m/z (%) 400 (M1, 0.5), 256 (98), 183 (99), 165 (100),
91(96). Calcd for C26H24O2S: M, 400.1497. Found: m/z
400.1506.
1-(1-Naphthyl)-4-phenyl-1-butene (14b). Colorless oil
(about E/Zˆ3:1 mixture); IR (neat) 3059, 3026, 2924,
1
2853, 1646, 1603, 1590, 1496, 1453, 777, 698 cm21; H
NMR d 2.44±2.51 (0.5H, m), 2.62±2.74 (2H, m), 2.88
(1.5H, t, Jˆ15.2 Hz), 5.97 (0.25H, dt, Jˆ11.4, 7.3 Hz),
6.24 (0.75H, dt, Jˆ15.2, 6.9 Hz), 6.89 (0.25H, d, Jˆ
11.4 Hz), 7.09 (0.75H, d, Jˆ15.5 Hz), 7.09±8.04 (12H,
m). MS m/z (%) 258 (M1, 25), 167 (100), 91 (7). Calcd
for C20H18: M, 258.1408. Found: m/z 258.1416.
(E)-1-(3,4-Methylendioxyphenyl)-4-phenyl-1-butene (16a).
Colorless oil; IR (neat) 3062, 3026, 2896, 2778, 1604, 1503,
1489, 1446, 1249, 1040, 964, 929, 749, 700 cm21; 1H NMR
d 2.49 (2H, dd, Jˆ14.9, 7.3 Hz), 2.77 (2H, t, Jˆ7.2 Hz),
5.93 (2H, s), 6.07 (1H, dt, Jˆ15.7, 6.8 Hz), 6.32 (1H, d,
Jˆ15.8 Hz), 6.73 (2H, s), 6.88 (1H, s), 7.17±7.32 (5H,
m). MS m/z (%) 252 (M1, 40), 161 (69), 131 (100), 103
(50), 77 (19). Calcd for C17H16O2: M, 252.1149. Found: m/z
252.1143.
1-(4-Methoxyphenyl)-4-phenyl-1-phenylsul®nyl-2-buta-
nol (12c). 12c-oil: Colorless oil (diastereomeric mixture);
IR (neat) 3381, 3025, 2933, 2837, 1609, 1513, 1454, 1444,
1609, 1513, 1253, 1086(SO), 1030(SO), 746, 700 cm21; 1H
NMR d 1.43±1.97 (2H, m), 2.57±2.87 (2H, m), 3.53±3.65
(1H, m), 3.75, 3.78 (each s, CH3), 4.56±4.81 (1H, m), 6.62±
7.51 (14H, m). 12c-crystal: Colorless crystals; IR (KBr)
3328, 3057, 3024, 2931, 2837, 1610, 1513, 1458, 1444,
1-(1-Naphthyl)-4-phenyl-2-phenylsul®nyl-1-butanol (15b).
Colorless crystals (diastereomeric mixture); IR (neat) 3284,
1596, 1508, 1444, 1085(SO), 1028(SO), 782, 739,
1
697 cm21; H NMR d 1.69±2.56 (4H, m), 2.77±3.14 (1H,
1
1248, 1088, 1038, 748, 698 cm21; H NMR d 1.64±2.12
m), 5.70±6.30 (1H, m), 6.28±7.90 (17H, m). MS m/z (%)
394 (M1, 0.1), 268 (48), 208 (44), 151 (100), 93 (69). Calcd
for C23H22O4S: M, 394.1239. Found: m/z 394.1209.
(2H, m), 2.68±2.94 (2H, m), 3.39 (0.52H, d, Jˆ5.9 Hz),
3.65 (0.46H, d, Jˆ10.3 Hz), 3.74 (1.63H, s), 3.75 (1.37H,
s), 4.50±4.62 (1H, m), 6.70±7.37 (14H, m). Anal. Calcd for
C23H24O3S: C, 72.60; H, 6.36; S, 8.43. Found: C, 72.53; H,
6.39; S, 8.51.
(E)-1-(1-Naphthyl)-4-phenyl-1-butene (16b). Colorless
oil; IR (neat) 3060, 3026, 2924, 2853, 1650, 1603, 1590,
1508, 1454, 792, 776, 747, 699 cm21;1H NMR d 2.66 (2H,
dd, Jˆ8.0, 14.9 Hz), 2.88 (2H, t, Jˆ8.0 Hz), 6.25 (1H, dt,
Jˆ15.6, 6.8 Hz), 7.10 (1H, d, Jˆ15.6 Hz), 7.20±8.03 (12H,
m). MS m/z (%) 258 (M1, 25), 167 (100), 152 (19), 91 (11).
Calcd for C20H18: M, 258.1407. Found: m/z 258.1407.
