Magnesium cyclopropylidenes generated from 1-chlorocyclopropyl phenyl sulfoxides with Grignard reagents: Their properties, and a sulfoxide version of the Doering-Moore-Skattebol reaction

Article abstract of DOI:10.1016/S0040-4020(01)00453-7

Magnesium cyclopropylidenes were generated from 1-chlorocyclopropyl phenyl sulfoxides with Grignard reagents (EtMgCl or i-PrMgCl) in THF at -78°C in high yields by a sulfoxide-magnesium exchange reaction. The generated magnesium cyclopropylidenes were found to be stable at below -60°C for at least 3 h. It was also found that the pyramidal inversion of the magnesium carbenoid was quite slow at below -60°C. When the sulfoxide-magnesium exchange reaction was conducted with phenylmagnesium chloride at 0°C, the 1-chlorocyclopropyl phenyl sulfoxides gave allenes in good to high yields.

Full text of DOI:10.1016/S0040-4020(01)00453-7

TETRAHEDRON
Pergamon
Tetrahedron 57 (2001) 5369±5375
Magnesium cyclopropylidenes generated from
1-chlorocyclopropyl phenyl sulfoxides with Grignard reagents:
their properties, and a sulfoxide version of the
Doering±Moore±Skattebol reaction
Tsuyoshi Satoh,p Toshiyuki Kurihara and Keisuke Fujita
Department of Chemistry, Faculty of Sciences, Science University of Tokyo, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Received 22 March 2001; accepted 23 April 2001
AbstractÐMagnesium cyclopropylidenes were generated from 1-chlorocyclopropyl phenyl sulfoxides with Grignard reagents (EtMgCl or
i-PrMgCl) in THF at 2788C in high yields by a sulfoxide±magnesium exchange reaction. The generated magnesium cyclopropylidenes were
found to be stable at below 2608C for at least 3 h. It was also found that the pyramidal inversion of the magnesium carbenoid was quite slow
at below 2608C. When the sulfoxide±magnesium exchange reaction was conducted with phenylmagnesium chloride at 08C, the 1-chloro-
cyclopropyl phenyl sulfoxides gave allenes in good to high yields. q 2001 Elsevier Science Ltd. All rights reserved.
Carbenes and carbenoids have been recognized as highly
reactive carbon species and are frequently used as useful
intermediates in organic synthesis.1 Cyclopropylidenes
(carbenacyclopropanes) are the carbenes or carbenoids of
cyclopropanes and are also known as interesting reactive
intermediates. Cyclopropylidenes are usually known as the
intermediates of the reaction of 1,1-dihalocyclopropanes
with alkylmetals giving allenes.2 This reaction is now called
the Doering±Moore±Skattebol reaction.3
were rearranged rapidly to allenes 3 in good to high yields
(Scheme 1).
1. Results and discussion
1.1. Synthesis of 1-chlorocyclopropyl phenyl sulfoxides
and generation of magnesium cyclopropylidenes by the
sulfoxide±magnesium exchange
Recently, we reported new methods for preparing lithium
and magnesium carbenoids4 and unstable carbanions5 by a
sulfoxide±metal exchange reaction.6 In continuation of our
study on the sulfoxide±metal exchange reaction in organic
synthesis, herein we report a new method for generation of
magnesium cyclopropylidenes 2 from 1-chlorocyclopropyl
phenyl sulfoxides 1 with Grignard reagents by the
sulfoxide±magnesium exchange reaction. The properties
and reactivity of the generated magnesium cyclopropyl-
idenes 2 were investigated, and we found that at 08C 2
In this study, ®rst of all, we selected 6 as a representative
example of 1-chlorocyclopropyl phenyl sulfoxide (Scheme
2). The ole®n 4, which was synthesized from commercially
available 4-(4-methoxyphenyl)-2-butanone by methylen-
ation with the Wittig reagent, was treated with chloromethyl
phenyl sul®de7 with 50% NaOH in the presence of benzyl-
triethylammonium chloride (TEBACl) to give cyclopropyl
phenyl sul®de 5 in 67% yield (conversion yield 94%).8
Chlorination of the sul®de 5 with NCS9 followed by oxida-
tion of the sulfur with m-chloroperoxybenzoic acid
Scheme 1.
Keywords: sulfoxides; sulfoxide±magnesium exchange; cyclopropylidenes; allenes; Doering±Moore±Skattebol reaction.
