Reaction of magnesium alkylidene carbenoids with lithium acetylides and lithium thiolates: A novel synthesis of conjugated enynes and vinyl sulfides

Article abstract of DOI:10.1016/j.tet.2005.02.084

Magnesium alkylidene carbenoids were generated from 1-chlorovinyl p-tolyl sulfoxides with i-PrMgCl at -78°C in THF or toluene via the sulfoxide-magnesium exchange reaction. Reaction of the generated magnesium alkylidene carbenoids with lithium acetylides or lithium thiolates gave conjugated enynes or vinyl sulfides, respectively, in moderate to good yields. The intermediate of this reaction was found to be the alkenyl anion and it could be trapped with some electrophiles to give tetra-substituted conjugated enynes and vinyl sulfides.

Full text of DOI:10.1016/j.tet.2005.02.084

Tetrahedron 61 (2005) 4409–4418
Reaction of magnesium alkylidene carbenoids with lithium
acetylides and lithium thiolates: a novel synthesis of conjugated
enynes and vinyl sulfides
*
Masanori Watanabe, Masatomo Nakamura and Tsuyoshi Satoh
Department of Chemistry, Faculty of Science, Tokyo University of Science; Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Received 28 January 2005; accepted 25 February 2005
Available online 22 March 2005
Abstract—Magnesium alkylidene carbenoids were generated from 1-chlorovinyl p-tolyl sulfoxides with i-PrMgCl at K78 8C in THF or
toluene via the sulfoxide–magnesium exchange reaction. Reaction of the generated magnesium alkylidene carbenoids with lithium acetylides
or lithium thiolates gave conjugated enynes or vinyl sulfides, respectively, in moderate to good yields. The intermediate of this reaction was
found to be the alkenyl anion and it could be trapped with some electrophiles to give tetra-substituted conjugated enynes and vinyl sulfides.
q 2005 Elsevier Ltd. All rights reserved.
Carbenes and carbenoids are a highly reactive carbon
species and are frequently used as useful intermediates in
organic synthesis.1 Alkylidene carbenes and carbenoids are
a quite interesting and highly reactive carbon species.2 The
carbenoids generated from alkylhalides or alkenylhalides
with alkylmetals, such as alkyllithium or a Grignard reagent
by halogen–metal or hydrogen–metal exchange reaction
have been known to have both nucleophilic and electro-
philic nature,3 because the carbenoids have the nature of
a-halocarbanion and a carbene–metal complex at the same
time.
substituted olefins 5, were obtatined.7 These reactions reveal
the electrophilic nature of the magnesium alkylidene
carbenoids 2.
In continuation of our interest in the study of the reactivity
of the magnesium alkylidene carbenoids generated from
1-chlorovinyl p-tolyl sulfoxides with a Grignard reagent, we
investigated the reaction of 2 with lithium acetylides and
lithium thiolates and found that the reactions give
conjugated enynes 6 and vinyl sulfides 7, respectively, in
moderate to good yields. In this paper the details of the
results are reported.
We recently reported generation of magnesium alkylidene
carbenoids 2 from 1-chlorovinyl p-tolyl sulfoxides 1, which
were synthesized from ketones and chloromethyl p-tolyl
sulfoxide in three steps in high overall yield, with a
Grignard reagent4 via sulfoxide–magnesium exchange
reaction.5 The reaction of the generated magnesium
alkylidene carbenoids 2 with water or benzaldehyde gave
chloroolefins 3 (EZH) or the adduct 3 (EZPhCH(OH)).4
These reactions reveal the nucleophilic nature of the
magnesium alkylidene carbenoids 2 (see Scheme 1).
1. Results and discussion
1.1. Generation of the magnesium alkylidene carbenoids
and the reaction with lithium acetylides to give
conjugated enynes
First, 1-chlorovinyl p-tolyl sulfoxide 8 was synthesized
from cyclopentadecanone and chloromethyl p-tolyl sulf-
oxide.8 The vinyl sulfoxide 8 was treated with tert-
butylmagnesium chloride (0.13 equiv) in THF at K78 8C
to remove a trace of moisture in the reaction mixture.6 To
this mixture was added isopropylmagnesium chloride
(3 equiv) at K78 8C. The sulfoxide–magnesium exchange
reaction took place instantaneously to afford the magnesium
alkylidene carbenoid 9 in a quantitative yield.6 To this
solution of the carbenoid 9, lithium carbanion of 1-hexyne
(3 equiv), generated from 1-hexyne with n-butyllithium,
was added through a cannula and the reaction mixture was
On the other hand, the reaction of the magnesium alkylidene
carbenoids 2 with some nucleophiles (such as Grignard
reagents4b and lithium a-sulfonyl carbanions6) gave the
adducts, alkenylmetal 4, from which allenes and tetra-
Keywords: Sulfoxides; Sulfoxide–magnesium exchange; Magnesium
alkylidene carbenoid; Conjugated enyne; Vinyl sulfide.
*
Corresponding author. Tel.: C81 3 5228 8272; fax: C81 3 3235 2214;
e-mail: tsatoh@ch.kagu.tus.ac.jp
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.02.084

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M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
Scheme 1.
Scheme 2.
stirred and slowly allowed to warm to room temperature
(Scheme 2).
With these improved conditions in hand, we investigated the
generality of this reaction and the results are summarized in
Table 2. The reaction was carried out under the best
conditions mentioned above. Arylacetylenes gave about
40–50% yield of the enyne 11 (entries 1–3). The
This reaction gave a somewhat complex mixture; however,
we obtained interesting compound 10 as a main product in
39% yield. The product 10 showed C22H38 as the molecular
formula and absorption at 2067 cmK1 in its IR spectrum
Table 1. Examination of the conditions for the synthesis of enyne 10 from
1-chlorovinyl p-tolyl sulfoxide 8
1
which indicated the presence of a triple bond. H NMR
showed one vinyl-H (d 5.26, singlet). From these data the
structure of the product was unambiguously determined to
be the conjugated enyne 10. The chemistry of this result is
quite interesting, because the carbon–carbon bond between
sp2 and sp carbons, which is recognized to be very difficult
by the ionic reactions, is realized.
