A new synthesis, including asymmetric synthesis, of spiro[4.n]alkenones from three components: Cyclic ketones, chloromethyl p-tolyl sulfoxide, and acetonitrile; and a formal total synthesis of racemic acorone

Article abstract of DOI:10.1016/j.tet.2003.09.099

1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of cyclic ketones and chloromethyl p-tolyl sulfoxide in good yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium at -78°C to room temperature gave spirocyclic enaminonitriles in high yields. Acidic treatment of the enaminonitriles afforded spiro[4.n]alkenones in good yields. By using an unsymmetrical cyclic ketone, α-tetralone, and optically active chloromethyl p-tolyl sulfoxide, this procedure afforded enantiomerically pure spiro[4.5]decenone in good yield with excellent asymmetric induction from the sulfoxide chiral center. By using this method a formal total synthesis of a racemic spirocyclic sesquiterpene, acorone, was realized.

Full text of DOI:10.1016/j.tet.2003.09.099

Tetrahedron 59 (2003) 9599–9607
A new synthesis, including asymmetric synthesis, of
spiro[4.n]alkenones from three components: cyclic ketones,
chloromethyl p-tolyl sulfoxide, and acetonitrile; and a formal total
synthesis of racemic acorone
a
b
b
Tsuyoshi Satoh,a Tadashi Kawashima, Satoru Takahashi and Ken Sakai
,
*
aDepartment of Chemistry, Faculty of Science, Tokyo University of Science; Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
bDepartment of Applied Chemistry, Faculty of Science, Tokyo University of Science; Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Received 4 September 2003; accepted 30 September 2003
Abstract—1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of cyclic ketones and chloromethyl p-tolyl sulfoxide in
good yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium at 2788C to room temperature gave spirocyclic
enaminonitriles in high yields. Acidic treatment of the enaminonitriles afforded spiro[4.n]alkenones in good yields. By using an
unsymmetrical cyclic ketone, a-tetralone, and optically active chloromethyl p-tolyl sulfoxide, this procedure afforded enantiomerically pure
spiro[4.5]decenone in good yield with excellent asymmetric induction from the sulfoxide chiral center. By using this method a formal total
synthesis of a racemic spirocyclic sesquiterpene, acorone, was realized.
q 2003 Elsevier Ltd. All rights reserved.
Spirocyclic compounds, which are compounds containing
one carbon atom common to two rings, are structurally quite
interesting. The spirocyclic structure is not unusual in
natural products such as terpenes and terpenoids.1 Many
methods have been published for the synthesis of spiro-
cyclic compounds;1,2 however, in view of the interesting
structure of the spirocyclic compounds, new methods are
still eagerly studied.3 The central carbon of the spirocycles
is a quaternary carbon, and investigation of the stereo-
selective construction of the carbon is also challenging in its
own right.4
2-cyclopentenones 5 by the reaction of cyanomethyllithium
and 1-chlorovinyl p-tolyl sulfoxides 3 which were
synthesized from acyclic ketones 1 and chloromethyl
p-tolyl sulfoxide 2 (Scheme 1).5
We thought that if cyclic ketones 6 could be used in these
reactions, this procedure would give a new method for the
synthesis of spiro[4.n]alkenones 9 through cyclic 1-chloro-
vinyl p-tolyl sulfoxides 7 and spirocyclic enaminonitriles 8.
This expectation was recently investigated, and quite
interesting results were obtained. In this paper, detailed
results of this study and a formal total synthesis of racemic
spirocyclic sesquiterpene acorone 10 are reported
(Scheme 2).
We recently reported a new procedure for the synthesis,
including asymmetric synthesis, of 4,4-disubstituted
Scheme 1.
Keywords: spirocycle; spiro[4.n]alkenone; chiral sulfoxide; asymmetric synthesis; acorone.
*
Corresponding author. Tel.: þ81-3-5228-8272; fax: þ81-3-3235-2214; e-mail: tsatoh@ch.kagu.tus.ac.jp
0040–4020/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2003.09.099

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T. Satoh et al. / Tetrahedron 59 (2003) 9599–9607
Scheme 2.
1. Results and discussion
precautions.5a Later, in some cases lithium diphenylamide
was found to work better than dimsylsodium.5c In the case
of 12c, both dimsylsodium and lithium diphenylamide
worked; however, the yields were not satisfactory. We
further investigated the bases and quite recently found that
N-lithio 2-piperidone was the base of choice. By the use of
this base at room temperature, 77% yield of 13c was
obtained with good reproducibility. In the case of entry 4,
the elimination gave 13d in quantitative yield without
requiring special precautions. A further advantage of using
this base is that it can be removed from the reaction mixture
by simple washing with water.
1.1. Synthesis of 1-chlorovinyl p-tolyl sulfoxides from
symmetrical and unsymmetrical cyclic ketones and
synthesis of spiro[4.n]alkenones
We started this study with cyclopentanone 11a, cyclo-
hexanone 11b, cyclodecanone 11c, and cyclopentadecanone
11d as representative examples of symmetrical cyclic
ketones (Table 1). First, chloromethyl p-tolyl sulfoxide
was treated with LDA in THF at 2788C followed by
cycloalkanones 11 to give the adducts, which were
acetylated under usual conditions to afford the acetate 12
in over 90% yield in all cases. The elimination of acetic acid
from 12 was carried out with three kind of bases (Ph2NLi,
dimsylsodium, and N-lithio 2-piperidone) and the desired
1-chlorovinyl p-tolyl sulfoxides 13 were obtained in good
yields.
The synthesized vinyl sulfoxides 13 were treated with
5 equiv. of cyanomethyllithium, obtained from acetonitrile
and n-BuLi in THF at 2788C, and the reaction temperature
was allowed to warm from 2788C to room temperature over
2 h. The reaction gave the desired enaminonitriles 14 up to
91% yields in all cases without any problem (Table 2).
The selection of these three bases requires some comments.
As the products, 1-chlorovinyl p-tolyl sulfoxides 13, are
sensitive to strong bases, the selection of the bases was
found to be essential to the deacetylation. Previously, we
used dimsylsodium in this elimination with special
Finally, 14 were heated under reflux in acetic acid
containing H3PO4 and a small amount of water, for about
40 h. The desired spiro[4.n]alkenones 15 were obtained in
somewhat variable yields from 66 to 91%. From these
Table 1. Synthesis of cyclic 1-chlorovinyl p-tolyl sulfoxides 13 from simple symmetrical cyclic ketones 11 and chloromethyl p-tolyl sulfoxide
Entry
11, n
12, Yield (%)
Base
13, Yield (%)
1
2
3
11a, 1
11b, 2
11c, 6
12a, 93
12b, 99
12c, 92
Ph2NLi
Ph2NLi
13a, 86
13b, 94
13c, 77
4
11d, 11
12d, 93
13d, 98

T. Satoh et al. / Tetrahedron 59 (2003) 9599–9607
9601
Table 2. Synthesis of spiro[4.n]alkenone 15 from 1-chlorovinyl p-tolyl sulfoxides 13 and cyanomethyllithium through the spiro-enaminonitrile 14
Entry
13, n
14, Yield (%)
15, Yield (%)
1
2
3
4
13a, 1
13b, 2
13c, 6
13d, 11
14a, 85
14b, 91
14c, 71
14d, 83
15a, 91
15b, 76
15c, 66
15d, 90
results the method presented here is found to be quite
general for the small to large-ringed ketones to give the
spiro[4.n]alkenones in good overall yields.