Corresponding author. Tel.: 181-3-5228-8272; fax: 181-3-3235-2214; e-mail: tsatoh@ch.kagu.sut.ac.jp
p
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(01)00453-7

5370
T. Satoh et al. / Tetrahedron 57 +2001) 5369±5375
mixture of two more polar diastereomers are somewhat
apart. We obtained the product 6 as less polar products
(expressed as 6-L; 42%) and the more polar products
(expressed as 6-P; 48%). A mixture of the two main polar
isomers 6-P was used in the following studies.
First, the a-chloro sulfoxide 6-P was treated with 2.5
equivalents of n-BuLi in THF at 2788C for 5 min (a
solution of 6-P in THF was added to a solution of n-BuLi
in THF). The starting material immediately disappeared;
however, the product was a mixture of some unknown
products, in which allene 8 was observed on TLC and the
1H NMR spectrum (see entry 1 in Table 1). The reaction
with t-BuLi gave a similar mixture of the products (entry 2).
These results suggested that the sulfoxide±lithium exchange
reaction4 took place to give lithium cyclopropylidene.
However, it was also suggested that the lithium cyclo-
propylidene was so reactive that several products including
the allene 10 were produced.
Scheme 2.
(MCPBA) gave the desired 1-chlorocyclopropyl phenyl
sulfoxide 6 in 90% yield as a mixture of diastereomers.
The product 6 has three stereogenic centers and, theoreti-
cally, four diastereomers are possible. On the silica gel TLC,
four products could be observed. The Rf-values of a spot of
a mixture of two less polar diastereomers and that of a
Next, 6-P was treated with 2.5 equivalents of EtMgCl in a
similar manner as above at 2788C for 5 min to give the
Table 1. Treatment of of 1-chlorocyclopropyl phenyl sulfoxides 6-P with 2.5 equivalents of alkylmetals under several conditions
Entry
Alkylmetal
Conditions
Electrophiles
Products (yield/%)
1
2
3
4
5
6
7
8
9
10
n-BuLi
t-BuLi
2788C, 5 min
2788C, 5 min
2788C, 5 min
2788C, 5 min
2788C, 5 min
2788C, 5 min
2788C, 1 h
278,2608C, 1 h
278,2608C, 1 h then 2608C, 3 h
2788C, 5 min
H2O
H2O
H2O
CD3OD
H2O
CD3OD
CD3OD
CD3OD
CD3OD
H2O
Complex mixturea
Complex mixturea
8-P (RˆH, 82)
9 (RˆD, 77)b
8-P (RˆH, 79)
9 (RˆD, 78)c
9 (RˆD, 80)d
9 (RˆD, 82)d
9 (RˆD, 81)d
6-P (89)
EtMgCl
EtMgCl
i-PrMgCl
i-PrMgCl
i-PrMgCl
i-PrMgCl
i-PrMgCl
PhMgCl
8-P (RˆH, trace)
11
12
13
14
PhMgCl
PhMgCl
PhMgCl
PhMgCl
2788C, 30 min
H2O
6-P (89)
8-P (RˆH, trace)
6-P (90)
2788C, 1 h
H2O
8-P (RˆH, trace)
278,2608C, 1 h
H2O
6-P (71)
8-P (RˆH, 23)
9 (RˆD, 88)e,f
10 (trace)
278,2608C, 1 h then 2608C, 6 h
CD3OD
11 (trace)
8 (RˆH, 84)f
15
PhMgCl
278,2508C, 1 h then 2508C, 3 h
H2O
10 (9)
11 (4)
16
17
18
PhMgCl
PhMgCl
PhMgCl
278,2508C, 1 h then 2508C, 3 h
08C, 10 min
CD3OD
H2O
9 (RˆD, 85)e,f
10 (9)
10 (82)
11 (14)
8 (RˆH, 5)f
08C, 10 ming
H2O
10 (85)
11 (7)
a
Some amount of the allene 10 was observed on TLC and 1H NMR spectrum of the reaction mixture. A similar result was obtained by using 1.5 eq. RLi.
D-content 91%.
D-content 93%.
D-content 95±96%.
D-content over 99%.
A mixture of two diastereomers.