2-Mesyloxy-1-(4-methoxyphenyl)-4-phenyl-1-phenylsul-
®nylbutane (13c). 13c-oil: Colorless oil (diastereomeric
mixture); IR (neat) 3061, 3026, 2931, 2857, 1609, 1514,
1456, 1360, 1253, 1173, 1084(SO), 1040(SO), 749,
1
700 cm21; H NMR d 1.89±2.36 (2H, m), 2.61±2.80 (2H,
m), 3.16, 3.38, 3.40 (each s, CH3), 3.75, 3.77, 3.97 (each s,
CH3), 5.39±5.52 (1H, m), 6.54±7.58 (14H, m). 13c-crystal:
Colorless crystals; IR (KBr) 3058, 3024, 2933, 2840, 1610,
1-(3,4-Methylenedioxyphenyl)-2-(1-naphthyl)-2-phenyl-
sul®nylethanol (15c). Colorless oil (diastereomeric
mixture); IR (neat) 3299, 3061, 2889, 2779, 1595, 1504,
1444, 1245, 1087 (SO), 1036 (SO), 998, 928, 802, 779,
1
1514, 1355, 1255, 1174, 1085, 1034, 748, 698 cm21; H
1
NMR d 2.63±2.69 (1H, m), 2.78±2.91 (2H, m), 2.97±
3.03 (3H, m), 3.40 (3H, s), 3.69 (1H, d, Jˆ11.0 Hz), 3.75
(3H, s), 5.44 (1H, dt, Jˆ11.0, 4.3 Hz), 6.64±7.38 (14H, m).
Anal. Calcd for C24H26O5S2: C, 62.86; H, 5.71; S, 13.98.
Found: C, 62.17; H, 5.78; S, 14.02.
749, 691 cm21, H NMR d 4.36 (0.3H, d, Jˆ12.7 Hz),
4.72 (0.5H, d, Jˆ10.2 Hz), 4.85 (0.1H, d, Jˆ9.5 Hz), 4.85
(0.1H, d, Jˆ10.3 Hz), 5.67±5.76 (1H, m), 6.01±6.02 (2H,
dd, Jˆ3.7, 1.5 Hz), 6.35±8.12 (10H, m).
(E)-1-(3,4-Methylenedioxyphenyl)-2-(1-naphthyl)ethene
(16c). Colorless crystals; mp 105±1078C (AcOEt±hexane);
IR (KBr) 3057, 3009, 2891, 2777, 1604, 1589, 1503, 1488,
1-(4-Methoxyphenyl)-4-phenyl-1-butane (14c) and (E)-
isomer. 14c: Colorless oil (about E/Zˆ1:3 mixture); IR
(neat) 3061, 3025, 3004, 2932, 2853, 1607, 1511, 1454,
1248, 1035, 746, 700 cm21;1H NMR d 2.36±2.79 (4H,
1
1446, 1253, 1233, 1040, 958, 932, 803, 790, 773 cm21; H
NMR d 6.00 (2H, s), 6.84 (1H, d, Jˆ7.9 Hz), 7.02 (1H, dd,

T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
6231
Jˆ7.8, 1.5 Hz), 7.07 (1H, d, Jˆ16.0 Hz, vinyl-H), 7.05 (1H,
d, Jˆ1.5 Hz), 7.71 (1H, d, Jˆ16.0 Hz, vinyl-H), 7.46±8.21
(7H, m). MS m/z (%) 274 (M1, 100), 215 (49), 152 (12).
Calcd for C19H14O2: M, 274.0993. Found: m/z 274.0995.
Anal. Calcd for C19H14O2: C, 83.19; H, 5.14. Found: C,
82.80; H, 5.01.
(E)-1-(4-Methoxyphenyl)-1-(1-naphthyl)ethene
(16f).
Colorless crystal; mp 92±938C (AcOEt±hexane); IR
(KBr) 2956, 1604, 1510, 1255, 1173, 1031, 825, 798, 782,
770 cm21; 1H NMR d 3.85 (3H, s), 6.94 (2H, d, Jˆ8.6 Hz),
7.10 (1H, d, Jˆ15.9 Hz, vinyl-H), 7.49 (1H, d, Jˆ15.9 Hz,
vinyl-H), 7.46±8.23 (9H, m). MS m/z (%) 260 (M1, 100),
229 (18), 215 (24), 152 (14). Calcd for C19H16O: M,
260.1201. Found: m/z 260.1205. Anal. Calcd for C19H16O:
C, 87.66; H, 6.20. Found: C, 87.34; H, 6.11.
1,2-Di(1-naphthyl)-2-phenylsul®nylethanol (15d). Color-
less oil (about 6:8:9:11 diastereomeric mixture); IR (neat)
3357, 3059, 3008, 1596, 1512, 1444, 1084(SO), 1036(SO),
778, 750 cm21; 1H NMR d 5.20 (0.32H, d, Jˆ7.6 Hz), 5.36
(0.18H, d, Jˆ9.0 Hz), 5.54 (0.24H, d, Jˆ9.3 Hz), 6.07
(0.26H, d, Jˆ8.5 Hz), 6.35 (0.32H, d, Jˆ9.3 Hz), 6.46
(0.24H, d, Jˆ9.3 Hz), 6.53 (0.26H, ddd, Jˆ8.6, 6.8,
1.5 Hz), 6.64 (0.18H, d, Jˆ9.3 Hz), 6.86±8.51 (19H, m).
MS m/z (%) 422 (M1, 0.09), 280 (30), 155 (100), 127
(54). Calcd for C28H22O2S: M, 422.1341. Found: m/z
422.1348.
1-(3-Phenyl-1-phenylsul®nylpropyl)cyclohexanol (17a).
Colorless crystals (about 3:19 diastereomeric mixture); IR
(KBr) 3382, 2937, 2855, 1444, 1088 (SO), 1027 (SO), 747,
698 cm21 1H NMR d 1.24±2.28 (14H, m), 2.47±2.49
;
(0.85H, m), 2.89±2.90 (0.15H, m), 6.74±7.83 (10H, m).