We next investigated improvement of the yield of the
conjugated enyne 10, and the results of the examination are
summarized in Table 1. Addition of 9 equiv of DMPU or
TMEDA as an additive gave disappointing results (entries 2
and 3). Addition of 9 equiv of DME was found to be
effective (entry 4) and from this result it was suggested that
ethers would give better yield. Use of 1,4-dioxane or
cyclopentyl methyl ether (CPME) was found to be effective
in this reaction and especially CPME worked to give 10 in
64% yield (entries 5 and 6). 12-Crown-4 showed some
effect in this reaction (entry 7). Toluene and CPME itself did
not give satisfactory results (entries 8 and 10).
Entry
Solvent
Additive
Yield of 10 (%)
1
2
3
4
5
6
7
8
9
10
THF
THF
THF
THF
THF
THF
THF
Toluene
Toluene
CPME
—
39
14
28
57
58
63
50
41
42
52
DMPU
TMEDA
DME
1,4-Dioxane
CPMEa
12-Crown-4
—
DME
—
a Cyclopentyl methyl ether. Nine equivalents of CPME was added as an
additive.

M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
4411
Table 2. Synthesis of enyne 11 from 1-chlorovinyl p-tolyl sulfoxide 8 with
some lithium acetylides
CD3OD and the deuterated enyne 13 was obtained in 63%
yield with 93% of deuterium incorporation (Scheme 3). We
tried to trap the intermediate 12 with some electrophiles in
the hope of getting further substituted conjugated enynes.
First, to the reaction mixture was added benzaldehyde. From
the tlc analysis the product was thought to be the adduct 14;
however, in the isolation process it decomposed rapidly.
The reaction with iodomethane gave an inseparable mixture
of the methylated product 15 and protonated product 10.
Treatment of the intermediate 12 with iodine gave the
desired iodide 16 in 44% yield.
Entry Lithium acetylide
Yield of 11a
(%)
1
2
11a
11b
41
49
We investigated this reaction with other 1-chlorovinyl
p-tolyl sulfoxide 174b with the lithium carbanion of
1-hexyne (Scheme 4). This reaction gave the desired
enyne 19a in 64% yield. Deuterium was incorporated by
the quenching with CD3OD and the deuterium incorporation
was found to be 96%. Treatment of this reaction with iodine
gave iodinated conjugated enyne 19c in 59% yield.
3
4
11c
11d
38
16
b
5
Complex mixture
24
Conjugated enynes are quite interesting and important
compounds in synthetic organic chemistry9 and several
methods for their synthesis have been reported.10 Although
the yields are not satisfactory, our method for the synthesis
of conjugated enynes described above is fairly unique.11
c
6
11e
a Isolated yield after silica gel column chromatography.
b Lithium acetylide ethylenediamine complex was used.
c Five equivalents of ethynylmagnesium chloride was added.
arylacetylene having an electron-donating group (OCH3)
gave better yield compared with that having electron-
withdrawing group (F) (entries 2 and 3). Trimethylsilyl-
acetylene gave the desired enyne; however, the yield was
found to be low. When lithium acetylide ethylenediamine
complex was used as an acetylide, only a complex mixture
was obtained (entry 5). However, excess ethynylmagnesium
chloride gave the desired enyne 11e in 24% yield.
1.2. Reaction of the magnesium alkylidene carbenoids
with lithium thiolate; a novel synthesis of tri-substituted
alkenyl sulfides including tetra-substituted alkenyl
sulfides
We investigated the reaction of the magnesium alkylidene
carbenoid with sulfur nucleophile (Scheme 5). The
magnesium alkylidene carbenoid 18 was generated from
1-chlorovinyl p-tolyl sulfoxide 17 as above in THF and then
3 equiv of lithium thiolate of p-toluenethiol, generated from
the thiol with n-BuLi, was added. The temperature of the
As the intermediate of this reaction is thought to be the
alkenyl carbanion 12,4,6 we quenched this reaction with
Scheme 3.
Scheme 4.

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M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
Scheme 5.
reaction mixture was slowly allowed to warm to 0 8C to give
the desired vinyl sulfide 20a in 51% yield (entry 1).
Finally, toluene with 10 equiv of DME was found to be the
choice for the solvent system of this reaction and 80% yield
of the vinyl sulfide 20a was obtained.
Improvement of the yield of 20a in this reaction was
investigated as shown in Scheme 5. Ten equivalents of the
additive, HMPA, TMEDA or DME, were added to the THF
solution and some effect was shown with DME (entry 2–4).
Changing the solvent to toluene gave better yield (entry 5).
Vinyl sulfides are important compounds in organic
synthesis, such as masked carbonyl compounds.12 Several
methods for synthesis of the vinyl sulfides have been
reported;13 however, synthesis of vinyl sulfide from
Table 3. Synthesis of vinyl sulfides 20 from 1-chlorovinyl p-tolyl sulfoxides with lithium thiolates via the magnesium alkylidene carbenoids
Entry
1-Chlorovinyl p-tolyl sulfoxide
RSLi
Yield of 20a
R1
R2
(%)
82
1
2
17
20b
20c
17
72
3
4
17
17
n-C12H25SLi
(CH3)3CSLi
20d
20e
60b
39
5
6
7
8
20f
20g
20h
51
77
68
21
22
CH3
Ph
CH3
Ph
8
9
23
24
65c
20i
20j
79d
a Isolated yield after silica gel column chromatography.
b THF was used as a solvent.
c The product was a mixture of Z-isomer 20i and E-isomer 20j (20i:20jZ3.5:1).
d The product was a mixture of E-isomer 20j and Z-isomer 20i (20i:20jZ1:5).

M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
4413
Scheme 6.
alkylidene carbenoid with thiolate is a unique way which
has not been reported yet.
but a complex mixture was obtained. After some investi-
gation it was found that the reaction was best conducted at
K40 8C and the adduct 28a was obtained in 64% yield
(entry 1). In the case of propanal the best yield was obtained
at 0 8C; however, the yield was much lower compared with
that of benzaldehyde (entry 2). All other reactions were best
carried out at K40 8C.
