A synthesis of diketones from carbonyl compounds and α,ω-dichloro-α,ω-disulfinylalkanes with two carbon-carbon bond-formation via bis-sulfinyloxiranes

Article abstract of DOI:10.1016/S0040-4020(02)00352-6

Bis-sulfinyloxiranes were synthesized in two steps from carbonyl compounds and α,ω-dichloro-α,ω-disulfinylalkanes, which were synthesized from α,ω-dibromoalkanes in three steps, in good yields. Treatment of the bis-sulfinyloxiranes with sodium benzenethiolate and piperidine gave α,α′-di(phenylthio) diketones and α,α′-diamino diketones, respectively, in high yields. From these products, some kinds of diketones were synthesized in good to high yields.

Full text of DOI:10.1016/S0040-4020(02)00352-6

TETRAHEDRON
Pergamon
Tetrahedron 58 +2002) 4217±4224
A synthesis of diketones from carbonyl compounds and
a,v-dichloro-a,v-disul®nylalkanes with two carbon±carbon
bond-formation via bis-sul®nyloxiranes
Tsuyoshi Satoh,p Daisaku Taguchi, Aki Kurabayashi and Makiko Kanoto
Department of Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Received 6 March 2002; accepted 29 March 2002
AbstractÐBis-sul®nyloxiranes were synthesized in two steps from carbonyl compounds and a,v-dichloro-a,v-disul®nylalkanes, which
were synthesized from a,v-dibromoalkanes in three steps, in good yields. Treatment of the bis-sul®nyloxiranes with sodium benzenethiolate
and piperidine gave a,a0-di+phenylthio) diketones and a,a0-diamino diketones, respectively, in high yields. From these products, some kinds
of diketones were synthesized in good to high yields. q 2002 Elsevier Science Ltd. All rights reserved.
Ketones and their derivatives are obviously among the most
important and fundamental compounds in organic and
synthetic organic chemistry.1 Innumerable studies on the
chemistry and synthesis of monoketones and their deriva-
tives have already been reported; however, good method for
preparation of diketones is quite limited.1h In view of the
importance of diketones in organic chemistry, new synthetic
methods are eagerly sought.
1. Results and discussion
1.1. Synthesis of bis-sul®nyloxiranes from acetone and
reactions with some nucleophiles
As mentioned above, we previously reported a versatile
procedure for the synthesis of a-substituted carbonyl
compounds 4 from carbonyl compounds 1 through sul®nyl-
oxiranes 3 +Scheme 1). We expected that if we could easily
synthesize the compounds having two sul®nyloxirane
groups in a molecule, we could obtain a diketone having
two a-substituents. We examined the feasibility of this
methodology and developed a new procedure for synthesis
of various kinds of diketones. The scope and limitation of
this method are also described.
We previously reported a versatile procedure for a synthesis
of homologated a-substituted carbonyl compounds 4 from
carbonyl compounds 1 by the use of aryl 1-chloroalkyl
sulfoxides 2 as the homologating agent via sul®nyloxiranes
3 +Scheme 1).2 In continuation of our study for homologa-
tion of carbonyl compounds3 by using aryl 1-chloroalkyl
sulfoxides as the homologating agent, we report herein a
procedure for a synthesis of diketones, including a,a0-
disubstituted dikentones 7 and unsaturated diketones 8,
from carbonyl compounds 1 and a,v-dichloro-a,v-di-
sul®nylalkanes 5 via bis-sul®nyloxiranes 6 +Scheme 2).
At ®rst, 1,4-dichloro-1,4-di+tolylsul®nyl)butane 9 was
synthesized from 1,4-dibromobutane by the procedure
described before.4 Sulfoxide 9 was treated with slight excess
of LDA at 2608C for 10 min followed by acetone. The
Scheme 1.
Keywords: diketone; thio ketone; amino ketone; a,b-unsaturated ketone; sul®nyloxirane.
Corresponding author. Tel.: 181-3-3260-4271 ext. 2468; fax: 181-3-3235-2214; e-mail: tsatoh@ch.kagu.sut.ac.jp
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020+02)00352-6

4218
T. Satoh et al. / Tetrahedron 58 *2002) 4217±4224
Scheme 2.
reaction worked, and the desired adduct 10 was obtained in
78% yield +Scheme 3). The adduct 10 has four chiral
centers, and theoretically the production of eight dia-
stereomers is possible; however, only two diastereomers
+expressed as less polar product +49%) and more polar
product +29%) on silica gel TLC) were obtained.
on a chiral stationary column +CHIRALCEL OD, Daicel)
and we found that only the more polar product is separated
in two peaks. By this investigation, we were able to deter-
mine the less polar product and the more polar product are
the meso-compound and the racemi-compound, respec-
tively. The relative con®gurations are shown in Scheme 3.
We have already observed that the reaction of the carbanion
having a chlorine and a sul®nyl group to carbonyl
compounds takes place with complete chiral induction
from the sulfur chiral center.5 So, the diastereomers must
be a meso- and a racemi-compound, respectively. In order to
know which is which, the products were analyzed by HPLC
Next, the adducts 10 were treated with potassium tert-
butoxide in a mixture of tert-butanol and THF at 08C.
