Asymmetric synthesis of both enantiomers of esters and γ-lactones from optically active 1-chlorovinyl p-tolyl sulfoxides and lithium ester enolates with the formation of a tertiary or a quaternary carbon stereogenic center at the β-position

Article abstract of DOI:10.1016/j.tetasy.2004.11.085

Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides having two different substituents at the 2-position, which were synthesized from aldehydes or unsymmetrical ketones and (R)-(-)-chloromethyl p-tolyl sulfoxide in two or three steps, with the l

Full text of DOI:10.1016/j.tetasy.2004.11.085

Tetrahedron:
Asymmetry
Tetrahedron: Asymmetry 16 (2005) 665–673
Asymmetric synthesis of both enantiomers of esters and
c-lactones from optically active 1-chlorovinyl p-tolyl sulfoxides
and lithium ester enolates with the formation of a tertiary or
a quaternary carbon stereogenic center at the b-position
Shimpei Sugiyama and Tsuyoshi Satoh*
Department of Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Received 13 October 2004; accepted 4 November 2004
Available online 26 January 2005
Abstract—Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides having two different substituents at the 2-position, which
were synthesized from aldehydes or unsymmetrical ketones and (R)-(ꢀ)-chloromethyl p-tolyl sulfoxide in two or three steps, with
the lithium enolate of tert-butyl acetate gave optically active adducts in 99% chiral induction from the sulfur stereogenic center. The
adducts were converted to optically active esters, carboxylic acids, and c-lactones, which have a tertiary or a quaternary carbon
stereogenic center at the b-position. A synthesis of optically active spiro-lactones was realized starting from 2-cyclohexenone by this
method.
Ó 2005 Elsevier Ltd. All rights reserved.
1. Introduction
nary carbon at the b-position from the adduct 4.6 The
key reaction was the addition of the lithium ester enolate
of tert-butyl acetate to 1-chlorovinyl p-tolyl sulfoxides 3,
which were derived from carbonyl compounds 1 and
chloromethyl p-tolyl sulfoxide 2, to afford the adducts
4 in almost quantitative yields (Scheme 1).
Carboxylic acids, esters, amides, and their derivatives
have long been recognized to be amongst the most
important and fundamental compounds in organic
chemistry,1 bioorganic chemistry,2,3 and synthetic or-
ganic chemistry. Innumerable studies on the preparation
and chemistry of these compounds have already been re-
ported. On the other hand, the synthesis of optically
active esters and lactones is quite interesting and
important in chemistry these days. Needless to say, the
optically active compounds are most important in the
science of drugs, bioactive compounds, and life.
We thought that if unsymmetrical ketones or aldehydes
1 and homochiral chloromethyl p-tolyl sulfoxide were
used in this reaction, optically active esters 5 and c-lac-
tones 6 could be synthesized. We recently investigated
this idea and actually were able to obtain optically active
esters, acids, and lactones with over 99% enantiomeric
excess in good chemical yields.
Control of the stereochemistry of the stereogenic carbon
of esters and lactones at the a-position is now relatively
easy. For example, chiral aldol-type reactions4 and chi-
ral substitution of the a-position of esters5 are widely
used. However, control of the stereochemistry of the ste-
reogenic carbon of esters and lactones at the b-position
is still not an easy task.
2. Results and discussion
2.1. Synthesis of optically active 1-chlorovinyl p-tolyl
sulfoxides from aldehydes and unsymmetrical ketones,
and reaction with lithium enolate of tert-butyl acetate
Recently, we reported a novel method for the synthesis
of esters 5 and lactones 6 having a tertiary or a quater-
For the substrates in this investigation, we synthesized
optically active (R)-1-chloro-4-phenyl-1-(p-tolylsulfin-
yl)-1-butene 3a and 3b and (R)-1-chloro-2-methyl-4-phen-
yl-1-(p-tolylsulfinyl)-1-butene 3c and 3d from enantio-
merically pure (R)-(ꢀ)-chloromethyl p-tolyl sulfoxide
*
Corresponding author. Tel.: +81 3 5228 8272; fax: +81 3 3235
2214; e-mail: tsatoh@ch.kagu.tus.ac.jp
0957-4166/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2004.11.085

666
S. Sugiyama, T. Satoh / Tetrahedron: Asymmetry 16 (2005) 665–673
O
TolSCH2Cl
2
R1 CH2COOC(CH3)3
R1
R2
R1
R2
Cl
LiCH2COOC(CH3)3
R1 CH2COOC(CH3)3
*
*
O
R2 CHS(O)Tol
Cl
R2 CH3
STol
O
3
1
5
4
O
R1
*
R2
O
6
Scheme 1.
(R)-27 and 3-phenylpropanal and 4-phenyl-2-butanone,
respectively. Thus, (R)-2 was treated with LDA in
THF at ꢀ65 °C followed by 3-phenylpropanal to give
adduct 7 as a mixture of two diastereomers in a quanti-
tative yield. The adduct was then treated with metha-
nesulfonyl chloride with triethylamine (TEA) in
CH2Cl2 at room temperature for 6 h to give a mixture
of vinyl sulfoxides 3a and 3b, which were separated by
silica gel column chromatography. The two-step overall
yields of 3a and 3b were 24% and 44%, respectively,
from 3-phenylpropanal (Scheme 2).
1, entries 1 and 2). Interestingly, although adducts 10a
and 10b have three stereogenic centers, only a single
product was obtained. No isomer was observed from de-
tailed inspection of their 1H NMR spectra. These results
implied that the addition reaction took place with high
1,3-asymmetric induction from the sulfoxide stereogenic
center. The enantiomeric excesses of 10a and 10b were
also confirmed to be 99% by HPLC using Chiralcel
OD as a chiral stationary column. The same reaction
with 3c and 3d also proceeded within 5 min to give the
single adducts 10c and 10d in high yields with about
99% diastereomeric excess (Table 1, entries 3 and 4).
We had no doubt that successful asymmetric synthesis
of carboxylic acids, which have a quaternary and a ter-
tiary stereogenic carbon center at the b-position could
be achieved at this stage.
The 1-chlorovinyl p-tolyl sulfoxides 3c and 3d were pre-
pared from 4-phenyl-2-butanone through the adduct 8
and its acetate 9. Finally, acetate 9 was treated with
N-lithio-2-piperidone8 to afford a 3:2 mixture of 3c
and 3d in 82% yield from 9. These were separable by sil-
ica gel column chromatography.