MS m/z (%) 342 (M1, 0.8), 217 (61), 117 (72), 91 (100).
Calcd for C21H26O2S: M, 342.1654. Found: m/z 342.1648.
1-(1-Acetoxycyclohexyl)-3-phenyl-1-phenylsul®nylpro-
pane (18a). To a solution of 17a (870 mg; 2.54 mmol) in
pyridine (3.6 ml) was added acetic anhydride (3.0 ml) and
DMAP (62.3 mg; 0.51 mmol) with stirring at room tempera-
ture and the reaction mixture was stirred at room tempera-
ture for 30 h. After removal of excess pyridine and acetic
anhydride under vacuum, the product was puri®ed by silica
gel column chromatography to give 18a (822 mg; 84%) as a
colorless oil (about 3:19 diastereomeric mixture). The
isomers were easily separated. 18a-L: Colorless oil; IR
(neat) 3060, 3026, 2935, 2862, 1730, 1496, 1478, 1445,
1369, 1284, 1263, 1233, 1131, 1086, 1047 (SO), 1020
(E)-1,2-Di(1-naphthyl)ethene (16d). Colorless crystals;
mp 162.5±164.58C (AcOEt±hexane); IR (neat) 3043,
1
1648, 1590, 1508, 800, 773 cm21; H NMR d 7.91 (2H,
s), 7.50±8.26 (14H, m). MS m/z (%) 280 (M1, 100), 152
(24). Calcd for C22H16: M, 280.1252. Found: m/z 280.1253.
Anal. Calcd for C22H16: C, 94.25; H, 5.75. Found: C, 93.78;
H, 5.68.
2-(4-Methoxyphenyl)-1-(3,4-methylendioxyphenyl)-2-
phenylsul®nylethanol (15e). Colorless crystals (about
3:3:6:13 diastereomeric mixture); IR (KBr) 3262, 2901,
2836, 1610, 1512, 1488, 1444, 1251, 1085 (SO), 1036
1
(SO), 754, 700 cm21; H NMR d 1.19±1.72 (10H, m),
1
(SO), 747 cm21; H NMR d 3.57 (0.52H, d, Jˆ8.6 Hz),
1.77 (1H, ddd, Jˆ12.1, 5.4, 2.9 Hz), 1.97 (1H, ddd,
Jˆ12.2, 6.4, 2.9 Hz), 2.13 (3H, s), 2.35±2.47 (2H, m),
3.76 (1H, dd, Jˆ6.4, 3.0 Hz), 6.81±7.62 (10H, m). MS
m/z (%) 384 (M1, 0.3), 199 (29), 167 (53), 125 (100), 91
(71), 78 (33). Calcd for C23H28O3S: M, 384.1759. Found:
m/z 384.1751. 18a-P: Colorless oil; IR (neat) 3026, 2936,
2863, 1731, 1714, 1445, 1359, 1318, 1234, 1154, 1127,
3.64 (0.12H, d, Jˆ2.7 Hz), 3.69 (0.36H, s), 3.73 (0.72H,
s), 3.76 (1.56H, s), 3.77(0.36H, s), 3.84 (0.24H, d, Jˆ
9.5 Hz), 3.87 (0.12H, d, Jˆ9.8 Hz), 5.42 (0.24H, d, Jˆ
10.2 Hz), 5.45 (0.52H, d, Jˆ8.5 Hz), 5.55 (0.12H, d, Jˆ
8.6 Hz), 5.65 (0.12H, d, Jˆ2.7 Hz), 5.83 (0.28H, dd, Jˆ
3.3, 1.4 Hz), 5.85 (0.28H, m), 6.00 (0.44H, dd, Jˆ5.1,
1.4 Hz), 6.51±7.43 (12H, m).
1
1086 (SO), 1047 (SO), 752, 700 cm21; H NMR d 1.18±
1.73 (10H, m), 1.78 (1H, ddd, Jˆ12.0, 5.6, 2.9 Hz), 1.98
(1H, ddd, Jˆ11.8, 6.6, 3.2 Hz), 2.31 (3H, s), 2.39±2.52 (2H,
m), 3.89 (1H, dd, Jˆ3.4, 3.0 Hz), 6.82±7.64 (10H, m).
(E)-1-(4-Methoxyphenyl)-2-(3,4-methylenedioxyphenyl)-
ethene (16e). Colorless crystals; mp 141±1438C (AcOEt±
hexane); IR (KBr) 2956, 2836, 1602, 1512, 1449, 1255,
1
1029, 964, 956, 924, 824, 791 cm21; H NMR d 6.78
1-Cyclohexylidene-3-phenylpropane (19a). This com-
pound was derived from the mixture of 18a-L and 18a-P;
colorless oil; IR (neat) 3062, 3026, 2926, 2852, 1604, 1495,
1446, 747, 698 cm21; 1H NMR d 1.37±1.54 (6H, m), 2.02±
2.07 (4H, m), 2.30 (2H, dd, Jˆ15.4, 7.4 Hz), 2.63 (2H, t,
Jˆ7.3 Hz), 5.12 (1H, t, Jˆ7.3 Hz), 7.17±7.29 (5H, m). MS
m/z (%) 200 (M1, 27), 109 (100), 91 (39), 67 (72). Calcd for
C15H20O: M, 200.1564. Found: m/z 200.1577.