Finally, the enaminonitrile 19a was treated under the acidic
conditions to give the desired spiro-enone in 61% yield;
however, the product was found to be a mixture of two
isomers 20 and 21. These could be separated by silica gel
column chromatography and the minor product 21 was
found to be the spiro-enone whose double bond was
migrated. The acidic treatment of 19b gave the desired,
structurally very interesting spiro dienedione 22; 2-cyclo-
pentenone and 2-cyclohexenone are connected by a carbon
at each g-position. However, the yield was somewhat lower
than those of the other examples.
Next, we investigated this procedure starting from unsym-
metrical cyclic ketones. We selected 2-cyclohexenone 16a
and 4,4-ethylenedioxy 2-cyclohexenone 16b as representa-
tive examples (Scheme 3). The reaction of the lithium
a-carbanion of chloromethyl p-tolyl sulfoxide with 16a and
16b gave 1,2-adducts in quantitative yields without any 1,4-
adducts. Acetylation of the adducts gave the acetates 17a
and 17b as a mixture of two diastereomers in near
quantitative yields.
1.2. Asymmetric synthesis of optically pure spiro[4.5]-
decenone from a-tetralone
The deacetylation of these acetates 17a and 17b was
conducted best with Ph2NLi to give 91% yield of 18a and
18b. The 1-chlorovinyl p-tolyl sulfoxides 18a and 18b were
obtained as separable geometrical isomers and the ratios are
shown in Scheme 3. The reaction of these vinyl sulfoxides
18 (a mixture of two geometric isomers was used) with
cyanomethyllithium gave the desired enaminonitriles 19a
and 19b in 76 and 87% yields, respectively, without any
problem.
Next, we planned the synthesis of optically active
spiro[4.n]alkenones based on the above-mentioned method.
We selected a-tetralone as an unsymmetrical cyclic ketone
and optically pure (R)-chloromethyl p-tolyl sulfoxide6 and
the results are indicated in Scheme 4.
In a similar manner, the addition reaction of lithium
a-sulfinyl carbanion of (R)-chloromethyl p-tolyl sulfoxide
Scheme 3.

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T. Satoh et al. / Tetrahedron 59 (2003) 9599–9607
Scheme 4.
to a-tetralone gave the adduct, which was acetylated to give
the acetate 24 in 91% overall yield. The acetate was a
mixture of two diastereomers (the isomers are expressed as
L and P), which were easily separated by silica gel column
chromatography. The elimination of acetate was most
conveniently carried out with dimsylsodium and the
1-chlorovinyl p-tolyl sulfoxide 25 was obtained in up to
90% yield. Quite interestingly, both acetates (24L and 24P)
gave the same vinyl sulfoxide 25.
determined to be E by X-ray crystallographic analysis7 as
shown in Scheme 4.
The 1-chlorovinyl p-tolyl sulfoxide 25 was treated with
5 equiv. of cyanomethyllithium in a similar way to that
described above to afford optically active enaminonitrile 26
in 83% yield. The optical purity was determined by using
HPLC with chiral stationary column (Daicel; CHIRALCEL
OD) and the ee was found to be over 99%. The absolute
configuration of the chiral center of this enaminonitrile 26
was established to be S as shown in Scheme 4 by X-ray
crystallographic analysis.8
Determination of the stereochemistry of 25 is very
important in the study of chiral induction. The NOESY
spectrum of 25 was measured, and weak NOE was observed
between the aromatic hydrogen depicted in Scheme 4 and
the aromatic hydrogen on the tolyl group. Finally, the
structure of the vinyl sulfoxide 25 was unambiguously
In the previous paper, we proposed a chelation model for the
asymmetric induction of the optically active 1-chlorovinyl
p-tolyl sulfoxides, derived from acyclic ketones, with the
Scheme 5.

T. Satoh et al. / Tetrahedron 59 (2003) 9599–9607
9603
cyanomethyllithium.5b From the absolute stereochemistries
of the 1-chlorovinyl p-tolyl sulfoxide 25 and the enamino-
nitrile 26, it was verified that the proposed model is quite
general for the asymmetric induction even if the 1-chloro-
vinyl p-tolyl sulfoxide group is included in a cyclic carbon
chain.
irradiation. In experiments requiring a dry reagent and
solvent, diisopropylamine, acetonitrile, pyridine, and
DMSO were distilled from CaH2 and THF was distilled
from diphenylketyl. Acetone was dried over CaSO4 and
distilled before use.
2.1.1. Acetic acid 1-[chloro-(toluene-4-sulfinyl)methyl]-
cyclopentyl ester (12a). A solution of 2 (1.0 g; 5.3 mmol)
in dry THF (1 ml) was added dropwise to a solution of LDA
(6.4 mmol) in 14 ml of THF at 2788C. The solution was
stirred at 2788C for 10 min, then cyclopentanone (0.56 ml;
6.4 mmol) in 1 ml of THF was added. The reaction mixture
was stirred for 20 min and the reaction was quenched by sat.
aq. NH4Cl. The whole was extracted with CHCl3. The
organic layer was washed once with water and dried over
MgSO4. The solvent was evaporated to leave colorless
crystals. The product was dissolved in a mixture of acetic
anhydride (10 ml) and pyridine (21 ml). 4-Dimethylamino-
pyridine (108 mg; 0.88 mmol) was added to the solution and
the reaction mixture was stirred at room temperature for
15 h. The acetic anhydride and pyridine were evaporated
under vacuum and the residue was purified by silica gel
column chromatography to give acetate 12a (1.55 g; 93%)
as colorless prisms; mp 87–888C (AcOEt–hexane); IR
(KBr) 2980, 2878, 1736 (CO), 1371, 1235, 1096, 1064 (SO),
The optically pure enaminonitrile 26 was hydrolyzed and
decyanated under the acidic conditions to give the optically
pure spiro[4.5]decenone 27 in almost quantitative yield.
1.3. A formal total synthesis of racemic acorone 10
Finally, we studied an application of this method to a total
synthesis of natural products. Sesquiterpene acorone 10 has
a spiro[4.5]decenone carbon skeleton and is suitable for the
application of our synthetic method. Several papers for the
total synthesis of racemic acorone 10 have already been
reported.9 Herein we report a formal total synthesis of
racemic acorone 10 from commercially available 1,4-
cyclohexanedione mono-ethylene ketal (Scheme 5).