1.5 Equivalents of PhMgCl was used in this experiment.
b
c
d
e
f
g

T. Satoh et al. / Tetrahedron 57 +2001) 5369±5375
5371
Scheme 3. (a) The conditions and the yield, see Table 1, entry 5. (b) The conditions and the yield, see Table 1, entry 8. (c) The conditions and the yield, see
Table 1, entry 9. (d) The ratio was determined by 1H NMR.
desul®nylated product 8-P in 82% yield without any trace of
the starting sulfoxide 6-P (entry 3). Even i-PrMgCl reacted
with 6-P at 2788C quickly to give the desul®nylated
product 8-P in good yield (entry 5). Quenching the above
two reactions with CD3OD gave the deuterated chlorocyclo-
propane 9 with over 90% deuterium incorporation (entries 4
and 6). These results showed that the intermediate of these
reactions was the magnesium cyclopropylidene 7-P4b (see
Scheme 3).
In detailed inspection of the 1H NMR spectra of the product
from the experiments in Table 1 (entrie 5, 8, and 9),
especially entry 9, we noticed that the product from 6-P
was a mixture of 8-P and 8-L (8-P:8-Lˆ5:2; see Scheme
3). We treated the 1-chlorocyclopropyl phenyl sulfoxide
6-L with i-PrMgCl under the same conditions as for 6-P
and the results are shown in the table in Scheme 3. From
the results in the table, we concluded that the con®gura-
tional stability of the magnesium cyclopropylidenes 7-P
and 7-L is high at below 2608C; however, the pyramidal
inversion of the carbenoid also slowly takes place at 2608C.
Quite interestingly, even though the starting material 6-P is
a mixture of two diastereomers, the product 8-P is a single
isomer. This result implies that the diastereomers of 6-P
must be caused by the sulfoxide stereogenic center. We
treated 6-L (a mixture of two diastereomers) with i-PrMgCl
under the same conditions to give the desul®nylated product
8-L in the same yield. The product 8-L was again a single
isomer, which is the diastereomer of 8-P. In order to deter-
mine the stereochemistry of 8-P and 8-L, NOESY spectum
of both compounds was measured. From a detailed
inspection of the spectra, we were able to determine
the unambiguous structure of 8-P and 8-L as shown in
Scheme 3. At the same time the stereochemistry of the
1-chlorocyclopropyl phenyl sulfoxides 6-P and 6-L was
determined.
As the chemical yield and the deuterium incorporation of
the sulfoxide±magnesium exchange reaction of 6 with
EtMgCl and i-PrMgCl were not satisfactory, we investi-
gated this reaction further with other Grignard reagents.
Treatment of 6-P with PhMgCl in THF at 2788C for
5 min gave mainly the starting material with a trace of
chlorocyclopropane 8-P (Table 1, entry 10). Entries 10, 11
and 12 show that 6-P hardly reacts with PhMgCl at 2788C.
The reaction temperature was then allowed to warm to
2608C for 1 h, and we found that 6-P reacted with PhMgCl
to give the desul®nylated product 8-P in 23% yield (entry
13). This result indicated that the sulfoxide±metal exchange
reaction of 6-P with PhMgCl took place at about 2608C.
The reaction mixture was further stirred at 2608C for 6 h,
and then the reaction was quenched with CD3OD (entry 14).
The chemical yield of the obtained cyclopropane 9 was
quite high and the deuterium incorporation was found to
be perfect.
To ascertain the stability of the carbenoid 7-P, the reaction
mixture was stirred at 2788C for 1 h and the reaction was
quenched with CD3OD (Table 1, entry 7). The result was
almost the same as that of entry 6. The reaction temperature
was slowly allowed to warm to 2608C over 1 h (entry 8). In
addition, the reaction was further left to stand at 2608C for
3 h (entry 9). Both reactions showed the same chemical
yield and deuterium content within experimental error. By
our study, for the ®rst time, the magnesium cyclopropyl-
idenes have been found to be stable at below 2608C for
at least 3 h.
The reaction mixture was further allowed to warm to 2508C
(entries 15 and 16). These experiments gave the chloro-
cyclopropanes 8 and 9; however, the formation of allene
10 was observed in 9% yield. From these experiments
described above, we concluded that the produced magne-
sium cyclopropylidene 7-P slowly rearranges to give allene

5372
T. Satoh et al. / Tetrahedron 57 +2001) 5369±5375
Table 2. Synthesis of 1-chlorocyclopropyl phenyl sulfoxides from ole®ns through cyclopropyl phenyl sul®des
a
The yield in parentheses is the conversion yield.
at above 2508C. As the chemical yield and deuterium
incorporation of the cyclopropane 9 was better when
PhMgCl was used instead of EtMgCl or i-PrMgCl, we
used PhMgCl throughout the studies described below.