(1H,d, Jˆ8.0 Hz), 6.88 (2H, d, Jˆ8.6 Hz), 6.88 (2H, s),
6.90 (1H,dd, Jˆ8.3, 1.9 Hz), 7.04 (1H, d, Jˆ1.9 Hz),
7.41 (2H, d, Jˆ8.9 Hz). MS m/z (%) 254 (M1, 100),
239 (12), 181 (15), 153 (20), 127 (7). Calcd for
C16H14O3: M, 254.0942. Found: m/z 254.0938. Anal.
Calcd for C16H14O3: C, 75.57; H, 5.55. Found: C, 75.17;
H, 5.40.
2-(4-Methoxyphenyl)-1-(1-naphthyl)-2-phenylsul®nyl-
ethanol (15f). Colorless crystals (diastereomeric mixture);
IR (KBr) 3313, 3055, 2930, 2835, 1609, 1509, 1458, 1442,
1252, 1085(SO), 1032(SO), 780, 747, 689 cm21; 1H NMR d
3.60 (0.78H, s), 3.62 (0.86H, s), 3.74 (0.27H, s), 3.75 (1.0H,
s), 4.03 (0.34H, d, Jˆ6.8 Hz), 4.21 (0.5H, b), 4.33 (0.32H, d,
Jˆ9.3 Hz), 4.40 (0.25H, d, Jˆ9.5 Hz), 6.24 (0.35H, d, Jˆ
9.2 Hz), 6.25 (0.38H, d, Jˆ7.1 Hz), 6.37 (0.27H, d, Jˆ
9.5 Hz), 6.44±8.35 (16H, m). MS m/z (%) 402 (M1, 0.07),
277 (46), 155 (99), 127 (99), 121 (100). Calcd for
C25H22O3S: M, 402.1290. Found: m/z 402.1293.
1-[(1-Naphthyl)(phenylsul®nyl)methyl]cyclohexanol (17b).
A mixture of colorless crystals and oil (about 4.5:5 dia-
stereomeric mixture); IR (KBr) 3357, 2930, 1509, 1444,
1
1013 (SO), 781, 750, 688 cm21; H NMR d 0.86±2.05
(9H, m), 2.25±2.45 (1H, m), 4.51 (0.53H, s), 4.99 (0.47H,
s), 6.89±8.30 (12H, m).
1-Acetoxy-1[(1-naphthyl)(phenylsul®nyl)methyl]cyclo-
hexane (18b). Colorless oil (about 1:2 diastereomeric
mixture), the isomers were easily separated by silica gel
column chromatography. 18b-L: Colorless oil; IR (neat)

6232
T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
3060, 2935, 2861, 1729, 1714, 1569, 1512, 1445, 1368,
1258, 1232, 1088, 1052 (SO), 1020 (SO), 803, 784, 751,
9.8, 5.2 Hz), 3.92 (1H, dd, Jˆ11.0, 2.1 Hz), 7.14±7.54 (9H,
m). Anal. Calcd for C22H28O2S: C, 74.12; H, 7.92; S, 8.99.
Found: C, 74.02; H, 7.93; S, 8.91.
1
691 cm21; H NMR d 0.96±1.04 (2H, m), 1.38±1.45 (2H,
m), 1.59±1.68 (2H, m), 1.77 (1H, ddt, Jˆ26.0, 12.9,
3.4 Hz), 1.95 (1H, dt, Jˆ12.9, 4.1 Hz), 2.31 (3H, s), 3.72
(1H, dd, Jˆ13.9, 1.9 Hz), 2.80 (1H, d, Jˆ13.4 Hz), 5.84
(1H, s), 6.91±8.14 (12H, m). 18b-P: Colorless oil; IR
(neat) 3053, 2935, 2864, 1732, 1714, 1596, 1512, 1445,
1359, 1323, 1241, 1129, 1082 (SO), 1049 (SO), 807, 786,
1-Acetoxy-3-phenyl-1-(1-p-tolylsul®nylcyclohexyl)pro-
pane (22). 22-L: Colorless oil; IR (neat) 3026, 2932, 2862,
1738, 1494, 1454, 1372, 1231, 1081 (SO), 1043 (SO), 812,
1
753, 700 cm21; H NMR d 1.26±1.31 (2H, m), 1.51±1.77
(10H, m), 1.86±1.98 (1H, m), 1.98 (3H, s), 2.42 (3H, s), 2.55
(1H, ddd, Jˆ14.4, 9.8, 5.1 Hz), 5.48 (1H, dd, Jˆ11.2,
2.2 Hz), 7.07±7.27 (5H, m), 7.29 (2H, d, Jˆ8.3 Hz), 7.48
(2H, d, Jˆ8.04 Hz). MS m/z (%) 399 (M1, 0.2), 216 (39),
198 (98), 91 (100), 77(20). Calcd for C24H31O3S: M,
399.1994. Found: m/z 399.2001. 22-P: Colorless oil; IR
(neat) 3026, 2934, 2964, 1738, 1494, 1454, 1372, 1232,
1
756, 690 cm21; H NMR d 1.03±1.07 (2H, m), 1.52±1.74
(7H, m), 2.12 (1H, dt, Jˆ12.4, 4.9 Hz), 2.35 (3H, s), 2.77
(1H, dd, Jˆ13.9, 2.2 Hz), 2.83 (1H, dd, Jˆ13.0, 2.9 Hz),
6.33 (1H, s), 6.87±7.91 (12H, m).