1-Chlorovinyl p-tolyl sulfoxide 2810 was synthesized from
1,4-cyclohexanedione mono-ethylene ketal by the above-
mentioned procedure in high overall yield. The ketal group
of 28 was deprotected in acetic acid containing water at
708C for 1 h to give a ketone 29 in a quantitative yield. The
Wittig methylenation of the ketone 29 was conducted in the
usual way to afford the methylenated product 30; however,
the yield was somewhat lower than expected.
1
1014, 822, 517 cm21; H NMR d 1.69–1.89 (4H, m), 2.12
(3H, s), 2.15–2.29 (3H, m), 2.40–2.46 (1H, m), 2.42 (3H,
s), 5.60 (1H, s), 7.33, 7.45 (each 2H, d, J¼8.0 Hz). Anal.
calcd for C15H19ClO3S: C, 57.23; H, 6.08; Cl, 11.26; S,
10.19. Found: C, 57.36; H, 6.12; Cl, 11.22; S, 9.95%.
The synthesis of the cyclopentadienyl enaminonitrile was
carried out by the above-mentioned procedure and the
expected product 31 was obtained in 81% yield without
problem. Finally, 31 was heated in acetic acid containing
H3PO4 and a small amount of water. The hydrolysis of the
enamine group, decyanation, and migration of the double
bond from exomethylene to tri-substituted olefin occurred in
one operation to give the desired enone 32 in 68% yield.
From the enone 32 total synthesis of racemic acorone has
already been reported by Dolby9a and Martin.9b
2.1.2. Acetic acid 1-[chloro-(toluene-4-sulfinyl)methyl]-
cyclohexyl ester (12b). Colorless needles; mp 104–1058C
(AcOEt–hexane); IR (KBr) 2958, 2940, 1733 (CO), 1371,
1
1224, 1088, 1062 (SO), 825, 515 cm21; H NMR d 1.22–
1.78 (7H, m), 1.93–1.99 (1H, m), 2.17 (3H, s), 2.39–2.48
(2H, m), 2.41 (3H, s), 5.39 (1H, s), 7.32, 7.45 (each 2H, d,
J¼8.0 Hz). Calcd for C16H21ClO3S: M, 328.0900. Found:
m/z 328.0898; MS m/z (%) 328 (Mþ, trace), 189 (67), 140
(86), 129 (72), 111 (12), 93 (45), 91 (34), 43 (100). Anal.
calcd for C16H21ClO3S: C, 58.44; H, 6.44; Cl, 10.78; S,
9.75. Found: C, 58.55; H, 6.48; Cl, 10.71; S, 9.81%.
In conclusion, we have developed a new method for the
synthesis of spiro[4.n]alkenones from several cyclic ketones
and chloromethyl p-tolyl sulfoxide in relatively short steps.
By using unsymmetrical cyclic ketones and optically active
chloromethyl p-tolyl sulfoxide, an asymmetric synthesis of
the spiro[4.n]alkenone was realized. A formal total
synthesis of racemic acorone was successful by our method
presented herein.
The acetates 12c and 12d are known compounds.10,11
2.1.3. [Chloro-(p-tolylsulfinyl)methylidene]cyclopentane
(13a). To a solution of 12a (270 mg; 0.86 mmol) in 3 ml of
dry THF was added dropwise with stirring a solution of
Ph2NLi (1.2 mmol) in 4 ml of THF at 08C. After 10 min, the
reaction was quenched by adding sat. aq. NH4Cl. The whole
was extracted with CHCl3 and washed once with water. The
organic layer was dried over MgSO4 and the product was
purified by silica gel flash column chromatography to give
13a (188 mg, 86%) as colorless crystals; mp 86–878C
(AcOEt–hexane); IR (KBr) 2964, 2951, 1494, 1087, 1056
2. Experimental
2.1. General
1
(SO), 880, 815 cm21; H NMR d 1.68–1.96 (4H, m), 2.42
1
(3H, s), 2.45–2.72 (3H, m), 3.04 (1H, dt, J¼18.3, 6.0 Hz),
7.32, 7.50 (each 2H, d, J¼8.0 Hz). Calcd for C13H15ClOS:
M, 254.0531. Found: m/z 254.0534. MS m/z (%) 254 (Mþ,
25), 239 (36), 237 (100), 201 (38), 123 (16), 91 (23), 79
(33). Anal. calcd for C13H15ClOS: C, 61.28; H, 5.93; Cl,
13.92; S, 12.59. Found: C, 61.30; H, 5.94; Cl, 13.78; S,
12.46%.
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. Silica gel 60
(MERCK) containing 0.5% fluorescence reagent 254 and
a quartz column were used for column chromatography and
the products having UV absorption were detected by UV

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T. Satoh et al. / Tetrahedron 59 (2003) 9599–9607
2.1.4. [Chloro-(p-tolylsulfinyl)methylidene]cyclohexane
(13b). Colorless crystals; mp 83–848C (AcOEt–hexane);
IR (KBr) 2936, 2849, 1446, 1091, 1053 (SO), 857, 806, 530,
J¼5.5 Hz). Calcd for C15H22N2: M, 230.1781. Found: m/z
230.1778; MS m/z (%) 230 (Mþ, 65), 187 (22), 173 (30),
159 (35), 145 (45), 133 (48), 118 (100), 106 (30), 94 (20).
Anal. calcd for C15H22N2: C, 78.21; H, 9.63; N, 12.16.
Found: C, 78.28; H, 9.60; N, 12.07%.
1
460 cm21; H NMR d 1.62–1.67 (5H, m), 1.79–1.82 (1H,
m), 2.41 (3H, s), 2.41–2.51 (2H, m), 2.79–2.84, 2.88–2.93
(each 1H, m), 7.32, 7.46 (each 2H, d, J¼8.0 Hz). Calcd for
C14H17ClOS: M, 268.0606. Found: m/z 268.0696; MS m/z
(%) 268 (Mþ, 15), 253 (40), 251 (100), 215 (10), 159 (12),
139 (8), 123 (12), 91 (30), 77 (19). Anal. calcd for
C14H17ClOS: C, 62.56; H, 6.37; Cl, 13.19; S, 11.93. Found:
C, 62.68; H, 6.42; Cl, 13.44; S, 11.86%.
2.1.9. 2-Aminospiro[4.14]nonadeca-1,3-diene-1-carbo-
nitrile (14d). Colorless crystals; mp 152–1548C (AcOEt–
hexane); IR (KBr) 3450, 3348 (NH), 2169 (CN),
1
1642 cm21; H NMR d 1.30–1.70 (28H, m), 4.48 (2H,
brs, NH2), 5.99, 6.55 (each 1H, d, J¼5.6 Hz). MS m/z (%)
300 (Mþ, 100), 119 (85), 118 (67). Anal. calcd for
C20H32N2: C, 79.94; H, 10.73; N, 9.32. Found: C, 79.53;
H, 10.68; N, 9.20%.