When this reaction was carried out at 08C, the allene 10
was obtained in good yield (entries 17 and 18). The mag-
nesiumcyclopropylidenes have been thought to be the inter-
mediates of the reaction of dibromocyclopropanes with
magnesium to give allenes. The results described above
further support this assumption. It is interesting to note
that in these cases phenylated cyclopropane 11 was obtained
in low yield.
1.2. A synthesis of allenes from ole®ns via a sulfoxide
version of the Doering±Moore±Skattebol reaction
To extend the chemistry described above to a new method
for the synthesis of allenes from ole®ns with one-carbon
Table 3. Reaction of 1-chlorocyclopropyl phenyl sulfoxides with 2.5 equivalents of PhMgCl under several conditions

T. Satoh et al. / Tetrahedron 57 +2001) 5369±5375
5373
elongation, three 1-chlorocyclopropyl phenyl sulfoxides
were synthesized from the corresponding ole®ns in good
overall yields. As shown in Table 2, cyclohexadecenone
derivatives, trans-stilbene, and 4-phenyl-1-butene gave the
desired cyclopropyl phenyl sul®des 12±14 in good yields.
The chlorination and the oxidation of the sul®des gave the
1-chlorocyclopropyl phenyl sulfoxides 15±17 in almost
quantitative yields without any problem.
2.1.2. 8,8-Ethylenedioxy-17-2phenylsulfenyl)bicyclo[14.1.0]-
heptadecane 212). Colorless oil (E,Z, endo,exo mixture):
IR (neat) 2925, 2854, 1585, 1479, 1457, 1439, 1077 cm21
;
1H NMR d 0.67±1.08 (2H, m), 1.19±1.75 (25H, m), 1.97±
2.08 (2H, m), 3.86±3.94 (4H, m), 7.10 (1H, t, Jˆ7.4 Hz),
7.24±7.34 (4H, m). MS m/z (%) 402 (M1, 79), 293 (100), 99
(50). Calcd for C25H38O2S: M, 402.2592. Found: m/z
402.2604.
Next, these 1-chlorocyclopropyl phenyl sulfoxides 15±17
were treated with 2.5 equivalents of PhMgCl (Table 3).
When the reaction was quenched at below 2308C consider-
able amounts of chlorocyclopropanes 19 and 21 were
obtained. These results show that the rearrangement of the
carbenoids to the allenes was somewhat slow at below
2308C (entries 1 and 3). Treatment of these three sulfoxides
with PhMgCl at 08C for 10 min gave the desired allenes 18,
20, and 22 in good to high yields (entries 2, 4, and 5).
2.1.3. trans-2,3-Diphenyl-1-2phenylsulfenyl)cyclopropane
213). Colorless oil: IR (neat) 1600, 1582, 1496, 1478,
1
1093, 1026, 757, 732, 698 cm21; H NMR d 2.70 (1H, t,
Jˆ5.5 Hz), 2.94 (1H, dd, Jˆ8.3, 5.5 Hz), 2.97 (1H, dd,
Jˆ8.3, 5.5 Hz), 7.06±7.37 (15H, m). MS m/z (%) 302
(M1, 0.2), 193 (100), 178(18), 115 (69). Calcd for
C21H18S: M, 302.1128. Found: m/z 302.1118.
2.1.4. 1-22-Phenylethyl)-2-2phenylsulfenyl)cyclopropane
214). Colorless oil (single isomer): IR (neat) 1584, 1495,
1
In conclusion, we were able to generate, for the ®rst time,
the magnesium cyclopropylidenes from 1-chlorocyclo-
propyl phenyl sulfoxides by the sulfoxide±magnesium
exchange. The carbenoids were found to be stable at
below 2608C for several hours. By this chemistry a new
and reliable strategy for the synthesis of allenes from ole®ns
was established.
1479, 1438, 1283, 1089, 1026, 739, 699 cm21; H NMR d
0.39 (1H, dt, Jˆ6.1, 5.0 Hz), 1.19±1.32 (2H, m), 1.78(1H,
m), 1.90 (1H, m), 2.33 (1H, dt, Jˆ7.7, 5.0 Hz), 2.67 (2H, t,
Jˆ7.8 Hz) 7.10±7.37 (10H, m). MS m/z (%) 254 (M1, 30),
145 (50), 144 (48), 109 (22), 91 (100). Calcd for C17H18S:
M, 254.1127. Found: m/z 254.1127.