Cyclohexylidene(1-naphthyl)methane (19b). Colorless
oil; IR (neat) 3042, 2926, 2852, 1655, 1590, 1446, 801,
1
1079 (SO), 1031 (SO), 812, 753, 700 cm21; H NMR d
1
781 cm21; H NMR d 1.51 (2H, m), 1.61 (2H, m), 1.73
1.32±1.49 (4H, m), 1.62±1.80 (6H, m), 1.86 (3H, s),
2.14±2.34 (2H, m), 2.42 (3H, s), 2.44±2.50 (1H, m),
2.54±2.62 (1H, m), 5.32 (1H, dd, Jˆ10.5, 2.2 Hz), 7.18±
7.31 (7H, m), 7.48 (2H, d, Jˆ8.0 Hz).
(2H, m), 2.18 (2H, t, Jˆ6.1 Hz), 2.42 (2H, t, Jˆ5.9 Hz),
6.58 (1H, s), 7.25±8.04 (7H, m). MS m/z (%) 222 (M1,
100), 179 (44), 165 (80), 141 (35), 128 (12). Calcd for
C17H18: M, 222.1407. Found: m/z 222.1397.
[(3,4-Methylenedioxyphenyl)(1-p-tolylsul®nylcyclohexyl)]-
methanol (21b). 21b-L: Colorless oil; IR (neat) 3319, 2934,
2863, 1597, 1504, 1488, 1452, 1240, 1093 (SO), 1040 (SO),
1-[(4-Methoxyphenyl)(phenylsul®nyl)methyl]cyclohexa-
nol (17c). Colorless crystals (about 1:2 diastereomeric
mixture); IR (KBr) 3366, 3051, 2931, 2846, 1610, 1511,
1458, 1444, 1253, 1180, 1083 (SO), 1032 (SO), 1012,
1
998, 932, 812, 733 cm21; H NMR d 1.09±1.82 (8H, m),
1.83±2.06 (1H, m), 2.48 (3H, s), 2.67±2.72 (1H, m), 4.83
(1H, s), 5.92 (2H, q), 6.12 (1H, s), 6.54 (1H, dd, Jˆ8.1,
1.5 Hz), 6.68, (1H, d, Jˆ8.0 Hz), 6.75 (1H, d, Jˆ1.7 Hz),
7.41 (2H, d, Jˆ7.8 Hz), 7.64 (2H, d, Jˆ7.8 Hz). MS m/z (%)
372 (M1, 0.5), 232 (94), 149 (100). Calcd for C21H24O4S:
M, 372.1392. Found: m/z 372.1396. 21b-P: Colorless
crystals; IR (KBr) 3310, 2938, 2862, 1500, 1485, 1449,
746, 693 cm21 1H NMR d 0.94±2.38 (10H, m), 3.57
;
(0.67H, s), 3.73 (2H, s), 3.79 (1H, s), 3.90 (0.33H, s),
7.07±7.26 (9H, m). MS m/z (%) 344 (M1, 0.02), 219
(100), 137 (41), 121 (56), 77 (11). Calcd for C20H24O3S:
M, 344.1446. Found: m/z 344.1452.
1-Acetoxy-1-[(4-methoxyphenyl)(phenylsul®nyl)methyl]-
cyclohexane (18c). Colorless crystals (diastereomeric
mixture); IR (KBr) 2936, 2862, 1732, 1714, 1609, 1512,
1242, 1041 (SO), 1021 (SO), 935, 815, 743 cm21 1H
;
NMR d 0.97 (1H, ddd, Jˆ14.4, 10.8, 4.2 Hz), 1.17±1.21
(1H, m), 1.36±1.41 (1H, m), 1.61 (2H, m), 1.74±2.01 (5H,
m), 2.41 (3H, s), 5.94 (2H, s), 6.73 (2H, s), 6.81 (1H, s), 7.33
(2H, d, Jˆ8.3 Hz), 7.62 (2H,d, Jˆ8.3 Hz). Anal. Calcd for
C21H24O4S: C, 67.12; H, 6.49; S, 8.61. Found: C, 67.18; H,
6.50; S, 8.56.
1444, 1253, 1181, 1128, 1086 (SO), 1047 (SO), 753 cm21
;
1H NMR d 1.11±1.63 (8H, m), 2.13, 2.26 (each s, CH3),
2.51±2.91 (2H, m), 3.74, 3.75 (each s, CH3), 4.45, 4.52
(each s), 6.67±7.53 (9H, m).
Cyclohexylidene(4-methoxyphenyl)methane (19c). Color-
less oil; IR (neat) 3032, 2998, 2927, 2852, 2834, 1608, 1509,
Cyclohexylidene(3,4-methylenedioxyphenyl)methane (23).
Colorless oil; IR (neat) 2927, 2853, 2775, 1649, 1605, 1503,
1487, 1434, 1240, 1192, 1103, 1041, 934, 874, 808,
1464, 1446, 1295, 1247, 1175, 1038, 864, 849, 821 cm21
;
1H NMR d 1.52±1.65 (6H, m), 2.23 (2H, t, Jˆ5.6 Hz), 2.35
(2H, t, Jˆ5.5 Hz), 3.80 (3H, s), 6.16 (1H, s), 6.85 (2H, dd,
Jˆ6.6, 1.9 Hz), 7.13 (2H, dd, Jˆ6.6, 1.9 Hz). MS m/z (%)
202 (M1, 100), 173 (15), 159 (24), 134 (30), 121 (65), 108
(9), 91 (15). Calcd for C14H18O: M, 202.1357. Found: m/z
202.1358.