Quite clean reaction took place to afford the desired bis-
sul®nyloxiranes 11 in quantitative yields. The bis-sul®nyl-
oxiranes, meso-11 and racemi-11, are both good crystalline
compounds and quite stable at room temperature. Finally,
Scheme 3. Synthesis of bis-sul®nyloxiranes 11 from acetone and 9, and reaction with benzenthiolate to give bis+phenylthio)diketone 12.

T. Satoh et al. / Tetrahedron 58 *2002) 4217±4224
4219
Scheme 4. Treatment of the bis-sul®nyloxiranes 11 with piperidine without a solvent.
these bis-sul®nyloxiranes were treated with excess sodium
benzenethiolate in re¯uxing ethanol to give the desired
diketone having two phenylthio groups on its a position
12 in good to high yield.6 As shown in Scheme 3, both 11
showed somewhat different reactivity toward the thiolate;
however, no problem was observed in the use of this
reaction for a practical preparation of the diketone 12.
In a similar manner as described above, the dianion of 9 was
reacted with 3-phenylpropanal to give the adduct 16. The
adduct has six chiral centers and the product 16 was found
to be a mixture of several diastereomers. After rough
puri®cation by silica gel column chromatography +the
yield of 16 was quantitative), the mixture was treated with
tert-BuOK at room temperature for 30 min, then excess
benzenethiol was added to the reaction mixture. The
thiolate reacted quite fast with the intermediate, bis-sul®nyl-
oxirane 17, at room temperature, and a rather clean
reaction mixture was obtained, from which the desired
diphenylthio diketone 18 was obtained in 75% yield from
the adduct 16.
As an extension of this procedure, transformation of 12 to
a,b-unsaturated diketone 14 was investigated.7 Sul®de 12
was oxidized in the usual way with m-chloroperbenzoic acid
+MCPBA) to give sulfoxide 13 as a mixture of dia-
stereomers. Without further puri®cation, a mixture of sulf-
oxide 13 was heated in re¯uxing toluene for 1 h. Enone 14
was obtained in 85% yield and we found that 14 was a
somewhat unstable compound and decomposed slowly on
standing at room temperature.
In the case of the synthesis of a-amino diketone, a mixture
of sul®nyloxiranes 17 was isolated from the reaction
mixture by extraction. After the solvent was evaporated
under vacuum, the residue was heated in piperidine without
a solvent to give the desired diketone 20 having two
piperidine moieties at both a-positions. As described
above, although the adduct 16 and bis-sul®nyloxirane 17
were a mixture of several diastereomers, the method
presented in this paper was found to be very useful for a
synthesis of diketones from aldehyde with almost no
problem.
In our previous study, we found that a sul®nyloxirane
reacted with amines to give a-amino ketones.5b,8 We applied
this reaction to the bis-sul®nyloxiranes, meso-11 and
racemi-11 +Scheme 4). The reaction was simply conducted
by heating 11 in piperidine without a solvent for 1±1.5 h.
This reaction worked quite smoothly to afford the desired
diketone having two piperidines on its a-position 15 in a
quantitative yield. Again some difference in the reaction of
meso-11 and racemi-11 was observed; however, it was
smaller than in the case of the reaction with benzenethiolate.
In order to con®rm the utility of this method, bis+phenylthio)
diketone 18 was converted to 1,10-diphenyl-4,7-decane-
dione 19 and 1,10-diphenyl-2,8-decadiene-4,7-dione 22.
Thus, bis+phenylthio) diketone 18 was treated with tributyl-
tin hydride in the presence of 2,20-azobisisobutyronitrile
+AIBN) in re¯uxing benzene to afford desulfurized 1,10-
diphenyl-4,7-decanedione 19 in 86% yield.10 It is worth
noting that this interesting diketone 19 was synthesized
from 9 and 3-phenylpropanal in only three operations.
We previously investigated some reactions of sul®nyl-
oxiranes 3 with sodium benzeneselenolate.9 This reaction
gave good yields of the ketones without a-substituents +4,
NuˆH). We applied this reaction to bis-sul®nyloxiranes 11;
however, only a complex mixture was obtained.
1.2. Synthesis of bis-sul®nyloxiranes from 3-phenyl-
propanal and reaction with benzenethiolate and
piperidine
a,b-Unsaturated diketone 22 was also synthesized in a
similar way as described above. The sulfur of 18 was
oxidized with MCPBA at 2608C, and the produced mixture
of the sulfoxides was roughly puri®ed and heated under
re¯ux in toluene to give the enone 22 in 82% yield from
18. The a,b-unsaturated diketone 22 was found to be quite
stable at room temperature.
Next, we tried to synthesize the bis-sul®nyloxirane from an
aldehyde and investigated if the bis-sul®nyloxirane could be
used in a syntheis of diketones. 3-Phenylpropanal was used
as a representative example of the aldehydes +Scheme 5).

4220
T. Satoh et al. / Tetrahedron 58 *2002) 4217±4224
Scheme 5. Synthesis of bis-sul®nyloxiranes 17 from 3-penylpropanal and 9, and some reactions.
1.3. Prolonging and shortening of the methylene chain of
the a,v-dichloro-a,v-disul®nylalkane; the scope and
limitation of this procedure
synthesized from 1,8-dibromooctane. The methylene
carbon chain in 23 is four-carbon longer than that in 9.