2.1.5. [Chloro-(p-tolylsulfinyl)methylidene]cyclodecane
(13c). A solution of 12c (211 mg, 0.55 mmol) in dry THF
(4 ml) was added dropwise to N-lithio 2-piperidone
[0.66 mmol; prepared from n-BuLi (0.66 mmol) and
2-piperidone (71 mg, 0.72 mmol) in THF (2 ml) at 08C] in
THF at 258C. The reaction mixture was stirred at 258C for
15 min. The reaction was quenched by sat. aq. NH4Cl and
the whole was extracted with CHCl3 and washed with water
three times. The organic layer was dried over MgSO4. The
solvent was evaporated to leave colorless crystals, which
were purified by silica gel column chromatography to give
137 mg (77%) of 13c.
2.1.10. Spiro[4.4]non-3-en-2-one (15a). To a solution of
14a (88 mg; 0.55 mmol) in acetic acid (38 ml) was added
phosphoric acid (85%; 17 ml) and water (3 ml). The
reaction mixture was stirred and heated under reflux for
50 h. The reaction mixture was neutralized with 10% NaOH
and the whole was extracted with Et2O and washed with
brine. The organic layer was dried over MgSO4 and the
product was purified by silica gel flash column chromato-
graphy to give 68.4 mg (91%) of 15a as a colorless oil; IR
(neat) 2954, 2871, 1715 (CO), 1586, 1407, 1180, 797 cm21
;
The 1-chlorovinyl p-tolyl sulfoxides 13c and 13d are known
compounds.10,11
1H NMR d 1.59–1.84 (8H, m), 2.26 (2H, s), 6.04, 7.50 (each
1H, d, J¼5.5 Hz). Calcd for C9H12O: M, 136.0888. Found:
m/z 136.0896; MS m/z (%) 136 (Mþ, 100), 121 (36), 108
(64), 95 (98), 79 (76), 66 (40).
2.1.6. 2-Aminospiro[4.4]nona-1,3-diene-1-carbonitirile
(14a). Acetonitrile (0.19 ml; 3.6 mmol) was added to a
solution of n-BuLi (3.5 mmol) in 8 ml of dry THF at 2788C
with stirring. The solution was stirred for 10 min, then a
solution of 13a (181 mg; 0.71 mmol) in THF was added
dropwise. The temperature of the reaction mixture was
gradually allowed to warm to room temperature for 2 h and
the reaction mixture was further stirred at room temperature
for 30 min. The product was isolated by silica gel flash
column chromatography to give 96 mg (85%) of 14a as
colorless plates; mp 110–1118C (AcOEt–hexane); IR
(KBr) 3429, 3349, 3262 (NH), 2951, 2172 (CN), 1642,
2.1.11. Spiro[4.5]dec-3-en-2-one (15b). Colorless oil; IR
(neat) 2927, 2855, 1714 (CO), 1589, 1452, 1198, 924,
1
795 cm21; H NMR d 1.28–1.54 (8H, m), 1.63–1.73 (2H,
m), 2.22 (2H, s), 6.03, 7.52 (each 1H, d, J¼5.5 Hz). Calcd
for C10H14O: M, 150.1043. Found: m/z 150.1040; MS m/z
(%) 150 (Mþ, 91), 135 (13), 122 (16), 107 (65), 95 (100), 82
(45), 68 (32).
2.1.12. Spiro[4.9]tetradec-3-en-2-one (15c). Colorless oil;
IR (neat) 2926, 2863, 1716 (CO), 1587, 1482, 1445,
1
1
1608, 1542, 1434, 771 cm21; H NMR d 1.70–2.00 (8H,
1188 cm21; H NMR d 1.53–1.67 (18H, m), 2.17 (2H, s),
m), 4.51 (2H, brs, NH2), 5.97, 6.56 (each 1H, d, J¼5.5 Hz).
Calcd for C10H12N2: M, 160.0999. Found: m/z 160.0995;
MS m/z (%) 160 (Mþ, 50), 132 (100), 118 (26), 106 (12), 91
(10). Anal. calcd for C10H12N2: C, 74.97; H, 7.55; N,
17.48%. Found: C, 74.91; H, 7.33; N, 17.40%.
6.01, 7.61 (each 1H, d, J¼5.8 Hz). Calcd for C14H22O: M,
206.1670. Found: m/z 206.1675. MS m/z (%) 206 (Mþ, 43),
163 (17), 149 (43), 135 (30), 121 (25), 109 (56), 95 (100), 79
(31), 66 (31), 55 (31).
2.1.13. Spiro[4.14]nonadec-3-en-2-one (15d). Colorless
oil; IR (neat) 2929, 2857, 1717 (CO), 1588, 1459, 1350,
2.1.7. 2-Aminospiro[4.5]deca-1,3-diene-1-carbonitrile
(14b). Colorless prisms; mp 135–1368C (AcOEt–hexane);
IR (KBr) 3432, 3345, 3238 (NH), 2925, 2166 (CN), 1653,
1
733 cm21; H NMR d 1.33–1.52 (28H, m), 2.17 (2H, s),
6.03, 7.60 (each 1H, d, J¼5.5 Hz). Calcd for C19H32O: M,
276.2451. Found: m/z 276.2449; MS m/z (%) 276 (Mþ, 85),
240 (25), 212 (26), 199 (81), 171 (55), 141 (35), 128 (30),
115 (49), 109 (88), 96 (100), 55 (38).
1
1642, 1610, 1544, 1430, 770 cm21; H NMR d 1.37–1.54
(5H, m), 1.69–1.77 (3H, m), 1.82–1.88 (2H, m), 4.50 (2H,
brs, NH2), 6.04, 6.84 (each 1H, d, J¼5.5 Hz). Calcd for
C11H14N2: M, 174.1155. Found: m/z 174.1150; MS m/z (%)
174 (Mþ, 100), 159 (15), 145 (55), 131 (38), 118 (61), 106
(28), 91 (18). Anal. calcd for C11H14N2: C, 75.82; H, 8.10;
N, 16.08. Found: C, 75.80; H, 8.17; N, 15.93%.
2.1.14. 1,4-Dioxaspiro[4.5]dec-6-en-8-one (16b). A sol-
ution of 1,4-cyclohexanedione monoethyleneketal (1.0 g;
6.4 mmol) in dry THF (5 ml) was added dropwise to a
solution of LDA (7.7 mmol) in 40 ml of THF at 2788C for
30 min, then a solution of phenylselenenyl bromide (3.11 g,
12.8 mmol) in 5 ml of THF was added. The reaction mixture
was stirred for 30 min and the reaction was quenched by sat.