Encouraged by the results described above, we studied the
generality of this reaction (Table 3). 4-Methoxybenzene-
thiol gave a similar yield of vinyl sulfide 20b (entry 1);
however, the benzenethiol having an electron-withdrawing
group, chlorine, at the 4-position gave vinyl sulfide 20c in
slightly lower yield (entry 2). As the lithium thiolate of
dodecanethiol was insoluble in toluene, the reaction with the
magnesium alkylidene carbenoid was carried out in THF,
and 60% yield of the vinyl sulfide 20d was obtained (entry
3). 2-Methyl-2-propanethiol gave a somewhat lower yield
of 20e and steric hindrance was thought to be the reason for
the low yield (entry 4).
Benzoylchloride gave the enone having a tolylsulfanyl
group at the a-position 28c in 54% yield. Ethyl chloro-
formate gave the desired product 28d in only 11% yield
(entry 4). The reaction with iodine gave the desired
alkenyliodide 28e in good yield. Iodomethane, styrene
oxide and carbon disulfide did not react at all with the
intermediate anion 27.
To investigate the generality of this reaction, the 1-chloro-
vinyl p-tolyl sulfoxide derived from acetone 21 was treated
with i-PrMgCl followed by lithium p-toluenethiolate and
the generated carbanion was treated with benzaldehyde and
iodine. This reaction afforded the adduct 28f and iodide 28g
in 58 and 72% yield, respectively (entries 6 and 7). Finally,
this reaction was carried out with 17 and p-methoxy-
benzenthiol followed by benzaldehyde to give 28h in 49%
yield. From the results described above, the generality of the
procedure was confirmed.
This reaction was investigated using the 1-chlorovinyl
p-tolyl sulfoxides derived from cyclopentadecanone (8),
acetone (21), benzophenone (22) and 4-phenyl-2-butanone
(23 and 24) with lithium p-toluenethiolate (Table 3, entries
5–9). As shown in Table 3, entries 5–7, 1-chlorovinyl
p-tolyl sulfoxides 8, 21 and 22 gave the desired vinyl
sulfides (20f, 20g, and 20h) in moderate to good yields.
Somewhat interestingly, the geometrical isomer E-vinyl
sulfide 23 gave Z-isomer 20i predominantly. In contrast to
this, Z-vinyl sulfoxide 24 gave E-vinyl sulfide 20j stereo-
specifically; however, the stereospecificity was not so high
(entries 8 and 9).
In conclusion, we have developed a new method for
synthesis of conjugated enynes and vinyl sulfides by the
reaction with magnesium alkylidene carbenoids and lithium
acetylides or lithium thiolates in moderate to good yields. In
some cases the intermediates, alkenyl anions, could be
trapped with electrophiles. These reactions offer a unique
and good procedure for the synthesis of highly substituted
enynes and vinyl sulfides.
As described above for the reaction of the magnesium
alkylidene carbenoid 9 with lithium acetylides (Scheme 3),
the intermediate of the reaction of the magnesium
alkylidene carbenoid 18 with lithium p-toluenethiolate
was again thought to be the alkenyl anion 25 (Scheme 6).
To confirm this, the reaction was quenched with D2O and
we obtained deuterated vinyl sulfide 26 in 80% yield with
98% deuterium incorporation. If the intermediate 25 would
react with other electrophiles, the reaction achieved a new
method for the synthesis of fully substituted vinyl sulfides.
We investigated this feasibility and the results are
summarized in Table 4.
2. Experimental
2.1. General
1
All melting points are uncorrected. H NMR spectra were
The vinylthio anion 27 was generated from 17 and lithium
p-toluenethiolate, as described above in Scheme 6 and
7 equiv of benzaldehyde was added to the reaction mixture
at 0 8C; however, not the desired adduct 28a (see Table 4)
measured in a CDCl3 solution with JEOL JNM-LA 400 and
500 spectrometer. Electron-impact mass spectra (MS) were
obtained at 70 eV by direct insertion. Silica gel 60
(MERCK) containing 0.5% fluorescence reagent 254 and

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M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
Table 4. Synthesis of tri-substituted vinyl sulfides 28 from 1-chlorovinyl p-tolyl sulfoxides with lithium thiolates and electrophiles via the magnesium
alkylidene carbenoids
Entry
1-Chlorovinyl
p-tolyl sulfoxide
RSLi
Electrophile and conditions
PhCHO, K40 8C, 15 min
CH3CH2CHO, K40–0 8C, 1 h
PhCOCl, K40 8C, 15 min
Yield of 28a
(%)
64
1
2
3
17
17
17
28a
39
54
28b
28c
4
5
6
17
17
21
ClCOOEt, K40 8C, 15 min
I2, K40 8C, 15 min
11
50
58
28d
28e
PhCHO, K40 8C, 15 min
28f
7
8
21
17
I2, K40 8C, 15 min
72
49
28g
28h
PhCHO, K40 8C, 15 min
a Isolated yield after silica gel column chromatography.
a quartz column were used for column chromatography and
the products having UV absorption were detected by UV
irradiation. In experiments requiring a dry reagent and
solvent, DMPU, TMEDA, toluene and HMPA were distilled
from CaH2 and THF, cyclopentyl methyl ether, 1,4-dioxane
and DME were distilled from diphenylketyl.
reaction mixture at K78 8C to give the magnesium
alkylidene carbenoid 9. n-BuLi (0.8 mmol) was added to a
solution of 1-hexyne (0.086 ml; 0.75 mmol) in 6 ml of dry
THF and dry CPME (0.27 ml; 2.3 mmol) in another flame-
dried flask at K78 8C under argon atmosphere to give a
white muddy solution. This solution was added to a solution
of the carbenoid 9 through a canula. Temperature of the
reaction mixture was gradually allowed to warm to room
temperature for 2 h. The reaction was quenched with satd aq
NH4Cl and the whole was extracted with hexane–AcOEt
and the extract was dried over MgSO4. After removal of the
solvent, the product was purified by silica gel column
2.1.1. (Hept-2-ynylidene)cyclopentadecane (10). To a
solution of 8 (100 mg; 0.25 mmol) in 20 ml of dry THF in
a flame-dried flask at K78 8C under argon atmosphere was
added t-BuMgCl (0.033 mmol) dropwise with stirring. After
10 min, i-PrMgCl (0.75 mmol) was added dropwise to the

M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
4415
chromatography to give 10 (48.4 mg; 64%) as a colorless
oil; IR (neat) 2930, 2858, 2067 (triple bond), 1638,
2.1.8. (1-Methylhept-2-ynylidene)cyclopentadecane (15).