2.1.5. 1-Chloro-2-22-24-methoxypheny)ethyl)-2-methyl-
1-2phenylsul®nyl)cyclopropane 26). A solution of 5
(567 mg, 1.9 mmol) in CCl4 (8 ml) was stirred with
N-chlorosuccinimmide (NCS) (330 mg, 2.47 mmol) at
room temperature for 20 h. The precipitate was ®ltered off
and the solvent was evaporated to give an oil. To a solution
of the oil in CH2Cl2 (10 ml) was added m-chloroperbenzoic
acid (515 mg, 2.09 mmol) at 2508C. The reaction mixture
was stirred and allowed to warm to 2308C for over 1 h.
After being stirred for 30 min at 2308C the reaction was
quenched by adding 5% NaOH and the solution was
extracted with CH2Cl2. The organic layer was dried over
MgSO4 and the solvent was evaporated to give an oil,
which was puri®ed by silica gel column chromatography
to afford 280 mg (42%) of less polar products 6-L, and
319 mg (48%) of more polar products 6-P. 6-L: Colorless
oil (a mixture of two diastereomers): IR (neat) 1513, 1244,
1088, 1059, 1036 (SO), 747 cm21; 1H NMR d 1.14 (0.5H, d,
Jˆ7.0 Hz), 1.23 (0.5H, d, Jˆ7.0 Hz), 1.42 (1.5H, s), 1.45
(0.5H, d, Jˆ7.0 Hz), 1.48 (1.5H, s), 1.90 (0.5H, d,
Jˆ7.0 Hz), 2.04±2.26 (2H, m), 2.70±3.00 (2H, m), 3.80
(3H, s), 6.84±6.87 (2H, m), 7.14±7.19 (2H, m), 7.50±7.53
(3H, m), 7.64,7.67 (2H, m). MS m/z (%) 348 (M1, 2), 331
(14), 121 (100). Calcd for C19H21ClO2S: M, 348.0951.
Found: m/z 348.0962. 6-P: Colorless oil (a mixture of two
diastereomers): IR (neat) 1513, 1244, 1094, 1057, 1036
2. Experimental
2.1. General
1H 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% ¯uores-
cence reagent 254 and a quartz column were used for
column chromatography and the products having UV
absorption were detected by UV irradiation. In experiments
requiring a dry solvent, THF was distilled from benzo-
phenone ketyl.
2.1.1. 1-22-24-Methoxyphenyl)ethyl)-1-methyl-2-2phenyl-
sulfenyl)cyclopropane 25). A 50% aqueous NaOH solution
(5 ml) was added to a solution of 4 (1.56 g, 8.85 mmol) and
chloromethyl phenyl sul®de (1.82 g, 11.5 mmol) and
benzyltriethylammonium chloride (203 mg, 0.89 mmol) in
CH2Cl2 (3 ml) and the solution was vigorously stirred at
room temperature for 24 h. The reaction was quenched by
adding saturated aqueous NH4Cl and the solution was
extracted with CH2Cl2. The organic layer was dried over
MgSO4 and the solvent was evaporated to give an oil,
which was puri®ed by silica gel column chromatography
to afford 1.77 g (66%, conversion yield 94%) of 5 and
462 mg (30%) of the starting ole®n 4. 5: Colorless oil
(about 5:1 diastereomeric mixture); IR (neat) 1513, 1245,
1
(SO), 750 cm21; H NMR d 1.15 (0.3H, d, Jˆ7.0 Hz),
1.36 (0.7H, d, Jˆ7.0 Hz), 1.51 (0.3H, d, Jˆ7.0 Hz), 1.65
(2H, s), 1.69 (1H, s), 1.73±1.87 (1H, m), 1.89 (0.7H, d,
Jˆ7.0 Hz), 1.94±2.03 (1H, m), 2.42±2.83 (2H, m), 3.76
(2H, s), 3.78(1H, s), 6.78±6.82 (2H, m), 7.01±7.10 (2H,
m), 7.52±7.56 (3H, m), 7.67±7.71 (2H, m). MS m/z (%)
348 (M1, 2), 187 (9), 121 (100). Calcd for C19H21ClO2S:
M, 348.0948. Found: m/z 348.0944.