764 cm21; H NMR d 1.56±1.61 (6H, m), 2.22 (2H, t, Jˆ
1
5.9 Hz), 2.34 (2H, t, Jˆ5.9 Hz), 5.93 (2H, s), 6.13 (1H, s),
6.65 (1H, dd, Jˆ8.1, 1.5 Hz), 6.69 (1H, s), 6.75 (1H, dd, Jˆ
7.8, 1.7 Hz). MS m/z (%) 216 (M1, 100), 135 (45), 115 (17).
Calcd for C14H16O2: M, 216.1150. Found: m/z 216.1147.
2-Mesyloxy-5-(4-methoxyphenyl)-1-phenylsul®nylpen-
tane (25). Colorless oil (about 1:2 diastereomeric mixture);
IR (neat) 3007, 2935, 1612, 1514, 1355, 1246, 1174, 1087
(SO), 1038 (SO), 908, 751, 692 cm21; 1H NMR d 1.59±1.80
(2H, m), 1.85±1.98 (2H, m), 2.54±2.63 (2H, m), 3.03
(1.88H, s), 3.20 (1.12H, s), 2.89±3.27 (2H, m), 3.78
(1.12H, s), 3.79 (1.88H, s), 5.01 (0.63H, quint, Jˆ5.6 Hz),
5.11±5.17 (0.37H, m), 6.79±6.84 (2H, m), 7.03±7.09 (2H,
m), 7.03±7.09 (2H, m), 7.51±7.68 (5H, m). MS m/z (%) 396
(M1, 2), 175 (25), 121 (100). Calcd for C19H24O5S2: M,
396.1052. Found: m/z 396.1052.
3-Phenyl-1-(1-p-tolylsul®nylcyclohexyl)-1-propanol (21a).
21a-L: Colorless oil; IR (neat) 3357, 3025, 2934, 2861,
1598, 1494, 1454, 1079 (SO), 1045 (SO), 999, 811, 752,
1
701 cm21; H NMR d 1.23±1.30 (1H, m), 1.38±1.43 (1H,
m), 1.55±1.81 (8H, m), 1.88±1.95 (2H, m), 2.45 (3H, s),
2.54 (1H, ddd, Jˆ16.5, 9.5, 7.0 Hz), 2.94 (1H, ddd, Jˆ14.0,
9.8, 4.5 Hz), 3.92 (1H, m), 7.13±7.25 (5H, m), 7.34 (2H, d,
Jˆ8.3 Hz), 7.50 (2H, d, Jˆ8.2 Hz). MS m/z (%) 357 (M1,
2), 216 (67), 111 (99), 91 (100). Calcd for C22H24O2S: M,
357.1888. Found: m/z 357.1902. 21a-P: Colorless crystals;
IR (KBr) 3320, 2927, 2854, 1492, 1449, 1076 (SO), 1054
(SO), 1019 (SO), 812, 750, 702 cm21; 1H NMR d 1.15±1.94
(12H, m), 2.41 (3H, s), 2.55 (1H, m), 2.86 (1H, ddd, Jˆ14.1,
5-(4-Methoxyphenyl)-1-pentene (26). Colorless oil; IR
(neat) 3074, 2975, 2932, 2855, 1640, 1613, 1513, 1464,

T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
6233
1
1
1441, 1246, 1177, 1039, 911, 831, 808 cm21; H NMR d
747, 698 cm21; H NMR d 1.74±1.78 (1H, m), 1.92±1.99
(2H, m), 2.13±2.17 (1H, m), 2.31 (1H, dt, Jˆ7.7, 3.7 Hz),
2.49±2.56 (2H, m), 2.71 (1H, ddd, Jˆ16.2, 9.2, 7.0 Hz),
2.92 (1H, ddd, Jˆ14.4, 9.5, 5.2 Hz), 4.02 (1H, dddd,
Jˆ9.2, 6.1, 5.5, 3.7), 6.83±7.60 (15H, m). MS m/z (%)
378 (M1, 0.7), 161 (25), 91 (100). Calcd for C24H26O2S:
M, 378.1654. Found: m/z 378.1657.
1.68 (2H, quint, Jˆ7.8 Hz), 2.08 (2H, q, Jˆ6.6 Hz), 2.56
(2H, t, Jˆ7.8 Hz), 3.79 (3H, s), 4.97 (1H, dd, Jˆ10.0,
1.9 Hz), 5.02 (1H, dq, Jˆ17.1, 1.9 Hz), 5.83 (1H, ddt,
Jˆ10.2, 17.1, 6.6 Hz), 7.10 (2H, dd, Jˆ6.6, 2.0 Hz). MS
m/z (%) 176 (M1, 19), 134 (57), 121 (100), 91 (10). Calcd
for C12H16O: M, 176.1178. Found: m/z 176.1189.
(E)-5-(4-Methoxyphenyl)-1-phenylsul®nyl-1-pentene (27).