To a solution of 8 (100 mg; 0.25 mmol) in 20 ml of dry THF
in a flame-dried flask at K78 8C under argon atmosphere
was added t-BuMgCl (0.033 mmol) dropwise with stirring.
After 10 min, i-PrMgCl (0.75 mmol) was added dropwise to
the reaction mixture at K78 8C to give the magnesium
alkylidene carbenoid 9. n-BuLi (0.8 mmol) was added to a
solution of 1-hexyne (0.086 ml; 0.75 mmol) in 6 ml of dry
THF and CPME (0.27 ml; 2.3 mmol) in another flame-dried
flask at K78 8C under argon atmosphere to give a white
muddy solution. This solution was added to a solution of the
carbenoid 9 through a canula. Temperature of the reaction
mixture was gradually allowed to warm to K10 8C for 2 h.
Iodomethane (1.75 mmol) was added dropwise to the
reaction mixture. Temperature of the reaction mixture was
gradually allowed to warm to room temperature for 30 min.
The reaction was quenched by adding satd aq NH4Cl and the
whole was extracted with AcOEt. The product was purified
by silica gel column chromatography. As this product was
an inseparable mixture with 10, only the data for 1H NMR is
1
1460 cmK1; H NMR d 0.92 (3H, t, JZ7.2 Hz), 1.32–1.55
(28H, m), 2.06 (2H, t, JZ7.3 Hz), 2.28 (2H, t, JZ7.4 Hz),
2.33 (2H, dt, JZ6.9, 2.1 Hz), 5.26 (1H, s). MS m/z (%) 302
(MC, 100), 259 (11), 245 (9), 161 (13), 147 (24), 136 (35),
121 (29), 105 (42). Calcd for C22H38: M, 302.2971. Found:
m/z 302.2981.
2.1.2. (3-Phenylprop-2-ynylidene)cyclopentadecane
(11a). Colorless oil; IR (neat) 2929, 2857, 2198 (triple
1
bond), 1595, 1489, 1459, 1443, 910, 754, 690 cmK1; H
NMR d 1.33–1.60 (24H, m), 2.15 (2H, t, JZ7.3 Hz), 2.40
(2H, t, JZ7.4 Hz), 5.51 (1H, s), 7.25–7.31 (3H, m), 7.39–
7.42 (2H, m). MS m/z (%) 322 (MC, 100), 169 (15), 167
(26), 128 (20), 91 (16). Calcd for C24H34: M, 322.2658.
Found: m/z 322.2653.
2.1.3. {3-(4-Methoxyphenyl)prop-2-ynylidene}cyclo-
pentadecane (11b). Colorless oil; IR (neat) 2930, 2857,
2192 (triple bond), 1603, 1508, 1459, 1442, 1290, 1247,
1171, 1038, 830 cmK1; 1H NMR d 1.24–1.59 (24H, m), 2.14
(2H, t, JZ7.2 Hz), 2.38 (2H, t, JZ7.3 Hz), 3.81 (3H, s),
5.49 (1H, s), 6.83 (2H, d, JZ8.8 Hz), 7.34 (2H, d, JZ
8.8 Hz). MS m/z (%) 352 (MC, 100), 197 (11), 185 (10), 171
(5), 145 (4) 121 (9). Calcd for C25H36O: M, 352.2685.
Found: m/z 352.2775.
1
reported: H NMR d 0.92 (3H, t, JZ7.0 Hz), 1.32–1.54
(28H, m), 1.78 (3H, s), 2.06 (2H, t, JZ7.4 Hz), 2.28 (2H, t,
JZ7.1 Hz), 2.34 (2H, t, JZ6.7 Hz).
2.1.9. (1-Iodohept-2-ynylidene)cyclopentadecane (16).
Yellow oil; IR (neat) 2929, 2858, 2208 (triple bond),
1458, 1350, 1325, 1104, 738 cmK1; 1H NMR d 0.92 (3H, t,
JZ7.0 Hz), 1.32–1.56 (28H, m), 2.24 (2H, t, JZ7.8 Hz),
2.38–2.43 (4H, m). MS m/z (%) 428 (MC, 96), 375 (16), 301
(72), 265 (27), 225 (35), 189 (17), 149 (32), 109 (62), 81
(100). Calcd for C22H37I: M, 428.1940. Found: m/z
428.1941.
2.1.4. {3-(4-Fluorophenyl)prop-2-ynylidene}cyclopenta-
decane (11c). Yellow oil; IR (neat) 2930, 2858, 2199 (triple
bond), 1599, 1506, 1460, 1231, 1155, 834 cmK1; 1H NMR d
1.33–1.58 (24H, m), 2.15 (2H, t, JZ7.4 Hz), 2.38 (2H, t,
JZ7.6 Hz), 5.49 (1H, s), 7.00 (2H, t, JZ8.6 Hz), 7.36–7.40
(2H, m). MS m/z (%) 340 (MC, 100), 185 (28), 173 (24),
146 (25), 109 (18). Calcd for C24H33F: M, 340.2609. Found:
m/z 340.2559.