aq. NH4Cl. The whole was extracted with CHCl3 and
washed with water. The organic layer was dried over
2.1.8. 2-Aminospiro[4.9]tetradeca-1,3-diene-1-carbo-
nitrile (14c). Colorless crystals; mp 132–1338C (AcOEt–
hexane); IR (KBr) 3453, 3355 (NH), 2930, 2862, 2167
(CN), 1638, 1606, 1541, 1422, 771 cm21; 1H NMR d 1.51–
1.84 (18H, m), 4.44 (2H, brs, NH2), 5.97, 6.54 (each 1H, d,

T. Satoh et al. / Tetrahedron 59 (2003) 9599–9607
9605
MgSO4. The product was purified by silica gel column
chromatography to give the selenate (1.51 g, 76%). To a
solution of the selenate (3.0 g; 9.6 mmol) in 95 ml of THF
was added acetic acid (2.5 ml) and 31% of hydrogen
peroxide (14 ml). The reaction mixture was stirred at room
temperature for 30 min and the reaction was quenched by
NaHCO3. The whole was extracted with Et2O and washed
with brine. The organic layer was dried over MgSO4. The
product was purified by silica gel flash column chromato-
graphy to give 16b (926 mg; 62%) as a colorless oil; IR
(neat) 2964, 2892, 1682 (CO), 1385, 1220, 1119, 1020,
125–1268C (AcOEt–hexane); IR (KBr) 2942, 2865, 1610,
1492, 1428, 1083, 1056 (SO), 957, 877, 807, 749,
1
523 cm21; H NMR d 1.80–1.91 (2H, m), 2.26–2.31 (2H,
m), 2.41 (3H, s), 2.73 (1H, ddd, J¼15.3, 10.0, 5.0 Hz), 3.21
(1H, ddd, J¼15.3, 7.0, 4.0 Hz), 6.33 (1H, dt, J¼10.0,
4.3 Hz), 6.55 (1H, dt, J¼10.0, 1.9 Hz), 7.30 (2H, d,
J¼8.0 Hz), 7.47 (2H, d, J¼8.0 Hz). Calcd for
C14H15ClOS: M, 266.0530. Found: m/z 266.0523; MS m/z
(%) 266 (Mþ, 73), 249 (81), 218 (42), 183 (25), 169 (13),
139 (20), 124 (40), 123 (32), 91 (100), 65 (62). Anal. calcd
for C14H15ClOS: C, 63.03; H, 5.67; Cl, 13.29, S, 12.02.
Found: C, 62.89; H, 5.53; Cl, 13.05, S, 12.30%
1
914 cm21; H NMR d 2.20 (2H, t, J¼6.1 Hz), 2.64 (2H, t,
J¼6.1 Hz), 4.05 (4H, m), 6.01, 6.61 (each 1H, d,
J¼10.4 Hz). Calcd for C8H10O3: M, 154.0629. Found: m/z
154.0623; MS m/z (%) 154 (Mþ, 13), 126 (100), 112 (12),
98 (53), 82 (10), 66 (10).
2.1.19. 8-[Chloro-(toluene-4-sulfinyl)methylene]-1,4-
dioxaspiro[4.5]dec-6-ene (18b). Colorless crystals (about
1:1 mixture of two diastereomers); mp 84–958C (AcOEt–
hexane); IR (KBr) 2965, 2891, 1397, 1187, 1109, 1087,
1
2.1.15. Acetic acid 1-[chloro-(toluene-4-sulfinyl)methyl]-
cyclohex-2-enyl ester (17a). Colorless needles (about 4:1
diastereomeric mixture); mp 89–1158C (AcOEt–hexane);
IR (KBr) 2941, 2915, 1726 (CO), 1370, 1237, 1086, 1059
(SO), 1018, 958, 821, 751 cm21; 1H NMR d 1.76–1.89 (2H,
m), 2.05 (0.6H, s), 2.14 (2.4H, s), 2.0–2.2 (4H, m), 2.42
(3H, s), 5.45 (0.8H, s), 5.47 (0.2H, s), 6.05 (0.8H, brd,
J¼10.0 Hz), 6.11 (0.8H, ddd, J¼10.0, 4.9, 2.5, Hz), 6.24
(0.2H, ddd, J¼10.0, 4.8, 2.8 Hz), 6.33 (0.2H, brd, J¼
10.4 Hz), 7.32 (2H, d, J¼8.2 Hz), 7.44 (1.6H, d, J¼8.2 Hz),
7.49 (0.4H, d, J¼8.2 Hz). Calcd for C16H18ClO3S: M,
326.0744. Found: m/z 326.0741; MS m/z (%) 187 (Mþ, 25),
182 (15), 140 (100), 139 (21), 109 (45), 91 (24), 81 (16).
Anal. calcd for C16H19ClO3S: C, 58.80; H, 5.86; Cl, 10.85;
S, 9.81. Found: C, 58.74; H, 5.80; Cl, 10.74; S, 10.12%.
1056 (SO), 1022, 906, 805, 532 cm21; H NMR d 1.88–
2.07 (2H, m), 2.41 (3H, s), 2.71–2.84 (1H, m), 2.96 (0.5H,
ddd, J¼15.5, 10.0, 4.6 Hz), 3.32 (0.5H, ddd, J¼15.5, 6.5,
1.8 Hz), 3.98–4.07 (4H, m), 5.99, 6.03, 6.66, 7.26 (each
0.5H, d, J¼10.0 Hz), 7.31 (2H, d, J¼8.0 Hz), 7.47, 7.48
(each 1H, d, J¼8.0 Hz). Calcd for C16H17ClO3S: M,
324.0587. Found: m/z 324.0583; MS m/z (%) 324 (Mþ,
10), 308 (17), 276 (100), 261 (12), 241 (20), 232 (15), 204
(40), 169 (15), 165 (15), 139 (24), 123 (31), 91 (28), 77 (32).
2.1.20. 2-Aminospiro[4.5]deca-1,3,6-triene-1-carbo-
nitrile (19a). Colorless crystals; mp 126–1278C (AcOEt–
hexane); IR (KBr) 3443, 3354, 3260, 3237 (NH), 2929,
2174 (CN), 1645, 1609, 1540, 1430, 778 cm21; 1H NMR d
1.67–2.19 (6H, m), 4.57 (2H, brs, NH2), 5.08 (1H, dt,
J¼10.0, 2.2 Hz), 5.94 (1H, dt, J¼10.0, 3.9 Hz), 6.03, 6.45
(each 1H, d, J¼5.4 Hz). Calcd for C11H12N2: M, 172.0999.
Found: m/z 172.0996; MS m/z (%) 172 (Mþ, 100), 157 (68),
144 (35), 130 (26), 118 (17), 103 (8), 91 (10), 77 (10). Anal.
calcd for C11H12N2: C, 76.71; H, 7.02; N, 16.27. Found: C,
76.77; H, 7.01; N, 16.20%.
2.1.16. Acetic acid 8-[chloro-(toluene-4-sulfinyl)methyl]-
1,4-dioxaspiro[4.5]dec-6-en-8-yl ester (17b). Colorless oil
(about 2:1 diastereomeric mixture); IR (neat) 2977, 2885,
1733 (CO), 1398, 1370, 1243, 1211, 1092, 1064 (SO), 1018,
960, 822 cm21; 1H NMR d 1.90–1.93 (1H, m), 2.09 (1H, s),
2.15 (2H, s), 2.13–2.19 (1H, m), 2.42 (3H, s), 2.40–2.46
(1H, m), 2.58 (1H, dt, J¼14.0, 3.4 Hz), 3.85–4.07 (4H, m),
5.42 (1H, s), 5.87 (0.7H, dd, J¼10.0, 1.5 Hz), 5.94 (0.3H, d,
J¼10.4 Hz), 6.23 (0.7H, dd, J¼10.0, 1.5 Hz), 6.46 (0.3H, d,
J¼10.4 Hz), 7.33 (2H, d, J¼8.2 Hz), 7.43 (1.5H, d, J¼
8.2 Hz), 7.48 (0.5H, d, J¼8.2 Hz). MS m/z (%) 245
([M2TolS(O)]þ, 55), 167 (93), 140 (81), 139 (35), 87
(100), 43 (64).