Next, the chlorine atom in adduct 10a was reduced with
tributyltin hydride in the presence of AIBN9 in benzene
to give 11a in high yield. The sulfinyl group in 11a was
reduced with Raney-nickel in refluxing ethanol to afford
ester 5a in a quantitative yield (see Scheme 3). Adduct
10b was also converted to the tert-butyl ester 5b via
11b, though the two-step overall yield was somewhat
lower. The enantiomeric excesses of 5a and 5b were
Initially, 5 equiv of the lithium ester enolate of tert-butyl
acetate were generated from tert-butyl acetate and LDA
in THF at ꢀ75 °C. To this solution were added 1-chlo-
rovinyl p-tolyl sulfoxides 3a and 3b. The desired addi-
tion reaction took place within 5 min to afford adducts
10a and 10b in 91% and 89%, respectively (see Table
Ph
OH
Cl
O
S
LDA
PhCH2CH2CHO
98%
MsCl / TEA
H
S
Tol
ClH2C
Tol
CH2Cl2
O
7
(R)-(-)-2
Ph
Cl
S
H
Cl
S
+
H
Ph
Tol
Tol
3b
44%
O
O
3a
24%
Ph
OH
Cl
Ph
OAc
O
S
(CH3CO)2O
LDA
PhCH2CH2COCH3
93%
H3C
S
H3C
S
Tol
Tol
ClH2C
Tol
DMAP
Pyridine
90%
Cl
O
O
9
8
(R)-(-)-2
NLi
O
Ph
Cl
S
H3C
Cl
+
H3C
Ph
S
82%
3c:3d=3:2
Tol
Tol
O
O
3d
3c
Scheme 2.

S. Sugiyama, T. Satoh / Tetrahedron: Asymmetry 16 (2005) 665–673
667
Table 1. Addition of lithium enolate of tert-butyl acetate to optically active 1-chlorovinyl p-tolyl sulfoxides
R1 CH2COOC(CH3)3
R1
R2
Cl
S
CH3COOC(CH3)3
R2
10
S
LDA / THF
-75 ºC
Tol
Tol
3
Cl
O
O
Entry
3
10
R1
R2
H
Yields (%)
De (%)a
1
2
3
4
3a
3b
3c
3d
PhCH2CH2
H
10a
91
89
86
91
99
99
99
99
PhCH2CH2
CH3
PhCH2CH2
10b
10c
10d
PhCH2CH2
CH3
Cl
S
5
3e
10e
97b
99
Tol
O
Cl
6
3f
10f
96b
99
S
Tol
O
a Diastereomeric excess (de) was determined from 1H NMR and HPLC using chiral stationary column.
b The reaction temperature was ꢀ75 to ꢀ40 °C.
Bu3SnH
AIBN
Ph
CH2COOC(CH3)3
Ph
CH2COOC(CH3)3
Ph
CH2COOC(CH3)3
CH3
Raney-Ni
H
S
H
S
benzene
94%
EtOH
97%
Tol
Tol
H
Cl
O
5a
O
11a
10a
[α]D25 = +11.6 (c 0.40, acetone)
Ph
CH2COOH
CH3
99%ee
CF3COOH
CH2Cl2
[α]D22 = +30.6 (c 0.19, benzene)
H
-50 ˚C, 97%
12a
Bu3SnH
AIBN
H
CH2COOC(CH3)3
H
CH2COOC(CH3)3
H
CH2COOC(CH3)3
CH3
Raney-Ni
benzene
84%
EtOH
87%
Ph
S
Ph
S
Ph
Tol
Tol
Cl
O
5b
O
10b
11b
[α]D26 = -11.6 (c 0.50, acetone)
H
CH2COOH
CH3
CF3COOH
CH2Cl2
[α]D25 = -32.1 (c 0.08, benzene)
{lit.10, [α]D20 = -66.1 (c 0.01, benzene)}
99%ee
Ph
-50 ˚C, 96%
12b
Scheme 3.
confirmed to be 99% by HPLC using Chiralpak AD as a
chiral stationary column.
genic center proved in some cases unsatisfactory.11 The
results described above are one of the best examples in
this category.
Finally, the tert-butyl esters 5a and 5b were treated with
trifluoroacetic acid in CH2Cl2 at ꢀ50 °C to give both 3-
methyl-5-phenylpentanoic acids 12a and 12b in quanti-
tative yields. Pyne reported that (S)-3-methyl-5-phenyl-
pentanoic acid had a negative specific rotation.10 In
our compound, carboxylic acid 12b, which was derived
from 3b, had a negative specific rotation. Thus, the
absolute configurations of all the compounds in Scheme
3 were unambiguously determined.
Previously, we reported a chiral addition reaction of
cyanomethyllithium to 1-chlorovinyl p-tolyl sulfoxides12
in which, we proposed a transition state model for the
chiral induction from the sulfoxide chiral center. At this
stage, in which the absolute configurations of all the
compounds in Scheme 3 were confirmed, we applied
the same transition state model in this investigation.
The results are shown in Scheme 4.
Conjugate addition of nucleophiles including organome-
tallic reagents to chiral vinyl sulfoxides is already
known; however, chiral induction from the sulfur stereo-
As carboxylic acid 12b has an (S)-configuration, the
absolute configuration of the b-carbon of adduct 10b
must be also S. This means that the lithium ester enolate

668
S. Sugiyama, T. Satoh / Tetrahedron: Asymmetry 16 (2005) 665–673
CH3
Ph
si
S(O)Tol
Ph
Ph
S
CH3
O
Li
H
Cl
H
Cl
3b
CH2COOH
H
H
CH2COOC(CH3)3
12b
re
10b
CH2COOC(CH3)3
Scheme 4.
should be introduced from the re face of the vinyl sulf-
oxide 3b. This result is in good accordance with the pro-
posed transition state model. Thus, the lithium cation
forms a five-membered chelate between the oxygen of
the sulfoxide and the chlorine atom. In this event, the
bulky 4-methylphenyl group strongly hinders the si face.
The lithium enolate of tert-butyl acetate was introduced
from the re face to afford 10b in very high chiral induc-
tion from the sulfoxide stereogenic center.
The same treatment of 10b afforded the enantiomer 6b,
via 13b, in somewhat higher yield. The enantiomeric ex-
cess of these two lactones was confirmed to be over 99%
by HPLC using Chiralpak AD as a chiral stationary
column.
A c-lactone having a quaternary stereogenic center at
the b-position was also synthesized starting from the ad-
duct 10d (Scheme 6). Thus, adduct 10d was treated with
TFAA as described above to give a c-lactone, which had
p-tolylsulfanyl group 13d in quantitative yield. The p-
tolylsulfanyl group was reduced with Bu3SnH to give
6d in 65% yield. Again, the enantiomeric excess was
found to be over 99% by using Chiralpak AD as a chiral
stationary column.
2.2. Synthesis of optically active lactones having a tertiary
and a quaternary carbon stereogenic center at the b-
position
Previously, we found that treatment of adducts 10 with
trifluoroacetic anhydride (TFAA) in the presence of NaI
gave c-lactones, which has a p-tolylsulfanyl group at the
c-position.6 We applied this reaction to the optically ac-
tive adducts 10a and 10b (Scheme 5). Thus, to a mixture
of 10a and NaI in acetone at ꢀ55 °C was added TFAA
to afford the desired c-lactone 13a in 60% yield. The p-
tolylsulfanyl group in 13a was reduced with Bu3SnH
to give c-lactone 6a in 63% yield.