2.1.10. 8-(Hept-2-ynylidene)-1,4-dioxaspiro[4,5]decane
(19a). Colorless oil; IR (neat) 2954, 2875, 2213 (triple
bond), 1634, 1442, 1374, 1271, 1249, 1228, 1120, 1083,
1
1035, 945, 908, 684 cmK1; H NMR d 0.92 (3H, t, JZ
7.3 Hz), 1.43 (2H, sextet, JZ7.3 Hz), 1.52 (2H, quintet, JZ
7.2 Hz), 1.71 (4H, quintet, JZ6.7 Hz), 2.29–2.35 (4H, m),
2.54 (2H, t, JZ6.4 Hz), 3.97 (4H, s), 5.26 (1H, s). MS m/z
(%) 234 (MC, 100), 205 (20), 191 (14), 148 (15), 133 (22),
119 (20), 105 (27), 91 (38). Calcd for C15H22O2; M,
234.1618. Found: m/z 234.1613.
2.1.5. {3-(Trimethylsilyl)prop-2-ynylidene}cyclopenta-
decane (11d). Colorless oil; IR (neat) 2929, 2858, 2132
(triple bond), 1615, 1461, 1249 (C–Si), 1085, 842, 759 cmK1
;
1H NMR d 0.18 (9H, s), 1.32–1.53 (24H, m), 2.08 (2H, t, JZ
7.1 Hz), 2.32 (2H, t, JZ7.7 Hz), 5.32 (1H, s). MS m/z (%)
318 (MC, 48), 303 (47), 244 (8), 194 (7), 73 (100). Calcd for
C21H38Si: M, 318.2741. Found: m/z 318.2751.
2.1.11. 8-(1-Deuteriohept-2-ynylidene)-1,4-dioxaspiro-
[4,5]decane (19b). Colorless oil; IR (neat) 2954, 2875,
2237 (triple bond), 1626, 1443, 1365, 1239, 1121, 1084,
2.1.6. (Prop-2-ynylidene)cyclopentadecane (11e). Color-
less oil; IR (neat) 3312, 2929, 2857, 2098 (triple bond),
1619, 1459, 1350, 1288, 1173 cmK1; 1H NMR d 1.32–1.53
(24H, m), 2.10 (2H, t, JZ7.3 Hz), 2.33 (2H, t, JZ7.4 Hz),
3.00 (1H, d, JZ2.4 Hz), 5.28 (1H, s). MS m/z (%) 246 (MC,
28), 147 (16), 133 (30), 119 (42), 107 (63), 93 (93), 80
(100). Calcd for C18H30: M, 246.2337. Found: m/z
246.2347.
1
1035, 942, 903, 664 cmK1; H NMR d 0.92 (3H, t, JZ
7.3 Hz), 1.39–1.46 (2H, m), 1.42 (2H, sextet, JZ7.3 Hz),
1.52 (2H, quintet, JZ7.2 Hz), 1.70 (4H, quintet, JZ
6.4 Hz), 2.32 (4H, quintet, JZ6.6 Hz), 2.54 (2H, t, JZ
6.4 Hz), 3.97 (4H, s). MS m/z (%) 235 (MC, 100), 206 (22),
192 (17), 149 (17), 134 (26), 120 (26), 106 (32), 92 (40).
Calcd for C15H21DO2: M, 235.1680, Found: m/z 235.1674.
2.1.7. {(1-Deuterio)hept-2-ynylidene}cyclopentadecane
(13). Colorless oil; IR (neat) 2930, 2858, 2238 (triple
bond), 1615, 1460, 1350, 1298, 730, 710 cmK1; 1H NMR d
0.92 (3H, t, JZ7.0 Hz), 1.32–1.55 (28H, m), 2.06 (2H, t,
JZ7.4 Hz), 2.28 (2H, t, JZ7.4 Hz), 2.33 (2H, t, JZ7.0 Hz).
MS m/z (%) 303 (MC, 100), 260 (13), 246 (10), 150 (14),
137 (42), 134 (31), 108 (30). Calcd for C22H37D: M,
303.3034. Found: m/z 303.3034.
2.1.12. 8-(1-Iodohept-2-ynylidene)-1,4-dioxaspiro[4,5]-
decane (19c). Yellow oil; IR (neat) 2956, 2875, 2208
(triple bond), 1678, 1633, 1435, 1366, 1277, 1236, 1218,
1
1121, 1083, 1034, 944, 908, 804 cmK1; H NMR d 0.92
(3H, t, JZ7.3 Hz), 1.39–1.47 (2H, m), 1.51–1.55 (2H, m),
1.68 (4H, quintet, JZ6.6 Hz), 2.41 (2H, t, JZ7.0 Hz), 2.54
(2H, t, JZ6.4 Hz), 2.70 (2H, t, JZ6.4 Hz), 3.97 (4H, s). MS
m/z (%) 360 (MC, 100), 322 (11), 233 (24), 232 (14), 195

4416
M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
(19), 189 (33), 151 (17), 147 (16), 105 (22). Calcd for
C15H21O2I: M, 360.0586. Found: m/z 360.0579.
1.33 (9H, s), 1.67 (2H, t, JZ6.6 Hz), 1.70 (2H, t, JZ
6.4 Hz), 2.36 (2H, t, JZ6.4 Hz), 2.48 (2H, t, JZ6.6 Hz),
3.97 (4H, s), 5.87 (1H, s). MS m/z (%) 242 (MC, 52), 186
(63), 153 (100), 124 (18), 99 (25), 86 (40), 57, (39). Calcd
for C13H22O2S: M, 242.1339. Found: m/z 242.1340.