2.1.21. 10-Amino-1,4-dioxadispiro[4.2.4.2]tetradeca-
6,9,11-triene-9-carbonitrile (19b). Colorless prisms; mp
1728C (AcOEt–hexane); IR (KBr) 3421, 3349, 3239 (NH),
2173 (CN), 1658, 1611, 1541, 1432, 1137, 1102, 945 cm21
;
1H NMR d 1.86–1.97 (2H, m), 2.07–2.20 (2H, m), 3.96–
4.06 (4H, m), 4.66 (2H, brs, NH2), 5.29 (1H, d, J¼9.8 Hz),
5.79 (1H, d, J¼9.8 Hz), 6.11, 6.48 (each 1H, d, J¼5.5 Hz).
Calcd for C13H14N2O2: M, 230.1054. Found: m/z 230.1056;
MS m/z (%) 230 (Mþ, 100), 202 (40), 186 (55), 171 (18),
158 (50), 143 (12), 130 (35), 118 (20), 103 (13), 77 (8).
Anal. calcd for C13H14N2O2: C, 67.81; H, 6.13; N, 12.17.
Found: C, 67.63; H, 5.91; N, 12.12%.
2.1.17. (E)-1-(Chloro-cyclohex-2-enylidene-methane-
sulfinyl)-4-methylbenzene (18a-E). Colorless needles;
mp 128–1298C (AcOEt–hexane); IR (KBr) 2954, 2922,
2911, 1615, 1493, 1084, 1057 (SO), 886, 877, 811, 746,
1
527 cm21; H NMR d 1.66–1.77 (1H, m), 1.79–1.86 (1H,
m), 2.22–2.26 (2H, m), 2.41 (3H, s), 2.53–2.64 (2H, m),
6.26 (1H, dt, J¼10.0, 4.3 Hz), 7.13 (1H, dt, J¼10.0, 2.2 Hz),
7.30 (2H, d, J¼8.0 Hz), 7.48 (2H, d, J¼8.0 Hz). Calcd for
C14H15ClOS: M, 266.0530. Found: m/z 266.0529; MS m/z
(%) 266 (Mþ, 10), 250 (10), 218 (100), 183 (33), 139 (12),
124 (37), 123 (22), 91 (65), 79 (25), 65 (25). Anal. calcd for
C14H15ClOS: C, 63.03; H, 5.67; Cl, 13.29, S, 12.02. Found:
C, 62.60; H, 5.54; Cl, 13.30, S, 12.16%
2.1.22. Spiro[4.5]deca-3,6-dien-2-one (20). Colorless oil;
IR (neat) 3018, 2927, 2859, 1717 (CO), 1584, 1406, 1340,
1205, 1179, 938, 802 cm21; 1H NMR d 1.60–1.86 (4H, m),
2.06 (2H, m), 2.31 (2H, d, J¼2.0 Hz), 5.37 (1H, brd,
J¼10.0 Hz), 5.82 (1H, dt, J¼10.0, 3.9 Hz), 6.08, 7.45 (each
1H, d, J¼5.5 Hz). Calcd for C10H12O: M, 148.0887. Found:
m/z 148.0887; MS m/z (%) 148 (Mþ, 83), 133 (25), 120 (71),
105 (39), 91 (100), 79 (44), 65 (18).
2.1.18. (Z)-1-(Chloro-cyclohex-2-enylidene-methane-
sulfinyl)-4-methylbenzene (18a-Z). Colorless prisms; mp
2.1.23. Spiro[4.5]deca-3,7-dien-2-one (21). Colorless oil;
IR (neat) 3026, 2919, 2842, 1714, 1588, 1439, 1408, 1189,

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T. Satoh et al. / Tetrahedron 59 (2003) 9599–9607
1
944, 796 cm21; H NMR d 1.63–1.72 (3H, m), 1.94–2.05
(1H, m), 2.16–2.28 (4H, m), 5.71, 5.77 (each 1H, brd,
J¼10.0 Hz), 6.09, 7.57 (each 1H, d, J¼5.5 Hz). Calcd for
C10H12O: M, 148.0887. Found: m/z 148.0884; MS m/z (%)
148 (Mþ, 100), 133 (12), 120 (28), 105 (11), 94 (68), 79
(20), 66 (67), 54 (95).
4.64 (2H, brs, NH2), 6.05, 6.73 (each 1H, d, J¼5.5 Hz), 6.84
(1H, d, J¼7.7 Hz), 7.00–7.04 (1H, m), 7.10 (2H, d,
J¼4.0 Hz). Calcd for C15H14N2: M, 222.1156. Found: m/z
222.1150: MS m/z (%) 222 (Mþ, 100), 207 (22), 194 (36),
180 (24), 167 (8). Anal. calcd for C15H14N2: C, 81.05; H,
6.35; N, 12.60. Found: C, 80.89; H, 6.30; N, 12.36%.
[a]2D4¼2430.5 (c 0.41, acetone; over 99% ee).
2.1.24. Spiro[4.5]deca-3,6-diene-2,8-dione (22). Colorless
plates; mp 84–858C (AcOEt–hexane); IR (KBr) 2927, 1712
(CO), 1683 (CO), 1583, 1390, 1347, 1208, 822 cm21; H
NMR d 2.09–2.26 (2H, m), 2.50 (2H, d, J¼2.4 Hz), 2.49–
2.71 (2H, m), 6.05 (1H, d, J¼10.0 Hz), 6.29 (1H, d,
J¼5.5 Hz), 6.59 (1H, d, J¼10.0 Hz), 7.57 (1H, d,
J¼5.5 Hz). Calcd for C10H10O2: M, 162.0680. Found: m/z
162.0686; MS m/z (%) 162 (Mþ, 100), 134 (99), 120 (29),
106 (85), 91 (48), 78 (85), 77 (19), 51 (22). Anal. calcd for
C10H10O2: C, 74.06; H, 6.21. Found: C, 74.04; H, 6.04%.
2.1.29. (2)-(S)-Spiro[4.5]alkenone (27). Colorless
needles; mp 108–1098C (AcOEt–hexane); IR (KBr)
2923, 1706 (CO), 1586, 1490, 1448, 1399, 1181, 817,
1
1
759 cm21; H NMR d 1.76–1.88 (2H, m), 1.92–2.05 (2H,
m), 2.52 (1H, d, J¼18.6 Hz), 2.56 (1H, d, J¼18.6 Hz),
2.81–2.90 (2H, m), 6.25 (1H, d, J¼5.5 Hz), 6.97–6.99 (1H,
m), 7.11–7.17 (3H, m), 7.54 (1H, d, J¼5.5 Hz). Calcd for
C14H14O: M, 198.1044. Found: m/z 198.1051: MS m/z (%)
198 (100), 183 (12), 169 (16), 155 (17), 141 (31), 128 (22),
115 (20). Anal. calcd for C14H14O; C, 84.81; H, 7.12.