2.3. Synthesis of optically active spiro-lactones by this
procedure
Spirocyclic compounds, which contain one carbon atom
common to two rings, are interesting in organic and
synthetic organic chemistry.13 Spirocyclic compounds
have a quaternary carbon, which is still difficult to
TFAA
NaI
Bu3SnH
AIBN
O
O
Ph
CH2COOC(CH3)3
Ph
Ph
O
O
O
H
S
acetone
60%
H
H
H
benzene
63%
Tol
Cl
O
STol
13a
6a
10a
[α]D25 = -20.5 (c 0.16, benzene)
TFAA
NaI
Bu3SnH
AIBN
O
O
H
CH2COOC(CH3)3
H
benzene
67%
acetone
86%
O
Ph
Ph
S
Ph
Tol
STol
Cl
O
6b
10b
[α]D26 = +22.8 (c 0.18, benzene)
13b
Scheme 5.
Bu3SnH
O
O
TFAA
NaI
H3C
H3C
H3C
CH2COOC(CH3)3
AIBN
benzene
65%
O
O
Ph
Ph
Ph
S
acetone
97%
Tol
Cl
O
STol
13d
6d
[α]D25 = +11.6 (c 0.36, benzene)
10d
Scheme 6.

S. Sugiyama, T. Satoh / Tetrahedron: Asymmetry 16 (2005) 665–673
669
TFAA
NaI
O
COOC(CH3)3
Cl
S
CH3COOC(CH3)3
LDA / THF
-75 ºC
acetone
70%
O
S
Tol
Tol
STol
Cl
3e
O
O
13e
10e
Bu3SnH
AIBN
O
O
benzene
65%
[α]D27 = +53.1 (c 0.23, acetone)
6e
TFAA
NaI
O
COOC(CH3)3
Cl
S
CH3COOC(CH3)3
LDA / THF
-75 ºC
Cl
acetone
83%
O
S
Tol
Tol
STol
O
O
3f
Bu3SnH
13f
10f
O
AIBN
benzene
68%
O
[α]D27 = -52.9 (c 0.54, acetone)
6f
Scheme 7.
construct.14 An even more difficult task is the enantio-
controlled synthesis of spirocycles. We extended our
procedure described above to a novel method for the
synthesis of optically active spiro-lactones (Scheme 7).
LA 500 and Burker XWIN-600 spectrometer. Elec-
tron-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 hav-
ing UV absorption were detected by UV irradiation. In
experiments requiring a dry reagent and solvent, ben-
zene, dichloromethane, N,N-diisopropylamine, and pyr-
idine were distilled from CaH2 while THF was distilled
from diphenylketyl. Acetone was dried over CaSO4
and distilled before use.
First, optically active 1-chlorovinyl p-tolyl sulfoxides 3e
and 3f were prepared from 2-cyclohexenone by the same
procedure as for the synthesis of 3c and 3d.8 The conju-
gate addition of 3e and 3f with the lithium ester enolate
of tert-butyl acetate gave again a single product in al-
most quantitative yield (see Table 1 and Scheme 7).
The enantiomeric excess of these adducts was found to
be over 99% by using Chiralcel OD as a chiral stationary
column.
4.1. (R)-(Z)-1-Chloro-4-phenyl-1-(p-tolylsulfinyl)-1-
butene 3a and the (E)-isomer 3b
The adducts were treated with TFAA in the presence of
NaI to give spirocyclic lactones having a p-tolylsulfanyl
group at the b-position (13e and 13f) in good yields.
Finally, the thioether was reduced with Bu3SnH to
afford the enantiomerically pure spiro-lactones 6e and
6f in about 65% yield.
A solution of (R)-(ꢀ)-2 (973 mg; 5.2 mmol) in 4 mL of
dry THF was added dropwise to a solution of LDA
(6.24 mmol) in 15 mL of THF at ꢀ65 °C. The solution
was stirred at ꢀ65 °C for 10 min, then 3-phenylpropanal
(0.82 mL; 6.24 mmol) was added. The reaction mixture
was stirred for 10 min and the reaction quenched by satd
aq NH4Cl after which it was extracted with CH2Cl2. The
organic layer was washed with satd aq NH4Cl and dried
over MgSO4. The solvent was evaporated to give chloro
alcohol 7 as a light yellow viscous oil (1.64 g; 98%, a
mixture of two diastereomers). IR (neat) 3351 (OH),
2925, 1086, 1047 (SO) cmꢀ1. To a solution of chloro
alcohol 7 (1.64 g; 5.1 mmol) in dry CH2Cl2 (10 mL)
was added triethylamine (5.1 mL; 38.2 mmol) followed
by methanesulfonyl chloride (1.15 mL; 15.3 mmol) with
stirring at 0 °C. The reaction mixture was stirred at 0 °C
for 10 min, then at room temperature for 6 h. The reac-
tion was quenched with water, and the whole was ex-
tracted with CH2Cl2. The organic layer was washed
successively with 10% HCl and satd NaHCO3. The usual
work-up followed by silica gel column chromatography
afforded 3a (379 mg; 24%) and 3b (680 mg; 44%).15
Compound 3a: light yellow viscous oil; IR (neat) 3027,
2924, 1596, 1495, 1455, 1089, 1063 (SO), 877,
3. Conclusion
In conclusion, we have developed a new and efficient
method for the synthesis of optically active esters and
lactones having a tertiary or a quaternary stereogenic
center at the c-position. The asymmetric induction from
the sulfur stereogenic center was found to be almost
complete and we believe that the method presented here
is useful for the synthesis of homochiral esters and
lactones.
4. Experimental
1
All melting points are uncorrected. H NMR spectra
were measured in a CDCl3 solution with JEOL JNM-

670
S. Sugiyama, T. Satoh / Tetrahedron: Asymmetry 16 (2005) 665–673
1
809 cmꢀ1; H NMR d 2.41 (3H, s), 2.66–2.70 (2H, m),
2.81–2.84 (2H, m), 6.78 (1H, t, J = 7.2 Hz), 7.18–7.46
57 °C (hexane); IR (KBr) 3029, 2924, 1601, 1494,
1
1454, 1087, 1055 (SO), 889, 808 cmꢀ1; H NMR d 2.25
(3H, s), 2.42 (3H, s), 2.56–2.61 (1H, m), 2.70–2.86
(9H, m). MS m/z (%) 304 (M+, 1), 287 (100), 91(90).
