Studies on intramolecular alkylation of an α-sulfinyl vinylic carbanion: A novel route to chiral 1-cycloalkenyl sulfoxides

Article abstract of DOI:10.1016/S0040-4020(00)00713-4

Intramolecular alkylation of various β-(ω-haloalkyl) substituted vinylic sulfoxides was investigated. Upon treatment with LDA in THF at -78°C, α-sulfinyl carbanion generated from vinylic sulfoxides cyclized at the α-sulfinyl position to give 1-cycloalkenyl sulfoxides with a five- to seven-membered ring. Although iodide or bromide is normally a good leaving group, chloride affords better results than the corresponding iodide and bromide when the reaction takes place at the benzylic position. The cyclization proceeded even with the secondary iodide in moderate yield. Not only the (E)-isomer but also the (Z)-isomer cyclized via rapid inversion of the olefin geometry. No loss of optical purity was observed during isomerization. Various 1-cycloalkenyl sulfoxides including a fused ring and a polyoxygenated rings were synthesized in good to moderate yields. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4020(00)00713-4

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 7927±7945
Studies on Intramolecular Alkylation of an a-Sul®nyl Vinylic
Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides
Naoyoshi Maezaki, Mayuko Izumi, Sachiko Yuyama, Hiroaki Sawamoto, Chuzo Iwata and
*
Tetsuaki Tanaka
Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan
Received 23 June 2000; accepted 10 August 2000
AbstractÐIntramolecular alkylation of various b-(v-haloalkyl) substituted vinylic sulfoxides was investigated. Upon treatment with LDA
in THF at 2788C, a-sul®nyl carbanion generated from vinylic sulfoxides cyclized at the a-sul®nyl position to give 1-cycloalkenyl sulfoxides
with a ®ve- to seven-membered ring. Although iodide or bromide is normally a good leaving group, chloride affords better results than the
corresponding iodide and bromide when the reaction takes place at the benzylic position. The cyclization proceeded even with the secondary
iodide in moderate yield. Not only the (E)-isomer but also the (Z)-isomer cyclized via rapid inversion of the ole®n geometry. No loss of
optical purity was observed during isomerization. Various 1-cycloalkenyl sulfoxides including a fused ring and a polyoxygenated rings were
synthesized in good to moderate yields. q 2000 Elsevier Science Ltd. All rights reserved.
Introduction
usually non-substituted or b-monosubstitued vinylic sul-
foxides, whose (E)-isomers are much more stable than the
corresponding (Z)-isomer not to afford a mixture of
geometric isomers.
In 1978, Posner1 and Okamura2 independently reported that
the a-proton of vinylic sulfoxides can be abstracted with a
base such as MeLi or LDA, and the resulting carbanions are
reacted with various electrophiles. The deprotonation at the
a-position predominates over that at the g-position to give
the a-substituted vinylic sulfoxides rather than the a-substi-
tuted allyl sulfoxides or g-substituted vinylic sulfoxides.
This methodology is very useful for the synthesis of substi-
tuted vinylic sulfoxides, which are highly selective in
diverse reactions such as Diels±Alder reaction, Michael
addition, and vinylogous Pummerer reaction.3 The stereo-
chemistry of the carbanions is especially noteworthy. a-Sul-
®nyl carbanions generated from (Z)-b-monosubstitued
vinylic sulfoxides are con®gurationally unstable and
rapidly isomerize to the thermodynamically more stable
(E)-isomer even at lower than 2788C.2 Therefore, vinylic
sulfoxides used for intermolecular reactions have been
In contrast to the intermolecular reaction, the intramolecular
version has been paid little attention.4 In our preceding
communication,5 we reported the intramolecular alkylation
of a-sul®nyl carbanions generated from the b-(v-halo-
alkyl)vinylic sulfoxides, which provides a method for
synthesizing ®ve- to seven-membered rings (Scheme 1).5
In the case of intramolecular reaction, contamination of
the geometric isomers by the E/Z-isomerization is not of
consequence, since only one isomer can cyclize to the
1-cycloalkenyl sulfoxide. Neither selective preparation of
the geometric isomers nor their separation is required.
Furthermore, both geometric isomers of b,b-disubstituted
vinylic sulfoxides can also be employed as substrates for
the intramolecular alkylation.
Scheme 1.
Keywords: vinylic sulfoxides; cyclization; alkylation; carbanions.
* Corresponding author. Tel.: 181-6-6879-8210; fax: 181-6-6879-8214; e-mail: t-tanaka@phs.osaka-u.ac.jp
0040±4020/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)00713-4

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N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
Scheme 2. Reagents and conditions: (a) LDA, (R)-methyl tolyl sulfoxide, THF, 2788C; (b) Et3SiH, BF3´OEt2, CH2Cl2, 08C!rt; (c) LDA, THF, 2788C;
(d) p-TsCl, Et3N, DMAP, CH2Cl2, 08C!rt; (e) MsCl, Et3N, CH2Cl2, 08C!rt; (f) NaI, NaHCO3, acetone, re¯ux; (g) NaBr, NaHCO3, acetone, re¯ux; (h) LiCl,
acetone, re¯ux; (i) Dess±Martin periodinane, CH2Cl2, rt; (j) MeMgBr, THF, 08C.
Scheme 3. Reagents and conditions: (a) LDA, (R)-methyl tolyl sulfoxide, THF, 2788C; (b) NaBH4, MeOH, 08C; (c) MsCl, Et3N, CH2Cl2, 08C!rt;
(d) t-BuOK, THF, 08C!rt; (e) NaI, NaHCO3, acetone, re¯ux.
Scheme 4. Reagents and conditions: (a) EtMgBr, ether, 08C!re¯ux then (S)-(2)-menthyl p-toluenesul®nate, toluene, 08C; (b) H2, RhCl(PPh3)3, benzene, rt;
(c) HF´pyridine, THF±pyridineˆ1:1, rt; (d) p-TsCl, Et3N, DMAP, CH2Cl2, 08C!rt; (e) NaI, NaHCO3, acetone, re¯ux.
Here, we wish to report full details of the intramolecular
alkylation of a-sul®nyl vinylic carbanions and the further
application to more functionalized systems.
promoted elimination of b-oxygenated sulfoxides; (2)
reduction of alkynyl sulfoxides; and (3) Horner±Wittig
reaction of (R)-dimethylphosphorylmethyl p-tolyl sulfox-
ide6 with aldehydes (Schemes 2±5). (E)-Vinylic sulfoxides
[(E)-7]±[(E)-13], the precursors of ®ve- and six-membered
ring vinylic sulfoxides, were synthesized by a series of
reactions: condensation of lithiated methyl p-tolyl sulfoxide
with lactones, reduction to the cyclic ethers, and base-
promoted b-elimination to give the (E)-vinylic sulfoxides
exclusively. Then, the hydroxyl group was converted into
Results and Discussion
²
Preparation of b-(v-haloalkyl)- and b-(v-sulfonyl-
oxyalkyl) vinylic sulfoxides
The b-(v-haloalkyl)- and b-(v-sulfonyloxyalkyl) vinylic
sulfoxides were prepared by three methods: (1) base-
²
Compounds 1 and 2 exist as a mixture of hemiacetal and ketol forms.

N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
7929
Scheme 5. Reagents and conditions: (a) p-TsCl, Et3N, DMAP CH2Cl2, 08C!rt; (b) Dess±Martin periodinane, CH2Cl2, rt; (c) n-BuLi, (MeO)2P(O)CH2-
Sp(O)Tol, THF, 2788C; (d) NaI, NaHCO3, acetone, re¯ux; (e) n-BuLi, (MeO)2P(O)CH2Sp(O)Tol, THF, 2788C!rt; (f) p-TsOH´H2O, MeOH, rt.
the sulfonates (OTs and OMs) or the halides (I, Br and Cl).
Synthesis of the secondary iodide 17 was carried out by
oxidation of (E)-5 with Dess±Martin periodinane, methyla-
tion of the resulting aldehyde with MeMgBr, mesylation,
and iodination. The substrate for seven-membered ring
formation was prepared via condensation of (R)-methyl
tolyl sulfoxide with e-caprolactone. In this case, ketol 18
was obtained instead of the lactol, which was converted into
bis-mesylate 20 followed by base-promoted b-elimination
and iodination to give the vinylic sulfoxide 22 as a 1:1
mixture of the E/Z-isomers (Scheme 3).
LTMP) also afforded the product in acceptable yields
(entries 6 and 7). However, hexamethyldisilazides afforded
a complex mixture (entries 8±10). Varying the solvent,
excluding THF, did not improve the yield (entries 11±13).
Based on the optimized reaction conditions (Table 1, entry
2), the most suitable leaving groups were examined (Table 2,
entries 1±5). The iodide and bromide provided the product
in good yields. On the other hand, the tosylate, mesylate and
chloride were poor leaving groups, causing sluggish reac-
tion. Then, we examined cyclization of b-(v-iodoalkyl)
vinylic sulfoxides (E)-10, (E)-22, and (E)-28 with different
chain lengths (entries 6±8). Five- to seven-membered rings
were formed in 79±82% yields. However, an eight-
membered ring was not formed even under highly diluted
conditions (0.001 M), yielding instead many unidenti®ed
products together with the dimer 49 (22%).11 We next
focused on the intramolecular alkylation of the (Z)-isomers.
(Z)-Vinylic sulfoxides (Z)-10 and (Z)-11 were selectively
synthesized according to Kosugi's procedure7 as shown in
Scheme 4. 5-tert-Butyldimethylsilyloxy-1-pentynylmagne-
sium bromide8 was coupled with (S)-(2)-menthyl
p-toluenesul®nate and the resulting alkynyl sulfoxide 25
was reduced to 27 with Wilkinson's catalyst. Deprotection
of TBS protection, tosylation, and iodination led 27 to the
iodide (Z)-10. In a similar manner, 249 was converted into
(Z)-11.
Table 1. Intramolecular alkylation of vinylic sulfoxide (E)-11 (the substrate
was treated with 1.5 equiv. of the base at 2788C under N2)
The Horner±Wittig approach affords another convenient
method for synthesizing the substrates. Thus, vinylic sulf-
oxides 32, 39 and 40 were synthesized from 1,7-heptanediol
and known ketones 33 and 34,10 respectively, as shown in
Scheme 5.
Intramolecular alkylation of b-(v-haloalkyl)- and b-(v-
sulfonyloxyalkyl) vinylic sulfoxides
Entry
Base (equiv.)
Additive
Solvent
Yield (%)a
1
2
3
4
5
6
7
8
LDA (1.1)
LDA (1.5)
LDA (2.0)
LDA (1.5)
LDA (1.5)
LICA (1.5)
LTMP (1.5)
LHMDA (1.5)
NHMDS (1.5)
KHMDS (1.5)
LDA (1.5)
±
±
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
DME
Ether
Toluene
76
82
Complex
55
62
75
65
Complex
Complex
Complex
39
10
21
Using (E)-6-iodo-1-hexenyl p-tolyl sulfoxide (E)-11, we
investigated the reaction conditions for cyclization (Table
1). Upon treatment with LDA (1.1±1.5 equiv.) in THF at
2788C, a solution of the vinylic sulfoxide (E)-11 rapidly
turned yellow and the reaction completed within 10 min to
give 1-cyclohexenyl p-tolyl sulfoxide 41 in good yield
(entries 1 and 2). Cyclization proceeded selectively at the
a-sul®nyl position. On use of two equivalents of LDA, no
cyclized product was obtained, and instead, a complex
mixture was formed (entry 3). The addition of chelating
agents (HMPA and TMEDA) slightly reduced the yields
(entries 4 and 5). Other lithium dialkylamides (LICA and
±
HMPA
TMEDA
±
±
±
±
±
±
±
±
9
10
11
12
13
LDA (1.5)
LDA (1.5)
a Isolated yield.

7930
N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
Table 2. Cyclization of vinylic sulfoxides and the optical purities of the products (the substrate was treated with 1.5 equiv. of LDA in THF at 2788C under N2)
b
Entry
Substrate
R
R0
n
X
Product
Yielda (%)
[a]D
eec (%)
1
2
3
4
5
6
7
8
(E)-9
(E)-8
H
H
H
H
H
H
H
H
H
H
H
Ph
Ph
Me
H
H
2
2
2
2
2
1
3
4
1
2
3
1
1
1
1
OMs
OTs
I
Br
Cl
I
I
I
I
I
41
41
41
41
41
42
43
44
42
41
43
45
45
46
47
Complex
24
82
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
(E)-11
(E)-12
(E)-13
(E)-10
(E)-22
(E)-28
(Z)-10
(Z)-11
(Z)-22
(E)-39
(Z)-39
(E/Z)-40
(E)-17
19
98
98
79
0d
81
157
110
79
0d
66
9
157
19
96
98
10
11
12
13
14
15
71
64
44
43
34
46
I
I
I
I
110
2421
2411
2155
I
a Isolated yield.
b Measured in CHCl3.
c Determined by chiral HPLC.
d (E)-13 and (E)-28 provided their dimers 48 and 49 in 30% and 22% yield, respectively.
As expected, cyclization of (Z)-10, (Z)-11, (Z)-22 provided
cyclized products 42, 41 and 43, respectively, in moderate
yields (64±71%) via isomerization of their ole®n geometry
(entries 9±11). b,b-Disubstituted vinylic sulfoxides are
attractive substrates for the intramolecular alkylation since
such substrates are rarely used for the intermolecular
version due to the close energy-difference between the
geometric isomers, which may afford a mixture of
geometric isomers via rapid E/Z-isomerization in inter-
molecular alkylation. Both isomers of the b-phenyl vinylic
sulfoxides (E)- and (Z)-39 underwent a-lithiation and subse-
quent a-alkylation to give the cyclized product 45 in 44 and
43% yield, respectively (entries 12 and 13). Intramolecular
alkylation of the b-methyl vinylic sulfoxide 40 (E/Zˆ1:1)
provided the 2-methyl-1-cyclopentenyl sulfoxide 46 in 34%
yield (entry 14). Alkylation proceeded even with the
secondary iodide. Thus, the vinylic sulfoxide (E)-17
cyclized to the product 47 in 46% yield (entry 15).
In our communication,5 we assumed that the isomerization
and the alkylation would proceed concertedly rather than
stepwise in the intramolecular alkylation in order to explain
the difference in loss of optical purity between Posner's
experiments and ours. An internal C±X bond may assist
the isomerization of carbanions and this interaction would
prevent racemization. To con®rm this speculation, we
examined whether racemization would occur by isomeriza-
tion using the (Z)-vinylic sulfoxide [(Z)-50] having no
leaving group on the b-substituent under the same reaction
conditions as those of the intramolecular alkylation as
shown in Scheme 6. Surprisingly, in both geometric isomers
of 50, no loss of optical purity was observed within experi-
mental error (,3%) even in prolonged reaction time (after
60 min), although the (Z)-isomer was completely isomer-
ized to the (E)-isomer. Although fears of racemization
were dismissed, the previous speculation should be revised
as a stepwise mechanism (isomerization followed by alkyl-
ation) cannot be ruled out in the intramolecular alkylation.
Recemization observed in Posner's experiments may have
Posner reported that a-deprotonation of optically pure (E)-
1-undecenyl p-tolyl sulfoxide followed by reprotonation
produced no racemization, whereas similar treatment of
the corresponding (Z)-isomer produced racemization (ca.
30% loss of optical purity).12 In the intramolecular alkyl-
ation, the 1-cycloalkenyl sulfoxides from the (Z)-isomers
have almost the same speci®c rotation as those from the
corresponding (E)-isomers within experimental error
(,3%). Furthermore, optical purity of the products 41 and
42 prepared from (E)- and (Z)-b-(v-iodoalkyl) vinylic
sulfoxides 11 and 10 was con®rmed to be high ($96% ee)
by chiral HPLC (Daicel Chiralcel OB). Racemization did
not occur during (Z)- to (E)-isomerization in the intra-
molecular alkylation of a-lithio vinylic sulfoxides.
Scheme 6. Reagents and conditions: (a) n-BuLi, (MeO)2P(O)CH2Sp(O)Tol,
THF, 2788C; (b) LDA, THF, 2788C then H2O.

N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
7931
Scheme 7. Reagents and conditions: (a) DHP, PPTS, CH2Cl2, rt; (b) Dess±Martin periodinane, CH2Cl2, rt; (c) n-BuLi, (MeO)2P(O)CH2Sp(O)Tol, THF,
2788C; (d) p-TsOH´H2O, MeOH, rt; (e) p-TsCl, Et3N, DMAP, CH2Cl2, 08C!rt; (f) NaBr, DMF/CH2Br2ˆ2:1, 1008C; (g) NaI, NaHCO3, acetone, rt; (h) LDA,
THF, 2788C.
occurred under the different reaction conditions, which have
not been reported in detail.
Next, we examined the reaction with more functionalized
substrates. We investigated the intramolecular alkylation of
a-sul®nyl vinylic carbanions having a polyoxygenated
b-substituent, which are of interest as a concise access to
synthesis of cyclitol derivatives, which are attracting
considerable attention by their potent glycosidase inhibitory
activity. Vinylic sulfoxide 63 prepared from 2,3-O-iso-
propylidene-d-erythrose 5913 was treated with LDA to
give the cyclitol derivetives 64 in 68% yield. In a similar
manner, vinylic sulfoxide 71 prepared from 2,3-O-iso-
propylidene-d-ribose derivative 6514 was led to the cyclitol
derivative 72 in 64% yield. In this case, elimination of HI
took place to give the vinylic ether 73 in 20% yield.
The newly developed intramolecular alkylation was applied
to the synthesis of fused ring compounds. Ring closure
between two substituents on the benzene ring in the chloride
(E)- and (Z)-55 afforded the indene derivative 58 in 64 and
54% yields, respectively. In the alkylation at the benzylic
position, chloride is the better leaving group than iodide and
bromide. The corresponding bromide (E)-56 and the iodide
(E)-57 afforded 58 in poor yields, presumably due to
instability of the substrates under the reaction conditions
(Schemes 7 and 8).
Scheme 8. Reagents and conditions: (a) n-BuLi, (MeO)2P(O)CH2Sp(O)Tol, THF, 2788C!rt; (b) LDA, THF, 2788C; (c) p-TsCl, Et3N, DMAP, CH2Cl2,
08C!rt; (d) NaI, NaHCO3, acetone, re¯ux; (e) MOMCl, i-PrNEt2, CH2Cl2, rt; (f) HF´pyridine, THF±pyridineˆ1:1, rt.