2.1.13. 8-{(p-Tolylsulfanyl)methylene}-1,4-dioxaspiro-
[4.5]decane (20a). To a solution of 17 (65.4 mg;
0.2 mmol) in 6 ml of dry toluene in a flame-dried flask at
K78 8C under argon atmosphere was added t-BuMgCl
(0.025 mmol) dropwise with stirring. After 10 min,
i-PrMgCl (0.60 mmol) was added dropwise to the reaction
mixture at K78 8C to give the magnesium alkylidene
carbenoid 18. n-BuLi (0.66 mmol) was added to a solution
of p-toluenethiol (74.5 mg; 0.6 mmol) in 6 ml of dry toluene
and dry DME (0.21 ml; 2 mmol) in another flame-dried
flask at K78 8C under argon atmosphere to give the thiolate
anion. This solution was added to a solution of the carbenoid
18 through a canula. Temperature of the reaction mixture
was gradually allowed to warm to 0 8C for 2 h. The reaction
was quenched by satd aq NH4Cl and the whole was
extracted with CHCl3. The organic layer was washed once
with water and dried over MgSO4. After removal of the
solvent, the product was purified by silica gel column
chromatography to give 20a (44.2 mg; 80%) as a colorless
oil; IR (neat) 2948, 2880, 1492, 1120, 1085, 1034, 908,
805 cmK1; 1H NMR d 1.71–1.76 (4H, m), 2.32 (3H, s), 2.40
(2H, t, JZ6.4 Hz), 2.53 (2H, t, JZ6.6 Hz), 3.98 (4H, s),
5.92 (1H, s), 7.10 (2H, d, JZ8.0 Hz), 7.21 (2H, d, JZ
8.3 Hz). MS m/z (%) 276 (MC, 100), 215 (12), 153 (63), 109
(27), 99 (17), 91 (17). Calcd for C16H20O2S: M, 276.1183.
Found: m/z 276.1179.
2.1.18. {(p-Tolylsulfanyl)methylene}cyclopentadecane
(20f). Colorless oil; IR (neat) 2928, 2857, 1492, 1459,
1216, 1092, 803, 759 cmK1; 1H NMR d 1.25–1.52 (24H, m),
2.16 (2H, t, JZ7.6 Hz), 2.27 (2H, t, JZ7.7 Hz), 2.31 (3H,
s), 5.90 (1H, s), 7.09 (2H, d, JZ7.9 Hz), 7.20 (2H, d, JZ
7.9 Hz). MS m/z (%) 344 (MC, 100), 124 (15), 95 (8), 69
(10), 55 (14). Calcd for C23H36S: M, 344.2535. Found: m/z
344.2529.
2.1.19. 2-Methylpropenyl p-tolyl sulfide (20g). Colorless
oil; IR (neat) 2967, 2910, 2727, 1892, 1492, 1440, 1372,
1
1302, 1171, 1091, 1062, 1017, 857, 804 cmK1; H NMR d
1.86, 1.87, 2.31 (each 3H, s), 5.88 (1H, s), 7.09, 7.20 (each
2H, d, JZ8.3 Hz). MS m/z (%) 178 (MC, 100), 163 (31),
135 (13), 105 (13), 91 (21). Calcd for C11H14S: M,
178.0815. Found: m/z 178.0806.
2.1.20. 2,2-Diphenylethenyl p-tolyl sulfide (20h). Color-
less needles; mp 84–85 8C, (AcOEt–hexane); IR (KBr)
3027, 1583, 1491, 1442, 816, 807, 775, 754, 701, 693 cmK1
;
1H NMR d 2.34 (3H, s), 6.82 (1H, s), 7.14–7.44 (14H, m).
Anal. Calcd for C21H18S: C, 83.40; H, 6.00; S, 10.60.
Found: C, 83.28; H, 5.96; S, 10.73%.
2.1.14. 8-{(4-Methoxyphenylsulfanyl)methylene}-1,4-
dioxaspiro[4.5]decane (20b). Colorless oil; IR (neat)
2949, 2883, 1593, 1494, 1287, 1245, 1120, 1084, 1033,
2.1.21. (Z)-2-Methyl-4-phenyl-1-(p-tolylsulfanyl)-1-
butene (20i). Colorless oil; IR (neat) 3026, 2922, 1604,
1493, 1454, 1376, 1091, 1032, 1017, 804, 743, 698 cmK1
;
1
908, 825, 757 cmK1; H NMR d 1.73 (4H, t, JZ6.5 Hz),
1H NMR d 1.86 (3H, d, JZ1.2 Hz), 2.31 (3H, s), 2.59 (2H,
dd, JZ8.3, 7.6 Hz), 2.76 (2H, dd, JZ8.6, 7.3 Hz), 5.91 (1H,
d, JZ1.2 Hz), 7.08 (2H, d, JZ8.0 Hz), 7.15–7.20 (3H, m),
7.23–7.24 (2H, m), 7.27–7.30 (2H, m). MS m/z (%) 268
(MC, 70), 177 (100), 149 (39), 144 (53), 129 (19), 91 (36).
Calcd for C18H20S: M, 268.1284. Found: m/z 268.1283.
2.37 (2H, t, JZ6.5 Hz), 2.52 (2H, t, JZ6.5 Hz), 3.79 (3H,
s), 3.98 (4H, s), 5.87 (1H, s), 6.85 (2H, d, JZ8.9 Hz), 7.29
(2H, d, JZ8.9 Hz). MS m/z (%) 292 (MC, 100), 231 (12),
153 (50), 139 (27), 109 (27). Calcd for C16H20O3S: M,
292.1132. Found: m/z 292.1138.
2.1.15. 8-{(4-Chlorophenylsulfanyl)methylene}-1,4-
dioxaspiro[4.5]decane (20c). Colorless needles; mp 50.5–
51.5 8C (hexane); IR (KBr) 2954, 2877, 1622, 1473, 1132,
2.1.22. (E)-2-Methyl-4-phenyl-1-(p-tolylsulfanyl)-1-
butene (20j). Colorless oil; IR (neat) 3026, 2921, 1601,
1493, 1454, 1376, 1091, 1030, 1017, 805, 745, 699 cmK1
;
1
1118, 1089, 1029, 913, 812, 682 cmK1; H NMR d 1.72
1H NMR d 1.88 (3H, s), 2.30 (3H, s), 2.47 (2H, t, JZ
7.8 Hz), 2.79 (2H, t, JZ7.8 Hz), 5.83 (1H, s), 7.05 (4H, s),
7.18–7.23 (3H, m), 7.29 (2H, t, JZ7.6 Hz). MS m/z (%) 268
(MC, 58), 177 (100), 149 (31), 144 (48), 129 (19), 91 (38).