29
D
light yellow viscous oil; IR (neat) 3026, 2924, 1602,
½aꢁ ¼ ꢀ47:5 (c 0.65, acetone; 99% ee). (E)-isomer 3b:
(3H, m), 7.31–7.40 (9H, m). Anal. Calcd for
C18H19ClOS: C, 67.80; H, 6.01. Found: C, 67.62; H,
27
D
1494, 1455, 1091, 1062 (SO), 877 cmꢀ1
2.40 (3H, s), 2.78–2.84 (1H, m), 2.91–3.04 (3H, m),
;
1H NMR d
5.75. ½aꢁ ¼ þ127:3 (c 1.0, acetone; 99% ee). Compound
3d: colorless crystals; mp 64–65 °C (hexane); IR (KBr)
3031, 2934, 1594, 1492, 1455, 1080, 1054 (SO), 814,
6.32 (1H, t, J = 7.8 Hz), 7.21–7.36 (9H, m). MS m/z
27
(%) 304 (M+, 20), 197 (59), 91 (100). ½aꢁ ¼ þ215:1 (c
1
702 cmꢀ1; H NMR d 2.07 (3H, s), 2.39 (3H, s), 2.85–
2.91 (1H, m), 2.94–3.01 (2H, m), 3.15–3.21 (1H, m),
D
0.47, acetone; 99% ee).
7.08–7.38 (9H, m). Anal. Calcd for C18H19ClOS: C,
67.80; H, 6.01. Found: C, 67.73; H, 5.89.
½aꢁ ¼ þ244:4 (c 1.0, acetone; 99% ee).
4.2. (R)-(Z)-1-Chloro-2-methyl-4-phenyl-1-(p-tolylsulfin-
yl)-1-butene 3c and the (E)-isomer 3d
28
D
A solution of (R)-(ꢀ)-2 (515 mg; 2.75 mmol) in 3 mL of
dry THF was added dropwise to a solution of LDA
(3.3 mmol) in 15 mL of THF at ꢀ65 °C. The solution
was stirred at ꢀ65 °C for 10 min, and then benzylactone
(0.5 mL; 3.3 mmol) added. The reaction mixture was
stirred for 10 min and the reaction quenched with satd
aq NH4Cl. The whole was then extracted with CH2Cl2.
The organic layer was washed with satd aq NH4Cl and
dried over MgSO4. The solvent was evaporated to give
chloro alcohol 8 as crystals (861 mg; 93%; about 3:2 dia-
stereomeric mixture). IR (KBr) 3384 (OH), 2924, 1494,
4.3. (R)-(E)-1-(Chlorocyclohex-2-enylidene-methanesulfin-
yl)-4-methylbenzene 3e and the (Z)-isomer 3f
These 1-chlorovinyl p-tolyl sulfoxides were synthesized
from 2-cyclohexenone and (R)-(ꢀ)-2 according to the
procedure described above in similar yields. Compound
3e: colorless crystals; mp 80–82 °C (AcOEt–hexane); IR
(KBr) 2931, 2909, 1615, 1493, 1397, 1085, 1053 (SO),
875, 810 cmꢀ1 1H NMR d 1.70–1.76 (1H, m), 1.80–
;
1.85 (1H, m), 2.23–2.27 (2H, m), 2.41 (3H, s), 2.54–
2.64 (2H, m), 6.26 (1H, dt, J = 12.0, 4.2 Hz), 7.13 (1H,
dt, J = 12.0, 1.8 Hz), 7.31, 7.48 (each 2H, d,
J = 7.8 Hz). MS m/z (%) 266 (M+, 10), 250 (10), 218
(100), 183 (33), 139 (12), 124 (37), 123 (22), 91 (65), 79
(25), 65 (25). Calcd for C14H15ClOS: M, 266.0530.
Found: m/z 266.0529. Anal. Calcd for C14H15ClOS: C,
1
1084, 1037 (SO), 807 cmꢀ1; H NMR d 1.59 (1.8H, s),
1.65 (1.2H, s), 2.09–2.20 (2H, m), 2.42 (3H, s), 2.75–
2.83 (2H, m), 4.30 (0.6H, s), 4.35 (0.4H, s), 7.18–7.49
(9H, m). MS m/z (%) 336 (M+, 0.3), 179 (8), 140 (68),
139 (34), 105 (24), 91 (100). Calcd for C18H21ClO2S:
M, 336.0951. Found: m/z 336.0954.
63.03; H, 5.67; Cl, 13.29; S, 12.02. Found: C, 62.60; H,
30
D
5.54; Cl, 13.30, S, 12.16. ½aꢁ ¼ þ319:5 (c 1.0, acetone;
4-(Dimethylamino)pyridine (51 mg, 0.41 mmol) was
added to a solution of 8 (860 mg, 2.5 mmol) in a mixture
of acetic anhydride (3.1 mL; 31.5 mmol) and pyridine
(9.3 mL; 110 mmol). The mixture was stirred at room
temperature for 11 h. The acetic anhydride and pyridine
were evaporated under vacuum and the residue was
purified by silica gel column chromatography to give 9
(853 mg; 90%) as a colorless oil (about 3:2 diastereo-
meric mixture). IR (neat) 3026, 2929, 1732 (CO), 1495,
99% ee). Compound 3f: colorless crystals; mp 92–
93 °C (AcOEt–hexane); IR (KBr) 2957, 2924, 1614,
1
1083, 1050 (SO), 952, 818 cmꢀ1; H NMR d 1.85–1.90
(2H, m), 2.27–2.31 (2H, m), 2.41 (3H, s), 2.73 (1H,
ddd, J = 15.3, 10.5, 4.2 Hz), 3.21 (1H, ddd, J = 15.3,
6.6, 4.2 Hz), 6.34 (1H, dt, J = 12.0, 4.2 Hz). 6.56 (1H,
dt, J = 12.0, 2.4 Hz), 7.31, 7.48 (each 2H, d,
J = 8.4 Hz). MS m/z (%) 266 (M+, 73), 249 (81), 218
(42), 183 (25), 169 (13), 139 (20), 124 (40), 123 (32), 91
(100), 65 (62). Calcd for C14H15ClOS: M, 266.0530.
Found: m/z 266.0523. Anal. Calcd for C14H15ClOS: C,
1
1455, 1369, 1243, 1092, 1065 (SO), 1017, 810 cmꢀ1; H
NMR d 1.70 (1.2H, s), 1.80 (1.8H, s), 2.09 (3H, s),
2.23–2.28 (0.6H, m), 2.31–2.37 (0.4H, m), 2.41 (1.2H,
s), 2.42 (1.8H, s), 2.49–2.57 (0.6H, m), 2.61–2.66
(0.4H, m), 2.71–2.79 (2H, m), 5.27 (0.6H, s), 5.40
(0.4H, s), 7.16–7.48 (9H, m). MS m/z (%) 378 (M+,
0.6), 239 (18), 179 (23), 140 (60), 139 (32), 91 (100).
Calcd for C20H23ClO3S: M, 378.1057. Found: m/z
378.1062.