1
1037, 738 cm21; H NMR d 0.51 (1H, t, Jˆ5.0 Hz), 1.00
(1H, dd, Jˆ8.4, 5.0 Hz), 1.27 (2.5H, s), 1.29 (0.5H, s), 1.51
(1H, m), 1.81 (1H, m), 2.09 (1H, dd, Jˆ8.4, 5.0 Hz), 2.57±
2.76 (2H, m), 3.76 (0.5H, s), 3.79 (2.5H, s), 6.77±7.31 (9H,
m). MS m/z (%) 298 (M1, 23), 189 (44), 135 (20), 121 (100).
Calcd for C19H22OS: M, 298.1390. Found: m/z 298.1397.
2.1.6. 17-Chloro-8,8-ethylenedioxy-17-2phenylsul®nyl)-
bicyclo[14.1.0]heptadecane 215). Colorless amorphous

5374
T. Satoh et al. / Tetrahedron 57 +2001) 5369±5375
(E,Z, endo,exo mixture): IR (neat) 1455, 1444, 1088, 1058
(SO) cm21; 1H NMR d 1.18±2.31 (28H, m), 3.90±3.94 (4H,
m), 7.51±7.71 (5H, m). MS m/z (%) 452 (M1, 3), 327 (100),
291 (9). Calcd for C25H37ClO3S: M, 452.2152. Found: m/z
452.2163.
2.1.12. 3-Methyl-5-24-methoxyphenyl)-1,2-pentadiene 210).
A solution of 6-P (70 mg, 0.2 mmol) in 1 ml of dry THF was
added to a solution of PhMgCl (2.0 mol/l in THF, 0.25 ml,
0.5 mmol) in 1 ml of dry THF at 08C. The reaction mixture
was stirred at 08C for 10 min, then the reaction was
quenched with saturated aqueous NH4Cl and the whole
was extracted with ethyl acetate. The extract was dried
over MgSO4 and the solvent was evaporated to give an
oil, which was puri®ed on silica gel column chromato-
graphy to give 10 (31 mg, 82%) and 11 (7.7 mg, 14%).
10: Colorless oil: IR (neat) 1959 (allene), 1612, 1513,
2.1.7. 1-Chloro-2,3-diphenyl-1-2phenylsul®nyl)cyclopro-
pane 216). Colorless amorphous (about 1:1 mixture of two
diastereomers): IR (neat) 1603, 1498, 1445, 1090, 1056
;
(SO), 755, 697 cm21 1H NMR d 3.34 (0.5H, d,
Jˆ9.0 Hz), 3.40 (0.5H, d, Jˆ8.3 Hz), 3.55 (0.5H, d,
Jˆ8.3 Hz), 4.07 (0.5H, d, Jˆ9.0 Hz), 6.98±7.75 (15H, m).
MS m/z (%) 353 (M1, 0.2), 227 (32), 191 (74), 149 (100).
Calcd for C21H18ClOS: M, 353.0766. Found: m/z 353.0758.
;
1246, 1177, 1038 cm21 1H NMR d 1.71 (3H, t,
Jˆ3.1 Hz), 2.17±2.22 (2H, m), 2.65±2.69 (2H, m),
3.78(3H, s), 4.61 (2H, sextet, Jˆ3.2 Hz), 6.82 (2H, d,
Jˆ8.8 Hz), 7.11 (2H, d, Jˆ8.8 Hz). MS m/z (%) 188 (M1,
26), 173 (25), 121 (100). Calcd for C13H16O: M, 188.1199.
Found: m/z 188.1195. 1-(2-(4-Methoxyphenyl)ethyl)-1-
methyl-2-phenylcyclopropane 11: Colorless oil (about 1:1
mixture of two diastereomers): IR (neat) 1612, 1512, 1455,
2.1.8. 1-Chloro-2-22-phenylethyl)-1-2phenylsul®nyl)cyclo-
propane 217). Colorless oil (a mixture of diastereomers):
1
IR (neat) 1496, 1444, 1089, 1056 (SO), 747, 698 cm21; H
NMR d 1.02±1.04 (1H, m), 1.63±1.70 (1H, m), 1.64±1.95
(4H, m), 2.35±2.46 (2H, m), 7.07±7.30 (5H, m), 7.50±7.71
(5H, m). MS m/z (%) 304 (M1, 1.7), 143 (16), 126 (25), 91
(100). Calcd for C17H17ClOS: M, 304.0688. Found: m/z
304.0688.