Calcd for C18H20S: M, 268.1284. Found: m/z 268.1277.
(2H, t, JZ6.7 Hz), 1.76 (2H, t, JZ6.6 Hz), 2.43 (2H, t, JZ
6.6 Hz), 2.53 (2H, t, JZ6.6 Hz), 3.98 (4H, s), 5.91 (1H, s),
7.21 (2H, d, JZ8.6 Hz), 7.25 (2H, d, JZ8.6 Hz). Anal.
Calcd for C15H17ClO2S: C, 60.70; H, 5.77; Cl, 11.94; S,
10.80. Found: C, 60.82; H, 5.74; Cl, 11.87; S, 10.88%.
2.1.23. 8-(Deuterio-p-tolylsulfanylmethylene)-1,4-dioxa-
spiro[4.5]decane (26). Colorless oil; IR (neat) 2949, 2880,
1492, 1440, 1364, 1274, 1226, 1122, 1087, 1034, 929, 899,
2.1.16. 8-{(Dodecylsulfanyl)methylene}-1,4-dioxaspiro-
[4.5]decane (20d). Colorless oil; IR (neat) 2926, 2854,
1
1
1120, 1085, 1035, 908 cmK1; H NMR d 0.88 (3H, t, JZ
806 cmK1; H NMR d 1.73 (4H, quintet, JZ6.1 Hz), 2.31
7.0 Hz), 1.22–1.32 (16H, m), 1.36–1.39 (2H, m), 1.60 (2H,
t, JZ7.5 Hz), 1.68 (4H, t, JZ6.4 Hz), 2.30 (2H, t, JZ
6.4 Hz), 2.40 (2H, t, JZ6.6 Hz), 2.62 (2H, t, JZ7.3 Hz),
3.97 (4H, s), 5.66 (1H, s). MS m/z (%) 354 (MC, 81), 293
(16), 185 (77), 153 (100), 99 (34). Calcd for C21H38O2S: M,
354.2590. Found: m/z 354.2581.
(3H, s), 2.40 (2H, t, JZ6.4 Hz), 2.53 (2H, t, JZ6.6 Hz),
3.98 (4H, s), 7.10 (2H, d, JZ8.3 Hz), 7.21 (2H, d, JZ
8.3 Hz). MS m/z (%) 277 (MC, 100), 216 (14), 154 (60), 110
(27). Calcd for C16H19DO2S: M, 277.1245. Found: m/z
277.1242.
2.1.24. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidene)-1-phenyl-2-
(p-tolylsulfanyl)ethanol (28a). To a solution of 17
(98.1 mg; 0.3 mmol) in 12 ml of dry toluene in a flame-
dried flask at K78 8C under argon atmosphere was added
2.1.17. 8-{(tert-Butylsulfanyl)methylene}-1,4-dioxaspiro-
[4.5]decane (20e). Colorless oil; IR (neat) 2955, 2881,
1457, 1364, 1270, 1120, 1085, 1035, 909 cmK1; 1H NMR d

M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
4417
t-BuMgCl (0.04 mmol) dropwise with stirring. After
10 min, i-PrMgCl (0.9 mmol) was added dropwise to the
reaction mixture at K78 8C to give the magnesium
alkylidene carbenoid 18. n-BuLi (0.96 mmol) was added
to a solution of p-toluenethiol (112 mg; 0.9 mmol) in 9 ml
of dry toluene and dry DME (0.31 ml; 3 mmol) in another
flame-dried flask at K78 8C under argon atmosphere to give
thiolate anion. This solution was added to the solution of the
carbenoid 18 through a canula. Temperature of the reaction
mixture was gradually allowed to warm to K40 8C for 1 h.
Benzaldehyde (2.1 mmol) was added dropwise to the
reaction mixture. After 15 min, the reaction was quenched
by satd aq NH4Cl. The whole was extracted with CHCl3 and
the organic layer was washed once with water and dried
over MgSO4. After removal of the solvent, the product was
purified by silica gel flash column chromatography to give
28a (73.4 mg; 64%) as a colorless oil; IR (neat) 3460 (OH),
2953, 2884, 1601, 1492, 1449, 1226, 1123, 1084, 1034, 944,
2.1.28. 8-{Iodo-(p-tolylsulfanyl)methylene}-1,4-dioxa-
spiro[4.5]decane (28e). Colorless needles; mp 106–
107 8C (AcOEt–hexane); IR (KBr) 2937, 2870, 1490,
1
1214, 1123, 1084, 1033, 906, 805 cmK1; H NMR d 1.69
(2H, t, JZ6.6 Hz), 1.78 (2H, t, JZ6.6 Hz), 2.33 (3H, s),
2.69 (2H, t, JZ6.6 Hz), 2.90 (2H, t, JZ6.6 Hz), 3.99 (4H,
s), 7.16 (4H, s). MS m/z (%) 402 (MC, 35), 275 (100), 189
(55), 155 (58), 135 (21), 99 (44). Calcd for C16H19IO2S: M,
402.0150. Found: m/z 402.0144. Anal. Calcd for
C16H19IO2S: C, 47.77; H, 4.76; I, 31.55; S, 7.97. Found:
C, 47.81; H, 4.60; I, 31.71; S, 7.59%.
2.1.29. 3-Methyl-1-phenyl-2-(p-tolylsulfanyl)but-2-en-1-
ol (28f). Colorless oil; IR (neat) 3437 (OH), 2922, 1622,
1
1600, 1492, 1449, 1017, 805, 700 cmK1; H NMR d 1.99
(3H, s), 2.11 (3H, s), 2.27 (3H, s), 2.80 (1H, d, JZ10.1 Hz,
OH), 5.94 (1H, d, JZ10.1 Hz), 7.00 (2H, d, JZ8.6 Hz),
7.04 (2H, d, JZ8.6 Hz), 7.23 (1H, t, JZ7.2 Hz), 7.30 (2H, t,
JZ7.6 Hz), 7.36 (2H, d, JZ7.7 Hz). MS m/z (%) 284 (MC,
100), 178 (27), 177 (35), 162 (33), 144 (29), 143 (78), 77
(32). Calcd for C18H20OS: M, 284.1233. Found: m/z
284.1230.