7932
N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
Diastereomeric isomers arising from racemization on the
sulfur atom were not detected at all.
(4/7H, td, Jˆ8.5, 6.1 Hz, 5-Ha), 4.06±4.14 (1/7H, m,
5-Hb), 4.04 (4/7H, td, Jˆ8.5, 6.1 Hz, 5-Ha), 4.36 (1/7H, s,
OHb), 5.43 (4/7H, s, OHa), 7.32 (2/7H, d, Jˆ8.5 Hz,
Ar-Hb), 7.34 (12/7H, d, Jˆ8.5 Hz, Ar-Ha and Ar-Hc),
7.53 (4/7H, d, Jˆ7.9 Hz, Ar-Hc), 7.56 (2/7H, d,
Jˆ8.5 Hz, Ar-Hb), 7.57 (8/7H, d, Jˆ7.9 Hz, Ar-Ha). 13C
NMR (major) d: 21.3, 24.4, 38.6, 63.8, 67.9, 104.5, 124.0
(2C), 130.0 (2C), 140.3, 142.0. MS (EI) m/z (rel. int. %):
240 (M1, 4.1), 139 (100). HRMS (EI) Calcd C12H16O3S:
240.0820. Found: 240.0812.
Conclusion
In conclusion, we have developed a novel method for the
synthesis of 1-cycloalkenyl sulfoxides by intramolecular
alkylation of b-(v-haloalkyl)vinylic sulfoxides. This
methodology provides a concise access to the substituted
1-cycloalkenyl sulfoxides having ®ve- to seven-membered
ring, including polyoxygenated rings.
2-[(R)-(p-Tolylsul®nyl)methyl]tetrahydro-2H-pyran-2-ol
(2). Using the procedure for 1, d-valerolactone (2.0 ml,
22 mmol) was converted into the hemiacetal 2 (major (a)/
minor (b)/ketosulfoxide (c)ˆca. 10:3:2, 5.89 g, 84%). A
yellow oil: IR (KBr) cm21: 3350, 2943, 1713, 1597, 1215,
1086, 1043, 1024, 1012. 1H NMR d: 1.41 (2/3H, ddt,
Jˆ12.8, 4.3, 2.4 Hz, 4-Ha), 1.50±1.70 (53/15H, m, 3-Ha±
b, 4-Ha±c, and 5-Ha±c), 1.77 (2/3H, br d, Jˆ12.2 Hz,
5-Ha), 1.91 (1/5H, tt, Jˆ12.9, 4.0 Hz, 3-Hb), 1.91±1.96
(2/3H, m, 3-Ha), 2.42 (3H, s, Ar-H), 2.51 (2/15H, dt,
Jˆ18.3, 6.7 Hz, 3-Hc), 2.60 (2/15H, dt, Jˆ18.3, 6.7 Hz,
3-Hc), 2.78 (2/3H, d, Jˆ12.8 Hz, S(O)CHa), 3.86 (2/15H,
d, Jˆ13.4 Hz, S(O)CHc), 2.99 (1/5H, d, Jˆ13.4 Hz,
S(O)CHb), 3.03 (2/3H, d, Jˆ12.8 Hz, S(O)CHa), 3.03
(1/5H, d, Jˆ13.4 Hz, S(O)CHb), 3.58±3.68 (1/5H, m,
6-Hb), 3.74 (2/15H, d, Jˆ13.4 Hz, S(O)CHc), 3.80±3.84
(2/3H, m, 6-Ha), 4.12 (1/5H, q, 6-Hb), 4.00 (4/15H, td,
Jˆ11.6, 3.1 Hz, 6-Hc), 4.18 (2/3H, td, Jˆ11.6, 3.1 Hz,
6-Ha), 7.32 (2/5H, d, Jˆ7.9 Hz, Ar-Hb), 7.34 (8/5H, d,
Jˆ7.9 Hz, Ar-Ha,c), 7.53 (4/15H, d, Jˆ7.9 Hz, Ar-Hc),
7.56 (4/3H, d, Jˆ7.9 Hz, Ar-Ha), 7.55 (2/5H, d,
Jˆ7.9 Hz, Ar-Hb). 13C NMR d: (major); 17.9, 21.4, 25.1,
35.7, 61.5, 64.5, 95.8, 124.0 (2C), 130.1 (2C), 140.2, 142.0.
MS (EI) m/z (rel. int. %): 254 (M1, 18.2), 139 (100). HRMS
(EI) Calcd C13H18O3S: 254.0976. Found: 254.0976.
Experimental
Melting points are uncorrected. Optical rotations were
measured using a JASCO DIP-360 digital polarimeter. IR
spectra were measured with a Horiba FT-210 IR spectro-
meter. 1H NMR spectra were measured with a JEOL JNM-
GX500 spectrometer (500 MHz) or a JEOL JNM-LA-500
spectrometer (500 MHz) in CDCl3 solution. 13C NMR spec-
tra were measured with a JEOL JNM-EX270 spectrometer
(68 MHz) or a JEOL JNM-AL300 spectrometer (75 MHz)
in CDCl3 solution. All signals are expressed as ppm down-
®eld from tetramethylsilane used as an internal standard (d
value). The following abbreviations are used: singlet (s),
doublet (d), triplet (t), quartet (q), and multiplet (m). Mass
spectra were taken with a Shimadzu QP-1000 mass spectro-
meter and a JEOL JMS-D300 mass spectrometer. High
resolution mass spectra were measured by a JEOL JMS-
D300 or a JEOL JMS-600. Merck Kieselgel 60 was used
as an adsorbent for column chromatography. For prepara-
tive TLC (PTLC), Kieselgel 60 F254 (Merck) was used.
Unless stated, all solvents were used after dryness and all
extracts were dried over MgSO4.
2-[(R)-( p-Tolylsul®nyl)methyl]tetrahydrofuran (3). BF3´
OEt2 (0.92 ml, 7.48 mmol) was added to a mixture of 1
(596 mg, 2.48 mmol) and Et3SiH (0.80 ml, 4.97 mmol) in
CH2Cl2 (25 ml) with stirring at 08C. The stirring was con-
tinued for 16 h at rt. The reaction was quenched with
saturated NH4Cl aqueous solution and the whole was
extracted with AcOEt. The extract was washed with water
and brine prior to drying and solvent evaporation. The
residue was chromatographed on silica gel with hexane±
AcOEt (1:1) to give 3 (503 mg, 90%, 2:1 diastereomeric
mixture) as a colorless oil. IR (KBr) cm21: 2924, 1086,
2-[(R)-(p-Tolylsul®nyl)methyl]tetrahydro-2-furanol (1).
A solution of (R)-methyl p-tolyl sulfoxide (500 mg,
3.24 mmol) in THF (5 ml) was added to a stirred LDA solu-
tion [prepared from n-BuLi (1.60 M in hexane, 3.0 ml,
4.80 mmol) and i-Pr2NH (0.68 ml, 4.85 mmol) in THF
(20 ml)] at 2788C under N2 and the mixture was stirred at
08C for 20 min. A solution of g-butyrolactone (0.27 ml,
3.51 mmol) in THF (5 ml) was added to the stirred mixture
at 2788C and stirring was continued at the same tempera-
ture for 20 min. The reaction was quenched with saturated
NH4Cl aqueous solution and the whole was extracted with
AcOEt. The extract was washed with water and brine prior
to drying and solvent evaporation. The residue was chroma-
tographed on silica gel with hexane±AcOEt (1:1) to give 1
(major (a)/minor (b)/ketosulfoxide (c)ˆca. 4:1:2, 661 mg,
85%) as a colorless oil along with (R)-methyl p-tolyl
sulfoxide (75 mg, 15%). IR (KBr) cm21: 3395, 2926,
1
1045. H NMR d: 1.46±1.54 (2/3H, m, 3-H), 1.63±1.75
(1/3H, m, 3-H), 1.78±1.98 (2H, m, 4-H and 3-H), 1.78±
2.43 (1H, m, 4-H and 3-H), 2.33 (3H, s, Ar-CH3), 2.74
(2/3H, dd, Jˆ12.8, 9.2 Hz, S(O)CH), 2.79 (1/3H, dd,
Jˆ12.8, 5.5 Hz, S(O)CH), 2.88 (2/3H, dd, Jˆ12.8, 3.7 Hz,
S(O)CH), 3.13 (1/3H, dd, Jˆ12.8, 5.5 Hz, S(O)CH), 3.65±
3.69 (1/3H, m, 2-H), 3.73±3.84 (2/3H, m, 5-H), 3.84±3.89
(4/3H, m, 5-H), 4.28±4.33 (2/3H, m, 2-H), 7.25 (4/3H, d,
Jˆ7.9 Hz, Ar-H), 7.26 (2/3H, d, Jˆ7.9 Hz, Ar-H), 7.47 (4/
3H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2/3H, d, Jˆ7.9 Hz, Ar-H).
13C NMR (major) d: 21.3, 25.6, 31.4, 64.3, 68.1, 72.8, 123.7
(2C), 129.8 (2C), 141.3 (2C). (minor) d: 21.3, 25.5, 31.2,
62.8, 68.2, 73.7, 124.2 (2C), 130.0 (2C), 140.3, 141.5. MS
(EI) m/z (rel. int. %): 224 (M1, 7.3), 85 (100). HRMS (EI)
Calcd C12H16O2S: 224.0871. Found: 224.0864.
1
1713, 1495, 1400, 1086, 1049, 1014. H NMR d: 1.72±
1.85 (8/7H, m, 4-Ha), 1.89±2.03 (4/7H, m, 3- and 4-Hb),
2.05±2.25 (12/7H, m, 4-Hc and 3-Ha), 2.42 (3H, s, Ar-CH3),
2.51±2.71 (4/7H, m, 3-Hc), 2.89 (4/7H, d, Jˆ12.8 Hz,
S(O)CHa), 3.12 (1/7H, d, Jˆ13.4 Hz, S(O)CHb), 3.25
(4/7H, d, Jˆ12.8 Hz, S(O)CHa), 3.27 (1/7H, d,
Jˆ13.4 Hz, S(O)CHb), 3.59 (4/7H, t, Jˆ5.5 Hz, 5-Hc),
3.82 (2/7H, d, Jˆ14.0 Hz, S(O)CHc), 3.90 (2/7H, d,
Jˆ14.0 Hz, S(O)CHc), 3.89±4.00 (1/7H, m, 5-Hb), 4.04

N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
7933
2-[(R)-(p-Tolylsul®nyl)methyl]tetrahydro-2H-pyran (4).
Using the procedure for 3, the hemiacetal 2 (3.21 g,
12.6 mmol) was converted into the cyclic ether 4 (2.53 g,
84%). The diastereomeric mixture was used in the next step
without further puri®cation. Analytical samples were puri-
®ed by column chromatography hexane±AcOEt (1:2) to
give 4a (less polar) and 4b (more polar) each as a colorless
oil. 4a: [a]2D6ˆ1236 (c 1.23, CHCl3). IR (KBr) cm21: 2937,
1090, 1045. 1H NMR d: 1.31±1.38 (1H, m, 3-H), 1.57±1.61
(4H, m, 3-H, 4-H and, 5-H), 1.85±1.88 (1H, m, 5-H), 2.41
(3H, s, Ar-CH3), 2.73 (1H, dd, Jˆ13.4, 10.4 Hz, S(O)CH2),
2.79 (1H, dd, Jˆ13.4, 2.4 Hz, S(O)CH2), 3.56±3.61 (1H, m,
6-H), 3.91±3.96 (1H, m, 2-H), 4.06 (1H, ddd, Jˆ11.6, 2.4,
1.8 Hz, 6-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.54 (2H, d,
Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.1, 21.1, 23.0, 31.3, 65.1,
68.3, 71.1, 123.5 (2C), 129.7 (2C), 141.1 (2C). MS (EI) m/z
(rel. int. %): 238 (M1, 19.7), 99 (100). HRMS (EI) Calcd
C13H18O2S: 238.1027. Found: 238.1029. 4b: [a]2D6ˆ179.0
(c 0.84, CHCl3). IR (KBr) cm21: 2935, 2850, 1495, 1086,
129.9 (2C), 134.8, 140.5, 140.7, 141.3. MS (EI) m/z (rel. int.
%): 238 (M1, 50.6), 131 (100). HRMS (EI) Calcd
C13H18O2S: 238.1027. Found: 238.1036.
(E)-5-[(R)-(p-Tolylsul®nyl)]-4-pentenyl p-toluenesulfo-
nate [(E)-7]. p-TsCl (288 mg, 1.51 mmol) was added to a
mixture of (E)-5 (282 mg, 1.26 mmol), Et3N (0.21 ml,
1.51 mmol), and DMAP (31 mg, 0.25 mmol) in CH2Cl2
(10 ml) with stirring at 08C. The stirring was continued at
rt for 3.5 h. The reaction was quenched with saturated
NH4Cl aqueous solution and the whole was extracted with
AcOEt. The extract was washed with water and brine prior
to drying and solvent evaporation. The residue was chroma-
tographed on silica gel with hexane±AcOEt (1:1) to give
(E)-7 (438 mg, 92%) as colorless oil. [a]2D8ˆ1107.7 (c
0.72, CHCl3). IR (KBr) cm21: 2924, 1597, 1358, 1176,
1
1045. H NMR d: 1.78±1.84 (2H, m, 2-H), 2.32 (2H, q,
Jˆ6.7 Hz, 3-H), 2.41 (3H, s, Ar-CH3), 2.49 (3H, s, Ar-
CH3), 4.03 (2H, t, Jˆ6.1 Hz, 1-H), 6.17 (1H, d,
Jˆ15.3 Hz, 5-H), 6.47 (1H, dt, Jˆ15.3, 6.7 Hz, 4-H), 7.31
(2H, d, Jˆ7.9 Hz, Ar-H), 7.34 (2H, d, Jˆ7.9 Hz, Ar-H),
7.47 (2H, d, Jˆ7.9 Hz, Ar-H), 7.76 (2H, d, Jˆ7.9 Hz, Ar-
H). 13C NMR d: 21.3, 21.6, 27.4, 27.7, 69.1, 124.6 (2C),
127.8 (2C), 129.9 (2C), 130.0 (2C), 132.8, 136.2, 137.3,
140.5, 141.6, 144.9. MS (EI) m/z (rel. int. %): 378 (M1,
11.0), 158 (100). HRMS (EI) Calcd C19H22O4S2:
378.0958. Found: 378.0957.
1
1043. H NMR d: 1.41±1.52 (3H, m, 3-H and 4-H), 1.54±
1.64 (1H, m, 5-H), 1.66±1.70 (1H, m, 5-H), 1.81±1.85 (1H,
m, 3-H), 2.42 (3H, s, Ar-CH3), 2.71 (1H, dd, Jˆ12.8,
4.9 Hz, S(O)CH2), 3.22 (1H, dd, Jˆ12.8, 7.3 Hz,
S(O)CH2), 3.33 (1H, dt, Jˆ11.6, 2.4 Hz, 6-H), 3.37±3.42
(1H, m, 2-H), 3.95 (1H, ddt, Jˆ11.6, 4.9, 1.8 Hz, 6-H), 7.33
(2H, d, Jˆ7.9 Hz, Ar-H), 7.56 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 21.1, 22.6, 25.1, 30.8, 63.4, 68.0, 72.5, 124.1 (2C),
129.6 (2C), 140.0, 141.3. MS (EI) m/z (rel. int. %): 238 (M1,
15.7), 99 (100). HRMS (EI) Calcd C13H18O2S: 238.1027.
Found: 238.1029.
(E)-6-[(R)-(p-Tolylsul®nyl)]-5-hexenyl p-toluenesulfonate
[(E)-8]. Using the procedure for (E)-7, the alcohol (E)-6
(600 mg, 2.52 mmol) was converted into (E)-8 (0.95 g,
96%). Colorless oil: [a]2D8ˆ185.4 (c 1.14, CHCl3).
IR (KBr) cm21: 2926, 1597, 1358, 1176, 1097, 1083,
(E)-5-[(R)-(p-Tolylsul®nyl)]-4-penten-1-ol [(E)-5].
A
solution of 3 (474 mg, 2.11 mmol) in THF (5 ml) was
added to a stirred LDA solution [prepared from n-BuLi
(1.60 M in hexane, 3.83 ml, 6.13 mmol) and i-Pr2NH
(0.89 ml, 6.35 mmol) in THF (25 ml)] at 2788C under N2
and the mixture was stirred at this temperature for 30 min.
The reaction was quenched with saturated NH4Cl aqueous
solution and the whole was extracted with AcOEt. The
extract was washed with water and brine prior to drying
and solvent evaporation. The residue was chromatographed
on silica gel with AcOEt to give (E)-5 (384 mg, 81%) as a
colorless oil. [a]2D7ˆ1114.5 (c 0.11, CHCl3). IR (KBr)
1
1043, 1016. H NMR d: 1.34±1.46 (2H, m, 3-H), 1.56±
1.61 (2H, m, 2-H), 2.12 (2H, dq, Jˆ6.7, 1.2 Hz, 4-H),
2.33 (3H, s, SO2CH3), 2.37 (3H, s, Ar-CH3), 3.94 (2H, t,
Jˆ6.1 Hz, 1-H), 6.11 (1H, dt, Jˆ15.3, 1.2 Hz, 6-H), 6.43
(1H, dt, Jˆ15.3, 6.7 Hz, 5-H), 7.24 (2H, d, Jˆ7.9 Hz, Ar-
H), 7.26 (2H, d, Jˆ7.9 Hz, Ar-H), 7.41 (2H, d, Jˆ7.9 Hz,
Ar-H), 7.70 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.4,
21.6, 24.0, 28.1, 31.1, 69.9, 124.5 (2C), 127.8 (2C), 129.8
(2C), 130.0 (2C), 132.9, 135.7, 139.0, 140.7, 141.5, 144.8.
MS (EI) m/z (rel. int. %): 392 (M1, 4.8), 91 (100). HRMS
(EI) Calcd C20H24O4S2: 392.1116. Found: 392.1116 (M1).
1
cm21: 3375, 2931, 1038. H NMR d: 1.67±1.73 (2H, m,
2-H), 2.30±2.34 (2H, m, 3-H), 2.40 (3H, s, Ar-CH3), 2.87
(1H, br, OH), 3.61 (2H, t, Jˆ6.7 Hz, 1-H), 6.24 (1H, d,
Jˆ15.3 Hz, 5-H), 6.60 (1H, dt, Jˆ15.3, 6.7 Hz, 4-H), 7.30
(2H, d, Jˆ8.5 Hz, Ar-H), 7.48 (2H, d, Jˆ8.5 Hz, Ar-H). 13C
NMR d: 21.4, 28.4, 30.8, 61.5, 124.6 (2C), 130.0 (2C),
135.1, 140.3, 140.5, 141.5. MS (EI) m/z (rel. int. %): 224
(M1, 62.8), 92 (100). HRMS (EI) Calcd C12H16O2S:
224.0871. Found: 224.0882.
(E)-6-[(R)-(p-Tolylsul®nyl)]-5-hexenyl methanesulfonate
[(E)-9]. MsCl (40 ml, 0.52 mmol) was added to a mixture of
(E)-6 (100 mg, 0.42 mmol) and Et3N (76 ml, 0.51 mmol) in
CH2Cl2 (3 ml) with stirring at 08C. The stirring was con-
tinued at rt for 20 min. The reaction was quenched with
saturated NH4Cl aqueous solution and the whole was
extracted with AcOEt. The extract was washed with water
and brine prior to drying and solvent evaporation. The resi-
due was chromatographed on silica gel with hexane±AcOEt
(1:1) to give (E)-9 (93.0 mg, 70%) as colorless powder. Mp
52.7±53.48C (ether). [a]2D8ˆ199.8 (c 0.81, CHCl3). IR
(E)-6-[(R)-(p-Tolylsul®nyl)]-5-hexen-1-ol [(E)-6]. Using
the procedure for (E)-5, the cyclic ether 4 (3.40 g,
14.3 mmol) was converted into (E)-6 (2.82 g, 83%). A
colorless oil: [a]2D8ˆ198.2 (c 1.40, CHCl3). IR (KBr)
1
(KBr) cm21: 2935, 1493, 1352, 1174. H NMR d: 1.58±
1
cm21: 3402, 2866, 1493, 1084, 1041, 1014. H NMR d:
1.64 (2H, m, 3-H), 1.75±1.80 (2H, m, 2-H), 2.29 (2H, q,
Jˆ7.3 Hz, 4-H), 2.41 (3H, s, Ar-CH3), 3.00 (3H, s,
SO2CH3), 4.22 (2H, t, Jˆ6.7 Hz, 1-H), 6.24 (1H, dt,
Jˆ15.3, 1.2 Hz, 6-H), 6.55 (1H, dt, Jˆ15.3, 6.7 Hz, 5-H),
7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, d, Jˆ7.9 Hz, Ar-
H). 13C NMR d: 21.5, 24.1, 28.6, 31.2, 37.4, 69.3, 124.5
1.55±1.57 (4H, m, 2-H and 3-H), 2.26 (2H, q, Jˆ6.7 Hz,
4-H), 2.41 (3H, s, Ar-CH3), 3.64 (2H, t, Jˆ6.1 Hz, 1-H),
6.22 (1H, d, Jˆ15.3 Hz, 6-H), 6.59 (1H, dt, Jˆ15.3, 6.7 Hz,
5-H), 7.31 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR d: 21.2, 24.2, 31.5, 31.8, 61.8, 124.4 (2C),