Generation of the dianion of 23 and reaction with acetone
was carried out under similar conditions as described for 9
to give the adduct 24 in 72% yield +Scheme 6). Again, the
product was a mixture of only two diastereomers, which
were dif®cult to separate. This time we used this mixture
In order to know the scope and limitation of this procedure
we studied these reactions starting from the a,v-dichloro-
a,v-disul®nyl alkanes having a longer or a shorter methyl-
ene chain. At ®rst, 1,8-dichloro-1,8-disul®nyloctane 23 was
Scheme 6. Synthesis of bis-sul®nyloxiranes 25 from acetone and 23, and reaction with benzenthiolate and piperidine.

T. Satoh et al. / Tetrahedron 58 *2002) 4217±4224
4221
Scheme 7. Synthesis of bis-sul®nyloxiranes 30 from 3-phenylpropanal and 23, and reaction with benzenthiolate and piperidine.
in the following experiments without isolation. In a similar
manner as described above, the mixture of the adducts 24
was treated with tert-BuOK to afford a mixture of bis-
sul®nyloxiranes 25 in a quantitative yield after silica gel
column chromatography.
Finally, we synthesized 1,3-dichloro-1,3-disul®nylpropane
34 from 1,3-dibromopropane. The synthesized 34 was found
to be stable at room temperature; however, 34 decomposed
quickly upon treatment with LDA at 2788C. In conse-
quence, we could not synthesize 1,3-diketones by this
method.
Treatment of 25 with sodium benzenethiolate and piperidine
was carried out under similar conditions as in the case with
11 to give a-thio diketone 26 and a-amino diketone 28 in
good yields. The yields and the reaction time were found to
be slightly different from the reaction with 11; however, we
concluded that there is no essential difference between 11
and 25 in chemical reactivity. The dithio diketone 26 was
converted to a,b-unsaturated diketone 27 in 85% yield in
two steps without problem.
In conclusion, we have established a new procedure for the
synthesis of several diketones from ketones and aldehydes
with a,v-dichloro-a,v-disul®nylalkanes with two carbon-
carbon bond-formation. a,a0-Dithio diketones, a,a0-
diamino diketones were synthesized in good overall yields
by this method. From the a,a0-dithio diketones, a,b-
unsaturated diketones and diketones having no a-sub-
stituent can be obtained in good yields. A limitation of
this procedure is that we can not synthesize the diketones
having one methylene between the two carbonyl carbons.
Scheme 7 shows the results of this procedure starting from
23 and 3-phenylpropanal. The reaction of the dianion of 23
with the aldehyde gave the adducts 29 as a mixture of
several diastereomers in quantitative yield after rough
chromatography. The adduct 29 was treated with excess
tert-BuOK at room temperature for 10 min, then benzene-
thiol was added to the reaction mixture. This treatment gave
the desired dithio diketone 31 in 91% yield. Synthesis of
a-amino diketone 23 was carried out in a similar way as
described for the synthesis of 20 to give 33 in 90% yield.
a,b-Unsaturated diketone 32 was synthesized from 31 in
76% yield in two steps +Scheme 8).
2. Experimental
2.1. General
1
All melting points are uncorrected. H NMR spectra were
measured in a CDCl3 solution with JEOL JNM-LA 400 and
500 spectrometer. Electron-impact mass spectra +MS) were
obtained at 70 eV by direct insertion. Silical gel 60
+MERCK) containing 0.5% ¯uorescence reagent 254 and
quartz column were used for column chromatography and
the products having UV absorption were detected by UV
irradiation. In experiments requiring a dry reagent and
solvent, diisopropylamine, piperidine, and benzene were
distilled from CaH2 and THF was distilled from diphenyl-
ketyl. Acetone was dried over CaSO4 and distilled before
Scheme 8.

4222
T. Satoh et al. / Tetrahedron 58 *2002) 4217±4224
use. Methanol and liquid N2 were used for the cooling bath
at 21008C.
C24H32Cl2O4S2: C, 55.48; H, 6.21; Cl, 13.65; S, 12.34.
Found: C, 55.64; H, 6.13; Cl, 14.06; S, 12.24. Racemi-10;
mp 126±1288C +CHCl3±hexane). IR +KBr) 3319 +OH),
1
2.1.1. a,v-Dichloro-a,v-disul®nylalkanes 09, 23, and
34). These compounds were synthesized from a,v-di-
bromoalkanes and p-toluenethiol in a similar way as
described before.4
1182, 1079, 1039 +SO), 756 cm21; H NMR d 1.35 +6H,
s), 1.52 +6H, s), 1.77±1.85 +2H, m), 2.16±2.21 +2H, m),
2.43 +6H, s), 7.31 +4H, d, Jˆ8.0 Hz), 7.60 +4H, d,
Jˆ8.0 Hz). MS m/z +%) 276 +20), 246 +77), 214 +64), 185
+88), 139 +100), 91 +100). Anal. Calcd for C24H32Cl2O4S2: C,
55.48; H, 6.21; Cl, 13.65; S, 12.34. Found: C, 55.23; H,
6.21; Cl, 13.31; S, 12.41.