1
908, 806, 754, 700, 662 cmK1; H NMR d 1.60–1.67 (2H,
m), 1.76–1.86 (2H, m), 2.26 (3H, s), 2.61–2.66 (1H, m),
2.72–2.77 (3H, m), 2.89 (1H, d, JZ9.8 Hz, OH), 3.97 (4H,
s), 5.97 (1H, d, JZ9.8 Hz), 6.99 (2H, d, JZ8.3 Hz), 7.04
(2H, d, JZ8.3 Hz), 7.23 (1H, t, JZ7.2 Hz), 7.29 (2H, t, JZ
7.2 Hz), 7.34 (2H, d, JZ7.2 Hz). MS m/z (%) 382 (MC, 98),
364 (27), 189 (37), 155 (100), 105 (39), 99 (48), 91 (44), 77
(33). Calcd for C23H26O3S: M, 382.1601. Found: m/z
382.1608.
2.1.30. 1-Iodo-2-methylpropenyl p-tolyl sulfide (28g).
Colorless needles; mp 44–45 8C, (AcOEt–hexane); IR
(KBr) 2908, 1489, 1204, 1183, 1071, 1016, 866, 803 cmK1
;
1H NMR d 2.10 (3H, s), 2.17 (3H, s), 2.33 (3H, s), 7.15 (4H,
s). MS m/z (%) 304 (MC, 39), 177 (100), 162 (38), 143 (60),
129 (18). Calcd for C11H13IS: M, 303.9782. Found: m/z
303.9771.
2.1.25. 1-(1,4-Dioxaspiro[4.5]dec-8-ylidene)-1-(p-tolyl-
sulfanyl)-2-butanol (28b). Colorless oil; IR (neat) 3468
(OH), 2959, 2877, 1492, 1123, 1085, 1034, 910, 805 cmK1
;
1H NMR d 0.87 (3H, t, JZ6.2 Hz), 1.45–1.53 (1H, m),
1.57–1.65 (3H, m), 1.68–1.83 (2H, m), 2.23 (1H, d, JZ
10.1 Hz, OH), 2.28 (3H, s), 2.54–2.73 (4H, m), 3.96 (4H, s),
4.66 (1H, dt, JZ10.1, 7.2 Hz), 7.04 (2H, d, JZ8.0 Hz), 7.21
(2H, t, JZ8.0 Hz). MS m/z (%) 334 (MC, 100), 243 (18),
230 (21), 215 (22), 193 (20), 107 (19), 99 (18). Calcd for
C19H26O3S: M, 334.1602. Found: m/z 334.1602.
2.1.31. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidene)-2-(4-meth-
oxyphenylsulfanyl)-1-phenylethanol (28h). Colorless oil;
IR (neat) 3461 (OH), 2952, 1594, 1493, 1449, 1244, 1122,
1033, 755 cmK1; 1H NMR d 1.59–1.70 (2H, m), 1.74–1.84
(2H, m), 2.65–2.80 (4H, m), 2.92 (1H, d, JZ9.8 Hz, OH),
3.75 (3H, s), 3.95–3.98 (4H, m), 5.96 (1H, d, JZ9.8 Hz),
6.72 (2H, dt, JZ9.6, 2.7 Hz), 7.08 (2H, dt, JZ9.6, 2.7 Hz),
7.22 (1H, t, JZ7.2 Hz), 7.29 (2H, t, JZ6.7 Hz), 7.33 (2H, d,
JZ7.4 Hz). MS m/z (%) 398 (MC, 100), 290 (8), 241 (10),
205 (26), 155 (24). Calcd for C23H26O4S: M, 398.1549.
Found: m/z 398.1543.
2.1.26. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidene)-1-phenyl-2-
(p-tolylsulfanyl)ethanone (28c). Colorless needles; mp
104.5–105.5 8C, (AcOEt–hexane); IR (KBr) 2964, 2898,
1662 (CO), 1492, 1448, 1208, 1089, 1028, 916, 809,
707 cmK1; 1H NMR d 1.72 (2H, t, JZ6.6 Hz), 1.86 (2H, t,
JZ6.6 Hz), 2.26 (3H, s), 2.40 (2H, t, JZ6.4 Hz), 2.90 (2H,
t, JZ6.6 Hz), 3.95–4.01 (4H, m), 7.01 (2H, d, JZ7.6 Hz),
7.13 (2H, d, JZ8.3 Hz), 7.40 (2H, t, JZ7.8 Hz), 7.52 (1H,
tt, JZ7.4, 1.4 Hz), 7.79 (2H, dd, JZ8.5, 1.4 Hz). MS m/z
(%) 380 (MC, 95), 257 (100), 213 (53), 189 (32), 105 (92),
77 (55). Calcd for C23H24O3S: M, 380.1446. Found: m/z
380.1441. Anal. Calcd for C23H24O3S: C, 72.60; H, 6.36; S,
8.43. Found: C, 72.59; H, 6.36; S, 8.36%.
Acknowledgements
We thank Zeon Corporation, Japan, for providing us
cyclopentyl methyl ether (CPME).
References and notes
2.1.27. (1,4-Dioxaspiro[4.5]dec-8-ylidene)-(p-tolylsul-
fanyl)acetic acid ethyl ester (28d). Colorless oil; IR
(neat) 2983, 1733 (CO), 1493, 1374, 1246, 1090, 1045,
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916, 757 cmK1; H NMR d 1.07 (3H, t, JZ7.2 Hz), 1.77
(2H, t, JZ6.6 Hz), 1.80 (2H, t, JZ6.6 Hz), 2.30 (3H, s),
2.64 (2H, t, JZ6.6 Hz), 2.79 (2H, t, JZ6.6 Hz), 3.98 (4H,
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