7934
N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
(2C), 130.0 (2C), 135.7, 138.7, 140.6, 141.4. MS (EI) m/z
(rel. int. %): 316 (M1, 8.8), 268 (100). HRMS (EI) Calcd
C14H20O4S2: 316.0803. Found: 316.0829.
mixture of (E)-8 (99 mg, 0.25 mmol) and LiCl (13 mg,
0.30 mmol) in acetone (2.5 ml) was re¯uxed for 3 h. The
reaction was quenched with water and the whole was
extracted with AcOEt. The extract was washed with water
and brine prior to drying and solvent evaporation. The resi-
due was chromatographed on silica gel with hexane±AcOEt
(1:1) to give (E)-13 (62 mg, 95%) as a colorless oil.
[a]D25ˆ1104.0 (c 0.77, CHCl3). IR (KBr) cm21: 2924,
(E)-(R)-5-Iodo-1-pentenyl p-tolyl sulfoxide [(E)-10]. A
mixture of (E)-7 (380 mg, 1.00 mmol), NaHCO3 (480 mg,
5.71 mmol), and NaI (300 mg, 2.00 mmol) in acetone
(10 ml) was re¯uxed for 5 h. The reaction was quenched
with water and the whole was extracted with AcOEt. The
extract was washed with saturated Na2S2O3 aqueous solu-
tion, saturated NaHCO3 aqueous solution, and brine prior to
drying and solvent evaporation. The residue was chromato-
graphed on silica gel with hexane±AcOEt (2:1) to give
(E)-10 (331 mg, 99%) as yellow oil. [a]2D8ˆ1107.4
(c 0.91, CHCl3). IR (KBr) cm21: 2931, 1597, 1493, 1084,
1
1493, 1084, 1045. H NMR d: 1.60±1.66 (2H, m, 4-H),
1.76±1.82 (2H, m, 5-H), 2.26 (2H, dq, Jˆ6.7, 1.2 Hz,
3-H), 2.41 (3H, s, Ar-CH3), 3.52 (2H, t, Jˆ6.7 Hz, 6-H),
6.24 (1H, dt, Jˆ15.3, 1.2 Hz, 1-H), 6.57 (1H, dt, Jˆ15.3,
6.7 Hz, 2-H), 7.31 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, d,
Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.4, 25.3, 31.1, 31.7, 44.5,
124.53 (2C) 130.0 (2C), 135.6, 139.3, 140.8, 141.4. MS (EI)
m/z (rel. int. %): 256 (M1, 10.8), 131 (100). HRMS (EI)
Calcd C13H17ClOS: 256.0689. Found: 256.0678.
1
1043. H NMR d: 1.95±2.00 (2H, m, 4-H), 2.36 (2H, dt,
Jˆ6.7, 1.2 Hz, 3-H), 2.41 (3H, s, Ar-CH3), 3.18 (2H, t,
Jˆ6.7 Hz, 5-H), 6.29 (1H, d, Jˆ15.3 Hz, 1-H), 6.53 (1H,
dt, Jˆ15.3, 6.7 Hz, 2-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H),
7.50 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 5.3, 21.3,
31.3, 32.4, 124.5 (2C), 130.0 (2C), 136.2, 137.2, 140.6,
141.5. MS (EI) m/z (rel. int. %): 334 (M1, 15.9), 286
(100), 131 (100). HRMS (EI) Calcd C12H15IOS: 333.9886.
Found: 333.9901.
(E)-5-[(R)-(p-Tolylsul®nyl)]-4-pentenal (14). Dess±Martin
periodinane (427 mg, 1.00 mmol) was added to a solution of
the alcohol (E)-5 (200 mg, 0.84 mmol) in CH2Cl2 (8 ml)
with stirring at 08C and the stirring was continued at rt for
15 min. Then, AcOEt, saturated Na2S2O3 aqueous solution,
and saturated NaHCO3 aqueous solution were added to the
mixture and the whole was stirred for 15 min. The organic
layer was separated and washed with water and brine prior
to drying and solvent evaporation. The residue was chroma-
tographed on silica gel with hexane±AcOEt (1:2) to give 14
(151 mg, 76%) as a colorless oil. [a]2D7ˆ1187.8 (c 0.15,
(E)-(R)-6-Iodo-1-hexenyl p-tolyl sulfoxide [(E)-11]. Using
the procedure for (E)-10, the tosylate (E)-8 (30 mg,
0.076 mmol) was converted into (E)-11 (24 mg, 92%).
Pale yellow powder: mp 42.3±43.28C (ether).
[a]D29ˆ181.4 (c 1.07, CHCl3). IR (KBr) cm21: 2926,
1493, 1217, 1084, 1043. 1H NMR d: 1.59 (2H, quint,
Jˆ7.3 Hz, 3-H), 1.83 (2H, quint, Jˆ7.3 Hz, 5-H), 2.26
(2H, q, Jˆ6.7 Hz, 3-H), 2.41 (3H, s, Ar-CH3), 3.17 (2H, t,
Jˆ7.3 Hz, 6-H), 6.24 (1H, d, Jˆ15.3 Hz, 1-H), 6.58 (1H, dt,
Jˆ6.7, 15.3 Hz, 2-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50
(2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 6.1, 21.3, 28.8, 30.7,
32.5, 124.3 (2C), 129.7 (2C), 135.4, 138.9, 140.5, 141.1. MS
(EI) m/z (rel. int. %): 348 (M1, 8.9), 300 (100). HRMS (EI)
Calcd C13H17IOS: 349.0045. Found: 348.0033.
1
CHCl3). IR (KBr) cm21: 1720, 1600, 1084. H NMR d:
2.33 (3H, s, Ar-CH3), 2.45±2.49 (2H, m, 3-H), 2.57 (2H,
t, Jˆ7.0 Hz, 2-H), 6.18 (1H, dd, Jˆ15.3, 1.2 Hz, 5-H), 6.49
(1H, dt, Jˆ15.3, 6.7 Hz, 4-H), 7.23 (2H, d, Jˆ7.9 Hz, Ar-
H), 7.40 (2H, d, Jˆ7.9 Hz, Ar-H), 9.69 (1H, s, CHO). 13C
NMR d: 21.4, 24.2, 41.9, 124.4 (2C), 129.9 (2C), 135.9,
137.2, 140.3, 141.4, 199.8. MS (EI) m/z (rel. int. %): 222
(M1, 11.6), 174 (100). HRMS (EI) Calcd C12H14O2S:
222.0714. Found: 222.0715.
(E)-6-[(R)-(p-Tolylsul®nyl)]-5-hexen-2-ol (15). MeMgBr
(0.86 M in ether, 0.86 ml, 0.74 mmol) was added to a solu-
tion of the aldehyde 14 (150 mg, 0.68 mmol) in THF (6 ml)
with stirring at 15 min. The reaction was quenched with
saturated NH4Cl aqueous solution and the whole was
extracted with AcOEt. The extract was washed with water
and brine prior to drying and solvent evaporation. The resi-
due was chromatographed on silica gel with hexane±AcOEt
(1:2) to give 15 (1:1 diastereomeric mixture, 105 mg, 66%)
as a pale yellow oil. IR (KBr) cm21: 3425, 3924, 1084,
(E)-(R)-6-Bromo-1-hexenyl p-tolyl sulfoxide [(E)-12]. A
mixture of (E)-8 (300 mg, 0.76 mmol), NaHCO3 (260 mg,
3.10 mmol), and NaBr (160 mg, 1.56 mmol) in acetone
(8 ml) was re¯uxed for 29 h. The reaction was quenched
with water and the whole was extracted with AcOEt. The
extract was washed with saturated Na2S2O3 aqueous solu-
tion, saturated NaHCO3 aqueous solution, and brine prior to
drying and solvent evaporation. The residue was chromato-
graphed on silica gel with hexane±AcOEt (2:1) to give
(E)-12 (198 mg, 86%) as a colorless oil. [a]2D9ˆ1103.4 (c
1.07, CHCl3). IR (KBr) cm21: 2935, 1628, 1597, 1244,
1
1041, 1014. H NMR d: 1.00±1.12 (3H, m, 1-H), 1.47±
1.52 (2H, m, 3-H), 2.07±2.63 (2H, m, 4-H), 2.41 (3H, s,
Ar-CH3), 3.69±3.76 (1H, m, 2-H), 6.13±6.20 (1H, m, 6-H),
6.47±6.56 (1H, m, 5-H), 7.23 (2H, d, Jˆ7.9 Hz, Ar-H), 7.41
(2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.4, 23.6, 28.3, 37.2,
66.9, 124.5 (2C), 130.0 (2C), 135.0, 140.4, 140.5, 141.4. MS
(EI) m/z (rel. int. %): 238 (M1, 60.1), 143 (100). HRMS (EI)
Calcd C13H18O2S: 238.1027. Found: 238.1024.
1
1084, 1045, 1016. H NMR d: 1.62 (2H, quint, Jˆ7.3 Hz,
4-H), 1.88 (2H, m, 5-H), 2.27 (2H, dq, Jˆ7.3, 1.2 Hz, 3-H),
2.41 (3H, s, Ar-CH3), 3.40 (2H, t, Jˆ6.7 Hz, 6-H), 6.24 (1H,
dt, Jˆ15.3, 1.2 Hz, 1-H), 6.56 (1H, dt, Jˆ15.3, 6.7 Hz,
2-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, d,
Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.1, 26.3, 30.7, 31.6,
33.0, 124.3 (2C) 129.8 (2C), 135.4, 139.0, 140.6, 141.1.
MS (EI) m/z (rel. int. %): 300 (M1, 9.0), 131 (100).
HRMS (EI) Calcd C13H17BrOS: 300.0183. Found:
300.0164.
(E)-6-[(R)-(p-Tolylsul®nyl)]-5-hexen-2-yl methanesulfo-
nate (16). Using the procedure for (E)-9, the alcohol 15
(50 mg, 0.21 mmol) was converted into 16 (1:1 diastereo-
meric mixture, 54 mg, 81%). A pale yellow oil: IR (KBr)
1
(E)-(R)-6-Chloro-1-hexenyl p-tolyl sulfoxide [(E)-13]. A
cm21: 3022, 1599, 1348, 1174, 1045. H NMR d: 1.35

N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
7935
(3/2H, d, Jˆ1.2 Hz, 1-H), 1.35 (3/2H, d, Jˆ1.2 Hz, 1-H),
1.71±1.87 (2H, m, 3-H), 2.29±2.34 (2H, m, 4-H), 2.34 (3H,
s, Ar-CH3), 2.92 (3/2H, s, SO2CH3), 2.93 (3/2H, s, SO2CH3),
4.68±4.81 (1H, m, 2-H), 6.21 (1/2H, d, Jˆ15.3 Hz, 6-H),
6.22 (1/2H, d, Jˆ15.3 Hz, 6-H), 6.49 (1H, dt, Jˆ15.3,
6.7 Hz, 5-H), 7.24 (2H, d, Jˆ8.5 Hz, Ar-H), 7.43 (2H, d,
Jˆ8.5 Hz, Ar-H). 13C NMR d: 21.0, 21.3, 27.5, 34.9, 38.6,
78.5, 124.5 (2C), 130.0 (2C), 135.7 (1/2C), 135.8 (1/2C),
137.8 (1/2C), 137.9 (1/2C), 140.4, 141.5. MS (EI) m/z (rel.
int. %): 316 (M1, 12.0), 143 (100). HRMS (EI) Calcd
C14H20O4S2: 316.0803. Found: 316.0818.
21.5, 24.8, 25.4, 32.4, 36.9, 62.3, 63.1, 65.6, 123.8 (2C),
130.0 (2C), 139.5, 141.4. MS (EI) m/z (rel. int. %): 270
(M1, 1.3), 140 (100). HRMS (EI) Calcd C14H22O3S:
270.1290. Found: 270.1286.
7-[(R)-(p-Tolylsul®nyl)]-6-[(methylsulfonyl)oxy]heptyl
methanesulfonate (20). MsCl (33 ml, 0.42 mmol) was
added to a mixture of 19 (52 mg, 0.19 mmol) and Et3N
(59 ml, 0.42 mmol) in CH2Cl2 (1.5 ml) with stirring at
08C. The stirring was continued at rt for 20 min. The reac-
tion was quenched with saturated NH4Cl aqueous solution
and the whole was extracted with AcOEt. The extract was
washed with water and brine prior to drying and solvent
evaporation. The residue was chromatographed on silica
gel with hexane±ether (1:1) to give 20 (2:1 diastereomeric
(E)-(R)-5-Iodo-1-hexenyl p-tolyl sulfoxide (17). Using the
procedure for (E)-10, the mesylate 16 (561 mg, 1.72 mmol)
was converted into 17 (1:1 diastereomeric mixture, 426 mg,
70%). A pale yellow oil: IR (KBr) cm21: 2920, 1595, 1084,
1043. 1H NMR d: 1.71±1.73 (1H, m, 3-H), 1.88±1.93 (1H,
m, 3-H), 1.88 (3H, d, Jˆ6.5 Hz), 2.28±2.33 (2H, m, 4-H),
2.37 (3H, s, Ar-CH3), 4.05±4.09 (1H, m, 5-H), 6.24 (1H, d,
Jˆ15.3 Hz, 1-H), 6.47±6.51 (1H, dt, Jˆ15.3, 6.7 Hz, 2-H),
7.28 (2H, d, Jˆ8.5 Hz, Ar-H), 7.46 (2H, d, Jˆ8.5 Hz,
Ar-H). 13C NMR d: 21.5, 28.4, 28.9, 32.3, 40.7, 124.5
(2C), 130.0 (2C), 135.8, 137.5, 140.5, 141.4. MS (EI) m/z
(rel. int. %): 348 (M1, 9.2), 300 (100). HRMS (EI) Calcd
C13H17IOS: 348.0045. Found: 348.0045.
mixture, 53 mg, 65%) as a pale yellow oil. IR (KBr) cm21
:
2935, 1600, 1344, 1172, 1083, 1039. 1H NMR d: 1.45±1.49
(4H, m, 3- and 4-H), 1.72±1.95 (4H, m, 2-H and 5-H), 2.43
(3H, s, Ar-CH3), 2.93 (1/3H, dd, Jˆ13.7, 3.4 Hz, 7-H),
2.97±3.05 (1/3H, m, 7-H), 3.00 (1H, s, SO2CH3), 3.02
(2H, s, SO2CH3), 3.06 (2H, s, SO2CH3), 3.07 (2/3H, dd,
Jˆ14.0, 6.1 Hz, 7-H), 3.22 (1H, s, SO2CH3), 3.25 (2/3H,
dd, Jˆ14.0, 5.5 Hz, 7-H), 4.30±4.24 (2H, m, 1-H), 4.98
(2/3H, quint, Jˆ6.1 Hz, 6-H), 5.10±5.20 (1/3H, m, 6-H),
7.36 (2H, d, Jˆ7.9 Hz, Ar-H), 7.54 (2/3H, d, Jˆ8.5 Hz,
Ar-H), 7.57 (4/3H, d, Jˆ7.9 Hz, Ar-H). 13C NMR (major)
d: 21.3, 24.1, 24.8, 28.7, 34.3, 37.2, 38.6, 61.7, 70.0, 76.6,
124.0 (2C), 130.1 (2C), 139.7, 142.1. (Minor) d: 21.3, 23.6,
24.9, 28.7, 34.9, 37.2, 38.3, 61.7, 70.0, 77.2, 123.7 (2C),
130.2 (2C), 139.5, 142.1. MS (EI) m/z (rel. int. %): 426
(M1, 0.2), 140 (100). HRMS (EI) Calcd C16H26O7S3:
426.0840. Found: 426.0858.
7-Hydroxy-1-[(R)-(p-tolylsul®nyl)]-2-heptanone
(18).
Using the procedure for 1, (R)-methyl p-tolyl sulfoxide
(739 mg, 4.79 mmol) and e-caprolactone (0.40 ml,
5.19 mmol) were converted into 18 (978 mg, 76%). Pale
yellow powder: mp 62.0±62.58C (hexane±AcOEt).
[a]D28ˆ1161.1 (c 1.14, CHCl3). IR (KBr) cm21: 3402,
2935, 1713, 1600, 1086, 1036. 1H NMR d: 1.31 (2H,
quint, Jˆ7.9 Hz, 5-H), 1.49±1.58 (4H, m, 4- and 6-H),
2.42 (3H, s, Ar-CH3), 2.43±2.55 (2H, m, 3-H), 3.58
(2H, t, Jˆ6.1 Hz, 7-H), 3.76 (1H, d, Jˆ3.8 Hz, 1-H), 3.89
(1H, d, Jˆ3.8 Hz, 1-H), 7.33 (2H, d, Jˆ8.6 Hz, Ar-H), 7.54
(2H, d, Jˆ8.6 Hz, Ar-H). 13C NMR d: 21.4, 22.7, 25.0, 32.2,
44.6, 62.1, 67.9, 123.8, 129.9, 139.2 (2C), 142.0 (2C),
201.5. MS (EI) m/z (rel. int. %): 268 (M1, 8.9), 139
(100). HRMS (EI) Calcd C14H20O3S: 268.1133. Found:
268.1133.
(E)- and (Z)-7-[(R)-(p-Tolylsul®nyl)]-6-heptenyl metha-
nesulfonate [(E)- and (Z)-21]. t-BuOK (19.9 mg,
0.18 mmol) was added to a solution of 20 (50 mg,
0.12 mmol) in THF (1.5 ml) with stirring at 08C. The stir-
ring was continued at rt for 1 h. The reaction was quenched
with saturated NH4Cl aqueous solution and the whole was
extracted with AcOEt. The extract was washed with water
and brine prior to drying and solvent evaporation. The resi-
due was chromatographed on silica gel with hexane±AcOEt
(1:3) to give (E)-21 (13 mg, 33%) as colorless powder and
(Z)-21 (13 mg, 33%) as a colorless oil. (E)-21: mp 61.4±
62.28C (hexane±AcOEt). [a]2D7ˆ174.0 (c 0.84, CHCl3). IR
(KBr) cm21: 2931, 1597, 1352, 1174, 1084, 1041. 1H NMR
d: 1.42±1.46 (2H, m, 3-H), 1.49±1.55 (2H, m, 4-H), 1.75
(2H, quint, Jˆ7.0 Hz, 2-H), 2.25 (2H, q, Jˆ6.7 Hz, 5-H),
2.41 (3H, s, Ar-CH3), 3.00 (3H, s, SO2CH3), 4.20 (2H, t,
Jˆ6.7 Hz, 1-H), 6.22 (1H, d, Jˆ15.3 Hz, 7-H), 6.57 (1H, dt,
Jˆ15.3, 6.7 Hz, 6-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.49
(2H, d, Jˆ8.3 Hz, Ar-H). 13C NMR d: 21.4, 24.9, 27.5, 28.8,
31.6, 37.3, 69.6, 124.4 (2C), 129.8 (2C), 135.3, 139.5,
140.7, 141.2. MS (EI) m/z (rel. int. %): 330 (M1, 7.5),
282 (100). HRMS (EI) Calcd C15H22O4S2: 330.0959.
Found: 330.0959. (Z)-21: [a]2D6ˆ1133.1 (c 0.14, CHCl3).
IR (KBr) cm21: 2935, 1597, 1352, 1174, 1038. 1H NMR d:
1.36±1.55 (4H, m, 3- and 4-H), 1.65±1.78 (2H, m, 2-H),
2.34 (3H, s, Ar-CH3), 2.37±2.51 (1H, m, 5-H), 2.56±2.67
(1H, m, 5-H), 2.95 (3H, s, SO2CH3), 4.18 (2H, t, Jˆ6.5 Hz,
1-H), 6.06±6.47 (2H, m, 6- and 7-H), 7.25 (2H, d,
Jˆ8.3 Hz, Ar-H), 7.42 (2H, d, Jˆ8.3 Hz, Ar-H). 13C
NMR d: 21.3, 24.9, 28.3, 28.8, 28.9, 37.3, 69.7, 124.0
7-[(R)-(p-Tolylsul®nyl)]-1,6-heptanediol (19). NaBH4
(12 mg, 0.45 mmol) was added to a solution of 18
(100 mg, 0.37 mmol) in MeOH (5 ml) with stirring at 08C.
The stirring was continued at rt for 10 min. After the
evaporation of MeOH, the residue was partitioned between
AcOEt and water. The organic layer was washed with water
and brine prior to drying and solvent evaporation. The
residue was chromatographed on silica gel with AcOEt to
give 19 (2:1 diastereomeric mixture, 93 mg, 93%) as a
yellow oil. IR (KBr) cm21: 3334, 2933, 1600, 1085, 1035.
1H NMR d: 1.33±1.49 (4H, m, 3- and 4-H), 1.53±2.52 (4H,
m, 2- and 5-H), 2.42 (3H, s, Ar-CH3), 2.54 (1H, br, OH),
2.74 (1/3H, dd, Jˆ13.4, 2.1 Hz, 7-H), 2.79 (2/3H, dd,
Jˆ13.4, 3.1 Hz, 7-H), 2.91 (1/3H, dd, Jˆ13.4, 10.4 Hz,
7-H), 3.02 (2/3H, dd, Jˆ13.4, 8.5 Hz, 7-H), 3.59 (2/3H, t,
Jˆ6.7 Hz, 1-H), 3.61 (4/3H, t, Jˆ6.7 Hz, 1-H), 4.18±4.24
(1H, m, 6-H), 7.34 (2H, d, Jˆ7.9 Hz, Ar-H), 7.52 (2/3H, d,
Jˆ7.9 Hz, Ar-H), 7.55 (4/3H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR (major) d: 21.5, 24.8, 25.5, 32.4, 37.0, 62.3, 63.1,
68.1, 123.9 (2C), 130.0 (2C), 140.1, 141.9. (minor) d:

7936
N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
(2C), 130.0 (2C), 137.3, 141.0, 141.1, 141.2. MS (EI) m/z
(rel. int. %): 330 (M1, 33.3), 313 (100). HRMS (EI) Calcd
C15H22O4S2: 330.0959. Found: 330.0945.
A colorless oil: [a]2D6ˆ138.4 (c 0.83, CHCl3). IR (KBr)
1
cm21: 2950, 2181, 1462, 1255, 1090, 1060. H NMR d:
0.03 (6H, s, Si(CH3)2), 0.88 (9H, s, SiC(CH3)3), 1.57±1.66
(4H, m, 4- and 5-H), 2.42 (3H, s, Ar-CH3), 2.45 (2H, t,
Jˆ6.7 Hz, 3-H), 3.60 (2H, t, Jˆ6.1 Hz, 6-H), 7.34 (2H, d,
Jˆ7.9 Hz, Ar-H), 7.75 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR
d: 25.5 (2C), 18.2, 19.5, 21.4, 24.1, 25.8 (3C), 31.6, 62.2,
78.3, 105.5, 125.0 (2C), 130.1 (2C), 141.2, 142.1. MS
(FAB) m/z: 351 (MH1). Anal. Calcd for C19H30O2SiS:
C; 65.09, H; 8.62, S; 9.15. Found: C; 65.03, H; 8.51,
S; 9.01.
(E)-(R)-7-Iodo-1-heptenyl p-tolyl sulfoxide [(E)-22].
Using the procedure for (E)-10, the mesylate (E)-21
(200 mg, 0.61 mmol) was converted into (E)-22 (191 mg,
87%). A colorless oil: [a]2D4ˆ165.4 (c 1.53, CHCl3). IR
1
(KBr) cm21: 2931, 1597, 1493, 1084, 1043. H NMR d:
1.38±1.44 (2H, m, 5-H), 1.46±1.52 (2H, m, 4-H), 1.81
(2H, quint, Jˆ6.7 Hz, 6-H), 2.24 (2H, dq, Jˆ6.7, 1.2 Hz,
3-H), 2.41 (3H, s, Ar-CH3), 3.17 (2H, t, Jˆ6.7 Hz, 7-H),
6.23 (1H, dt, Jˆ15.3, 1.2 Hz, 1-H), 6.56 (1H, dt, Jˆ15.3,
6.7 Hz, 2-H), 7.31 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, d,
Jˆ7.9 Hz, Ar-H). 13C NMR d: 6.6, 21.3, 26.9, 29.7, 31.6,
32.9, 124.5 (2C), 129.9 (2C), 135.3, 139.8, 140.8, 141.3. MS
(FAB) m/z: 363 (MH1). HRMS (FAB) Calcd C14H20IOS
(MH1): 363.0280. Found: 363.0275.
(Z)-(R)-5-[[tert-Butyl(dimethyl)silyl]oxy]-1-pentenyl p-tolyl
sulfoxide (27). A mixture of 25 (100 mg, 0.30 mmol) and
RhCl(PPh3)3 (10 mg, 0.011 mmol) in degassed benzene
(4.5 ml) was stirred under hydrogen (1 atm) at rt for 24 h.
The mixture was ®ltered and the ®ltrate was concentrated
under the reduced pressure to give 27 (83 mg, 83%) as a
colorless oil. [a]2D7ˆ2204.3 (c 1.05, CHCl3). IR (KBr)
cm21: 2929, 2856, 1597, 1471, 1462, 1255, 1105, 1043.
1H NMR d: 0.05 (6H, s, Si(CH3)2), 0.89 (9H, s,
SiC(CH3)3), 1.63±1.75 (2H, m, 4-H), 2.38 (3H, s, Ar-
CH3), 2.61±2.66 (2H, m, 3-H), 3.65 (1H, dt, Jˆ12.8,
6.1 Hz, 5-H), 3.67 (1H, dt, Jˆ12.8, 6.1 Hz, 5-H), 6.17
(1H, d, Jˆ7.9 Hz, 2-H), 6.19 (1H, d, Jˆ7.9 Hz, 1-H), 7.28
(2H, d, Jˆ7.9 Hz, Ar-H), 7.49 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 25.4 (2C), 18.2, 21.3, 25.9 (3C), 26.0, 32.1, 62.0,
124.0 (2C), 129.9 (2C), 137.3, 141.0, 141.3, 131.4. MS
(FAB) m/z: 339 (MH1). HRMS (FAB) Calcd C18H31O2SSi
(MH1): 339.1814. Found: 339.1823.
(Z)-(R)-7-Iodo-1-heptenyl p-tolyl sulfoxidfe [(Z)-22].
Using the procedure for (E)-10, the mesylate (Z)-21
(200 mg, 0.61 mmol) was converted into (Z)-22 (184 mg,
84%). A colorless oil: [a]2D4ˆ2160.4 (c 1.30, CHCl3). IR
1
(KBr) cm21: 2931, 1597, 1493, 1084, 1041. H NMR d:
1.46±1.59 (4H, m, 4- and 5-H), 1.86 (2H, quint,
Jˆ6.7 Hz, 6-H), 2.41 (3H, s, Ar-CH3), 2.50±2.57 (1H, m,
3-H), 2.62±2.70 (1H, m, 3-H), 3.20 (2H, t, Jˆ6.7 Hz, 7-H),
6.17 (1H, dt, Jˆ9.8, 7.3 Hz, 2-H), 6.23 (1H, d, Jˆ9.8 Hz,
1-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR d: 6.6, 21.3, 27.9, 29.0, 29.9, 33.0, 124.0
(2C), 129.9 (2C), 137.3, 141.1 (2C), 141.2. MS (FAB) m/z:
363 (MH1). HRMS (FAB) Calcd C14H20IOS (MH1):
363.0280. Found: 363.0285.
(Z)-(R)-6-[[tert-Butyl(dimethyl)silyl]oxy]-1-hexenyl p-tolyl
sulfoxide (28). Using the procedure for 27, the alcohol 26
(100 mg, 0.29 mmol) was converted into 28 (95 mg, 93%).
A colorless oil: [a]2D7ˆ2183.2 (c 0.94, CHCl3). IR (KBr)
cm21: 2950, 2858, 1462, 1255, 1101, 1045. 1H NMR d: 0.03
(6H, s, Si(CH3)2), 0.87 (9H, s, SiC(CH3)3), 1.53±1.56 (4H,
m, 4-H and 5-H), 2.37 (3H, s, Ar-CH3), 2.50±2.60 (1H, m,
3-H), 2.58±2.63 (1H, m, 3-H), 3.62 (2H, dt, Jˆ5.8, 1.8 Hz,
6-H), 6.12±6.19 (2H, m, 1- and 2-H), 7.27 (2H, d,
Jˆ7.9 Hz, Ar-H), 7.47 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 25.3 (2C), 18.2, 21.3, 25.4, 25.9 (3C), 29.0,
32.1, 62.5, 124.0 (2C), 129.9 (2C), 137.1, 141.0, 141.3,
131.6. MS (FAB) m/z: 353 (MH1). Anal. Calcd for
C19H32O2SiS: C; 64.72, H; 9.15, S; 9.09. Found: C; 64.58,
H; 8.95, S; 9.03.
(R)-5-[[tert-Butyl(dimethyl)silyl]oxy]-1-pentynyl p-tolyl
sulfoxide (25). EtMgBr (2.5 M in ether, 3.00 ml,
8.75 mol) was added to a solution of 23 (2.49 g,
12.6 mmol) in ether (5 ml) with stirring at 08C under N2
and the whole was re¯uxed for 1.5 h. Then, a solution of
(S)-(2)-menthyl p-tolylsul®nate (1.85 g, 6.28 mmol) in
toluene (20 ml) was added to the mixture with stirring at
08C and the stirring was continued at the same temperature
for 2 h and at rt for 1 h. The reaction was quenched with
saturated NH4Cl aqueous solution and the whole was
extracted with AcOEt. The extract was washed with brine
prior to drying and solvent evaporation. The residue was
chromatographed on silica gel with hexane±AcOEt (10:1)
to give 25 (1.75 g, 82%) as a colorless oil. [a]2D7ˆ149.86 (c
0.68, CHCl3). IR (KBr) cm21: 2954, 2856, 1597, 1471,
(Z)-5-[(R)-(p-Tolylsul®nyl)]-4-penten-1-ol [(Z)-5]. HF´
pyridine (663 mg, 4.68 mmol) was added to a solution of
27 (1.32 g, 3.90 mmol) in a 1:1 mixture of pyridine and THF
(40 ml) with stirring at rt. The stirring was continued for
3 days. The reaction was quenched with water and the
whole was extracted with AcOEt. The extract was washed
with brine prior to drying and solvent evaporation. The
residue was chromatographed on silica gel with hexane±
AcOEt (10:1) to give (Z)-5 (851 mg, 97%) as a colorless
oil. [a]2D6ˆ2147.8 (c1.07, CHCl3). IR (KBr) cm21: 3390,
2937, 1597, 1493, 1084, 1038, 1012. 1H NMR d: 1.69±1.77
(2H, m, 2-H), 2.27±2.29 (1H, m, OH), 2.42 (3H, s, Ar-CH3),
2.53±2.60 (1H, m, 3-H), 2.87±2.95 (1H, m, 3-H), 3.72 (2H,
q, Jˆ5.5 Hz, 1-H), 6.23 (1H, dt, Jˆ9.8, 6.7 Hz, 4-H), 6.28
(1H, dt, Jˆ9.8, 1.2 Hz, 5-H), 7.33 (2H, d, Jˆ7.9 Hz, Ar-H),
7.52 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.2, 25.6, 31.4,
1
1105, 1092, 1063. H NMR d: 0.01 (6H, s, Si(CH3)2),
0.86 (9H, s, SiC(CH3)3), 1.75 (2H, quint, Jˆ6.7 Hz, 4-H),
2.41 (3H, s, Ar-CH3), 2.51 (2H, t, Jˆ6.7 Hz, 5-H), 3.63 (2H,
t, Jˆ6.7 Hz, 3-H), 7.33 (2H, d, Jˆ7.9 Hz, Ar-H), 7.68 (2H,
d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 25.4 (2C), 16.2, 18.2,
21.4, 25.8 (3C), 30.5, 61.0, 78.3, 105.4, 125.0 (2C), 130.1
(2C), 141.3, 142.5. MS (FAB) m/z: 337 (MH1). HRMS
(FAB) Calcd C18H29O2SiS (MH1): 337.1658. Found:
337.1674.
(R)-6-[[tert-Butyl(dimethyl)silyl]oxy]-1-hexynyl p-tolyl
sulfoxide (26). Using the procedure for 25, the alcohol 24
(5.42 g, 25.5 mmol) and (S)-(2)-menthyl p-tolylsul®nate
(4.00 g, 13.6 mmol) was converted into 26 (3.42 g, 72%).

N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
7937
60.7, 124.0 (2C), 129.9 (2C), 136.7, 140.5, 141.2, 142.1. MS
(EI) m/z (rel. int. %): 224 (M1, 14.1), 207 (100). HRMS (EI)
Calcd C12H16O2S: 224.0871. Found: 224.0895.
m/z (rel. int. %): 334 (M1, 1.4), 91 (100). MS (EI) m/z (rel.
int. %): 334 (M1, 1.4), 91 (100). HRMS (EI) Calcd
C12H15IOS: 333.9889. Found: 333.9906.
(Z)-6-[(R)-(p-Tolylsul®nyl)]-5-hexen-1-ol [(Z)-6]. Using
the procedure for (Z)-5, the alcohol 28 (58 mg,
0.16 mmol) was converted into (Z)-6 (34 mg, 87%). A
colorless oil: [a]2D8ˆ2236.8 (c 0.58, CHCl3). IR (KBr)
(Z)-(R)-6-Iodo-1-hexenyl p-tolyl sulfoxide [(Z)-11]. Using
the procedure for (E)-10, the tosylate (Z)-8 (100 mg,
0.26 mmol) was converted into (Z)-11 (82 mg, 92%). A
yellow oil: [a]2D8ˆ2177.4 (c 1.05, CHCl3). IR (KBr)
1
1
cm21: 3408, 2933, 1493, 1454, 1028. H NMR d: 1.49±
cm21: 2933, 1492, 1450, 1081, 1041. H NMR d: 1.64
1.60 (4H, m, 2- and 3-H), 2.32 (3H, s, Ar-CH3), 2.34±
2.49 (2H, m, 4-H and OH), 2.57±2.64 (1H, m, 4-H), 3.59
(2H, t, Jˆ6.7 Hz, 1-H), 6.12 (2H, m, 5- and 6-H), 7.23 (2H,
d, Jˆ7.9 Hz, Ar-H), 7.41 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 21.3, 25.2, 28.9, 31.8, 61.9, 124.0 (2C), 130.0
(2C), 136.8, 140.9, 141.2, 141.9. MS (FAB) m/z: 239
(MH1). HRMS (FAB) Calcd C13H19O2S (MH1):
239.1106. Found: 239.1107.
(2H, quint, Jˆ7.3 Hz, 4-H), 1.88±1.92 (2H, m, 5-H), 2.41
(3H, s, Ar-CH3), 2.57 (1H, quint, Jˆ7.3 Hz, 3-H), 2.66 (1H,
quint, Jˆ7.3 Hz, 3-H), 3.27 (2H, t, Jˆ7.3 Hz, 6-H), 6.14±
6.19 (1H, m, 2-H), 6.25 (1H, d, Jˆ9.2 Hz, 1-H), 7.32 (2H, d,
Jˆ7.9 Hz, Ar-H), 7.51 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR
d: 6.1, 21.4, 28.1, 29.7, 32.6, 124.1 (2C), 130.0 (2C), 137.7,
140.7, 141.1, 141.2. MS (FAB) m/z: 349 (MH1). Anal.
Calcd for C13H17IOS: C; 44.84, H; 4.92. Found: C; 44.52,
H; 4.89.
(Z)-5-[(R)-(p-Tolylsul®nyl)]-4-pentenyl p-toluenesulfonate
[(Z)-7]. Using the procedure for (E)-7, the alcohol (Z)-5
(433 mg, 1.93 mmol) was converted into (Z)-7 (595 mg,
81%). A colorless oil: [a]2D7ˆ2175.2 (c 1.15, CHCl3). IR
(KBr) cm21: 2924, 1597, 1493, 1358, 1190, 1176, 1041. 1H
NMR d: 1.83±1.90 (2H, m, 2-H), 2.41 (3H, s, Ar-CH3), 2.45
(3H, s, Ar-CH3), 2.56±2.62 (1H, m, 3-H), 2.64±2.72 (1H, m,
3-H), 4.06±4.14 (2H, m, 1-H), 6.08 (1H, dt, Jˆ9.2, 7.3 Hz,
4-H), 6.23 (1H, dt, Jˆ9.2, 1.2 Hz, 5-H), 7.32 (2H, d,
Jˆ8.5 Hz, Ar-H), 7.37 (2H, d, Jˆ8.5 Hz, Ar-H), 7.47 (2H,
d, Jˆ8.5 Hz, Ar-H), 7.81 (2H, d, Jˆ8.5 Hz, Ar-H). 13C
NMR d: 21.3, 21.5, 25.3, 28.3, 69.2, 124.0 (2C), 127.8
(2C), 129.9 (2C), 130.0 (2C), 132.8, 138.2, 139.2, 140.9,
141.3, 144.9. MS (FAB) m/z: 379 (MH1). HRMS (FAB)
Calcd C19H23O4S2 (MH1): 3791034. Found: 379.1040.
7-Hydroxyheptyl p-toluenesulfonate (29). Using the
procedure for (E)-7, 1,7-heptanediol (3.00 g, 22.7 mmol)
was converted into 29 (5.66 g, 87%). A colorless oil: IR
1
(KBr) cm21: 3350, 2929, 1356, 1176. H NMR d: 1.24±
1.34 (6H, m, 3-, 4-, and 5-H), 1.52 (2H, quint, Jˆ7.3 Hz,
6-H), 1.64 (2H, quint, Jˆ6.7 Hz, 2-H), 1.78 (1H, s, OH),
2.45 (3H, s, Ar-CH3), 3.61 (2H, t, Jˆ6.7 Hz, 7-H), 4.02 (2H,
t, Jˆ6.7 Hz, 1-H), 7.35 (2H, d, Jˆ8.5 Hz, Ar-H), 7.87 (2H,
d, Jˆ8.5 Hz, Ar-H). 13C NMR d: 21.7, 25.3, 25.5, 28.7,
28.7, 32.5, 62.8, 70.6, 127.7 (2C), 129.7 (2C), 133.0,
144.5. MS (EI) m/z (rel. int. %): 286 (M1, 16.7), 91 (100).
HRMS (EI) Calcd C14H22O4S: 286.1239. Found: 286.1226.
7-Oxoheptyl p-toluenesulfonate (30). Using the procedure
for 14, the alcohol 29 (289 mg, 1.01 mmol) was converted
(Z)-6-[(R)-(p-Tolylsul®nyl)]-5-hexenyl p-toluenesulfonate
[(Z)-8]. Using the procedure for (E)-7, the alcohol (Z)-6
(600 mg, 2.52 mmol) was converted into (Z)-8 (708 mg,
72%). A colorless oil: [a]2D8ˆ2130.0 (c 1.30, CHCl3). IR
into 30 (256 mg, 90%). A colorless oil: IR (KBr) cm21
:
2941, 1724, 1599, 1356, 1188. 1H NMR d: 1.24±1.36
(4H, m, 3- and 4-H), 1.58 (2H, quint, Jˆ7.3 Hz, 5-H),
1.64 (2H, quint, Jˆ6.7 Hz, 2-H), 2.41 (2H, dt, Jˆ7.3,
1.8 Hz, 6-H), 2.45 (3H, s, Ar-CH3), 4.02 (2H, t, Jˆ6.7 Hz,
1-H), 7.36 (2H, d, Jˆ7.9 Hz, Ar-H), 7.78 (2H, d, Jˆ7.9 Hz,
Ar-H), 9.74 (1H, t, Jˆ1.8 Hz, CHO). 13C NMR d: 21.6,
21.7, 25.1, 28.4, 28.6, 43.6, 70.3, 127.6 (2C), 129.6 (2C),
132.9, 144.5, 202.2. MS (EI) m/z (rel. int. %): 284 (M1, 1.7),
173 (100). HRMS (EI) Calcd C14H20O4S: 284.1082. Found:
284.1054.
1
(KBr) cm21: 1493, 1356, 1178, 1097, 1038. H NMR d:
1.48 (2H, quint, Jˆ7.9 Hz, 3-H), 1.61±1.68 (2H, m, 2-H),
2.31 (3H, s, Ar-CH3), 2.35 (3H, s, Ar-CH3), 2.40 (1H, quint,
Jˆ7.3 Hz, 4-H), 2.51 (1H, quint, Jˆ7.3 Hz, 4-H), 3.98 (2H,
dt, Jˆ4.3, 1.8 Hz, 1-H), 6.01 (1H, dt, Jˆ7.3, 1.2 Hz, 5-H),
6.12 (1H, d, Jˆ7.3 Hz, 6-H), 7.22 (2H, d, Jˆ8.3 Hz, Ar-H),
7.26 (2H, d, Jˆ8.3 Hz, Ar-H), 7.39 (2H, d, Jˆ8.3 Hz, Ar-
H), 7.70 (2H, d, Jˆ8.3 Hz, Ar-H). 13C NMR d: 21.2, 21.4,
24.7, 28.0, 28.3, 69.7, 123.9 (2C), 127.7 (2C), 129.7 (2C),
129.9 (2C), 132.7, 137.5, 140.5, 140.9, 141.1, 144.7. MS
(FAB) m/z: 393 (MH1). HRMS (FAB) Calcd C20H25O4S2
(MH1): 393.1195. Found: 393.1185.
(E)- and (Z)-8-[(R)-(p-Tolylsul®nyl)]-7-octenyl p-toluene-
sulfonate [(E)- and (Z)-31]. n-BuLi (1.54 M in hexane,
0.45 ml, 0.69 mmol) was added to a solution of (R)-
dimethylphosphorylmethyl p-tolyl sulfoxide (180 mg,
0.69 mmol) in THF (5 ml) with stirring at 2788C and the
stirring was continued at the same temperature for 30 min.
Then, a solution of the aldehyde 30 (150 mg, 0.53 mmol) in
THF (3 ml) was added to the mixture and the stirring was
continued at 2788C for 30 min. The reaction was quenched
with water and the whole was extracted with AcOEt. The
extract was washed with water and brine prior to drying and
solvent evaporation. The residue was chromatographed on
silica gel with hexane±AcOEt (1:1) to give (E)-31 (67 mg,
30%) as colorless powder and (Z)-31 (102 mg, 46%) as a
yellow oil. (E)-31: mp 49.7±50.78C (hexane±AcOEt).
[a]2D8ˆ151.5 (c 0.48, acetone). IR (KBr) cm21: 2927,
(Z)-(R)-5-Iodo-1-pentenyl p-tolyl sulfoxide [(Z)-10].
Using the procedure for (E)-10, the tosylate (Z)-7
(381 mg, 1.01 mmol) was converted into (Z)-10 (294 mg,
87%). A colorless oil: [a]2D4ˆ2208.4 (c 1.84, CHCl3). IR
(KBr) cm21: 2922, 1595, 1493, 1205, 1082, 1041, 1014. 1H
NMR d: 1.98±2.09 (2H, m, 4-H), 2.41 (3H, s, Ar-CH3),
2.62±2.70 (1H, m, 3-H), 2.73±2.80 (1H, m, 3-H), 3.22
(1H, dt, Jˆ12.2, 6.7 Hz, 5-H), 3.24 (1H, dt, Jˆ12.2,
6.7 Hz, 5-H), 6.13 (1H, dt, Jˆ9.8, 7.3 Hz, 2-H), 6.28 (1H,
dt, Jˆ9.8, 1.2 Hz, 1-H), 7.33 (2H, d, Jˆ7.9 Hz, Ar-H), 7.52
(2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 5.0, 21.2, 29.8, 32.2,
123.9 (2C), 129.9 (2C), 138.2, 138.9, 140.9, 141.1. MS (EI)
1
1597, 1358, 1188, 1176, 1097, 1084, 1043. H NMR d:

7938
N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
1.24±1.33 (4H, m, 3- and 4-H), 1.41 (2H, quint, Jˆ7.3 Hz,
5-H), 1.62 (2H, quint, Jˆ6.2 Hz, 2-H), 2.18 (2H, q,
Jˆ6.7 Hz, 6-H), 2.41 (3H, s, Ar-CH3), 2.45 (3H, s, Ar-
CH3), 4.00 (2H, t, Jˆ7.3 Hz, 1-H), 6.19 (1H, d,
Jˆ15.2 Hz, 8-H), 6.55 (1H, dt, Jˆ15.2, 6.7 Hz, 7-H), 7.31
(2H, d, Jˆ8.2 Hz, Ar-H), 7.35 (2H, d, Jˆ8.2 Hz, Ar-H),
7.49 (2H, d, Jˆ8.5 Hz, Ar-H), 7.78 (2H, d, Jˆ8.5 Hz, Ar-
H). 13C NMR d: 21.4, 21.7, 25.1, 27.8, 28.3, 28.7, 31.8,
70.3, 124.4 (2C), 127.7 (2C), 129.7 (2C), 129.8 (2C),
133.0, 135.1, 140.1, 140.1, 141.2, 144.5. MS (EI) m/z (rel.
int. %): 420 (M1, 11.5), 124 (100). HRMS (EI) Calcd
C22H28O4S2: 420.1429. Found: 420.1434. (Z)-31:
[a]2D8ˆ2149.3 (c 0.29, acetone). IR (KBr) cm21: 2929,
[a]D24ˆ260.4 (c 1.25, CHCl3). IR (KBr) cm21: 2941,
1
1597, 1120, 1038. H NMR d: 1.50±1.59 (4H, m, THP),
1.68±1.80 (2H, m, 4-H), 1.83±1.88 (2H, m, THP), 2.41 (3H,
s, Ar-CH3), 3.08±3.23 (2H, m, 3-H), 3.40±3.46 (1H, m,
5-H), 3.48±3.53 (2H, m, OCH2), 3.77±3.79 (1/2H, t,
Jˆ6.1 Hz, 5-H), 3.79±3.81 (1/2H, t, Jˆ6.1 Hz, 5-H),
4.55±4.56 (1/2H, dd, Jˆ4.9, 3.1 Hz, O±CH±O), 4.58±
4.59 (1/2H, dd, Jˆ4.9, 3.1 Hz, O±CH±O), 6.33 (1H, s,
1-H), 7.31±7.34 (5H, m, Ar-H), 7.38±7.40 (2H, m, Ar-H),
7.56±7.58 (1H, d, Jˆ7.9 Hz, Ar-H), 7.57±7.58 (1H, d,
Jˆ7.9 Hz, Ar-H). 13C NMR d: 19.5 (1/2C), 19.7 (1/2C),
21.3, 25.4, 28.1 (1/2C), 28.3 (1/2C), 28.7 (1/2C), 29.1
(1/2C), 30.6, 62.2 (1/2C), 62.5 (1/2C), 66.1 (1/2C), 66.4
(1/2C), 98.7 (1/2C), 99.0 (1/2C), 124.1 (2C), 126.6 (2C),
128.6 (2C), 129.2, 130.0 (2C), 133.9 (1/2C), 134.2 (1/2C),
138.3 (1/2C), 138.4 (1/2C), 141.0, 141.6, 152.0 (1/2C),
152.4 (1/2C). MS (FAB) m/z: 385 (MH1). HRMS (FAB)
Calcd C23H29O3S (MH1): 385.1837. Found: 385.1836. (Z)-
35 (a colorless oil): [a]2D4ˆ2216.7 (c 1.05, CHCl3). IR
1
1597, 1358, 1176, 1041. H NMR d: 1.32±1.37 (4H, m,
3- and 4-H), 1.46 (2H, quint, Jˆ6.7 Hz, 5-H), 1.66 (2H,
quint, Jˆ6.7 Hz, 2-H), 2.41 (3H, s, Ar-CH3), 2.45 (3H, s,
Ar-CH3), 2.46±2.55 (1H, m, 6-H), 2.55±2.63 (1H, m, 6-H),
4.03 (2H, t, Jˆ6.7 Hz, 1-H), 6.12±6.17 (1H, dt, Jˆ9.7,
7.9 Hz, 7-H), 6.21 (1H, d, Jˆ9.7 Hz, 8-H), 7.31 (2H, d,
Jˆ8.5 Hz, Ar-H), 7.35 (2H, d, Jˆ8.5 Hz, Ar-H), 7.49 (2H,
d, Jˆ7.9 Hz, Ar-H), 7.79 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 21.3, 21.6, 25.1, 28.4, 28.6, 28.7, 29.1, 70.4,
124.0 (2C), 127.8 (2C), 129.8 (2C), 130.0 (2C), 137.0,
141.1, 133.0, 141.1, 141.6, 144.7. MS (EI) m/z (rel. int.
%): 420 (M1, 40.8), 140 (100). HRMS (EI) Calcd
C22H28O4S2: 420.1429. Found: 420.1420.
1
(KBr) cm21: 2943, 1595, 1078, 1036. H NMR d: 1.49±
1.51 (4H, m, THP), 1.66±1.70 (3H, m, 4-H and THP), 1.71±
1.78 (1H, m, 4-H), 2.41 (3H, s, Ar-CH3), 2.57±2.64 (2H, m,
3-H), 3.30±3.33 (1H, m, 5-H), 3.34±3.47 (1H, m, THP),
3.66±3.74 (1H, m, 5-H), 3.75±3.82 (1H, m, THP), 4.43±
4.44 (1/2H, m, O±CH±O), 4.45±4.51 (1/2H, m, O±CH±O),
6.33±6.34 (1H, m, 1-H), 7.29±7.48 (9H, m, Ar-H). 13C
NMR d: 19.5, 21.3, 25.3, 27.4, 30.5, 35.7, 62.2 (1/2C),
62.3 (1/2C), 66.1 (1/2C), 66.2 (1/2C), 98.7 (1/2C), 98.8
(1/2C), 124.3 (2C), 128.2 (2C), 128.4 (2C), 128.6, 129.9
(2C), 133.8, 137.6, 140.9, 141.9, 154.2 (1/2C), 154.3
(1/2C). MS (FAB) m/z: 385 (MH1). HRMS (FAB) Calcd
C23H29O3S (MH1): 385.1837. Found: 385.1839.
(E)-(R)-8-Iodo-1-octenyl p-tolyl sulfoxide [(E)-32]. Using
the procedure for (E)-10, the tosylate (E)-31 (735 mg,
1.75 mmol) was converted into (E)-32 (564 mg, 87%).
Colorless powder: mp 60.8±61.58C (hexane±AcOEt).
[a]2D8ˆ178.3 (c 0.69, acetone). IR (KBr) cm21: 2929,
1
1625 1082, 1045. H NMR d: 1.29±1.42 (4H, m, 5- and
6-H), 1.47 (2H, quint, Jˆ7.3 Hz, 4-H), 1.79 (2H, quint,
Jˆ7.3 Hz, 7-H), 2.23 (2H, q, Jˆ6.7 Hz, 3-H), 2.41 (3H, s,
Ar-CH3), 3.16 (2H, t, Jˆ6.7 Hz, 8-H), 6.21 (1H, d,
Jˆ15.3 Hz, 1-H), 6.58 (1H, dt, Jˆ15.3, 6.7 Hz, 2-H), 7.31
(2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 7.0, 21.4, 27.8, 27.9, 30.1, 31.8, 33.2, 124.4, 129.8
(2C), 135.1 (2C), 140.1, 140.8, 141.2. MS (EI) m/z (rel. int.
%): 376 (M1, 15.1), 359 (100). Anal. Calcd for C15H21IOS:
C, 47.88; H, 5.63. Found: C, 48.04; H, 5.54.
(R)-2-Methyl-5-(tetrahydro-2H-pyran-2-yloxy)-1-pente-
nyl p-tolyl sulfoxide (36). Using the procedure for 31, the
ketone 34 (352 mg, 1.89 mmol) was converted into 36 (1:1
E/Z mixture, 550 mg, 90%). A colorless oil: IR (KBr) cm21
:
2941, 2868, 1597, 1493, 1440, 1379, 1352, 1120, 1080,
1
1036. H NMR d: 1.50±1.65 (6H, m, THP), 1.67±1.80
(2H, m, 4-H), 1.89 (3/2H, s, 2-CH3), 2.17 (3/2H, s,
2-CH3), 2.21±2.27 (1H, m, 3-H), 2.40 (3H, s, Ar-CH3),
2.53±2.70 (1H, m, 3-H), 3.29±3.38 (1H, m, 5-H), 3.43±
3.55 (1H, m, THP), 3.67±3.72 (1H, m, 5-H), 3.72±3.90
(1H, m, THP), 4.44±4.62 (1H, m, O±CH±O), 6.03±6.05
(1H, m, 1-H), 7.30 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, m,
Ar-H). 13C NMR d: 18.6 (1/4C), 18.7 (1/4C), 19.6 (1/4C),
19.7 (1/4C), 21.3, 23.1 (1/4C), 23.2 (1/4C), 25.4, 27.1
(1/2C), 27.2 (1/2C), 28.2 (1/2C), 28.4 (1/2C), 30.5 (1/4C),
30.6 (1/4C), 30.7 (1/2C), 35.8 (1/2C), 62.3 (1/4C), 62.4
(1/2C), 62.5 (1/4C), 66.4 (1/2C), 66.5 (1/4C), 66.7 (1/4C),
98.9 (1/2C), 99.0 (1/2C), 124.0, 124.1, 129.9 (2C), 132.1
(1/4C), 132.2 (1/4C), 132.8 (1/4C), 133.0 (1/4C), 140.7
(1/2C), 140.8 (1/2C), 141.9 (1/2C), 141.9 (1/2C), 151.5
(1/4C), 151.6 (1/4C), 151.9 (1/2C). MS (FAB) m/z: 323
(MH1). HRMS (FAB) Calcd C18H27O3S (MH1):
323.1681. Found: 323.1681.
(Z)-(R)-8-Iodo-1-octenyl p-tolyl sulfoxide [(Z)-32]. Using
the procedure for (E)-10, the tosylate (Z)-31 (1.20 g,
2.86 mmol) was converted into (Z)-32 (842 mg, 78%). A
pale yellow oil: [a]2D8ˆ2183.1 (c 0.31, acetone). IR (KBr)
cm21: 2927, 1618, 1493, 1084, 1039. 1H NMR d: 1.38±1.57
(6H, m, 4-, 5-, and 6-H), 1.84 (2H, quint, Jˆ7.3 Hz, 7-H),
2.41 (3H, s, Ar-CH3), 2.48±2.55 (1H, m, 3-H), 2.61±2.69
(1H, m, 3-H), 3.20 (2H, t, Jˆ7.3 Hz, 8-H), 6.14±6.19 (1H,
m, 2-H), 6.21±6.23 (1H, d, Jˆ9.8 Hz, 1-H), 7.32 (2H, d,
Jˆ8.5 Hz, Ar-H), 7.50 (2H, d, Jˆ8.5 Hz, Ar-H). 13C NMR
d: 7.0, 21.4, 28.1, 28.9, 29.2, 30.2, 33.3, 124.0 (2C), 129.9
(2C), 137.1, 141.0, 141.2, 141.4. MS (EI) m/z (rel. int. %):
376 (M1, 23.7), 328 (100). Anal. Calcd for C15H21IOS: C,
47.88; H, 5.63. Found: C, 47.66; H, 5.57.
(E)-5-[(R)-(p-Tolylsul®nyl)]-4-phenyl-4-pentenyl p-toluene-
sulfonate [(E)-37]. p-TsOH´H2O (375 mg, 1.97 mmol) was
added to a solution of (E)-35 (379 mg, 0.99 mmol) in MeOH
(10 ml) with stirring at rt. The stirring was continued at rt for
1 h. The reaction was quenched with saturated NaHCO3
aqueous solution and the whole was extracted with
(E)-(R)- and (Z)-(R)-2-Phenyl-5-(tetrahydro-2H-pyran-
2-yloxy)-1-pentenyl p-tolyl sulfoxide [(E)- and (Z)-35].
Using the procedure for 31, the ketone 33 (500 mg,
2.02 mmol) was converted into (E)-35 (234 mg, 30%) and
(Z)-35 (496 mg, 64%). (E)-35 (a colorless oil):

N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
7939
AcOEt. The extract was washed with water and brine prior
to drying and solvent evaporation. The residue was chroma-
tographed on silica gel with hexane±AcOEt (1:5) to give the
alcohol (239 mg, 81%) as a colorless oil. [a]2D6ˆ239.0 (c
0.75, CHCl3). IR (KBr) cm21: 3396, 2951, 1597, 1493,
3-H), 2.41 (3H, s, Ar-CH3), 2.45 (3H, s, Ar-CH3), 2.55±2.71
(1H, m, 3-H), 4.00 (1H, t, Jˆ6.1 Hz, 1-H), 4.11 (1H, t,
Jˆ6.1 Hz, 1-H), 5.97 (1/2H, d, Jˆ1.2 Hz, 5-H), 6.05 (1/
2H, d, Jˆ1.2 Hz, 5-H), 7.31 (2H, d, Jˆ7.9 Hz, Ar-H),
7.33 (1H, d, Jˆ7.9 Hz, Ar-H), 7.35 (1H, d, Jˆ7.9 Hz,
Ar-H), 7.45 (1H, d, Jˆ7.9 Hz, Ar-H), 7.46 (1H, d,
Jˆ8.5 Hz, Ar-H), 7.75 (1H, d, Jˆ7.9 Hz, Ar-H), 7.81 (1H,
d, Jˆ8.5 Hz, Ar-H). 13C NMR d: 18.7 (1/2C), 21.3, 21.6,
23.1 (1/2C), 26.4 (1/2C), 27.6 (1/2C), 29.8 (1/2C), 34.8
(1/2C), 69.2 (1/2C), 69.5 (1/2C), 124.0, 124.1, 127.7,
127.8, 129.9, 129.9, 129.9 (2C), 132.5 (1/2C), 132.9,
133.3 (1/2C), 141.0, 141.1 (1/2C), 141.2 (1/2C), 144.9
(1/2C), 144.9 (1/2C), 150.1 (1/2C), 150.5 (1/2C). MS
(FAB) m/z: 411 (MH1). HRMS (FAB) Calcd C20H25O4S2
(MH1): 393.1194. Found: 393.1207.
1
1038, 1011. H NMR d: 1.60±1.68 (1H, m, 2-H), 1.77±
1.86 (1H, m, 2-H), 2.41 (3H, s, Ar-CH3), 2.75 (1H, t,
Jˆ6.1 Hz, OH), 3.04 (1H, quint, Jˆ6.7 Hz, 3-H), 3.44
(1H, quint, Jˆ6.7 Hz, 3-H), 3.61±3.67 (2H, m, 1-H), 6.50
(1H, s, 5-H), 7.33 (2H, d, Jˆ7.9 Hz, Ar-H), 7.35±7.36 (3H,
m, Ar-H), 7.39±7.41 (2H, m, Ar-H), 7.57 (2H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR d: 21.3, 27.4, 30.9, 60.4, 124.2 (2C), 126.6
(2C), 128.7 (2C), 129.3, 130.0 (2C), 133.8, 138.2, 140.7,
141.3, 153.9. MS (FAB) m/z: 301 (MH1). HRMS (FAB)
Calcd C18H21O2S (MH1): 301.1262. Found: 301.1263.
Using the procedure for (E)-7, the alcohol (82 mg,
0.27 mmol) was converted into (E)-37 (111 mg, 90%). A
colorless oil: [a]2D7ˆ231.0 (c 1.09, CHCl3). IR (KBr)
(E)-(R)-5-Iodo-2-phenyl-1-pentenyl p-tolyl sulfoxide
[(E)-39]. Using the procedure for (E)-10, the tosylate (E)-
37 (50 mg, 0.11 mmol) was converted into (E)-39 (45 mg,
quant). A yellow oil: [a]2D7ˆ265.8 (c 0.89, CHCl3). IR
1
cm21: 1597, 1360, 1176, 1039. H NMR d: 1.71±1.87
(2H, m, 2-H), 2.38 (3H, s, Ar-CH3), 2.41 (3H, s, Ar-CH3),
3.06 (2H, t, Jˆ7.3 Hz, 3-H), 4.05 (2H, t, Jˆ6.1 Hz, 1-H),
6.39 (1H, s, 5-H), 7.27±7.32 (9H, m, Ar-H), 7.51 (2H, d,
Jˆ8.5 Hz, Ar-H), 7.76 (2H, d, Jˆ8.5 Hz, Ar-H). 13C NMR
d: 21.3, 21.6, 27.6, 28.2, 69.4, 124.2 (2C), 126.6 (2C), 127.8
(2C), 128.8 (2C), 129.4, 129.8 (2C), 130.1 (2C), 132.9,
134.8, 137.9, 141.3 (2C), 144.8, 150.9. MS (EI) m/z (rel.
int. %): 454 (M1, 1.8), 91 (100). HRMS (EI) Calcd
C25H26O4S2: 454.1272. Found: 454.1263.
1
(KBr): 2954, 1597, 1211, 1082, 1039. H NMR d: 1.87±
2.06 (2H, m, 4-H), 2.38 (3H, s, Ar-CH3), 3.09±3.20 (4H, m,
3-H and 5-H), 6.44 (1H, s, 1-H), 7.30±7.36 (7H, m, Ar-H),
7.55 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 5.4, 21.5, 32.4
(2C), 124.2 (2C), 126.6 (2C), 128.7 (2C), 129.4, 130.0 (2C),
134.8, 138.0, 141.2, 141.3, 150.8. MS (EI) m/z (rel. int. %):
410 (M1, 9.4), 362 (100). HRMS (EI) Calcd C18H19IOS:
410.0202. Found: 410.0186.
(Z)-5-[(R)-(p-Tolylsul®nyl)]-4-phenyl-4-pentenyl p-toluene-
sulfonate [(Z)-37]. Using the procedure for (E)-37, (Z)-35
(179 mg, 0.47 mmol) was converted into the alcohol
(132 mg, 94%). A colorless oil: [a]2D6ˆ2298.4 (c 0.71,
CHCl3). IR (KBr) cm21: 3386, 2947, 1595, 1493, 1442,
(Z)-(R)-5-Iodo-2-phenyl-1-pentenyl p-tolyl sulfoxide
[(Z)-39]. Using the procedure for (E)-10, the tosylate (Z)-
37 (73 mg, 0.16 mmol) was converted into (Z)-39 (60 mg,
92%). A colorless oil: [a]2D6ˆ2210.9 (c 1.11, CHCl3). IR
(KBr) cm21: 2951, 1595, 1217, 1036. 1H NMR d: 1.87 (2H,
quint, Jˆ7.3 Hz, 4-H), 2.41 (3H, s, Ar-CH3), 2.60 (1H, dd,
Jˆ14.6, 7.5 Hz, 3-H), 2.66 (1H, dd, Jˆ14.6, 7.0 Hz, 3-H),
3.10 (1H, dt, Jˆ11.6, 6.7 Hz, 5-H), 3.12 (1H, dt, Jˆ11.6,
6.7 Hz, 5-H), 6.37 (1H, s, 1-H), 7.31 (2H, d, Jˆ7.9 Hz, Ar-
H), 7.34±7.45 (5H, m, Ar-H), 7.47 (2H, d, Jˆ7.9 Hz, Ar-H).
13C NMR d: 5.3, 21.5, 30.7, 39.6, 124.3 (2C), 128.1 (2C),
128.5 (2C), 128.9, 129.9 (2C), 134.7, 137.0, 141.1, 141.7,
152.4. MS (FAB) m/z: 411 (MH1). HRMS (FAB) Calcd
C18H19IOS (MH1): 411.0284. Found: 411.0277.
1
1082, 1024. H NMR d: 1.63±1.67 (2H, m, 2-H), 2.41
(3H, s, Ar-CH3), 2.56±2.66 (2H, m, 3-H), 3.61 (2H, br s,
5-H), 6.34 (2H, t, Jˆ1.2 Hz, 1-H), 7.30 (2H, d, Jˆ8.5 Hz,
Ar-H), 7.35±7.37 (2H, m, Ar-H), 7.40±7.44 (3H, m, Ar-H),
7.46 (2H, d, Jˆ8.5 Hz, Ar-H). 13C NMR d: 21.3, 29.9, 35.4,
61.2, 124.3 (2C), 128.1 (2C), 128.4 (2C), 128.7, 129.9 (2C),
133.6, 137.5, 141.1, 141.4, 154.7. MS (FAB) m/z: 301
(MH1). HRMS (FAB) Calcd C18H21O2S (MH1):
301.1262. Found: 301.1263. Using the procedure for (E)-
37, the alcohol (179 mg, 0.60 mmol) was converted into (Z)-
37 (238 mg, 88%). A colorless oil: [a]2D7ˆ2174.2 (c 0.35,
CHCl3). IR (KBr) cm21: 1358, 1597, 1176, 1036. 1H NMR
d: 1.69±1.74 (2H, m, 2-H), 2.41 (3H, s, Ar-CH3), 2.44 (3H,
s, Ar-CH3), 2.52 (2H, t, Jˆ6.7 Hz, 3-H), 3.97 (2H, t,
Jˆ6.1 Hz, 1-H), 6.26 (1H, s, 5-H), 7.28±7.32 (6H, m, Ar-
H), 7.41±7.45 (5H, m, Ar-H), 7.72 (2H, d, Jˆ8.5 Hz, Ar-H).
13C NMR d: 21.3, 21.6, 26.5, 34.8, 69.2, 124.2 (2C), 127.7
(2C), 128.1 (2C), 128.5, 128.9 (2C), 129.8 (2C), 129.9 (2C),
132.6, 134.4, 136.9, 141.1, 141.5, 144.8, 152.6. MS (FAB)
m/z: 455 (MH1). HRMS (FAB) Calcd C25H27O4S2 (MH1):
455.1351. Found: 455.1348.
(R)-5-Iodo-2-methyl-1-pentenyl p-tolyl sulfoxide (40).
Using the procedure for (E)-10, the tosylate 38 (483 mg,
1.23 mmol) was converted into 40 (1:1 E/Z mixture,
370 mg, 86%). A colorless oil: IR (CHCl3): 2918, 1597,
1
1302, 1082, 1038. H NMR d: 1.87 (3/2H, d, Jˆ1.2 Hz,
2-CH3), 1.91±1.96 (1H, m, 4-H), 1.99±2.05 (1/2H, m,
4-H), 2.07±2.12 (1/2H, m, 4-H), 2.14 (3/2H, d, Jˆ1.2 Hz,
2-CH3), 2.22±2.25 (1H, t, Jˆ7.3 Hz, 3-H), 2.39 (3H, s, Ar-
CH3), 2.64±2.73 (1H, m, 3-H), 3.06±3.14 (1H, m, 5-H),
3.18±3.26 (1H, m, 5-H), 6.04±6.05 (1/2H, br s, 1-H), 6.06
(1/2H, br s, 1-H), 7.29 (1H, d, Jˆ7.9 Hz, Ar-H), 7.30 (1H, d,
Jˆ7.9 Hz, Ar-H), 7.46 (1H, d, Jˆ7.9 Hz, Ar-H), 7.49 (1H,
d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 5.0 (1/2C), 5.1 (1/2C),
18.8 (1/2C), 21.5, 23.4 (1/2C), 30.2 (1/2C), 31.6 (1/2C),
34.3 (1/2C), 39.2 (1/2C), 123.7, 123.9, 129.7 (2C), 132.7
(1/2C), 133.4 (1/2C), 140.7 (1/2C), 140.8 (1/2C), 141.2,
149.4 (1/2C), 149.9 (1/2C). MS (EI) m/z (rel. int. %): 348
(M1, 46.5), 300 (100). HRMS (EI) Calcd C13H17IOS:
348.0045. Found: 348.0064.
4-Methyl-5-[(R)-(p-tolylsul®nyl)]-4-pentenyl p-toluene-
sulfonate (38). Using the procedure for 37, 36 (630 mg,
1.95 mmol) was converted into 38 (1:1 E/Z mixture,
559 mg, 73%). A colorless oil: IR (KBr) cm21: 2924,
1
1597, 1358, 1176, 1038. H NMR d: 1.78±1.83 (1H, m,
2-H), 1.85 (3/2H, d, Jˆ1.2 Hz, 4-CH3), 1.86±1.97 (1H, m,
2-H), 2.12 (3/2H, d, Jˆ1.2 Hz, 4-CH3), 2.17±2.20 (1H, m,