1,4-Dichloro-1,4-di*p-tolylsul®nyl)butane *9). N-Chloro-
succinimide +recrystallized from benzene; 2.98 g;
22 mmol) was added to a solution of 1,4-di+p-tolylthio)-
butane +3.03 g; 10 mmol) in carbontetrachloride +50 ml).
The suspension was stirred at room temperature for 1.5 h.
The precipitates were ®ltered off and the solvent of the
®ltrate was evaporated under vacuum. The residue was
dissolved with CH2Cl2 +50 ml) and the solution was cooled
to 2608C. To the solution was added m-CPBA +5.43 g;
22 mmol) in one portion with stirring and the reaction
mixture was stirred at 2608C for 2.5 h. The solution was
washed twice with 5% NaOH followed by sat. aq. NH4Cl.
The solution was dried over MgSO4 and the solvent was
evaporated. The product was puri®ed by silica gel column
chromatography to give 3.58 g +89%) of 9 +diastereomeric
mixture) as a mixture of crystals and oil. IR +neat) 2923,
1596, 1448, 1179, 1044 +SO), 754 cm21; 1H NMR d 2.18±
2.69 +4H, m), 2.44 +6H, s, CH3), 4.34±4.60 +2H, m), 7.34±
7.36 +4H, m), 7.56±7.65 +4H, m). MS m/z +%) 402 +M1,
trace), 263 +48), 140 +100), 92 +63). Calcd for
C18H20Cl2O2S2: M, 402.0282. Found: m/z 402.0272.
2.1.3. 2,6-Diepoxy-2,7-dimethyl-3,6-di0p-tolylsul®nyl)-
octane 011). To a solution of tert-BuOK +280 mg;
2.4 mmol) in tert-BuOH +6 ml) and THF +6 ml) at 08C
was added dropwise with stirring a solution of Meso-10
+520 mg; 1 mmol) in THF. The reaction mixture was stirred
for 40 min. The reaction was quenched by sat. aq. NH4Cl
and the whole was extracted with CHCl3. The solution was
dried over MgSO4 and the solvent was evaporated. The
product was puri®ed by silica gel column chromatography
to give 442 mg +99%) of Meso-11 as colorless crystals.
Meso-11; mp 194±1958C +CHCl3±hexane). IR +KBr)
1
1378, 1080, 1048 +SO), 810 cm21; H NMR d 1.15 +6H,
s), 1.27±1.33 +2H, m), 1.70 +6H, s), 2.06±2.13 +2H, m),
2.41 +6H, s), 7.28 +4H, d, Jˆ8.2 Hz), 7.49 +4H, d,
Jˆ8.2 Hz). MS m/z +%) 246 +trace), 167 +100), 139 +52),
91 +65), 69 +79); Anal. Calcd for C24H30O4S2: C, 64.54; H,
6.77; S, 14.36. Found: C, 64.26; H, 6.68; S, 14.39. Racemi-
11; mp 159±1608C +CHCl3±hexane). IR +KBr) 1492, 1451,
1092, 1047 +SO), 808 cm21; 1H NMR d 1.35±1.47 +2H, m),
1.38 +6H, s), 1.74 +6H, s), 1.88±1.98 +2H, m), 2.38 +6H, s),
7.28 +4H, d, Jˆ8.0 Hz), 7.48 +4H, d, Jˆ8.0 Hz). MS m/z +%)
447 +[M1H]1, trace), 167 +100), 139 +40), 123 +46), 69
+76). Calcd for C24H31O4S2: [M1H], 447.1664. Found:
m/z 447.1649. Anal. Calcd for C24H30O4S2: C, 64.54; H,
6.77; S, 14.36. Found: C, 64.17; H, 6.69; S, 14.41.
1,8-Dichloro-1,8-di*p-tolylsul®nyl)octane *23). Colorless
oil +diasteromeric mixture); IR +neat) 2924, 2856, 1087,
1047 +SO), 810 cm21 1H NMR d 1.36±1.71 +8H, m),
;
1.88±1.97 +2H, m), 2.19±2.24 +2H, m), 2.43 +6H, s, CH3),
4.36±4.41 +1.6H, m), 4.49±4.53 +0.4H, m), 7.33±7.64 +8H,
m). MS m/z +%) 458 +M1, trace), 140 +100), 92 +32). Calcd
for C22H28Cl2O2S2: M, 458.0908. Found: m/z 458.0912.
2.1.4.
2,7-Dimethyl-2,7-di0phenylsulfenyl)octane-3,6-
1,3-Dichloro-1,3-di*p-tolylsul®nyl)propane *34). Colorless
oil +diastereomeric mixture). IR +neat) 3004, 2953, 1087,
dione 012). To a solution of NaH +60% oil suspension;
360 mg; 9 mmol) in EtOH +9 ml) at 08C was added drop-
wise with stirring a solution of PhSH +0.86 ml; 8.4 mmol).