Colorless oil; IR (neat) 3056, 2997, 2932, 2834, 1612, 1513,
1443, 1246, 1178, 1085 (SO), 1040 (SO), 883, 816, 748,
691 cm21; 1H NMR d 1.76 (2H, quint, Jˆ7.8 Hz), 2.24 (2H,
ddd, Jˆ15.1, 7.1, 1.2 Hz), 2.57 (2H, t, Jˆ7.6 Hz), 3.78 (3H,
s), 6.23 (1H, dt, Jˆ15.1, 1.5 Hz), 6.62 (1H, dt, Jˆ15.1,
6.8 Hz), 6.81 (2H, d, 8.6 Hz), 7.04 (2H, d, Jˆ8.8 Hz),
7.47±7.62 (5H, m). MS m/z (%) 300 (M1, 4.6), 283 (7),
166 (69), 149(80), 121(100). Calcd for C18H20O2S: M,
300.1182. Found: m/z 300.1180.
Acknowledgements
This work was supported by a Grant-in-Aid for Scienti®c
Research No. 08672451 and 11640545 from the Ministry of
Education, Science, Sports, and Culture, and Fugaku
Foundation for Drug Discovery, which are gratefully
acknowledged.
References
(Z)-5-(4-Methoxyphenyl)-1-phenylsul®nyl-1-pentene (28).
Colorless oil; IR (neat) 3057, 2998, 2933, 2856, 1612, 1513,
1246, 1178, 1084 (SO), 1037 (SO), 833, 815, 746,
1. Carruthers, W. Some Modern Methods of Organic Synthesis,
3rd ed.; Cambridge University: Cambridge, 1986; pp 111±182.
2. Mundy, B. P.; Ellerd, M. G. Name Reactions and Reagents in
Organic Synthesis, Wiley: New York, 1988.
1
690 cm21; H NMR d 1.74±1.89 (2H, m), 2.51±2.74 (4H,
m), 3.79 (3H, s), 6.22 (1H, dd, Jˆ10.2, 7.0 Hz), 6.23 (1H, d,
Jˆ10.2 Hz), 6.85 (2H, dd, Jˆ6.5, 2.1 Hz), 7.12 (2H, dd,
Jˆ6.7, 2.0 Hz), 7.44±7.60 (5H, m). MS m/z (%) 300
([M2C18H20O2S]1, 4), 149 ([M2C10H13O]1, 100), 121
([M2C8H9O]1, 86).
3. (a) Julia, M.; Paris, J.-M. Tetrahedron Lett. 1973, 4833.
(b) Kocienski, P. P.; Lythgoe, B.; Ruston, S. J. Chem. Soc., Perkin
Trans. 1 1978, 829. (c) Simpkins, N. S. Sulphones in Organic
Synthesis; Pergamon: Oxford, 1993; pp 254±262.
4. Jones, A. B.; Villalobos, A.; Linde II, G. R.; Danishefsky, S. J.
J. Org. Chem. 1990, 55, 2786.
(E)-5-(4-Methoxyphenyl)-1-tert-butylsul®nyl-1-pentene
(29). Colorless oil; IR (neat) 2931, 2860, 1612, 1513, 1458,
5. (a) Ihara, M.; Suzuki, S.; Taniguchi, T.; Tokunaga, Y.;
Fukumoto, K. Synlett 1994, 859. (b) Keck, G. E.; Savin, K. A.;
Welgarz, M. A. J. Org. Chem. 1995, 60, 3194. (c) Marko, I. E.;
Murphy, F.; Dolan, S. Tetrahedron Lett. 1996, 37, 2089.
6. Lee, G. H.; Lee, H. K.; Choi, E. B.; Kim, B. T.; Pak, C. S.
Tetrahedron Lett. 1995, 36, 5607.
1
1246, 1178, 1037 (SO), 816, 752 cm21; H NMR d 1.22
(9H, s), 1.76 (2H, quint, Jˆ7.8 Hz), 2.29 (2H, ddd, Jˆ
15.2, 7.1, 1.5 Hz), 2.59 (2H, t, Jˆ7.8 Hz), 3.79 (3H, s),
6.12 (1H, dt, Jˆ15.1, 1.5 Hz), 4.56 (1H, dt, Jˆ15.1,
6.8 Hz), 6.83 (2H, dd, Jˆ6.6, 2.2 Hz), 7.08 (2H, dd,
Jˆ6.6, 2.2 Hz); 13C NMR (DEPT) d 23.25 (CH3), 30.67
(CH2), 32.12 (CH2), 34.72 (CH2), 54.73 (C), 55.64 (CH3),
114.19 (CH), 128.57 (CH), 129.69 (CH), 134.06 (C), 142.70
(CH), 158.23 (C). MS m/z (%) 224 (54), 207 (44), 121
([M2C8H9O]1, 100), 57 ([M2C4H9O]1, 86).
7. Shono, T.; Matsumura, Y.; Kashimura, S. Chem. Lett. 1978, 69.
8. Blakemore, P. R.; Cole, W. J.; Kocienski, P. J.; Morley, A.
Synlett 1998, 26; Blakemore, P. R.; Kocienski, P. J.; Marzcak,
S.; Wicha, J. Synthesis 1999, 1209.
9. Hart, D. J.; Wu, W.-L. Tetrahedron Lett. 1996, 37, 5283.
10. The pKa value for CH3SOCH3 is 35 and that for CH3SO2CH3 is
31; Block, E. Reactions of Organosulfur Compounds; Academic:
New York, 1978; pp 46±47.