7940
N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
Typical procedure for intramolecular alkylation of
iodides
(R)-2-Methyl-1-cyclopentenyl p-tolyl sulfoxide (46).
Colorless powder: mp 104.0±104.68C (ether). [a]2D4ˆ
2155.0 (c 0.21, CHCl3). IR (KBr) cm21: 2858, 1597,
1
1083, 1043, 1026, 1014. H NMR d: 1.69±1.84 (1H, m,
(R)-1-Cyclohexenyl p-tolyl sulfoxide (41). A solution of
the iodide (E)-11 (43 mg, 0.12 mmol) in dry THF (2.3 ml)
was added to a solution of LDA (1.5 equiv.) (prepared from
i-Pr2NH (25 ml, 0.18 mmol) and 1.58 M n-BuLi in hexane
(115 ml, 0.18 mmol) in THF (2.3 ml)]. The solution was
stirred at 2788C under N2. After 30 min, the reaction was
quenched with saturated aqueous NH4Cl solution and the
whole was extracted with AcOEt. The extract was washed
with brine prior to drying and solvent evaporation. The
crude product was puri®ed by preparative TLC on silica
gel with hexane±AcOEt (2:1) to give the 1-cycloalkenyl
sulfoxide 41 (22 mg, 82%). Colorless powder: mp 59.8±
60.28C (ether). [a]2D5ˆ18.60 (c 0.48, CHCl3). IR (KBr)
4-H), 1.82±1.91 (1H, m, 4-H), 1.92±1.95 (1H, m, 3-H),
2.10 (3H, s, 2-CH3), 2.37 (3H, s, Ar-CH3), 2.43±2.48 (2H,
m, 5-H), 2.70±2.75 (1H, m, 3-H), 7.26 (2H, d, Jˆ7.9 Hz,
Ar-H), 7.40 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 15.0,
21.3 (2C), 27.5, 39.4, 124.0 (2C), 129.6 (2C), 138.6,
139.7, 140.4, 150.9. MS (EI) m/z (rel. int. %): 220 (M1,
76.6), 124 (100). HRMS (EI) Calcd C13H16OS: 220.0922.
Found: 220.0926.
(Rs)-5-Methyl-1-cyclopentenyl p-tolyl sulfoxide (47). A
1
colorless oil: IR (KBr) cm21: 2956, 1598, 1082, 1014. H
NMR d: 0.89 (3/2H, d, Jˆ6.7 Hz, 5-CH3), 1.04 (3/2H, d,
Jˆ6.7 Hz, 5-CH3), 1.51±1.53 (1H, m, 4-H), 2.04±2.16 (1H,
m, 4-H), 2.29±2.40 (1H, m, 3-H), 2.42±2.60 (3/2H, m, 3-
and 5-H), 2.34 (3H, s, Ar-CH3), 2.72 (1/2H, m, 5-H), 6.33
(1/2H, s, 2-H), 6.44 (1/2H, s, 2-H), 7.22 (1H, d, Jˆ7.9 Hz,
Ar-H), 7.23 (1H, d, Jˆ7.9 Hz, Ar-H), 7.43 (1H, d,
Jˆ7.9 Hz, Ar-H), 7.46 43 (1H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 19.6 (1/2C), 20.2 (1/2C), 21.4 (1/2C), 21.5
(1/2C), 31.1, 33.5 (1/2C), 33.6 (1/2C), 38.8 (1/2C), 39.0
(1/2C), 124.9, 125.5, 129.7, 129.9, 135.0, 139.8, 141.0,
141.8. MS (EI) m/z (rel. int. %): 220 (M1, 100), 172 (89).
HRMS (EI) Calcd C13H16OS: 220.0922. Found: 220.0925.
1
cm21: 2933, 1493, 1084, 1049, 1014. H NMR d: 1.48±
1.56 (1H, m, 4-H), 1.58±1.67 (4H, m, 3-, 4-, and 5-H),
2.13±2.16 (1H, m, 3-H), 2.24±2.25 (2H, m, 6-H), 2.40
(3H, s, Ar-CH3), 6.67±6.68 (1H, m, 2-H), 7.28±7.29 (2H,
d, Jˆ7.9 Hz, Ar-H), 7.28±7.29 (2H, d, Jˆ7.9 Hz, Ar-H).
13C NMR d: 19.5, 21.3, 21.7, 22.0, 25.7, 124.8 (2C),
129.7 (2C), 133.7, 139.5, 140.9, 143.7. MS (EI) m/z (rel.
int. %): 220 (M1, 100). HRMS (EI) Calcd C13H16OS:
220.0922. Found: 220.0941.
(R)-1-Cyclopentenyl p-tolyl sulfoxide (42). Colorless
powder: mp 64.9±65.78C (ether). [a]2D8ˆ156.9 (c 0.65,
1
CHCl3). IR (KBr) cm21: 2926, 1597, 1039. H NMR d:
6-Chloro-1-hexenyl p-tolyl sulfoxide dimer (48). A color-
1
less oil: IR (KBr) cm21: 2937, 2929, 1493, 1084, 1043. H
1.86±1.98 (2H, m, 4-H), 2.07±2.13 (1H, m, 3-H), 2.38
(3H, s, Ar-CH3), 2.40±2.56 (3H, m, 3-H and 5-H), 6.52
(1H, t, Jˆ1.8 Hz, 2-H), 7.28 (2H, d, Jˆ7.9 Hz, Ar-H),
7.47 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.4, 23.0,
28.0, 32.9, 124.6 (2C), 129.8 (2C), 137.9, 139.4, 140.1,
147.8. MS (EI) m/z (rel. int. %): 206 (M1, 72.9), 158
(100), 143 (100). HRMS (EI) Calcd C12H14OS: 206.0765.
Found: 206.0773.
NMR (major) d: 1.04±1.27 (2H, m), 1.38±1.86 (8H, m),
2.29 (2H, td, Jˆ7.9, 7.3 Hz, CH2CHv), 2.41 (3H, s, Ar-
CH3), 2.42 (3H, s, Ar-CH3), 2.29 (1H, dd, Jˆ12.8, 4.3 Hz,
CH2S(O)Tol), 2.72 (1H, dd, Jˆ12.8, 10.4 Hz, CH2S(O)Tol),
2.81±2.92 (1H, m, CHCv), 3.30±3.43 (2H, m, CH2Cl),
3.55 (2H, t, Jˆ6.4 Hz, CH2Cl), 6.47 (1H, t, Jˆ7.6 Hz,
CH2CHv), 7.27 (2H, d, Jˆ8.5 Hz, Ar-H), 7.28 (2H, d,
Jˆ8.5 Hz, Ar-H), 7.36 (2H, d, Jˆ8.5 Hz, Ar-H), 7.48 (2H,
d, Jˆ8.5 Hz, Ar-H). 13C NMR d: 21.4 (2C), 24.6, 26.2, 28.0,
31.5, 32.0, 32.1, 33.1, 44.5, 44.8, 61.8, 124.1 (2C), 125.8
(2C), 129.9 (2C), 130.0 (2C), 135.3, 139.6, 140.6, 141.7,
142.0, 144.9. MS (FAB) m/z: 513 (MH1). HRMS (FAB)
Calcd C26H35Cl2O2S2 (MH1): 513.1456. Found: 513.1449.
(R)-1-Cycloheptenyl p-tolyl sulfoxide (43). Colorless oil:
[a]2D4ˆ110.4 (c 0.52, CHCl3). IR (KBr) cm21: 2922, 1597,
1
1446, 1082, 1047. H NMR d: 1.26±1.38 (2H, m, 5-H),
1.52±1.58 (2H, m, 4-H), 1.63±1.66 (1H, m, 6-H), 1.68±
1.72 (1H, m, 6-H), 2.01 (1H, ddd, Jˆ15.9, 6.7, 2.4 Hz,
3-H), 2.19 (1H, ddd, Jˆ15.9, 6.7, 2.4 Hz, 3-H), 2.30±2.38
(2H, m, 7-H), 2.40 (3H, s, Ar-CH3), 6.80 (1H, t, Jˆ6.7 Hz,
2-H), 7.28 (2H, d, Jˆ7.9 Hz, Ar-H), 7.47 (2H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR d: 21.3, 24.9, 26.2, 26.6, 29.0, 31.3, 125.1
(2C), 130.0 (2C), 137.2, 139.7, 140.9, 148.0. MS (EI) m/z
(rel. int. %): 234 (M1, 70.1), 124 (100). HRMS (EI) Calcd
C14H18OS: 234.1078. Found: 234.1075.
8-Iodo-1-octenyl p-tolyl sulfoxide dimer (49). A colorless
oil: IR (KBr) cm21: 2927, 1597, 1493, 1460, 1081, 1047. 1H
NMR d: 0.95±1.44 (14H, m), 1.62±1.77 (4H, m), 2.15±
2.19 (2H, m, CH2CHv), 2.30±2.45 (1H, m, CHCv), 2.35
(6H, s, Ar-CH3), 2.59±2.75 (2H, m, CH2S(O)Tol), 3.07±
3.11 (4H, m, CH2I), 6.39 (1H, t, Jˆ7.3 Hz, CH2CHv),
7.20±7.22 (4H, m, Ar-H), 7.29 (2H, d, Jˆ7.9 Hz, Ar-H),
7.42 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 7.1, 7.0, 21.5
(2C), 27.1, 28.3 (2C), 28.8 (2C), 30.3 (2C), 32.3, 33.2, 33.3
(2C), 62.0, 124.0 (2C), 125.8 (2C), 129.8 (4C), 135.4, 139.7,
140.7, 141.5, 141.6, 144.4. MS (EI) m/z (rel. int. %): 234
(M1, 70.1), 124 (100). MS (FAB) m/z: 753 (MH1). HRMS
(FAB) Calcd C30H43I2O2S2 (MH1): 753.0776. Found:
753.0793.
(R)-2-Phenyl-1-cyclopentenyl p-tolyl sulfoxide (45).
Colorless powder: mp 96.3±97.18C (ether). [a]2D6ˆ2420.6
(c 0.53, CHCl3). IR (KBr) cm21: 1597, 1491, 1080, 1041,
1014. 1H NMR d: 1.79±1.88 (1H, m, 4-H), 1.92±2.00 (1H,
m, 4-H), 2.06±2.11 (1H, m, 3-H), 2.33 (3H, s, Ar-CH3),
2.85±2.93 (3H, m, 3-H and 5-H), 7.22 (2H, d, Jˆ7.9 Hz,
Ar-H), 7.29±7.38 (5H, m, Ar-H), 7.43 (2H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR d: 21.3, 21.6, 28.8, 38.8, 124.4 (2C),
127.6, 128.0, 128.3 (2C), 128.5 (2C), 128.9, 129.6, 129.8
(2C), 131.7, 140.7. MS (EI) m/z (rel. int. %): 282 (M1, 4.3),
234 (100). HRMS (FAB) Calcd C18H19OS (MH1):
283.1157. Found: 283.1169.
(E)-(R)- and (Z)-(R)-1-Hexenyl p-tolyl sulfoxide [(E)- and
(Z)-50]. Using the procedure for 31, n-pentanal (1.99 g,
23.1 mmol) was converted into (E)-50 (1.85 g, 36%) and
(Z)-50 (2.48 g, 48%). (E)-50 (a colorless oil):