63.03; H, 5.67; Cl, 13.29; S, 12.02. Found: C, 62.89; H,
29
D
5.53; Cl, 13.05; S, 12.30. ½aꢁ ¼ þ550:4 (c 1.0, acetone;
99% ee).
4.4. (ꢀ)-tert-Butyl 3-[chloro(p-tolylsulfinyl)methyl]-5-
phenylpentanoate 10a
tert-Butyl acetate (0.064 mL; 0.48 mmol) was added to a
solution of LDA (0.48 mmol) in 4 mL of dry THF at
ꢀ78 °C with stirring. The solution was stirred for
10 min and then a solution of 3a (73 mg; 0.24 mmol)
in THF (1 mL) was added. The solution was stirred
for 5 min, then the reaction quenched by adding satd
aq NH4Cl. The whole was extracted with hexane–
AcOEt. The product was purified by silica gel column
chromatography to afford 10a (92.4 mg; 91%). Colorless
oil; IR (neat) 3027, 2929, 1732 (CO), 1598, 1367, 1154,
A solution of 9 (928 mg, 2.45 mmol) in dry THF (4 mL)
was added dropwise to N-lithio-2-piperidone (7.2 mmol)
prepared from n-BuLi (4.5 mL; 7.2 mmol) and 2-piperi-
done (730 mg, 7.2 mmol) in THF (12 mL) at 0 °C in
THF at room temperature. The reaction mixture was
stirred at room temperature for 1 h. The reaction was
quenched by satd aq NH4Cl and the whole extracted
with CHCl3 and washed with water. The organic layer
was dried over MgSO4. The solvent was evaporated
and the residue purified by silica gel column chromato-
graphy to give 625 mg (82%) of 3c and 3d as an about
3:2 mixture. Compound 3c: colorless crystals; mp 56–
1
1055 (SO), 812 cmꢀ1; H NMR d 1.45 (9H, s), 1.71–
1.77 (1H, m), 2.17–2.23 (1H, m), 2.43 (3H, s), 2.44
(1H, dd, J = 15.6, 7.8 Hz), 2.59 (1H, dd, J = 16.2,

S. Sugiyama, T. Satoh / Tetrahedron: Asymmetry 16 (2005) 665–673
671
4.8 Hz), 2.75–2.81 (2H, m), 3.08–3.12 (1H, m), 4.66 (1H,
4.9. (ꢀ)-tert-Butyl {1-[chloro(p-tolylsulfinyl)methyl]-
cyclohex-2-enyl}acetate 10f
d, J = 1.8 Hz), 7.20–7.27 (3H, m), 7.26–7.33 (4H, m),
7.67 (2H, d, J = 8.4 Hz). MS m/z (%) 420 (M+, trace),
347 (14), 188 (18), 140 (95), 129 (38), 91 (96). Calcd
Colorless oil; IR (neat) 2979, 2934, 1722 (CO), 1367,
1
for C23H29ClO3S: M, 420.1526. Found: m/z 420.1521.
1152, 1053 (SO), 812, 756 cmꢀ1; H NMR d 1.45 (9H,
32
D
½aꢁ ¼ ꢀ84:0 (c 0.15, acetone; 99% de).
s), 1.63–1.72 (1H, m), 1.75–1.81 (1H, m), 2.04–2.11
(3H, m), 2.29–2.38 (1H, m), 2.42 (3H, s), 2.65, 3.19 (each
1H, d, J = 15.9 Hz), 5.33 (1H, s), 5.71 (1H, d,
J = 10.7 Hz), 5.87–5.90 (1H, m), 7.23, 7.70 (each 2H,
d, J = 8.3 Hz). MS m/z (%) 382 (M+, 90), 309 (13), 187
4.5. (ꢀ)-tert-Butyl 3-[chloro(p-tolylsulfinyl)methyl]-5-
phenylpentanoate 10b
Colorless oil; IR (neat) 2930, 1731 (CO), 1597, 1455,
;
(15), 140 (100), 91(30). Calcd for C20H27ClO3S: M,
26
D
1368, 1258, 1152, 1055 (SO), 812 cmꢀ1
1H NMR d
382.1369. Found: m/z 382.1383. ½aꢁ ¼ ꢀ30:0 (c 0.35,
1.46 (9H, s), 1.85–1.89 (1H, m), 1.95–1.97 (1H, m),
2.38 (1H, dd, J = 16.2, 9.6 Hz), 2.44 (3H, s), 2.65 (2H,
t, J = 8.4 Hz), 2.86 (1H, dd, J = 16.2, 3.6 Hz),
3.07–3.09 (1H, m), 7.15–7.20 (3H, m), 7.25–7.29 (2H,
m), 7.33, 7.63 (each 2H, d, J = 8.4 Hz). MS m/z (%)
420 (M+, trace), 347 (8), 188 (28), 140 (62), 129
acetone; 99% de).
4.10. (ꢀ)-tert-Butyl 3-(p-tolylsulfinyl)methyl-5-phenyl-
pentanoate 11a
AIBN (10 mg; 0.06 mmol) was added to a solution of
10a (91 mg; 0.22 mmol) and Bu3SnH (0.086 mL;
0.33 mmol) in 4 mL of dry benzene. The atmosphere
in the flask was replaced with Ar, and the reaction mix-
ture stirred and refluxed for 20 min. The benzene was
evaporated, and the residue was purified by silica gel
column chromatography to afford 11a (79.6 mg; 94%)
as a colorless oil; IR (neat) 2928, 1728 (CO), 1495,
(29), 91 (94). Calcd for C23H29ClO3S: M, 420.1526.
28
D
Found: m/z 420.1526. ½aꢁ ¼ ꢀ113:6 (c 0.29, acetone;
99% de).
4.6. (ꢀ)-tert-Butyl 3-[chloro(p-tolylsulfinyl)methyl]-3-
methyl-5-phenylpentanoate 10c
Colorless oil; IR (neat) 2978, 2931, 1731 (CO), 1597,
1455, 1367, 1219, 1155, 1054 (SO), 812 cmꢀ1
1455, 1367, 1150, 1045 (SO), 810 cmꢀ1 1H NMR d
;
;
1H
1.44 (9H, s), 1.76–1.83 (1H, m), 1.91–1.98 (1H, m),
2.39–2.42 (1H, m), 2.42 (3H, s), 2.39, 2.52 (each 1H,
dd, J = 12, 6 Hz), 2.63–2.66 (2H, m), 2.77, 2.95 (each
1H, dd, J = 12, 5.4 Hz), 7.13–7.28 (5H, m), 7.31, 7.51
(each, 2H, d, J = 7.8 Hz). MS m/z (%) 386 (M+, 4),
370 (15), 369 (9), 313 (68), 191 (23), 173 (12), 140 (76),
NMR d 1.48 (9H, s), 1.51 (3H, s), 1.99–2.02 (2H, m),
2.43 (3H, s), 2.58–2.63 (1H, m), 2.66–2.71 (1H, m),
2.83, 3.07 (each 1H, d, J = 15.6 Hz), 5.12 (1H, s),
7.16–7.30 (5H, m), 7.32, 7.74 (each 2H, d, J = 7.8 Hz).