The structure of this compound was further con®rmed by
oxidation of 29 with m-CPBA to give a sulfone ((E)-5-(4-
Methoxyphenyl)-1-tert-butylsulfonyl-1-pentene) colorless
oil; IR (neat) 3014, 2971, 2935, 2859, 1613, 1513, 1301,
11. Satoh, T. J. Syn. Org. Chem. Jpn 1996, 54, 481.
12. Synthesis of haloalkenes, acetylenes, and allenes by the
sulfoxide±metal exchange: Satoh, T.; Itoh, N.; Onda, K.-i.,
Kitoh, Y.; Yamakawa, K. Tetrahedron Lett. 1992, 33, 1483;
Satoh, T.; Itoh, N.; Watanabe, S.; Koike, H.; Matsuno, H.;
Matsuda, K.; Yamakawa, K. Tetrahedron 1995, 51, 9327; Satoh,
T.; Kuramochi, Y.; Inoue, Y. Tetrahedron Lett. 1999, 40, 8815.
13. Preliminary results of this study were reported as a commu-
nication: Satoh, T.; Yamada, N.; Asano, T. Tetrahedron Lett. 1998,
39, 6935.
1
1285, 1247 (SO2), 1130, 816, 754 cm21; H NMR d 1.35
(9H, s), 1.80 (2H, quint, Jˆ7.8 Hz), 2.32 (2H, ddd, Jˆ 15.1,
7.1, 1.2 Hz), 2.61 (2H, t, Jˆ7.6 Hz), 3.79 (3H, s), 6.25 (1H,
dt, Jˆ15.1, 1.5 Hz), 6.84 (2H, d, Jˆ8.6 Hz), 6.94 (1H, dt,
Jˆ15.1, 6.8 Hz), 7.08 (2H, d, Jˆ8.6 Hz); MS m/z (%) 296
(M1, 35), 240 (14), 175 (20), 121 (60), 57 (100). Calcd for
C16H24O3S: M, 296.1446. Found: m/z 296.1438.
4-Phenyl-1-(2-phenylethyl)-1-phenylsul®nyl-2-butanol
(30). anti-30: Colorless oil; IR (neat) 3357, 3083, 3060,
3025, 2930, 2860, 1496, 1454, 1444, 1084 (SO), 1030
14. We have investigated the best amounts of the alkylmetal in
this reaction. Mechanistically this reaction requirs equimolar
amout of the alkylmetal; however, because of the trace moisture
in THF and for the reduction of the reaction time, 4 equiv. of the
alkylmetal was found to be the amount of choice.
(SO), 748, 699 cm21 1H NMR d 1.67±2.13 (5H, m),
;
2.51±2.90 (4H, m), 4.35 (1H, m, half high widthˆ18.9 Hz),
6.80±7.64 (15H, m). Anal. Calcd for C24H26O2S: C, 76.29;
H, 7.06; S, 8.47. Found: C, 76.15; H, 6.92; S, 8.47. syn-30:
Colorless crystals; IR (KBr) 3414, 3081, 3056, 3026, 2944,
2874, 1495, 1454, 1443, 1086 (SO), 1073 (SO), 1038(SO),
15. Geometry of the produced ole®ns 8 was determined by their
chemical shift of allylic carbon. The 13C NMR of the allylic carbon
of the main isomer and minor isomer showed d 29.15 and 34.37,
respectively, from which the geometry can be determined to be Z

6234
T. Satoh et al. / Tetrahedron 56 (2000) 6223±6234
and E, respectively. See: Kalinowski, H.-O.; Berger, S.; Braun, S.
Carbon-13 NMR Spectroscopy; Wiley: Chichester, 1988; pp 132±
133.
18. Wakabayashi, S.; Ishida, M.; Takeda, T.; Oae, S. Tetrahedron
Lett. 1988, 29, 4441; Oae, S.; Kakeda, T.; Wakabayashi, S.
Tetrahedron Lett. 1988, 29, 4445; Furukawa, N.; Shibutani, T.;
Fujihara, H. Tetrahedron Lett. 1989, 30, 7091; Oae, S. Reviews
on Heteroatom Chemistry; Oae, S., Ed.; MYU: Tokyo, 1991;
pp 195±225.
19. The half high width of the 1H NMR signal of the hydrogen on
the carbon bearing the hydroxyl group of acyclic b-hydroxy
sulfoxides was reported to be about 18 Hz (anti) and 24 Hz
(syn), respectively. Bravo, P.; Resnati, G.; Viani, F.; Arnone, A.
Tetrahedron 1987, 43, 4635.
16. As mentioned, this reaction proceeds through the sulfoxide±
metal exchange. The sul®nyl group of 7 reacts with alkylmetal, for
example EtMgBr to give ethyl phenyl sulfoxide in almost quanti-
tative yield.
17. Neef, G.; Eder, U.; Seeger, A. Tetrahedron Lett. 1980, 21, 903;
Theobald, P. G.; Okamura, W. H. Tetrahedron Lett. 1987, 28,
6565; Thoebald, P. G.; Okamura, W. H. J. Org. Chem. 1990, 55,
741; Craig, A. S.; Norman, A. W.; Okamura, W. H. J. Org. Chem.
1992, 57, 4374.