The reaction mixture was stirred for 10 min, then Meso-11
+268.0 mg; 0.6 mmol) in EtOH at rt was added and the
solution was heated under re¯ux for 2 h. The reaction was
quenched by sat. aq. NH4Cl and 5% NaOH and the whole
was extracted with CHCl3. The solution was dried over
MgSO4 and the solvent was evaporated. The product was
puri®ed by silica gel column chromatography to give
220 mg +95%) of 12 as colorless crystals. Mp 88±898C
+AcOEt±hexane). IR +KBr) 2924, 1692 +CO), 1437, 1301,
1
1058 +SO), 812, 755 cm21; H NMR d 2.43±3.04 +2H,
CH2), 2.43, 2.44, 2.45, 2.46 +CH3), 4.61±4.66 +0.6H, m),
4.82±5.06 +1.4H, m), 7.29±7.63 +8H, m). MS m/z +%) 388
+M1, trace), 249 +56), 139 +100), 123 +82), 91 +64). Calcd for
C17H18Cl2O2S2: M, 388.0125. Found: m/z 388.0134.
2.1.2. 3,6-Dichloro-2,7-dimethyl-3,6-di0p-tolylsul®nyl)-
octane-2,7-diol 010). To a solution of LDA +5 mmol) in
12 ml of THF at 2608C was added dropwise with stirring
a solution of 9 +804 mg; 2 mmol) in THF. The reaction
mixture was stirred for 10 min, then acetone +0.44 ml;
6 mmol) was added and the solution was stirred for
10 min. The reaction was quenched by sat. aq. NH4Cl and
the whole was extracted with CHCl3. The solution was dried
over MgSO4 and the solvent was evaporated. The product
was puri®ed by recrystallization and silica gel column chro-
matography to give less polar product +meso-10; 507 mg;
49%) and more polar product +racemi-10; 300 mg; 29%).
Meso-10; mp 157±1588C +CHCl3±hexane). IR +KBr) 3304
+OH), 1490, 1145, 1068, 1032 +SO), 809 cm21; 1H NMR d
1.19 +6H, s), 1.55 +6H, s), 1.99 +4H, m), 2.43 +6H, s), 7.33
+4H, d, Jˆ8.6 Hz), 7.60 +4H, d, Jˆ8.6 Hz). MS m/z +%) 246
+52), 140 +68), 139 +65), 123 +74), 91 +100); Anal. Calcd for
1
1048 cm21; H NMR d 1.46 +12H, s), 3.11 +4H, s), 7.29±
7.37 +10H, m). MS m/z +%) 386 +M1, 3), 235 +10), 151
+100), 110 +8). Calcd for C22H26O2S2: M, 386.1374.
Found: m/z 386.1369. Anal. Calcd: C, 68.36; H, 6.78; S,
16.59. Found: C, 68.09; H, 6.68; S, 16.76.
2.1.5. 2,7-Dimethyl-1,7-octadiene-3,6-dione 014). The
thioketone 12 +39 mg; 0.1 mmol) was dissolved with
CH2Cl2 +50 ml) and the solution was cooled to 2608C. To
the solution was added m-CPBA +66 mg; 0.27 mmol) in one
portion with stirring and the reaction mixture was stirred at
2608C for 1 h. The solution was washed twice with 5%
NaOH followed by sat. aq. NH4Cl. The solution was dried

T. Satoh et al. / Tetrahedron 58 *2002) 4217±4224
4223
over MgSO4. The solvent was evaporated to give a residue,
which was used in the next reaction without further puri-
®cation. Toluene +2 ml) was added to the residue and the
reaction mixture was heated under re¯ux for 2.5 h. Sat. aq.
NH4Cl was added to the reaction mixture and the whole was
extracted with CHCl3. The solution was dried over MgSO4
and the solvent was evaporated. The product was puri®ed by
silica gel column chromatography to give 14 mg +85%) of
the enone 14 as a colorless oil. IR +neat) 2925, 1673 +CO),
1368, 1070, 935 cm21; 1H NMR d 1.89 +6H, s), 3.04 +4H, s),
5.80 +2H, s), 6.07 +2H, s). MS m/z +%) 166 +M1, 5), 138
+25), 125 +20), 97 +21), 69 +100), 41 +85). Calcd for
C10H14O2: M, 166.0993. Found: m/z 166.0999.
+M1, 17), 218 +62), 147 +34), 114 +100), 91 +92). Calcd for
C22H26O2: M, 322.1931. Found: m/z 322.1934.
2.1.10. 1,10-Diphenyl-3,8-di0N-piperidinyl)decane-4,7-
dione 020). To a solution of tert-BuOK +33.7 mg;
0.3 mmol) in tert-BuOH +2 ml) and THF +2 ml) at 08C
was added dropwise with stirring a solution of 16 +67 mg;
0.1 mmol) in THF. The reaction mixture was stirred for
10 min. The reaction was quenched by sat. aq. NH4Cl
and the whole was extracted with CHCl3. The solution
was dried over MgSO4 and the solvent was evaporated.
The residue +16) was heated at 1008C in piperidine for
1 h. The excess piperidine was evaporated under vacuum.