MS m/z (%) 434 (M+, trace), 361 (12), 203 (15), 140
(99), 91 (72). Calcd for C24H31ClO3S: M, 434.1682.
129 (100), 91 (96). Calcd for C23H30O3S: M, 386.1916.
Found: m/z 386.1923. ½aꢁ ¼ ꢀ94:3 (c 0.22, acetone).
28
D
29
D
Found: m/z 434.1695. ½aꢁ ¼ ꢀ44:5 (c 0.85, acetone;
99% de).
4.11. (ꢀ)-tert-Butyl 3-(p-tolylsulfinyl)methyl-5-phenyl-
4.7. (ꢀ)-tert-Butyl 3-[chloro(p-tolylsulfinyl)methyl]-3-
pentanoate 11b
methyl-5-phenylpentanoate 10d
Colorless oil; IR (neat) 2978, 2923, 1724 (CO), 1495,
1455, 1367, 1150, 1045 (SO), 810, 751 cmꢀ1 1H
;
Colorless oil; IR (neat) 2976, 2926, 1718 (CO), 1597,
;
1491, 1458, 1364, 1160, 1055 (SO), 812 cmꢀ1
1H
NMR d 1.43 (9H, s), 1.78–1.81(2H, m), 2.39–2.44 (1H,
m), 2.41 (3H, s), 2.55 (2H, d, J = 6 Hz), 2.58–2.64 (1H,
m), 2.66–2.71 (1H, m), 2.88 (2H, d, J = 7.2 Hz), 7.14–
7.27 (5H, m), 7.31, 7.48 (each 2H, d, J = 8.4 Hz). MS
m/z (%) 386 (M+, 3), 370 (20), 369 (9), 313 (68), 191
(23), 173 (13), 140 (73), 129 (99), 91 (98). Calcd
NMR d 1.42 (3H, s), 1.47 (9H, s), 2.19, 2.29 (each 1H,
dt, J = 9.6, 5.4 Hz), 2.42 (3H, s), 2.67, 3.07 (each 1H,
d, J = 15.6 Hz), 2.68, 2.75 (each 1H, dt, J = 12.6,
5.4 Hz), 5.21 (1H, s), 7.18 (1H, m), 7.23–7.26 (2H, m),
7.28–7.31 (4H, m), 7.72 (2H, d, J = 8.4 Hz). MS
m/z (%) 434 (M+, 0.5), 361 (13), 203 (20), 140
for C23H30O3S: M, 386.1916. Found: m/z 386.1927.
27
D
(100), 91 (69). Calcd for C24H31ClO3S: M, 434.1682.
½aꢁ ¼ ꢀ110:9 (c 0.30, acetone).
28
D
Found: m/z 434.1689. ½aꢁ ¼ ꢀ117:0 (c 0.06, acetone;
99% de).
4.12. (R)-(+)-tert-Butyl 3-methyl-5-phenylpentanoate 5a
4.8. (ꢀ)-tert-Butyl {1-[chloro(p-tolylsulfinyl)methyl]-
A solution of 11a (82 mg; 0.21 mmol) and excess of
Raney-Ni in 8 mL of EtOH was stirred and refluxed
for 15 min. The Raney-Ni was filtered off, and the fil-
trate was evaporated to give a residue, which was puri-
fied by silica gel column chromatography to give 5a
(50.4 mg; 97%) as a colorless oil; IR (neat) 2975, 2931,
cyclohex-2-enyl}acetate 10e
Colorless oil; IR (neat) 2978, 2933, 1723 (CO), 1367,
1
1151, 1056 (SO), 812, 756 cmꢀ1; H NMR d 1.45 (9H,
s), 1.68–1.78 (3H, m), 2.05–2.08 (2H, m), 2.11–2.16
(1H, m), 2.42 (3H, s), 2.68, 2.83 (each 1H, d,
J = 15.3 Hz), 5.20 (1H, s), 5.88–5.95 (2H, m), 7.31,
7.69 (each 2H, d, J = 8.0 Hz). MS m/z (%) 382 (M+,
90), 309 (10), 187 (15), 151 (45), 140 (100), 105 (35), 91
1731 (CO), 1455, 1367, 1147 cmꢀ1 1H NMR d 1.00
;
(3H, d, J = 7.0 Hz), 1.44 (9H, s), 1.47–1.69 (2H, m),
1.94–2.03 (1H, m), 2.05–2.10 (1H, m), 2.23–2.28 (1H,
m), 2.56–2.65 (2H, m), 7.13–7.28 (5H, m). MS m/z
(%) 248 (M+, 3), 192 (49), 174 (37), 131 (60), 91 (100).
Calcd for C16H24O2: M, 248.1775. Found: m/z
(58). Calcd for C20H27ClO3S: M, 382.1369. Found: m/z
26
D
382.1371. ½aꢁ ¼ ꢀ29:2 (c 0.40, acetone; 99% de).

672
S. Sugiyama, T. Satoh / Tetrahedron: Asymmetry 16 (2005) 665–673
25
248.1773. ½aꢁ ¼ þ11:6 (c 0.40, acetone). (S)-(ꢀ)-5b:
stirred and refluxed for one day. The benzene was
evaporated and the residue purified by silica gel col-
umn chromatography to give 6a (37 mg; 63%) as a
colorless oil; IR (neat) 2925, 1777 (CO), 1172, 1022,
D
26
D
½aꢁ ¼ ꢀ11:6 (c 0.50, acetone).
4.13. (R)-(+)-3-Methyl-5-phenylpentanoic acid 12a
751, 701 cmꢀ1 1H NMR d 1.78–1.87 (2H, m), 2.21
;
Trifluoroacetic acid (TFA) (0.12 mL; 0.6 mmol) was
added to a solution of 5a (50 mg; 0.20 mmol) in 5 mL
of CH2Cl2 at ꢀ50 °C. The reaction mixture was stirred
for 30 min and the reaction quenched by adding satd
aq NaHCO3. The whole was extracted with CH2Cl2
and the aqueous layer washed with CH2Cl2. The aque-
ous layer was acidified with 10% HCl and extracted with
CH2Cl2. The organic solvent was evaporated to give
12a (37 mg; 97%) as a colorless oil; IR (neat) 2929,
(1H, dd, J = 16.8, 7.8 Hz), 2.55 (1H, sep, J = 7.2 Hz),
2.60–2.68 (3H, m), 3.94 (1H, dd, J = 9.0, 7.2 Hz), 4.40
(1H, dd, J = 9.0, 7.8 Hz), 7.15–7.31 (5H, m). MS m/z
(%) 190 (M+, 42), 159 (19), 130 (12), 104 (48),
91 (100), 65 (11). Calcd for C12H14O2: M, 190.0992.