1
1300, 1245, 1177, 1037 cm21; H NMR d 0.74±0.90 (2H,
m), 0.83 (1.5H, s), 1.25±1.32 (1H, m), 1.28 (1.5H, s), 1.57±
1.80 (1H, m), 1.89±1.97 (1H, m), 2.36±2.49 (1H, m), 2.73
(1H, m), 3.73 (1.5H, s), 3.80 (1.5H, s), 6.68±6.85 (3H, m),
7.10±7.28 (6H, m). MS m/z (%) 266 (M1, 25), 161 (23), 131
(12), 121 (100). Calcd for C19H22O: M, 266.1668. Found:
m/z 266.1660.
2.1.9. 21S*,2S*)-1-Chloro-2-22-24-methoxyphenyl)ethyl)-
2-methylcyclopropane 28-P). A solution of 6-P (70 mg,
0.2 mmol) in 1 ml of dry THF was added dropwise with
stirring to a solution of i-PrMgCl (2.0 mol/l in THF,
0.25 ml, 0.5 mmol) in dry THF (1 ml) in a ¯ame-dried
¯ask at 2788C. After being stirred for 5 min, the reaction
was quenched by adding saturated aqueous NH4Cl and the
solution was extracted with ethyl acetate. The organic layer
was dried over MgSO4 and the solvent was evaporated to
give an oil, which was puri®ed by silica gel column chro-
matography to afford 36.7 mg (82%) of 8-P. Colorless oil:
IR(neat) 1612, 1513, 1463, 1301, 1247, 1176, 1038,
2.1.13. 10,10-Ethylenedioxy-1,2-cycloheptadecadiene 218).
Colorless oil: IR (neat) 1961 (allene), 1456, 1121,
1
1076 cm21; H NMR d 1.25±1.58 (22H, m), 1.85±2.10
(4H, m), 3.91 (4H, s), 5.03±5.15 (2H, m). MS m/z (%) 292
(M1, 10), 209 (12), 155 (25), 99 (100). Calcd for C19H32O2:
M, 292.2401. Found: m/z 292.2407.
2.1.14. 17-Chloro-8,8-Ethylenedioxybicyclo[14.1.0]hep-
tadecane 219). Colorless oil (E,Z, endo,exo mixture): IR
1
821 cm21; H NMR d 0.58 (1H, dd, Jˆ6.1, 4.0 Hz), 0.86
(neat) 1459, 1351, 1272, 1199, 1127, 1077 cm21 1H
;
(1H, dd, Jˆ7.4, 6.1 Hz), 1.12 (3H, s), 1.71±1.77 (1H, m),
1.80±1.86 (1H, m), 2.61±2.67 (1H, m), 2.74±2.80 (1H, m),
2.92 (1H, dd, Jˆ7.4, 4.0 Hz), 3.79 (3H, s), 6.83 (2H, d,
Jˆ8.6 Hz), 7.13 (2H, d, Jˆ8.6 Hz). MS m/z (%) 224 (M1,
10), 121 (100). Calcd for C13H17ClO: M, 224.0966. Found:
m/z 224.0956.
NMR d 0.67±0.75 (2H, m), 1.09±2.54 (26H, m), 2.83±
2.87 (1H, m), 3.91±3.92 (4H, m). MS m/z (%) 328 (M1,
1.5), 293 (22), 292 (22), 99 (100). Calcd for C19H33ClO2: M,
328.2166. Found: m/z 328.2160.
2.1.15. 1,3-Diphenyl-1,2-propadiene 220). Colorless oil:
IR(neat) 1936 (allene), 1596, 1492, 1450, 1256, 1072,
1
2.1.10. 21R*,2S*)-1-Chloro-2-22-24-methoxyphenyl)ethyl)-
2-methylcyclopropane 28-L). Colorless oil: IR (neat) 1612,
1513, 1455, 1301, 1246, 1177, 1037, 820 cm21; 1H NMR d
0.55 (1H, dd, Jˆ6.1, 4.0 Hz), 0.86 (1H, dd, Jˆ7.7, 6.1 Hz),
1.29 (3H, s), 1.49±1.53 (2H, m), 2.63 (2H, t, Jˆ8.2 Hz),
2.84 (1H, dd, Jˆ7.7, 4.0 Hz), 3.78(3H, s), 6.81 (2H, d,
Jˆ8.4 Hz), 7.06 (2H, d, Jˆ8.4 Hz). MS m/z (%) 224 (M1,
9), 121(100). Calcd for C13H17ClO: M, 224.0967. Found:
m/z 224.0968.