Found: C, 84.74; H, 7.13%. [a]2D3¼2135.9 (c 0.40,
acetone).
2.1.25. (2)-Acetic acid 1-[chloro-(toluene-4-sulfinyl)-
methyl]-1,2,3,4-tetrahydronaphthalen-1-yl ester (24L).
Colorless amorphous; IR (KBr) 2940, 1747 (CO), 1492,
1451, 1367, 1234, 1089, 1063 (SO), 812, 753 cm21; H
NMR d 1.96–2.04 (1H, m), 2.00 (3H, s), 2.08–2.18 (1H,
m), 2.40 (3H, s), 2.42–2.55 (2H, m), 2.86–2.97 (2H, m),
5.32 (1H, s), 7.26–7.33 (7H, m), 7.50 (1H, d, J¼7.4 Hz).
MS m/z (%) 237 ([M2TolS(O)]þ, 20), 178 (82), 159 (100),
129 (80), 83 (64), 43 (55). [a]2D3¼25.68 (c 0.41, acetone).
1
2.1.30. 4-[Chloro-(toluene-4-sulfinyl)methylene]cyclo-
hexanone (29). The ketal 2810 (700 mg, 2.14 mmol) was
dissolved in a mixture of acetic acid (18 ml) and water
(4.5 ml) and the reaction mixture was stirred and heated at
758C for 2 h. The reaction mixture was neutralized with
10% NaOH and the whole was extracted with CHCl3 and
the organic layer was washed with water. The organic layer
was dried over MgSO4. The product was purified by silica
gel flash column chromatography to give 29 (599 mg, 99%)
as colorless needles; mp 108–1098C (AcOEt–hexane); IR
(KBr) 2970, 1711 (CO), 1085, 1053 (SO), 872, 807,
2.1.26. (2)-Acetic acid 1-[chloro-(toluene-4-sulfinyl)-
methyl]-1,2,3,4-tetrahydronaphthalen-1-yl ester (24P).
Colorless crystals; mp 111–1128C (AcOEt–hexane); IR
(KBr) 2926, 1752 (CO), 1495, 1366, 1226, 1091, 1068 (SO),
1017, 974, 820, 773, 743, 513 cm21; 1H NMR d 1.93–2.02
(1H, m), 2.10–2.19 (1H, m), 2.13 (3H, s), 2.43 (3H, s), 2.57
(1H, ddd, J¼14.7, 11.0, 4.3 Hz), 2.63 (1H, dt, J¼14.7,
4.6 Hz), 2.77 (1H, ddd, J¼16.5, 11.0, 5.5 Hz), 2.85 (1H, dt,
J¼16.5, 5.0 Hz), 5.41 (1H, s), 7.13–7.25 (3H, m), 7.34 (2H,
d, J¼8.0 Hz), 7.48 (1H, d, J¼8.0 Hz), 7.53 (2H, d,
J¼8.0 Hz). MS m/z (%) 182 (42), 140 (100), 131 (40), 91
(25). Anal. calcd for C20H21ClO3S, C, 63.73; H, 5.62; Cl,
9.41; S, 8.51. Found: C, 63.69; H, 5.49; Cl, 9.27; S, 8.48%.
[a]2D3¼2111.9 (c 0.42, acetone).
1
528 cm21; H NMR d 2.43 (3H, s), 2.50–2.64 (4H, m),
2.78 (1H, dt, J¼17.1, 7.0 Hz), 2.86–2.93 (1H, m), 3.07 (1H,
ddd, J¼15.6, 9.6, 5.5 Hz), 3.45 (1H, dt, J¼15.6, 6.1 Hz),
7.34, 7.50 (each 2H, d, J¼8.0 Hz). Calcd for C14H15ClO2S:
M, 282.0481. Found: m/z 282.0487: MS m/z (%) 282 (Mþ,
45), 265 (80), 229 (95), 223 (21), 187 (20), 139 (35), 123
(100), 105 (22), 91 (43), 79 (33), 77 (32). Anal. calcd for
C14H15ClO2S; C, 59.46; H, 5.35; Cl, 12.54; S, 11.34. Found:
C, 59.52; H, 5.32; Cl, 12.51; S, 11.32%.
2.1.31. 1-[Chloro-(4-methylene-cyclohexylidene)-
methanesulfinyl]-4-methylbenzene (30). A solution of 29
(89.6 mg, 0.32 mmol) in dry THF (1 ml) was added
dropwise to a solution of methylenetriphenylphosphorane
(0.7 mmol; prepared from n-BuLi (0.7 mmol) and methyl-
triphenylphosphonium bromide (274 mg, 0.77 mmol) in
THF (1.5 ml)) in THF at room temperature. The reaction
mixture was stirred at room temperature for 3 h and the
reaction was quenched by sat. aq. NH4Cl. The whole was
extracted with CHCl3 and washed with water. The organic
layer was dried over MgSO4. The product was purified by
silica gel flash column chromatography to give 30 (54.5 mg;
61%) as colorless crystals; mp 94–958C (AcOEt–hexane);
IR (KBr) 2941, 1651, 1491, 1438, 1087, 1058 (SO), 892,
867, 813 cm21; 1H NMR d 2.26–2.41 (3H, m), 2.41 (3H, s),
2.43–2.53 (2H, m), 2.62 (1H, ddd, J¼13.9, 7.8, 5.2 Hz),
2.86 (1H, ddd, J¼13.7, 8.7, 5.0 Hz), 3.04 (1H, ddd, J¼13.7,
7.8, 5.0 Hz), 4.80 (2H, s), 7.32, 7.48 (each 2H, d, J¼8.2 Hz).
Calcd for C15H17ClOS: M, 280.0687. Found: m/z 280.0685:
MS m/z (%) 280 (Mþ, 33), 263 (100), 227 (33), 171 (20),
139 (28), 124 (21), 105 (34), 91 (45), 77 (30), 65 (20). Anal.
2.1.27. (1)-(E)-1-[Chloro-(toluene-4-sulfinyl)methyl-
ene]-1,2,3,4-tetrahydronaphthalene
needles; mp 147.5–1488C (AcOEt–hexane); IR (KBr)
2949, 1084, 1056 (SO), 863, 815, 763, 534 cm21 1H
(25).