N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
7941
[a]2D7ˆ1109.3 (c 1.19, CHCl3). IR (KBr) cm21: 2926, 1084,
1047. 1H NMR d: 0.84 (3H, t, Jˆ7.3 Hz, 6-H), 1.28 (2H, dt,
Jˆ14.6, 7.3 Hz, 5-H), 1.38 (2H, quint, Jˆ7.3 Hz, 4-H), 2.16
(2H, dd, Jˆ14.6, 6.7 Hz, 3-H), 2.41 (3H, s, Ar-CH3), 6.15
(1H, dd, Jˆ15.3, 1.2 Hz, 1-H), 6.54 (1H, dt, Jˆ15.3, 7.9 Hz,
2-H), 7.25 (2H, d, Jˆ7.9 Hz, Ar-H), 7.44 (2H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR d: 13.7, 21.3, 21.4, 22.1, 30.1, 31.6, 124.5,
129.9 (2C), 135.0 (2C), 141.0, 141.2. MS (FAB) m/z: 223
(MH1). HRMS (FAB) Calcd C13H19OS (MH1): 223.1157.
Found: 223.1149. (Z)-50 (a colorless oil): [a]2D5ˆ2307.2 (c
Jˆ7.3, 1.2 Hz, Ar-H), 7.64 (1H, t, Jˆ7.9 Hz, Ar-H), 7.86
(1H, dd, Jˆ7.3, 1.2 Hz, Ar-H), 10.26 (1H, s, CHO). 13C
NMR d: 19.3, 25.3, 30.5, 62.3, 66.3, 98.3, 127.5, 128.3,
131.9, 133.4, 133.7, 140.8, 192.6. MS (EI) m/z(%): 220
(M1, 2.5), 213 (100). HRMS (EI) Calcd C13H16O3:
220.1099. Found: 220.1090.
(E)-(R)- and (Z)-(R)-2-[2-[(Tetrahydro-2H-pyran-2-yloxy)-
methyl]phenyl]ethenyl p-tolyl sulfoxide [(E)-53 and (Z)-
53]. Using the procedure for 31, the aldehyde 52 (5.77 g,
26.1 mmol) was converted into (E)-53 (5.15 g, 55%) and
(Z)-53 (3.41 g, 37%). (E)-53 (a colorless oil):
[a]D26ˆ198.4 (c 0.43, CHCl3). IR (KBr) cm21: 3022,
1
0.45, CHCl3). IR (KBr) cm21: 2954, 1082, 1041. H NMR
d: 0.88 (3H, t, Jˆ6.7 Hz, 6-H), 1.33 (2H, dt, Jˆ6.7,
15.3 Hz, 5-H), 1.41 (2H, quint, Jˆ6.7 Hz, 4-H), 2.33 (3H,
s, Ar-CH3), 2.45 (1H, dt, Jˆ14.0, 6.7 Hz, 3-H), 2.56 (1H, dt,
Jˆ14.0, 6.7 Hz, 3-H), 6.08±6.14 (2H, m, 1-H, 2-H), 7.24
(2H, d, Jˆ7.9 Hz, Ar-H), 7.42 (2H, d, Jˆ7.3 Hz, Ar-H). 13C
NMR d: 13.7, 21.3, 22.1, 29.0, 31.1, 124.0 (2C), 129.9 (2C),
136.8, 141.0, 141.2, 141.9. MS (FAB) m/z: 223 (MH1).
HRMS (FAB) Calcd C13H19OS (MH1): 223.1157. Found:
223.1146.
1
3959, 1120, 1038. H NMR d: 1.54±1.87 (6H, m, THP),
2.41 (3H, s, Ar-CH3), 3.56±3.59 (1H, m, THP), 3.90±3.95
(1H, m, THP), 4.59 (2/3H, d, Jˆ12.2 Hz, THPOCH2),
4.61 (1/3H, d, Jˆ12.2 Hz, THPOCH2), 4.62±4.74 (1H, m,
O±CH±O), 4.90 (2/3H, d, Jˆ12.2 Hz, THPOCH2), 4.92
(1/H, d, Jˆ12.2 Hz, THPOCH2), 6.80 (1H, d, Jˆ15.9 Hz,
1-H), 7.28±7.34 (4H, m, Ar-H), 7.42 (1H, d, Jˆ7.3 Hz, Ar-
H), 7.46 (1H, d, Jˆ7.3 Hz, Ar-H), 7.57 (2H, d, Jˆ8.5 Hz,
Ar-H), 7.72 (1H, dd, Jˆ15.9, 2.4 Hz, 2-H). 13C NMR d:
19.3 (1/3C), 19.4 (2/3C), 21.4, 25.4, 30.5, 62.2 (1/3C),
62.3 (2/3C), 66.9 (1/3C), 67.0 (2/3C), 98.0 (1/3C), 98.1
(2/3C), 124.8 (2C), 126.9, 128.2, 129.5, 129.7, 130.1 (2C),
133.2, 133.6, 135.1, 136.5, 140.7, 141.6. MS (FAB) m/z:
379 (MNa1). HRMS (FAB) Calcd C21H24NaO3S (MNa1):
379.1344. Found: 379.1329. (Z)-53 (a colorless oil):
[a]D26ˆ2313.7 (c 0.37, CHCl3). IR (KBr) cm21: 2943,
Deprotonation and reprotonation of (E)- and (Z)-50
A solution of the vinylic sulfoxide (Z)-50 (114 mg,
0.51 mmol) in THF (2 ml) was added to a stirred LDA solu-
tion [prepared from n-BuLi (1.50 M in hexane, 0.51 ml,
0.77 mmol) and i-Pr2NH (0.12 ml, 0.82 mmol) in THF
(5 ml)] at 2788C under N2 and the mixture was stirred at
2788C. The reaction was quenched with water, and the
whole was extracted with AcOEt. The extract was washed
with water and brine prior to drying and solvent evapora-
tion. The residue was chromatographed on silica gel with
hexane±acetone (5:2) to give (E)-50 (94 mg, 83%).
1
2870, 1080, 1036. H NMR d: 1.52±1.84 (6H, m, THP),
2.41 (3H, s, Ar-CH3), 3.51±3.56 (1H, m, THP), 3.84±3.88
(1H, m, THP), 4.47 (2/3H, d, Jˆ12.2 Hz, THPOCH2),
4.49 (1/3H, d, Jˆ12.2 Hz, THPOCH2), 4.66±4.67 (1H, m,
O±CH±O), 4.76 (1/3H, dd, Jˆ12.2 Hz, THPOCH2), 4.79
(2/3H, dd, Jˆ12.2 Hz, THPOCH2), 6.53 (1H, dd, Jˆ10.1,
6.7 Hz, 2-H), 7.35 (2H, d, Jˆ7.9 Hz, Ar-H), 7.37±7.42 (3H,
m, Ar-H), 7.46±7.52 (3H, m, Ar-H), 7.56 (1H, dd,
Jˆ6.7 Hz, 2-H). 13C NMR d: 19.3, 21.4, 25.4, 30.5, 62.3,
66.9, 97.9 (1/3C), 98.0 (2/3C), 124.4 (2C), 127.8 (1/3C),
127.8 (2/3C), 129.0, 129.4, 130.0 (2C), 130.2, 133.1,
136.5, 137.2, 138.4, 141.4, 141.5. MS (FAB) m/z: 357
(MH1). HRMS (FAB) Calcd C21H25O3S (MH1):
357.1525. Found: 357.1549.
2-[(Tetrahydro-2H-pyran-2-yloxy)methyl]phenylmetha-
nol (51). A mixture of o-xyleneglycol (5.00 g, 36.2 mmol)
and dihydropyran (3.27 ml, 36.2 mmol) in the presence of
PPTS (909 mg, 3.62 mmol) in CH2Cl2 (200 ml) was stirred
at rt for 1 h. The reaction was quenched with saturated
NaHCO3 aqueous solution and the whole was extracted
with AcOEt. The extract was washed with water and brine
prior to drying and solvent evaporation. The residue was
chromatographed on silica gel with hexane±AcOEt (1:2)
to give 51 (5.39 g, 67%) as a colorless oil. IR (KBr)
1
cm21: 3415, 2947, 1454, 1122, 1024. H NMR d: 1.50±
[2-[(E)-2-[(R)-(p-Tolylsul®nyl)]ethenyl]phenyl]methanol
[(E)-54]. Using the procedure for (E)-37, the THP ether (E)-
53 (1.92 g, 5.38 mmol) was converted into (E)-54 (1.11 g,
76%). Colorless prisms: mp 233.0±133.08C (CHCl3).
[a]D26ˆ1189.7 (c 0.47, CHCl3). IR (KBr) cm21: 3354,
1.60 (4H, m, THP), 1.68±1.81 (2H, m, THP), 3.53±3.57
(1H, m, THP), 3.85±3.90 (1H, m, THP), 4.56 (1H, d,
Jˆ11.6 Hz, THPOCH2), 4.66 (1H, dd, Jˆ11.6, 6.1 Hz,
CH2OH), 4.68 (1H, dd, Jˆ11.6, 6.1 Hz, CH2OH), 4.71
(1H, t, Jˆ3.7 Hz, O±CH±O), 4.88 (1H, d, Jˆ11.6 Hz,
THPOCH2), 7.26±7.39 (4H, m, Ar-H). 13C NMR d: 19.0,
25.1, 30.3, 62.1, 63.2, 67.6, 97.7, 127.7, 128.4, 129.1, 129.7,
135.6, 140.1. MS (FAB) m/z: 223 (MH1). HRMS (FAB)
Calcd C13H19O3 (MH1): 223.1334. Found: 223.1318.
1
3030, 1084, 1039. H NMR d: 2.40 (3H, s, Ar-CH3), 4.81
(2H, d, Jˆ5.5 Hz, CH2OH), 6.77 (1H, d, Jˆ15.3 Hz, 1-H),
7.25±7.28 (1H, m, Ar-H), 7.30 (2H, d, Jˆ7.9 Hz, Ar-H),
7.33 (1H, dd, Jˆ7.3, 1.2 Hz, Ar-H), 7.43 (2H, d, Jˆ7.3 Hz,
Ar-H), 7.56 (2H, d, Jˆ7.9 Hz, Ar-H), 7.70 (1H, d,
Jˆ15.3 Hz, 2-H). 13C NMR d: 21.4, 62.7, 125.0 (2C),
126.9 (2C), 128.0, 128.8, 129.6, 130.1, 132.5, 133.4,
135.0, 139.3, 149.2, 141.8. MS (FAB) m/z: 273 (MH1).
HRMS (FAB) Calcd C16H17O2S (MH1): 273.0949. Found:
273.0940.
2-[(Tetrahydro-2H-pyran-2-yloxy)methyl]benzaldehyde
(52). Using the procedure for 14, the alcohol 51 (3.00 g,
13.5 mmol) was converted into 52 (2.15 g, 72%). A color-
less oil: IR (KBr) cm21: 2941, 1697, 1201, 1034. 1H NMR
d: 1.54±1.89 (6H, m, THP), 3.53±3.57 (1H, m, THP), 3.87±
3.91 (1H, m, THP), 4.77 (1H, t, Jˆ3.7 Hz, O±CH±O), 4.94
(1H, d, Jˆ14.0 Hz, THPOCH2), 5.18 (1H, d, Jˆ14.0 Hz,
THPOCH2), 7.46 (1H, t, Jˆ7.3 Hz, Ar-H), 7.59 (1H, dt,
[2-[(Z)-2-[(R)-(p-Tolylsul®nyl)]ethenyl]phenyl]methanol
[(Z)-54]. Using the procedure for (E)-37, the THP ether (Z)-
53 (1.24 g, 3.47 mmol) was converted into (Z)-54 (663 mg,

7942
N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
70%). A colorless oil: [a]2D8ˆ2384.1 (c 0.77, CHCl3). IR
(KBr) cm21: 3332, 2922, 1082, 1022. 1H NMR d: 2.39 (3H,
s, Ar-CH3), 4.62 (2H, d, Jˆ5.5 Hz, CH2OH), 6.49 (1H, d,
Jˆ10.4 Hz, 1-H), 7.28 (2H, d, Jˆ8.5 Hz, Ar-H), 7.35 (1H,
dd, Jˆ7.3, 1.2 Hz, Ar-H), 7.37 (1H, dd, Jˆ7.3, 1.2 Hz, Ar-H),
7.39 (1H, d, Jˆ10.4 Hz, 2-H), 7.39±7.44 (2H, m, Ar-H), 7.47
(2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.4, 62.8, 124.4 (2C),
127.5 (2C), 128.3, 129.4, 129.9, 130.0, 132.5, 137.8, 138.1,
139.3, 140.8, 141.5. MS (FAB) m/z: 273 (MH1). HRMS
(FAB) Calcd C16H17O2S (MH1): 273.0949. Found: 273.0947.
NaHCO3 (424 mg, 5.04 mmol), and NaI (941 mg,
6.28 mmol) in acetone (12 ml) was stirred at rt for 4 h.
The reaction was quenched with water and the whole was
extracted with AcOEt. The extract was washed with satu-
rated Na2S2O3 aqueous solution, saturated NaHCO3 aqueous
solution, and brine prior to drying and solvent evaporation.
The residue was chromatographed on silica gel with
hexane±AcOEt (2:1) to give (E)-57 (374 mg, 84%) as color-
less needles. Mp 216.5±219.08C (CHCl3). [a]3D0ˆ1160.8 (c
1
0.32, CHCl3). IR (KBr) cm21: 3024, 2974, 115, 1045. H
NMR d: 2.41 (3H, s, Ar-CH3), 4.55 (2H, s, CH2I), 6.85 (1H,
d, Jˆ15.3 Hz, 1-H), 7.24±7.28 (2H, m, Ar-H), 7.34 (2H, d,
Jˆ7.9 Hz, Ar-H), 7.36±7.40 (2H, m, Ar-H), 7.63 (2H, d,
Jˆ7.9 Hz, Ar-H), 7.69 (2H, d, Jˆ15.3 Hz, 2-H). 13C NMR
d: 2.8, 21.4, 124.9, 125.0, 127.5 (2C), 128.6, 129.8, 129.9,
130.1, 132.1, 132.6, 135.7, 137.7, 140.2, 141.8. MS (FAB)
m/z: 383 (MH1). HRMS (FAB) Calcd C16H16IOS (MH1):
382.9966. Found: 382.9983.
(E)-(R)-2-[2-(Chloromethyl)phenyl]ethenyl p-tolyl sulf-
oxide [(E)-55]. Using the procedure for (E)-7, the alcohol
(E)-54 (1.05 g, 3.86 mmol) was converted into (E)-55
(711 mg, 64%). Colorless needles: mp 205.0±106.08C
(CHCl3). [a]2D7ˆ1167.1 (c 0.47, CHCl3). IR (KBr) cm21
:
3022, 2922, 1263, 1084. 1H NMR d: 2.40 (3H, s, Ar-CH3),
4.68 (1H, d, Jˆ11.6 Hz, CH2Cl), 4.71 (1H, d, Jˆ11.6 Hz,
CH2Cl), 6.83 (1H, d, Jˆ15.3 Hz, 1-H), 7.28±7.38 (5H, m,
Ar-H), 7.43±7.46 (1H, m, Ar-H), 7.59 (2H, d, Jˆ7.9 Hz,
Ar-H), 7.73 (1H, d, Jˆ15.3 Hz, 2-H). 13C NMR d: 21.1,
43.7, 124.6 (2C), 127.1, 128.9, 129.4, 129.9 (2C), 130.2,
131.4, 133.0, 135.3, 136.0, 140.1, 141.5. MS (FAB) m/z:
291 (MH1). HRMS (FAB) Calcd C16H16ClOS (MH1):
291.0611. Found: 291.0605.
(R)-2-Indenyl p-tolyl sulfoxide (58). Using the procedure
for (E)-41, the chloride (E)-55 (50 mg, 0.17 mmol) was
converted into 58 (28 mg, 64%). Colorless needles: mp
148.5±149.58C (hexane±AcOEt). [a]2D6ˆ166.8 (c 0.61,
1
CHCl3). IR (KBr) cm21: 2923, 1080, 1045. H NMR d:
2.40 (3H, s, Ar-CH3), 3.26 (1H, d, Jˆ22.9 Hz, 1-H), 3.56
(1H, d, Jˆ22.9 Hz, 1-H), 7.25±7.27 (1H, m, 5-H, Ar-H),
7.29±7.32 (3H, m, 6-H, Ar-H), 7.38 (1H, d, Jˆ7.3 Hz, 7-H),
7.47 (1H, d, Jˆ7.3 Hz, 4-H), 7.48 (1H, s, 3-H), 7.56 (2H, d,
Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.4, 35.2, 122.8, 124.2,
124.5 (2C), 127.0 (2C), 130.0 (2C), 136.5, 140.6, 141.5,
141.9, 143.9, 150.4. MS (FAB) m/z: 225 (MH1). HRMS
(FAB) Calcd C16H15OS (MH1): 255.0844. Found:
255.0840.
(Z)-(R)-2-[2-(Chloromethyl)phenyl]ethenyl p-tolyl sulf-
oxide [(Z)-55]. Using the procedure for (E)-7, the alcohol
(Z)-54 (600 mg, 2.20 mmol) was converted into (Z)-55
(532 mg, 83%). A colorless oil: [a]2D6ˆ2352.8 (c 0.90,
1
CHCl3). IR (KBr) cm21: 3022, 1493, 1082, 1038. H NMR
d: 2.41 (3H, s, Ar-CH3), 4.51 (1H, d, Jˆ11.6 Hz, CH2Cl),
4.62 (1H, d, Jˆ11.6 Hz, CH2Cl), 6.62 (1H, d, Jˆ10.4 Hz,
1-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.41±7.44 (4H, m, Ar-
H), 7.50 (2H, d, Jˆ7.9 Hz, Ar-H), 7.56±7.57 (1H, m, 2-H).
13C NMR d: 21.3, 44.0, 124.3 (2C), 128.8, 129.6, 130.0
(2C), 130.0, 130.5, 133.5, 135.4, 136.0, 139.6, 140.9,
141.5. MS (FAB) m/z: 383 (MH1). HRMS (FAB) Calcd
C16H16ClOS (MH1): 382.9966. Found: 382.9983.
(R)-[(3S,4R)-3,4-(Isopropylidenedioxy)-2,5-epoxy-1-pente-
nyl] p-tolyl sulfoxide (60). Using the procedure for 31, 2-O-
isopropylidene-d-erythrose 59 (760 mg, 4.75 mmol) was
converted into 60 (6:1 diastereomeric mixture, 1.35 g,
96%). Colorless powder: mp 122.0±123.08C (hexane±
AcOEt). IR (KBr) cm21: 2931, 1597, 1381, 1209, 1090,
1
(E)-(R)-2-[2-(Bromomethyl)phenyl]ethenyl p-tolyl sulf-
oxide [(E)-56]. A mixture of (E)-55 (50 mg, 0.17 mmol)
and NaBr (89 mg, 0.86 mmol) in DMF±CH2Br2 (1.5 ml)
was re¯uxed at 1008C for 2 h. After cooling, the reaction
was quenched with brine and the whole was extracted with
ether. The extract was washed with brine prior to drying and
solvent evaporation. The residue was chromatographed on
silica gel with hexane±AcOEt (3:1) to give (E)-56 (46 mg,
82%) as colorless needles. Mp 121.5±122.58C (hexane±
1045. H NMR d: (major): 1.29 (5/2H, s, C(CH3)2), 1.44
(5/2H, s, C(CH3)2), 2.42 (5/2H, s, Ar-CH3), 3.01 (5/6H,
dd, Jˆ13.4, 9.8 Hz, 1-H), 3.06 (5/6H, dd, Jˆ13.4, 3.1 Hz,
1-H), 3.60 (5/6H, dd, Jˆ11.0, 3.67 Hz, 5-H), 4.01±4.04
(5/6H, m, 2-H), 4.10 (5/6H, d, Jˆ11.0 Hz, 5-H), 4.59
(5/6H, dd, Jˆ6.1, 3.7 Hz, 3-H), 4.83 (5/6H, dd, Jˆ6.1,
3.7 Hz, 4-H), 7.34 (10/6H, d, Jˆ7.9 Hz, Ar-H), 7.57 (10/
6H, d, Jˆ7.9 Hz, Ar-H) (minor): 1.31 (3/6H, s, C(CH3)2),
1.47 (3/6H, s, C(CH3)2), 2.42 (3/6H, s, Ar-CH3), 2.86 (1/6H,
dd, Jˆ13.4, 5.5 Hz, 1-H), 3.12 (1/6H, dd, Jˆ13.4, 7.3 Hz,
1-H), 4.01±4.04 (1/6H, m, 5-H), 4.10 (1/6H, d, Jˆ11.0 Hz,
5-H), 4.14±4.16 (1/6H, m, 2-H), 4.73 (1/6H, dd, Jˆ6.1,
1.8 Hz, 3-H), 4.88 (1/6H, dt, Jˆ6.1, 3.1 Hz, 4-H), 7.34
(2/6H, d, Jˆ7.9 Hz, Ar-H). 7.57 (2/6H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR (major): d: 21.4, 24.6, 24.9, 25.9, 58.2,
73.1, 75.9, 80.9, 112.4, 123.9 (2C), 130.0 (2C), 141.1,
141.6. MS (EI) m/z (rel. int. %): 296 (M1, 8.7), 157 (100).
HRMS (EI) Calcd C15H20O4S: 296.1075. Found:
296.1082.
AcOEt). [a]2D6ˆ1151.5 (c 0.51, CHCl3). IR (KBr) cm21
:
1
3018, 1493, 1032. H NMR d: 2.41 (3H, s, Ar-CH3), 4.59
(1H, d, Jˆ11.0 Hz, CH2Br), 4.62 (1H, d, Jˆ11.0 Hz,
CH2Br), 6.84 (1H, d, Jˆ15.3 Hz, 1-H), 7.29 (1H, m, Ar-
H), 7.30 (1H, m, Ar-H), 7.33 (2H, d, Jˆ7.9 Hz, Ar-H),
7.37 (1H, m, Ar-H), 7.44 (1H, m, Ar-H), 7.60 (2H, d,
Jˆ7.9 Hz, Ar-H), 7.70 (1H, d, Jˆ15.3 Hz, 2-H). 13C NMR
d: 21.4, 30.7, 124.9 (2C), 127.5, 129.2, 129.8, 130.2 (2C),
130.6, 132.0, 133.3, 135.9, 136.2, 140.3, 141.9. MS (FAB)
m/z: 335 (MH1). HRMS (FAB) Calcd C16H16BrOS (MH1):
335.0105. Found: 335.0103.
(E)-(2R,3S)-2,3-(Isopropylidenedioxy)-5-[(R)-(p-tolyl-
sul®nyl)]-4-penten-1-ol (61). Using the procedure for
(E)-5, 60 (600 mg, 2.02 mmol) was converted into 61
(E)-(R)-2-[2-(Iodomethyl)phenyl]ethenyl p-tolyl sulfox-
ide [(E)-57]. A mixture of (E)-55 (342 mg, 1.18 mmol),