25
D
Found: m/z 190.0990. ½aꢁ ¼ ꢀ20:5 (c 0.16, benzene;
25
99% ee). (S)-(+)-6b: ½aꢁ ¼ þ22:8 (c 0.18, benzene; 99%
D
ee).
1706 (CO), 1455, 1304, 943 cmꢀ1
;
1H NMR d 1.04
4.17. 4-Methyl-4-(2-phenylethyl)-5-(p-tolylsulfanyl)-
dihydrofuran-2-one 13d
(3H, d, J = 6.8 Hz), 1.50–1.58 (1H, m), 1.66–1.73 (1H,
m), 2.03 (1H, octet, J = 7.0 Hz), 2.17 (1H, dd,
J = 15.0, 8.0 Hz), 2.41 (1H, dd, J = 15.0, 5.8 Hz), 2.57–
2.71 (2H, m), 7.18–7.29 (5H, m). MS m/z (%) 192
(M+, 25), 174 (23), 132 (14), 117 (15), 105 (25), 91
Colorless oil (about 7:3 diastereomeric mixture); IR
1
(neat) 2926, 1790 (CO), 1495, 1179, 957, 812 cmꢀ1; H
NMR d 1.31 (3H, s), 1.77–1.82 (1H, m), 1.98–2.02
(1H, m), 2.40–2.49 (2H, m), 2.54–2.59 (1H, m), 2.72–
2.79 (1H, m), 5.41 (0.7H, s), 5.45 (0.3H, s), 7.13–7.46
(9H, m). MS m/z (%) 326 (M+, 3), 203 (25), 157 (12),
143 (79), 124 (22), 105 (11), 91 (100), 77 (9). Calcd for
C20H22O2S: M, 326.1338. Found: m/z 326.1330.
(100), 77 (11). Calcd for C12H16O2: M, 192.1148. Found:
22
D
m/z 192.1147. ½aꢁ ¼ þ30:6 (c 0.19, benzene). (S)-(ꢀ)-
25
12b: ½aꢁ ¼ ꢀ32:1 (c 0.08, benzene).
D
4.14. 4-(2-Phenylethyl)-5-(p-tolylsulfanyl)dihydrofuran-2-
one 13a
4.18. (S)-(+)-4-Methyl-4-(2-phenylethyl)dihydrofuran-2-
one 6d
TFAA (0.48 mL; 2.6 mmol) was added dropwise with
stirring to a suspension of 10a (217 mg; 0.52 mmol)
and NaI (394 mg; 2.6 mmol) in 5 mL of dry acetone at
ꢀ55 °C for 5 min and the reaction quenched by satd
aq NaHCO3 and satd aq Na2SO3. The whole was ex-
tracted with ether–benzene. The organic layer was
washed with satd aq NaHCO3 and dried over MgSO4.
The solvent was evaporated, and the residue purified
by silica gel column chromatography to give 13a
(97 mg; 60%) as a colorless oil (about 3:2 diastereomeric
mixture); IR (neat) 3026, 2922, 2859, 1783 (CO), 1495,
Colorless oil; IR (neat) 2919, 1774 (CO), 1495, 1176,
1078, 812 cmꢀ1 1H NMR d 1.26 (3H, s), 1.79–1.82
;
(2H, m), 2.31, 2.43 (each 1H, d, J = 17.4 Hz), 2.61–
2.64 (2H, m), 3.99, 4.07 (each 1H, d, J = 9 Hz),
7.17–7.31 (5H, m). MS m/z (%) 204 (M+, 45), 173 (31),
144 (9), 129 (12), 104 (48), 91 (100), 77 (8). Calcd
for C13H16O2: M, 204.1148. Found: m/z 204.1144.
25
D
½aꢁ ¼ þ11:6 (c 0.36, benzene; 99% ee).
1
1456, 1144, 957, 812 cmꢀ1; H NMR d 1.72–1.77 (1H,
4.19. 1-(p-Tolylsulfanyl)-2-oxaspiro[4.5]dec-6-en-3-one
13e
m), 2.34 (3H, s), 2.54–2.81 (6H, m), 5.34 (0.6H, d,
J = 6.0 Hz), 5.78 (0.4H, d, J = 6.0 Hz). 7.12–7.45 (9H,
m). MS m/z (%) 312 (M+, 25), 189 (19), 143 (17), 129
(100), 124 (35), 91 (68). Calcd for C19H20O2S: M,
312.1182. Found: m/z 312.1160.
Colorless oil (about 1:1 diastereomeric mixture); IR
(neat) 2929, 1790 (CO), 1493, 1197, 1156, 959,
1
812 cmꢀ1; H NMR d 1.57–2.12 (6H, m), 2.34 (3H, s),
2.43, 2.58 (each 0.5H, d, J = 17 Hz), 2.45, 2.69 (each
0.5H, d, J = 17.5 Hz), 5.45 (0.5H, s), 5.47 (0.5H, s),
5.56, 5.73 (each 0.5H, d, J = 10 Hz), 5.87–5.91 (0.5H,
m), 5.97–6.00 (0.5H, m), 7.14 (2H, d, J = 6.5 Hz),
7.42–7.44 (2H, m). MS m/z (%) 274 (M+, 21), 151
(100), 133 (20), 109 (18), 94 (24), 81 (20), 79 (41). Calcd
for C16H18O2S: M, 274.1026. Found: m/z 274.1026.
4.15. 4-(2-Phenylethyl)-5-(p-tolylsulfanyl)dihydrofuran-2-
one 13b
Colorless oil (about 5:1 diastereomeric mixture); IR
(neat) 3026, 2924, 1790 (CO), 1495, 1455, 1205, 1149,
958, 813 cmꢀ1 1H NMR d 1.71–1.77 (1H, m), 2.34
;
(3H, s), 2.33–2.46 (2H, m), 2.54–2.79 (4H, m), 5.34
(0.83H, d, J = 6.0 Hz), 5.78 (0.17H, d, J = 6.6 Hz),
7.11–7.67 (9H, m). MS m/z (%) 312 (M+, 9), 189 (18),
143 (20), 129 (100), 91 (91), 77 (11). Calcd for
C19H20O2S: M, 312.1183. Found: m/z 312.1188.