1028, 793, 758, 720 cm21; H NMR d 6.58 (2H, s), 7.20±
7.36 (10H, m). MS m/z (%) 192 (M1, 100), 191 (80), 115
(15), 77 (27). Calcd for C15H12: M, 192.0938. Found: m/z
192.0949.
2.1.16. 1-Chloro-2,3-diphenylcyclopropane 221). Color-
less oil: IR (neat) 1601, 1496, 1450, 1293, 1027, 758, 742,
1
697 cm21; H NMR d 2.70±2.76 (2H, m), 3.60 (1H, dd,
Jˆ7.4, 4.4 Hz), 7.20±7.40 (10H, m). MS m/z (%) 228
(M1, 0.3), 193 (100), 115 (77), 91 (19). Calcd for
C15H13Cl: M, 228.0705. Found: m/z 228.0700.
2.1.11. 21S*,2S*)-1-Chloro-1-deuterio-2-22-24-methoxy-
phenyl)ethyl)-2-methylcyclopropane 29). Colorless oil:
IR (neat) 1612, 1513, 1465, 1301, 1244, 1176, 1037,
2.1.17. 5-Phenyl-1,2-pentadiene 222). Colorless oil: IR
1
1
820 cm21; H NMR d 0.58 (1H, d, Jˆ6.1 Hz), 0.85 (1H,
(neat) 1955 (allene), 1603, 1496, 1454, 843, 698 cm21; H
d, Jˆ6.1 Hz), 1.12 (3H, s), 1.71±1.77 (1H, m), 1.80±1.86
(1H, m), 2.61±2.67 (1H, m), 2.74±2.80 (1H, m), 3.79 (3H,
s), 6.83 (2H, d, Jˆ8.6 Hz), 7.13 (2H, d, Jˆ8.6 Hz). MS m/z
(%) 225 (M1, 10), 121 (100). Calcd for C13H16DClO: M,
225.1030. Found: m/z 225.1035.
NMR d 2.22±2.35 (2H, m), 2.73 (2H, t, Jˆ7.8 Hz), 4.66
(1H, t, Jˆ3.2 Hz), 4.68 (1H, t, Jˆ3.2 Hz), 5.15 (1H, quint,
Jˆ6.6 Hz), 7.17±7.30 (5H, m). MS m/z (%) 144 (M1, 35),
129 (79), 91 (100). Calcd for C11H12: M, 144.0938. Found:
m/z 144.0930.

T. Satoh et al. / Tetrahedron 57 +2001) 5369±5375
5375
synthesis: (a) Doering, W. von E.; LaFlamme, P. M.
Tetrahedron 1958, 2, 75. (b) Moore, W. R.; Ward, H. R.
J. Org. Chem. 1960, 25, 2073. (c) Skattebol, L. Tetrahedron
Lett. 1961, 167. (d) Moore, W. R.; Ward, H. R. J. Org. Chem.
1962, 27, 4179.
Acknowledgements
This work was supported by a Grant-in-Aid for Scienti®c
Research No. 11640545 from the Ministry of Education,
Science, Sports and Culture, Japan, which is gratefully
acknowledged.
4. (a) Satoh, T.; Itoh, N.; Gengyo, K.; Takada, S.; Asakawa, N.;
Yamani, Y.; Yamakawa, K. Tetrahedron 1994, 50, 11839.
(b) Satoh, T.; Takano, K. Tetrahedron 1996, 52, 2349.
(c) Satoh, T.; Unno, H.; Mizu, Y.; Hayashi, Y. Tetrahedron
1997, 53, 7843. (d) Satoh, T.; Takano, K.; Ota, H.; Someya,
H.; Matsuda, K.; Koyama, M. Tetrahedron 1998, 54, 5557.
(e) Satoh, T.; Kurihara, T. Tetrahedron Lett. 1998, 39, 9215.
(f) Satoh, T.; Ota, H. Tetrahedron 2000, 56, 5113.
References
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3. Some papers for the Doering±Moore±Skattebol allene