N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
7943
(550 mg, 92%). Colorless powder: mp 66.0±67.08C
(hexane±AcOEt). [a]2D9ˆ1206.0 (c 0.90, CHCl3). IR
(KBr) cm21: 3388, 1049. 1H NMR d: 1.30 (3H, s,
C(CH3)2), 1.42 (3H, s, C(CH3)2), 2.34 (3H, s, Ar-CH3),
2.98 (1H, s, OH), 3.55 (2H, d, Jˆ6.1 Hz, 1-H), 4.31 (1H,
dt, Jˆ6.1 Hz, 2-H), 4.78 (1H, dd, Jˆ6.1, 4.9 Hz, 3-H), 6.48
(1H, d, Jˆ15.3 Hz, 5-H), 6.56 (1H, dd, Jˆ15.3, 4.9 Hz, 4-
H), 7.25 (2H, d, Jˆ7.9 Hz, Ar-H), 7.45 (2H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR d: 21.5, 25.2, 27.6, 61.4, 76.0, 78.1, 109.2,
124.8 (2C), 130.0 (2C), 132.6, 136.3, 139.7, 141.8. MS (EI)
m/z (rel. int. %): 296 (M1, 31.0), 279 (100). HRMS (EI)
Calcd C15H20O4S: 296.1082. Found: 296.1079. Anal. Calcd
C15H20O4S: C, 60.79; H, 6.80; S, 10.82. Found: C, 61.05; H,
6.70; S, 10.63.
155 (100). HRMS (EI) Calcd C15H18O3S: 278.0977.
Found: 278.0977.
(R)-[(3S,4R,5R)-6-[[tert-Butyl(dimethyl)silyl]oxy]-3,4-
(isopropylidenedioxy)-2,5-epoxyhexyl] p-tolyl sulfoxide
(66). Using the procedure for 31, the lactol 65 (1.76 g,
5.78 mmol) was converted into 66a (less polar: 1.95 g,
77%) and 66b (more polar: 0.32 g, 13%). 66a (a colorless
oil): [a]2D7ˆ169.0 (c 0.81, CHCl3). IR (KBr) cm21: 2929,
1
1257, 1209, 1163, 1099, 1049. H NMR d: 0.09 (3H, s,
SiCH3), 0.10 (3H, s, SiCH3), 0.91 (9H, s, SiC(CH3)3), 1.31
(3H, s, C(CH3)2), 1.44 (3H, s, C(CH3)2), 2.41 (3H, s, Ar-
CH3), 2.93 (1H, dd, Jˆ13.4, 9.8 Hz, 1-H), 3.03 (1H, dd,
Jˆ13.4, 3.1 Hz, 1-H), 3.72±3.78 (2H, m, 6-H), 4.18 (1H,
t, Jˆ3.7 Hz, 5-H), 4.59±4.62 (1H, m, 2-H), 4.62±4.65 (1H,
m, 3-H), 4.87 (1H, d, Jˆ6.1 Hz, 4-H), 7.32 (2H, d,
Jˆ7.9 Hz, Ar-H), 7.57 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 25.7, 25.5, 18.2, 21.4, 24.7, 25.9 (3C), 26.2,
59.6, 64.5, 76.1, 82.4, 83.3, 84.8, 112.4, 124.0 (2C), 129.9
(2C), 141.4 (2C). MS (FAB) m/z: 441 (MH1). HRMS (FAB)
Calcd C22H37O5SiS (MH1): 441.2151. Found: 441.2153.
66b (a colorless oil): [a]2D7ˆ126.4 (c 0.55, CHCl3). IR
(E)-(2R,3S)-2,3-(Isopropylidenedioxy)-5-[(R)-(p-tolylsul-
®nyl)]-4-pentenyl p-toluenesulfonate (62). Using the
procedure for (E)-7, 61 (414 mg, 1.40 mmol) was converted
into 62 (585 mg, 93%). A colorless oil: [a]2D7ˆ1159.3 (c
1
0.89, CHCl3). IR (KBr) cm21: 1597, 1365, 1176. H NMR
d: 1.32 (3H, s, C(CH3)2), 1.39 (3H, s, C(CH3)2), 2.41 (3H, s,
Ar-CH3), 2.46 (3H, s, Ar-CH3), 3.90±3.96 (2H, m, 1-H),
4.42 (1H, dt, Jˆ6.7, 6.1 Hz, 2-H), 4.42 (1H, ddd, Jˆ6.7,
4.9, 1.2 Hz, 3-H), 6.47 (1H, dd, Jˆ4.9, 14.6 Hz, 4-H), 6.57
(1H, dd, Jˆ14.6, 1.2 Hz, 5-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-
H), 7.37 (2H, d, Jˆ7.9 Hz, Ar-H), 7.51 (2H, d, Jˆ7.9 Hz,
Ar-H), 7.83 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.5,
21.8, 25.2, 27.5, 67.6, 75.1, 75.7, 109.9, 124.8 (2C), 127.9
(2C), 129.7, 129.8 (2C), 130.1 (2C), 132.5, 138.0, 139.8,
141.9, 145.0. MS (EI) m/z (rel. int. %): 450 (M1, 8.3), 91
(100). HRMS (EI) Calcd C22H26O6S2: 450.1171. Found:
450.1180.
1
(KBr) cm21: 2929, 1084. H NMR d: 0.08 (3H, s, SiCH3),
0.09 (3H, s, SiCH3), 0.91 (9H, s, SiC(CH3)3), 1.32 (3H, s,
C(CH3)2), 1.45 (3H, s, C(CH3)2), 2.42 (3H, s, Ar-CH3), 2.98
(1H, dd, Jˆ12.8, 4.9 Hz, 1-H), 3.27 (1H, dd, Jˆ12.8,
6.7 Hz, 1-H), 3.75 (2H, d, Jˆ2.4 Hz, 6-H), 4.00±4.03
(1H, m, 2-H), 4.07 (1H, q, Jˆ3.1 Hz, 5-H), 4.64 (1H, dd,
Jˆ6.1, 4.3 Hz, 3-H), 4.68 (1H, dd, Jˆ6.1, 3.1 Hz, 4-H), 7.33
(2H, d, Jˆ7.9 Hz, Ar-H), 7.58 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 25.4, 25.3, 18.4, 21.5, 25.5, 26.0 (3C), 27.3, 60.9,
63.8, 80.0, 81.8, 84.3, 85.4, 113.9, 124.4 (2C), 129.9 (2C),
140.2, 141.7. MS (FAB) m/z: 441 (MH1). HRMS (FAB)
Calcd C22H37O5SiS (MH1): 441.2147. Found: 441.2149.
(R)-[(E)-(3S,4R)-5-Iodo-3,4-(isopropylidenedioxy)-1-pente-
nyl] p-tolyl sulfoxide (63). Using the procedure for (E)-10,
62 (250 mg, 0.55 mmol) was converted into 63 (186 mg,
83%). A colorless oil: [a]2D7ˆ1164.8 (c 1.22, CHCl3). IR
(E)-(2R,3R,4S)-1-[tert-Butyl(dimethyl)silyl]oxy-3,4-(iso-
propylidenedioxy)-6-[(R)-(p-tolylsul®nyl)]-5-hexen-2-ol
(67). Using the procedure for (E)-5, the lactol 66 (6:1 dia-
stereomeric mixture, 2.13 g, 4.84 mmol) was converted into
67 (1.98 g, 93%). A colorless oil: [a]2D8ˆ1102.2 (c 0.91,
CHCl3). IR (KBr) cm21: 2931, 1597, 1255, 1059. 1H NMR
d: 0.09 (6H, s, Si(CH3)2), 0.92 (9H, s, SiC(CH3)3), 1.34 (3H,
s, C(CH3)2), 1.43 (3H, s, C(CH3)2), 2.40 (3H, s, Ar-CH3),
2.63 (1H, d, Jˆ5.5 Hz, OH), 3.56 (1H, m, 2-H), 3.65 (1H,
dd, Jˆ10.4, 5.5 Hz, 1-H), 3.80 (1H, dd, Jˆ10.4, 3.1 Hz,
1-H), 4.12 (1H, dd, Jˆ9.8, 6.7 Hz, 3-H), 4.89 (1H, ddd,
Jˆ6.7, 4.9, 1.8 Hz, 4-H), 6.54 (1H, dd, Jˆ14.6, 1.8 Hz,
6-H), 6.82 (1H, dd, Jˆ14.6, 4.9 Hz, 5-H), 7.30 (2H, d,
Jˆ7.9 Hz, Ar-H), 7.54 (2H, d, Jˆ7.9 Hz, Ar-H). 13C
NMR d: 25.6, 25.4, 18.2 (3C), 21.3, 25.1, 25.8, 27.5,
64.4, 69.5, 76.7, 77.3, 109.3, 124.9 (2C), 129.9 (2C),
134.5, 135.9, 140.4, 141.5. MS (EI) m/z (rel. int. %): 440
(M1, 4.2), 383 (100). HRMS (EI) Calcd C22H36O5SiS:
440.2053. Found: 440.2044.
1
(KBr) cm21: 2987, 1597, 1219, 1083, 1043. H NMR d:
1.37 (3H, s, C(CH3)2), 1.50 (3H, s, C(CH3)2), 2.41(3H, s,
Ar-CH3), 3.00 (1H, dd, Jˆ10.4, 6.7 Hz, 5-H), 3.15 (1H, dd,
Jˆ10.4, 6.7 Hz, 5-H), 4.52 (1H, td, Jˆ6.7, 6.1 Hz, 4-H),
4.84 (1H, dt, Jˆ6.1, 1.8 Hz, 3-H), 6.60 (2H, d, Jˆ1.8 Hz,
1-H and 2-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.53 (2H, d,
Jˆ7.9 Hz, Ar-H). 13C NMR d: 2.6, 21.4, 25.4, 28.0, 76.9,
78.4, 109.7, 124.9 (2C), 130.2 (2C), 130.6, 138.2, 140.0,
142.0. MS (EI) m/z (rel. int. %): 406 (M1, 6.3), 85 (100).
HRMS (EI) Calcd C15H19IO3S: 406.0100. Found: 406.0098.
Anal. Calcd C15H19IO3S: C, 44.35; H, 4.71. Found: C,
44.30; H, 4.67.
(R)-[(E)-(3S,4R)-3,4-(Isopropylidenedioxy)-1-cyclopen-
tenyl] p-tolyl sulfoxide (64). Using the procedure for 41, 63
(30 mg, 0.074 mmol) was converted into 64 (14 mg, 68%).
Yellow powder: mp 80.4±81.38C (hexane±AcOEt).
[a]D29ˆ1145.2 (c 1.13, CHCl3). IR (KBr) cm21: 2929,
1597, 1379, 1371, 1228, 1209, 1084, 1053, 1014. 1H
NMR d: 1.31 (3H, s, C(CH3)2), 1.35 (3H, s, C(CH3)2),
2.41 (3H, s, Ar-CH3), 2.47±2.48 (2H, m, 5-H), 4.78±4.81
(1H, m, 4-H), 5.16±5.18 (1H, d, Jˆ5.5 Hz, 3-H), 6.44 (1H,
d, Jˆ1.2 Hz, 2-H), 7.39 (2H, d, Jˆ7.9 Hz, Ar-H), 7.51 (2H,
d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.4, 25.8, 27.5, 34.9,
78.0, 84.3, 110.7, 125.1 (2C), 130.0 (2C), 132.9, 138.5,
142.1, 150.0. MS (EI) m/z (rel. int. %): 278 (M1, 16.2),
(R)-[(E)-(3S,4R,5R)-6-[tert-Butyl(dimethyl)silyl]oxy-3,4-
(isopropylidenedioxy)-5-(methoxymethoxy)-1-hexenyl]
p-tolyl sulfoxide (68). Chloromethyl methyl ether (0.12 ml,
1.58 mmol) was added to a mixture of 67 (602 mg,
1.37 mmol) and i-Pr2NEt (0.29 ml, 1.67 mmol) in CH2Cl2
(10 ml) with stirring at 08C. The stirring was continued at rt
for 3 days. The reaction was quenched with saturated NH4Cl
aqueous solution, and the whole was extracted with AcOEt.

7944
N. Maezaki et al. / Tetrahedron 56 (2000) 7927±7945
The extract was washed with water and brine prior to drying
and solvent evaporation. The residue was chromatographed
on silica gel with hexane±AcOEt (3:1) to give 68 (605 mg,
91%) as a colorless oil. [a]2D7ˆ195.5 (c 1.04, CHCl3). IR
(methoxymethoxy)-1-hexenyl] p-tolyl sulfoxide (71).
Using the procedure for (E)-10, the alcohol 70 (264 mg,
0.50 mmol) was converted into 71 (229 mg, 95%). A color-
less oil: [a]2D7ˆ1155.7 (c 1.34, CHCl3). IR (KBr) cm21
:
1
1
(KBr) cm21: 2929, 1597, 1255, 1215, 1051. H NMR d:
2931, 1597, 1373, 1151, 1086, 1039. H NMR d: 1.37
(3H, s, C(CH3)2), 1.44 (3H, s, C(CH3)2), 2.40 (3H, s, Ar-
CH3), 2.94 (1H, dt, Jˆ2.4, 8.5 Hz, 5-H), 3.47 (3H, s, OCH3),
3.54 (1H, dd, Jˆ11.0, 2.4 Hz, 6-H), 3.64 (1H, dd, Jˆ2.4,
11.0 Hz, 6-H), 4.27 (1H, dd, Jˆ6.7, 8.5 Hz, 4-H), 4.59
(1H, d, Jˆ7.3 Hz, OCH2O), 4.62 (1H, d, Jˆ7.3 Hz,
OCH2O), 4.87 (1H, ddd, Jˆ6.7, 4.3, 1.2 Hz, 3-H), 6.53
(1H, dd, Jˆ14.6, 1.2 Hz, 1-H), 6.65 (1H, dd, Jˆ14.6,
4.3 Hz, 2-H), 7.31 (2H, d, Jˆ7.9 Hz, Ar-H), 7.51 (2H, d,
Jˆ7.9 Hz, Ar-H). 13C NMR d: 12.1, 21.8, 25.5, 28.0, 57.8,
75.1, 76.6, 79.5, 97.9, 109.6, 125.2 (2C), 130.5 (2C), 132.7,
136.3, 140.6, 142.2. MS (FAB) m/z: 481 (MH1). HRMS
(FAB) Calcd C18H26IO5S (MH1): 481.0546. Found:
481.0052. Anal. Calcd C18H25IO5S: C, 45.01; H, 5.25.
Found: C, 45.06; H, 5.22.
0.06 (6H, s, Si(CH3)2), 0.92 (9H, s, SiC(CH3)3), 1.33 (3H,
s, C(CH3)2), 1.42 (3H, s, C(CH3)2), 2.39 (3H, s, Ar-CH3),
3.39 (3H, s, OCH3), 3.50 (1H, dt, Jˆ7.9, 3.1 Hz, 5-H), 3.75
(1H, dd, Jˆ11.0, 3.1 Hz, 6-H), 3.95 (1H, dd, Jˆ11.0,
2.4 Hz, 6-H), 4.40 (1H, dd, Jˆ7.9, 6.1 Hz, 4-H), 4.62 (1H,
d, Jˆ6.7 Hz, OCH2O), 4.68 (1H, d, Jˆ6.7 Hz, OCH2O),
4.82 (1H, ddd, Jˆ6.1, 4.9, 1.2 Hz, 3-H), 6.50 (1H, dd,
Jˆ14.6, 1.2 Hz, 1-H), 6.72 (1H, dd, Jˆ14.6, 4.9 Hz, 2-H),
7.29 (2H, d, Jˆ7.9 Hz, Ar-H), 7.50 (2H, d, Jˆ7.9 Hz, Ar-
H). 13C NMR d: 25.6, 25.5, 18.3, 21.4, 25.2, 25.8 (3C),
27.6, 55.9, 62.8, 76.0, 76.6, 77.4, 96.7, 108.9, 124.7 (2C),
130.0 (2C), 134.4, 136.3, 140.5, 141.6. MS (FAB) m/z: 485
(MH1). Anal. Calcd C24H40O6SiS: C, 59.42; H, 8.32; S,
6.61. Found: C, 59.29; H, 8.14; S, 6.57.
(E)-(2S,3R,4S)-3,4-(Isopropylidenedioxy)-2-(methoxy-
methoxy)-6-[(R)-(p-tolylsul®nyl)]-5-hexen-1-ol (69). Using
the procedure for (Z)-5, the TBS ether 68 (558 mg,
1.15 mmol) was converted into 69 (398 mg, 93%). Color-
less powder: mp 47.9±48.68C (hexane±AcOEt).
[a]D27ˆ1212.1 (c 0.94, CHCl3). IR (KBr) cm21: 3404,
2935, 1246, 1217, 1039. 1H NMR d: 1.35 (3H, s,
C(CH3)2), 1.46 (3H, s, C(CH3)2), 1.78 (1H, br, OH), 2.41
(3H, s, Ar-CH3), 3.42 (3H, s, OCH3), 3.43 (1H, ddd, Jˆ9.2,
6.7, 2.4 Hz, 5-H), 3.62 (1H, dd, Jˆ12.2, 6.7 Hz, 6-H), 3.87
(1H, dd, Jˆ12.2, 2.4 Hz, 6-H), 4.20 (1H, dd, Jˆ9.2, 6.1 Hz,
4-H), 4.54 (1H, d, Jˆ6.7 Hz, OCH2O), 4.64 (1H, d,
Jˆ6.7 Hz, OCH2O), 4.87 (1H, ddd, Jˆ6.1, 4.9, 1.2 Hz,
3-H), 6.54 (1H, dd, Jˆ14.6, 1.2 Hz, 1-H), 6.64 (1H, dd,
Jˆ14.6, 4.9 Hz, 2-H), 7.32 (2H, d, Jˆ7.9 Hz, Ar-H), 7.51
(2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.3, 25.1, 27.5, 55.9,
63.9, 76.6, 77.2, 81.4, 97.6, 109.2, 124.7 (2C), 130.1 (2C),
132.3, 135.6, 140.2, 141.8. MS (FAB) m/z: 371 (MH1).
HRMS (FAB) Calcd C18H27O6S (MH1): 371.1501. Found:
371.1503.
(R)-[(3S,4R,5R)-3,4-(Isopropylidenedioxy)-5-(methoxy-
methoxy)-1-cyclohexenyl] p-tolyl sulfoxide (72) and (R)-
[(3S,4R,E)-3,4-(isopropylidenedioxy)-5-(methoxy-
methoxy)-1,5-hexadienyl] p-tolyl sulfoxide (73). Using
the procedure for 41, 71 (200 mg, 0.42 mmol) was
converted into 72 (94 mg, 64%) along with 73 (29 mg,
20%). 72 (a yellow oil): [a]2D6ˆ142.9 (c 0.97, CHCl3). IR
(KBr) cm21: 2931, 1597, 1381, 1371, 1221, 1111, 1086,
1
1061, 1038. H NMR d: 1.28 (3H, s, C(CH3)2), 1.38 (3H,
s, C(CH3)2), 2.01±2.07 (1H, m, 6-H), 2.16 (1H, dd, Jˆ15.9,
5.5 Hz, 6-H), 2.40 (3H, s, Ar-CH3), 3.31 (3H, s, OCH3), 3.89
(1H, ddd, Jˆ10.4, 5.5, 1.8 Hz, 5-H), 4.48 (1H, dd, Jˆ5.5,
1.8 Hz, 4-H), 4.68 (2H, s, OCH2O), 4.78±4.83 (1H, m, 3-H),
6.47 (1H, t, Jˆ3.1 Hz, 2-H), 7.28 (2H, d, Jˆ7.9 Hz, Ar-H),
7.50 (2H, d, Jˆ7.9 Hz, Ar-H). 13C NMR d: 21.3, 23.6, 26.5,
27.8, 55.5, 72.8, 73.3, 75.0, 95.4, 114.3, 125.3 (3C), 129.9
(2C), 138.7, 142.2, 142.8. MS (EI) m/z (rel. int. %): 352
(M1, 5.2), 123 (100). HRMS (EI) Calcd C18H24O5S:
352.1344. Found: 352.1342. 73 (a yellow oil):
[a]D26ˆ1142.6 (c 0.21, CHCl3). IR (KBr) cm21: 1215,
1155, 1084, 1055, 1016. 1H NMR d: 1.39 (3H, s,
C(CH3)2), 1.53 (3H, s, C(CH3)2), 2.40 (3H, s, Ar-CH3),
3.43 (3H, s, OCH3), 4.39 (1H, d, Jˆ2.4 Hz, 6-H), 4.42
(1H, d, Jˆ2.4 Hz, 6-H), 4.65 (1H, d, Jˆ7.3 Hz, 4-H), 4.88
(1H, d, Jˆ6.1 Hz, OCH2O), 4.88 (1H, dd, Jˆ7.3, 4.8 Hz,
3-H), 4.94 (1H, d, Jˆ6.1 Hz, OCH2O), 6.48 (1H, d,
Jˆ14.7 Hz, 1-H), 6.53 (1H, dd, Jˆ14.7, 4.8 Hz, 2-H),
7.30 (2H, d, Jˆ7.9 Hz, Ar-H), 7.49 (2H, d, Jˆ7.9 Hz,
Ar-H). 13C NMR d: 21.4, 25.1, 27.1, 56.6, 77.8, 76.9,
86.6, 94.2, 109.8, 124.8 (2C), 130.0 (2C), 133.7, 136.6,
140.4, 141.6, 155.8. MS (FAB) m/z: 353 (MH1). HRMS
(FAB) Calcd C18H25O5S (MH1): 353.1422. Found:
353.1456.
[(E)-(2R,3R,4S)-3,4-(Isopropylidenedioxy)-2-(methoxy-
methoxy)-6-[(R)-(p-tolylsul®nyl)]-5-hexenyl] p-toluene-
sulfonate (70). Using the procedure for (E)-7, the alcohol
69 (320 mg, 0.86 mmol) was converted into 70 (417 mg,
92%). A colorless oil: [a]2D7ˆ1139.2 (c 0.78, CHCl3). IR
(KBr) cm21: 2987, 1362, 1215, 1176, 1084, 1055, 1005. 1H
NMR d: 1.19 (3H, s, C(CH3)2), 1.26 (3H, s, C(CH3)2), 2.32
(3H, s, Ar-CH3), 2.37 (3H, s, Ar-CH3), 3.20 (3H, s, OCH3),
3.46 (1H, ddd, Jˆ8.5, 3.1, 1.8 Hz, 2-H), 4.09 (1H, dd,
Jˆ10.4, 3.1 Hz, 1-H), 4.21 (1H, dd, Jˆ8.5, 6.1 Hz, 3-H),
4.30 (1H, dd, Jˆ10.4, 1.8 Hz, 1-H), 4.44±4.49 (2H, m,
OCH2O), 4.76 (1H, dd, Jˆ6.1, 4.9 Hz, 4-H), 6.44 (1H, d,
Jˆ15.3 Hz, 6-H), 6.53 (1H, dd, Jˆ15.3, 4.9 Hz, 5-H), 7.23
(2H, d, Jˆ7.9 Hz, Ar-H), 7.27 (2H, d, Jˆ7.9 Hz, Ar-H),
7.42 (2H, d, Jˆ7.9 Hz, Ar-H), 7.73 (2H, d, Jˆ7.9 Hz, Ar-
H). 13C NMR d: 21.4, 21.6, 25.0, 27.4, 56.1, 69.6, 75.2,
75.7, 76.2, 97.4, 109.1, 124.7 (2C), 128.1 (2C), 129.7
(2C), 130.1 (2C), 131.7, 132.8, 136.3, 140.1, 141.8, 144.7.
MS (FAB) m/z: 525 (MH1). HRMS (FAB) Calcd
C25H33O8S2 (MH1): 525.1614. Found: 525.1614.
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