Colorless
;
NMR d 1.80–1.88 (2H, m), 2.41 (3H, s), 2.61–2.69, 2.71–
2.77 (each 1H, m), 2.82 (2H, t, J¼7.0 Hz), 7.24–7.32 (2H,
m), 7.31 (2H, d, J¼8 Hz), 7.37 (1H, dt, J¼6.5, 1.0 Hz), 7.47
(2H, d, J¼8.0 Hz), 7.62 (1H, d, J¼7.7 Hz). Calcd for
C18H17ClOS: M, 316.0688. Found: m/z 316.0688: MS m/z
(%) 316 (Mþ, 28), 300 (100), 265 (30), 237 (25), 207 (18),
181 (28), 141 (94), 115 (58), 91 (32). Anal. calcd for
C18H17ClOS: C, 68.23; H, 5.41; Cl, 11.19; S, 10.12. Found:
C, 68.24; H, 5.26; Cl, 11.17; S, 10.09%. [a]2D4¼þ394.6 (c
0.40, acetone).
2.1.28. (2)-(S)-Spiro[4.5]enaminonitrile (26). Colorless
needles; mp 225–2268C (AcOEt–hexane); IR (KBr) 3439,
3357, 3240 (NH), 2929, 2166 (CN), 1659, 1641, 1609, 1540,
1421, 759 cm21; 1H NMR d 1.85–1.95 (2H, m), 2.09–2.19
(2H, m), 2.83 (1H, dt, J¼16.8, 5.5 Hz), 2.90–2.96 (1H, m),

T. Satoh et al. / Tetrahedron 59 (2003) 9599–9607
9607
Spitzner, D. Synlett 2002, 1712. (h) Du, Y.; Lu, X.; Yu, Y.
J. Org. Chem. 2002, 67, 8901.
calcd for C15H17ClOS; C, 64.16; H, 6.10; Cl, 12.62; S,
11.42. Found: C, 64.32; H, 6.08; Cl, 12.53; S, 11.36%.
4. (a) Martin, S. F. Tetrahedron 1980, 36, 419. (b) Fuji, K. Chem.
Rev. 1993, 93, 2037. (c) Corey, E. J.; Guzman-Perez, A.
Angew Chem. Int. Ed. 1998, 37, 388.
2.1.32. 2-Amino-8-methylenespiro[4.5]deca-1,3-diene-1-
carbonitrile (31). Colorless plates; mp 167–1688C
(AcOEt–hexane); IR (KBr) 3435, 3345, 3237 (NH), 2935,
5. (a) Satoh, T.; Ota, H. Tetrahedron 2000, 56, 5113. (b) Satoh,
T.; Yoshida, M.; Ota, H. Tetrahedron Lett. 2001, 42, 9241.
(c) Satoh, T.; Yoshida, M.; Takahashi, Y.; Ota, H.
Tetrahedron: Asymmetry 2003, 14, 281.
1
2167 (CN), 1651, 1610, 1547, 1430, 885, 775 cm21; H
NMR d 1.53–1.57 (2H, m), 1.86 (2H, dt, J¼12.5, 4.3 Hz),
2.26 (2H, dt, J¼12.0, 4.3 Hz), 2.48 (2H, dt, J¼14.0, 4.6 Hz),
4.54 (2H, brs, NH2), 4.72 (2H, s), 6.09, 6.89 (each 1H, d,
J¼5.5 Hz). Calcd for C12H14N2: M, 186.1157. Found: m/z
186.1160: MS m/z (%) 186 (Mþ, 100), 171 (38), 131 (35),
118 (88), 91 (19). Anal. calcd for C12H14N2; C, 77.38; H,
7.58; N, 15.04. Found: C, 77.06; H, 7.36; N, 14.70.
6. (a) Satoh, T.; Oohara, T.; Ueda, Y.; Yamakawa, K.
Tetrahedron Lett. 1988, 29, 313. (b) Satoh, T.; Oohara, T.;
Ueda, Y.; Yamakawa, K. J. Org. Chem. 1989, 54, 3130.
7. Crystallographic data for 25. C18H17ClOS, M¼316.83,
orthorhombic, space group P212121 (#19), a¼8.0065(7),
3
˚
˚
b¼12.4937(11), c¼15.9413(14) A, V¼1594.6(2) A , Z¼4,
2.1.33. (6)-8-Methylspiro[4.5]deca-3,7-dien-2-one (32).
Colorless oil; IR (KBr) 2918, 1716 (CO), 1587, 1439, 1188,
795 cm21; 1H NMR d 1.61–1.71 (2H, m), 1.70 (3H, s), 1.93
(1H, brd, J¼16.8 Hz), 2.00–2.22 (3H, m), 2.16 (1H, d,
J¼18.5 Hz), 2.23 (1H, d, J¼18.5 Hz), 5.39 (1H, m), 6.07,
7.56 (each 1H, d, J¼5.5 Hz). Calcd for C11H14O: M,
162.1044. Found: m/z 162.1049: MS m/z (%) 162 (Mþ, 72),
95 (40), 91 (13), 68 (100), 67 (20).
F(000)¼664, Dcalc¼1.320 g cm23, m(Mo Ka)¼3.66 cm21
,
˚
T¼296 K, radiation¼0.71073 A, R1¼0.0620 for I.2.0s(I),
wR2¼0.1328 for all data (3648 reflections), GOF¼1.105 (219
parameters), crystal dimensions 0.35£0.10£0.10 mm3. A
quality single crystal of 25 was mounted on a glass fiber.
Diffraction data were measured on a Bruker APEX CCD-
Detector X-ray diffractometer with monochromated Mo Ka
radiation. A part of the cyclohexane methylene moiety was
treated as being disordered over two sites (C3A, C4A, C5A;
C3B, C4B, C5B), where the occupation factors of two sites
were refined and converged at 42(2) and 58(2)%, respectively.
The data reduction, structure solution and refinement, and all
the necessary computational data processes were performed
using SMART, SAINT, SHELXTL, KENX, and TEXSAN
programs. Data deposited at the Cambridge Crystallographic
Data Centre; deposition number CCDC 214890.
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific
Research No. 11640545 from the Ministry of Education,
Culture, Sports, Science and Technology, Japan, which is
gratefully acknowledged.
8. Crystallographic data for 26. C15H14N2, M¼222.28, ortho-
rhombic, space group P212121 (#19), a¼6.8893(6),
3
˚
˚
b¼11.5269(10), c¼15.5172(13) A, V¼1232.26(18) A , Z¼4,
References
F(000)¼472, Dcalc¼1.198 g cm23, m(Mo Ka)¼0.72 cm21
,
˚
T¼296 K, radiation¼0.71073 A, R1¼0.0638 for I.2.0s(I),
wR2¼0.1458 for all data (2840 reflections), GOF¼1.173 (154
parameters), crystal dimensions 0.341£0.215£0.070 mm3.
Other details are similar to those described above for 25.
Data deposited at the Cambridge Crystallographic Data
Centre; deposition number CCDC 214891.
1. Ho, T.-L. Carbocyclic Construction in Terpene Synthesis;
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Tetrahedron 2001, 57, 3845. (g) Oesterreich, K.; Klein, I.;
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(b) Martin, S. F.; Chou, T.-S. J. Org. Chem. 1978, 43, 1027.
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10. Satoh, T.; Takano, K.; Ota, H.; Someya, H.; Matsuda, K.;
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