The product was puri®ed by silica gel column chromato-
graphy to give 32 mg +94%) of 20 as a colorless oil. IR
2.1.6. 2,7-Dimethyl-2,7-di0N-piperidinyl)octane-3,6-dione
015). A solution of meso-11 +45 mg; 0.1 mmol) in piper-
idine +2 ml) was heated at 1008C for 1.5 h. The excess
piperidine was evaporated under vacuum. The product
was puri®ed by silica gel column chromatography to give
32 mg +94%) of 15 as colorless crystals. Mp 105±1068C
+EtOH±H2O). IR +KBr) 2920, 2804, 1708 +CO), 1360,
1
+neat) 2933, 1713 +CO), 1454, 1115, 788 cm21; H NMR
d 1.42 +4H, m), 1.57 +8H, m), 1.89±2.04 +4H, m), 2.50
+8H, m), 2.62±2.91 +8H, m), 3.15 +2H, m), 7.16±7.29
+10H, m). MS m/z +%) 488 +M1, trace), 203 +16), 202
+100), 91 +10). Calcd for C32H44N2O2: M, 488.3402.
Found: 488.3388.
1
1199, 1044 cm21; H NMR d 1.11 +12H, s), 1.43±1.53
+4H, m), 1.57 +8H, m), 2.37 +8H, t, Jˆ4.9 Hz), 2.91 +4H,
s). MS m/z +%) 336 +M1, trace), 127 +10), 126 +100). Calcd
for C20H36O2N2: M, 336.2777. Found: m/z 336.2799. Anal.
Calcd: C, 71.38; H, 10.78; N, 8.32. Found: C, 71.48; H,
10.98; N, 8.23.
2.1.11. 0E)-1,10-Diphenyl-2,8-decadiene-4,7-dione 022).
Colorless crystals; mp 57.5±588C +AcOEt±hexane). IR
1
+KBr) 3027, 1673 +CO), 1146, 1101, 981 cm21; H NMR
d 2.87 +4H, s), 3.54 +4H, d, Jˆ6.7 Hz), 6.11 +2H, dt, Jˆ15.8,
1.5 Hz), 7.00 +2H, dt, Jˆ15.8, 6.8 Hz), 7.20±7.40 +10H, m).
MS m/z +%) 318 +M1, 45), 201 +100), 145 +91), 117 +67), 91
+71). Calcd for C22H22O2: M, 318,1618. Found: m/z
318.1609. Anal. Calcd: C, 82.99; H, 6.96. Found: C,
82.64; H, 6.58.
2.1.7. 4,7-Dichloro-1,10-diphenyl-4,7-di0p-tolylsul®nyl)-
decane-3,8-diol 016). A mixture of colorless crystals and
oil +a mixture of several diastereomers); IR +neat) 3370
1
+OH), 1494, 1454, 1081, 1032 +SO), 752 cm21; H NMR
d 1.55±3.10 +18H, m), 3.65±4.0 +2H, m), 7.0±7.7 +18H, m).
2.1.12. 3,10-Dichloro-2,11-dimethyl-3,10-di0p-tolyl-
sul®nyl)dodecane-2,11-diol 024). Colorless oil +a mixture
of two diastereomers); IR +neat) 3348 +OH), 2937, 1081,
2.1.8. 1,10-Diphenyl-3,8-di0phenylsulfenyl)octane-4,7-
dione 018). To a solution of tert-BuOK +50 mg; 0.4 mmol)
in tert-BuOH +2 ml) and THF +2 ml) at 08C was added drop-
wise with stirring a solution of 16 +67 mg; 0.1 mmol) in
THF. The mixture was stirred for 10 min, then benzenethiol
+0.03 ml; 0.3 mmol) was added to the reaction mixture.
After 20 min, the reactions were quenched by sat. aq.
NH4Cl and 5% NaOH and the whole was extracted with
CHCl3. The solution was dried over MgSO4 and the solvent
was evaporated. The product was puri®ed by silica gel
column chromatography to give 54 mg +75%) of 18 as a
1
1042 +SO), 809 cm21; H NMR d 1.04±2.25 +12H, m,
CH2), 1.40, 1.60, 2.43 +CH3), 7.32±7.35 +4H, m), 7.54±
7.67 +4H, m).
2.1.13.
2,10-Diepoxy-2,11-dimethyl-3,10-di0p-tolyl-
sul®nyl)dodecane 025). A mixture of light yellow oil and
crystals +a mixture of two diastereomers); IR +neat) 2927,
1494, 1378, 1085, 1054 +SO), 813 cm21; 1H NMR d 0.76±
0.90 +4H, m), 1.05±1.12 +2H, m), 1.36 +6H, s), 1.52±1.63
+4H, m), 1.79 +6H, s), 1.83±1.91 +2H, m), 2.42 +6H, s), 7.30
+4H, d, Jˆ7.9 Hz), 7.52±7.54 +4H, m). MS m/z +%) 341 +4),
246 +25), 223 +77), 140 +100), 123 +44), 69 +66).
colorless oil. IR +neat) 2922, 1705 +CO), 1439, 748 cm21
;
1H NMR d 1.94±2.04 +2H, m), 2.13±2.30 +2H, m), 2.70±
2.82 +6H, m), 2.93±3.02 +2H, m), 3.64 +2H, m), 7.16±7.34
+20H, m). MS m/z +%) 538 +M1, 21), 434 +14), 117 +86), 91
+100). Calcd for C34H34O2S2: M, 538.2000. Found: m/z
538.1998.