4.20. 1-(p-Tolylsulfanyl)-2-oxaspiro[4.5]dec-6-en-3-one
13f
Colorless oil (about 3:2 diastereomeric mixture); IR
(neat) 2928, 1790 (CO), 1493, 1179, 1156, 958 cmꢀ1
;
4.16. (R)-(ꢀ)-4-(2-Phenylethyl)dihydrofuran-2-one 6a
1H NMR d 1.56–2.15 (6H, m), 2.34 (3H, s), 2.43, 2.59
(each 0.4H, d, J = 18 Hz), 2.46, 2.69 (each 0.6H, d,
J = 18 Hz), 5.46 (0.6H, s), 5.48 (0.4H, s), 5.56 (0.4H,
d, J = 9.6 Hz), 5.73 (0.6H, d, J = 10.2 Hz), 5.87–5.92
(0.4H, m), 5.97–6.02 (0.6H, m), 7.14 (2H, d,
J = 7.8 Hz), 7.43–7.46 (2H, m). MS m/z (%) 274 (M+,
AIBN (51 mg; 0.31 mmol) was added to a solution of
13a (97 mg; 0.31 mmol) and Bu3SnH (0.33 mL;
1.24 mmol) in 7 mL dry benzene. The atmosphere in
the flask was replaced with Ar, and the reaction mixture

S. Sugiyama, T. Satoh / Tetrahedron: Asymmetry 16 (2005) 665–673
673
3. Recent monograph and reviews for the chemistry and
synthesis of b-amino acids: (a) Enantioselective Synthesis
of b-Amino Acids; Juaristi, E., Ed.; Wiley-VCH: New
York, 1997; (b) Palomo, C.; Aizpurua, J. M.; Ganboa, I.;
Oiarbide, M. Synlett 2001, 1813; (c) Liu, M.; Sibi, M. P.
Tetrahedron 2002, 58, 7991.
23), 151 (100), 123 (23), 109 (18), 94 (27), 81 (28), 79
(57). Calcd for C16H18O2S: M, 274.1025. Found: m/z
274.1019.
4.21. (R)-(+)-2-Oxaspiro[4.5]dec-6-en-3-one 6e
4. Heathcock, C. H. The Aldol Addition Reaction. In
Asymmetric Synthesis; Morrison, J. D., Ed.; Academic:
Orland, 1984; Vol. 3, Part B, pp 111–212.
Colorless oil; IR (neat) 2928, 1780 (CO), 1417,
1216, 1168, 1020, 840 cmꢀ1 1H NMR d 1.61–1.67
;
(4H, m), 2.02–2.05 (2H, m), 2.36, 2.50 (each 1H, d,
J = 17.4 Hz), 4.02, 4.08 (each 1H, d, J = 9.0 Hz),
5.51 (1H, d, J = 9.6 Hz), 5.86–5.88 (1H, m). MS m/z
(%) 152 (M+, 10), 124 (8), 94 (100), 79 (72). Calcd
5. Some recent papers concerning this chemistry: (a) Shioiri,
T. Farumashia 1997, 33, 599; (b) Horikawa, M.; Busch-
Petersen, J.; Corey, E. J. Tetrahedron Lett. 1999, 40, 3843;
(c) Nelson, A. Angew. Chem., Int. Ed. 1999, 38, 1583; (d)
Ooi, T.; Kameda, M.; Tannai, H.; Maruoka, K. Tetrahe-
dron Lett. 2000, 41, 8339; (e) Trost, B. M.; Jiang, C. Org.
Lett. 2003, 5, 1563; (f) Ooi, T.; Maruoka, K. J. Synth. Org.
Chem. Jpn. 2003, 61, 1195; (g) Ooi, T.; Uematsu, Y.;
Maruoka, K. Tetrahedron Lett. 2004, 45, 1675.
6. (a) Satoh, T.; Sugiyama, S.; Ota, H. Tetrahedron Lett.
2002, 43, 3033; (b) Satoh, T.; Sugiyama, S.; Kamide, Y.;
Ota, H. Tetrahedron 2003, 59, 4327.
for
C9H12O2:
M,
152.0835.
Found:
m/z
27
D
152.0832. ½aꢁ ¼ þ53:1 (c 0.23, acetone). (S)-(ꢀ)-6f:
27
½aꢁ ¼ ꢀ52:9 (c 0.54, acetone).
D
Acknowledgements
This work was supported by a Grant-in-Aid for Scien-
tific Research from the Ministry of Education, Culture,
Sports, Science and Technology, Japan, which is grate-
fully acknowledged.
7. Satoh, T.; Oohara, T.; Ueda, Y.; Yamakawa, K. J. Org.
Chem. 1989, 54, 3130.
8. Satoh, T.; Kawashima, T.; Takahashi, S.; Sakai, K.
Tetrahedron 2003, 59, 9599.
9. (a) Ramaiah, M. Tetrahedron 1987, 43, 3541; (b) Satoh,
T.; Sato, T.; Oohara, T.; Yamakawa, K. J. Org. Chem.
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References
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amides, lactones, and their derivatives: (a) Patai, S. The
Chemistry of Carboxylic Acids and Esters; John Wiley and
Sons: London, 1969; (b) Zabicky, J. The Chemistry of
Amides; John Wiley and Sons: London, 1970; (c) Patai, S.
The Chemistry of Acid Derivatives; John Wiley and Sons:
Chichester, 1979; Parts 1 and 2; (d) Comprehensive
Organic Chemistry; Sutherland, I. O., Ed.; Pergamon:
Oxford, 1979; Vol. 2, Part 9; (e) Patai, S. The Chemistry of
Acid Derivatives; John Wiley and Sons: Chichester, Parts
1 and 2.
11. (a) Posner, G. H. Addition of Organometallic Reagents to
Chiral Vinyl Sulfoxides. In Asymmetric Synthesis; Morri-
son, J. D., Ed.; Academic: New York, 1983; Vol. 2, Part
A, pp 225–241; (b) Mikolajczk, M.; Drabowicz, J.;
Kielbasinski, P.. Chiral Sulfur Reagents; CRC: New York,
1997; pp 144–194; (c) Westwell, A. D.; Rayner, C. M. In
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Aspects; Page, P., Ed.; Academic: San Diego, 1998; pp
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12. Satoh, T.; Yoshida, M.; Takahashi, Y.; Ota, H. Tetrahe-
dron: Asymmetry 2003, 14, 281.
2. Recent monographs and reviews for the chemistry and
synthesis of a-amino acids: (a) Chemistry and Biochemistry
of the Amino Acids; Barrett, G. C., Ed.; Chapman and
Hall: London, 1985; (b) Williams, R. M. Synthesis of
Optically Active a-Amino Acids; Pergamon: Oxford, 1989;
(c) Cativiela, C.; Diaz-de-Villegas, M. D. Tetrahedron:
Asymmetry 2000, 11, 645; (d) Beller, M.; Eckert, M.
Angew. Chem., Int. Ed. 2000, 39, 1010.
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Chem. Rev. 1993, 93, 2037; (c) Corey, E. J.; Guzman-
Perez, A. Angew. Chem., Int. Ed. 1998, 37, 388; (d)
Christoffers, J.; Mann, A. Angew. Chem., Int. Ed. 2001, 40,
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15. Satoh, T.; Ota, H. Tetrahedron 2000, 56, 5113.