2.1.14. 2,11-Dimethyl-2,11-di0phenylsulfenyl)dodecane-
3,10-dione 026). Colorless crystals; mp 86.5±87.58C
+Hexane). IR +KBr) 2929, 1696 +CO), 1465, 1368, 1075,
1
759 cm21; H NMR d 1.36±1.39 +4H, m), 1.41 +12H, s),
2.1.9. 1,10-Diphenyldecane-4,7-dione 019). To a solution
of tributyltin hydride +0.22 ml; 0.8 mmol) and AIBN
+16 mg; 0.1 mmol) in distilled benzene +4 ml) was added
dropwise with stirring a solution of 18 +54 mg; 0.1 mmol)
in benzene. The reaction mixture was heated under re¯ux
for 10 min. The solvent was evaporated under vacuum and
the residue was puri®ed by silica gel column chromato-
graphy to give 19 +28 mg; 86%) as a low melting solid. IR
1.61±1.64 +4H, m), 2.77 +4H, t, Jˆ7.5 Hz), 7.24±7.35 +10H,
m). MS m/z +%) 442 +M1, 3), 165 +10), 151 +100). Calcd for:
C26H34O2S2: M, 442.2001. Found: m/z 422.2007. Anal.
Calcd: C, 70.55; H, 7.74; S, 14.48. Found: C, 70.80; H,
7.75; S, 14.62.
2.1.15. 2,11-Dimethyl-1,11-dodecadiene-3,10-dione 027).
Colorless oil; IR +neat) 2929, 2852, 1678 +CO), 1451,
+KBr) 2947, 1702 +CO), 1497, 1410, 1357, 1072 cm21; H
1371, 1059, 932 cm21 1H NMR d 1.33 +4H, quint,
;
1
NMR d 1.91 +4H, quint, Jˆ7.4 Hz), 2.46 +4H, t, Jˆ7.4 Hz),
Jˆ3.6 Hz), 1.61 +4H, m), 1.87 +6H, s), 2.67 +6H, t,
2.59±2.64 +8H, m), 7.15±7.30 +10H, m). MS m/z +%) 322
Jˆ7.3 Hz), 5.75 +2H, s), 5.95 +2H, s). MS m/z +%) 222

4224
T. Satoh et al. / Tetrahedron 58 *2002) 4217±4224
+M1, 9), 139 +22), 97 +10), 84 +28), 69 +100). Calcd for
C14H22O2: M, 222.1619. Found: m/z 222.1621.
References
1. Some monographs and reviews concerning the chemistry and
synthesis of carbonyl compounds: +a) The Chemistry of the
Carbonyl Groups; Patai, S., Ed.; Wiley: London, 1966.
+b) Zabicky, J., Ed.; The Chemistry of the Carbonyl Group;
Wiley: London, 1970; Vol. 2. +c) Stoddart, J. F., Ed.; Compre-
hensive Organic Chemistry; Pergamon: Oxford, 1979; Vol. 1.
+d) Hase, T. A. Umpoled Synthons; Wiley: New York, 1987.
+e) The Chemistry of Enons, Part 1 and 2; Patai, S., Rappoport,
Z., Eds.; Wiley: Chichester, 1989. +f) Seebach, D. Angew.
Chem., Int. Ed. Engl. 1979, 18, 239. +g) Dieter, R. K.
Tetrahedron 1999, 55, 4177. +h) Echavarren, A. M.; Perez,
M.; Castano, A. M.; Cuerva, J. M. J. Org. Chem. 1994, 59,
4179 and the references cited therein.
2.1.16. 2,11-Dimethyl-2,11-di0N-piperidinyl)dodecane-
3,10-dione 028). Colorless oil; IR +neat) 2933, 1713 +CO),
1
1362, 1197, 1033, 755 cm21; H NMR d 1.07 +12H, s),
1.25±1.31 +4H, m), 1.51±1.58 +12H, m), 2.32 +8H, t,
Jˆ4.9 Hz), 2.65 +4H, t, Jˆ7.6 Hz). MS m/z +%) 392 +M1,
trace), 250 +4), 218 +8), 161 +6), 126 +100), 109 +8). Calcd
for C24H44O2N2: M, 392.3403. Found: m/z 392.3398.
2.1.17. 4,11-Dichloro-1,14-diphenyl-4,11-di0p-tolyl-
sul®nyl)tetradecane-3,12-diol 029). Colorless oil +a
mixture of several diastereomers); IR +neat) 3376 +OH),
;
1495, 1455, 1080, 1033 +SO), 753 cm21 1H NMR d
1.07±3.16 +20H, m), 2.41, 2.45 +CH3), 3.51±4.14 +2H, m),
7.08±7.66 +18H, m). MS m/z +%) 428 +10), 396 +16), 357
+14), 223 +25), 140 +100), 105 +100).
2. +a) Satoh, T.; Yamakawa, K. Synlett 1992, 455. +b) Satoh, T.;
Kubota, K. Tetrahedron Lett. 2000, 41, 2121 and the
references cited therein.
3. Some references for the homologation of carbonyl compound
other than ours: +a) William Lever, Jr., O. Tetrahedron 1976,
32, 1943. +b) Martin, S. F. Synthesis 1979, 633. +c) Stowell,
J. C. Chem. Rev. 1984, 84, 409.
2.1.18. 1,14-Diphenyl-3,12-di0phenylsulfenyl)tetradecane-
4,11-dione 031). Light yellow oil; IR +neat) 2931, 1705
1
+CO), 1455, 1439, 748, 670 cm21; H NMR d 1.19±1.25
+4H, m), 1.47±1.58 +4H, m), 1.99 +2H, quint, Jˆ7.1 Hz),
2.15 +2H, quint, Jˆ7.1 Hz), 2.47 +2H, dt, Jˆ17.1, 7.3 Hz),
2.60 +2H, dt, Jˆ17.1, 7.4 Hz), 2.67±2.79 +4H, m), 3.56 +2H,
t, Jˆ7.3 Hz), 7.14±7.34 +20H, m). MS m/z +%) 594 +M1, 7),
490 +20), 149 +12), 117 +100), 91 +70) Calcd for:
C38H42O2S2: M, 594.2627. Found: m/z 594.2642.
4. Satoh, T.; Taguchi, D.; Suzuki, C.; Fujisawa, S. Tetrahedron
2001, 57, 493.
5. +a) Satoh, T.; Oohara, T.; Yamakawa, K. Tetrahedron Lett.
1988, 29, 2851. +b) Satoh, T.; Oohara, T.; Ueda, Y.;
Yamakawa, K. J. Org. Chem. 1989, 54, 3130. +c) Satoh, T.;
Sato, T.; Oohara, T.; Yamakawa, K. J. Org. Chem. 1989, 54,
3973.
2.1.19. 0E)-1,14-Diphenyl-2,12-tetradecadiene-4,11-dione
032). Light yellow oil; IR +neat) 2933, 1695 +CO), 1669,
6. +a) Satoh, T.; Kaneko, Y.; Kumagawa, T.; Yamakawa, K.
Chem. Lett. 1984, 1957. +b) Satoh, T.; Kumagawa, T.;
Yamakawa, K. Bull. Chem. Soc. Jpn 1985, 58, 2849.
+c) Satoh, T.; Motohashi, S.; Yamakawa, K. Tetrahedron
Lett. 1986, 27, 2889. +d) Satoh, T.; Motohashi, S.; Tokutake,
N.; Yamakawa, K. Bull. Chem. Soc. Jpn 1992, 65, 2966.
7. +a) Satoh, T.; Kumagawa, T.; Yamakawa, K. Tetrahedron
Lett. 1986, 27, 2471. +b) Satoh, T.; Kumagawa, T.; Sugimoto,
A.; Yamakawa, K. Bull. Chem. Soc. Jpn 1987, 60, 301.
+c) Satoh, T.; Itoh, M.; Ohara, T.; Yamakawa, K. Bull.
Chem. Soc. Jpn 1987, 60, 1839.
1
1627, 1496, 1454, 982, 750, 700 cm21; H NMR d 1.29
+4H, m), 1.59 +4H, m), 2.51 +4H, t, Jˆ7.4 Hz), 3.53 +4H,
d, Jˆ6.8 Hz), 6.08 +2H, dt, Jˆ15.9, 1.7 Hz), 6.93 +2H, dt,
Jˆ15.9, 6.6 Hz), 7.16±7.38 +10H, m). MS m/z +%) 374 +M1,
39), 257 +16), 231 +7), 211 +16), 145 +70), 117 +100), 91
+47). Calcd for C26H30O2: M, 374.2244. Found: m/z
374.2227.
2.1.20. 1,14-Diphenyl-3,12-di0N-piperidinyl)tetradecane-
4,11-dione 033). Colorless oil; IR +neat) 2933, 1712 +CO),
1454, 1115, 751, 670 cm21; 1H NMR d 1.28±1.57 +20H, m),
1.87±1.99 +4H, m), 2.40±2.64 +16H, m), 3.07±3.10 +2H,
m), 7.16±7.29 +10H, m). MS m/z +%) 544 +M1, trace),
202 +100), 110 +5), 91 +10). Calcd for C36H52O2N2: M,
544.4029. Found: m/z 544.4026.
8. +a) Satoh, T.; Kaneko, Y.; Sakata, K.; Yamakawa, K. Chem.
Lett. 1985, 585. +b) Satoh, T.; Kaneko, Y.; Sakata, K.;
Yamakawa, K. Bull. Chem. Soc. Jpn 1986, 59, 457.
9. Satoh, T.; Kaneko, Y.; Izawa, T.; Sakata, K.; Yamakawa, K.
Bull. Chem. Soc. Jpn 1985, 58, 1983.
10. +a) Gutierrez, C. G.; Stringham, R. A.; Nitasaka, T.;
Glasscock, K. G. J. Org. Chem. 1980, 45, 3393. +b) Gutierrez,
C. G.; Summerhays, L. R. J. Org. Chem. 1984, 49, 5206.
+c) Watanabe, Y.; Araki, T.; Ueno, Y.; Endo, T. Tetrahedron
Lett. 1986, 27, 5385. +d) Satoh, T.; Kubota, K. Tetrahedron
Lett. 2000, 41, 2121.
Acknowledgements
This work was supported by a Grant-in-Aid for Scienti®c
Research No. 11640545 from the Ministry of Education,
Culture, Sports, Science and Technology, Japan, which is
gratefully acknowledged.