A synthesis of di- and tri-substituted β,γ-unsaturated esters from aldehydes by the magnesium carbenoid 1,2-CH and 1,2-CC insertion as the key reaction

Article abstract of DOI:10.1016/j.tet.2008.11.013

Addition reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from aldehydes, with lithium enolate of tert-butyl acetate at -78 °C in THF gave adducts in high yields. Treatment of these adducts with Grignard reagents resulted in the formation

Full text of DOI:10.1016/j.tet.2008.11.013

Tetrahedron 65 (2009) 613–627
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A synthesis of di- and tri-substituted b,g-unsaturated esters from aldehydes
by the magnesium carbenoid 1,2-CH and 1,2-CC insertion as the key reaction
*
Hironori Yamashita, Tsuyoshi Satoh
Department of Chemistry, Faculty of Science, Tokyo University of Science, Ichigaya-funagawara-machi 12, Shinjuku-ku, Tokyo 162-0826, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 9 October 2008
Received in revised form 6 November 2008
Accepted 6 November 2008
Available online 12 November 2008
Addition reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from aldehydes, with lithium
enolate of tert-butyl acetate at ꢀ78 ꢁC in THF gave adducts in high yields. Treatment of these adducts
with Grignard reagents resulted in the formation of magnesium carbenoids via the sulfoxide–magnesium
exchange reaction. When the adducts were derived from alkyl aldehydes or electron-deficient aromatic
aldehydes, carbenoid 1,2-CH insertion reaction took place from the magnesium carbenoids to afford
b
,
g
-unsaturated butyric esters having a substituent at the
ducts were derived from electron-rich aromatic aldehydes, carbenoid 1,2-CC insertion reaction took
place from the magnesium carbenoids to give -unsaturated butyric esters having the aromatic group
at the -position. Highly stereospecific 1,2-CC insertion reactions were observed in the latter reactions.
When the addition reactions were quenched with iodoalkanes, the alkylated adducts were obtained in
quantitative yields. Tri-substituted -unsaturated esters, or in some case -unsaturated esters, were
obtained by the treatment of the alkylated adducts with EtMgCl. These procedures provide a good way
b-position. On the other hand, when the ad-
Keywords:
Magnesium carbenoid
Sulfoxide-magnesium exchange reaction
b,g-Unsaturated ester
1,2-CH insertion
1,2-CC insertion
b,g
g
b,
g
g,d
for a new synthesis of di- and tri-substituted
carbon–carbon bond-formations.
b
,g
-unsaturated esters from aldehydes with two or three
Ó 2008 Elsevier Ltd. All rights reserved.
1. Introduction
esters.8 Reductive deconjugation of
a-bromo a,b-unsaturated
esters.9 Modified Knoevenagel condensation10 and others.11
Recently, we are interested in the development of new synthetic
methods utilizing magnesium carbenoids as the key inter-
mediates.12 In continuation of the investigation, we found that the
reaction of 1-chloroalkyl phenyl sulfoxide having a tertiary carbon
next to the carbon bearing a sulfinyl group 1 with i-PrMgCl resulted
in the formation of olefin 3 by the 1,2-CH insertion of magnesium
carbenoid intermediate 2 (Scheme 1).13 Stimulated by this result,
we expected that the reaction of esters having a tertiary carbon at
Carboxylic acids and their derivatives are one of the most
important and fundamental compounds in organic, synthetic or-
ganic,1 and bioorganic chemistry.2 In synthetic organic chemistry,
a
,b
-unsaturated and
b,g-unsaturated carboxylic acids are more
versatile compounds compared with the saturated ones.
Unsaturated carboxylic acids and their derivatives are usually
synthesized from saturated carboxylic acid derivatives by, for
a,b-
example, sulfenylation or selenenylation of the a-carbon followed
by oxidation and syn-elimination.3 From aldehydes and ketones,
the
b
-position and chlorine and a sulfinyl group at the
g-position 4
Horner–Wadsworth–Emmons reaction4 with two-carbon elonga-
with i-PrMgCl results in the formation of b,g-unsaturated esters 6
tion was extensively used. Thus, the synthesis of
a
,b
-unsaturated
via the magnesium carbenoid intermediates 5.
carboxylic acids and their derivatives is thought to be quite easy.
In contrast to this, no universal method for the synthesis of
We studied above-mentioned idea and indeed we could develop
a new method for a synthesis of b,g-unsaturated esters (11, 12, and
b
,
g
-unsaturated carboxylic acid derivatives has been reported.
Methods so far reported for the synthesis of -unsaturated
carboxylic acids and their derivatives are as follows. One-carbon
elongation of
-unsaturated esters or aldehydes.5 Deconjugative
protonation of
-unsaturated esters.6 Photo deconjugation of
unsaturated esters.7 Deconjugative alkylation of
-unsaturated
15 in Scheme 2) from aldehydes. The essence of this study is as
follows. Thus, 1-chlorovinyl p-tolyl sulfoxides 7 were derived from
aldehydes with chloromethyl p-tolyl sulfoxide in two steps in good
yields.14 Addition reaction of 7 with lithium enolate of tert-butyl
b,g
a,b
a,
b
a
,b
-
acetate resulted in the formation of a-sulfinyl lithium carbenoid
a
,b
intermediate 8. Quenching 8 with water gave adducts 9 in high
yield.14b Quenching 8 with iodoalkanes gave alkylated adducts 13 in
quantitative yields.
Treatment of adducts 9 with Grignard reagent gave magnesium
carbenoid intermediates 10, from which b,g-unsaturated esters 11
* Corresponding author. Tel.: þ81 3 5228 8272; fax: þ81 3 5261 4631.
E-mail address: tsatoh@rs.kagu.tus.ac.jp (T. Satoh).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.11.013

614
H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
CH2OTHP
CH2OTHP
H
CH2OTHP
i-PrMgCl
1,2-CH insertion
Lit. 13
H
H3C
H
H3C
Cl
H
S(O)Ph
Cl
H3C
H
MgCl
H
3
2
1
CH2COOR
H
CH2COOR
Cl
CH2COOR
Cl
H
i-PrMgCl
H
R1
R1
R1
H
H
H
S(O)Ar
MgCl
6
4
5
Scheme 1.
t
CH2COO Bu
R1
S(O)Tol
Cl
t
TolS(O)CH2Cl
in two steps
H
LiCH2COO Bu
R1CHO
Cl
Li
R1
H
7
S(O)Tol
8
t
t
t
CH2COO Bu
CH2COO Bu
CH2COO Bu
Cl
H+
H
R1
H
RMgX
1,2-CH insertion
β
H
Cl
R1
H
R1
β
γ
γ
H
H
H
S(O)Tol
MgX
11
9
t
Stereospecific
1,2-CC insertion
t
CH2COO Bu
CH2COO Bu
H
R1
β
H
Cl
γ
R1
H
MgX
12
10
t
t
Stereoselective
1,2-CH insertion
t
CH2COO Bu
CH2COO Bu
CH2COO Bu
R2CH2I
H
R1
RMgX
H
R1
β
Cl
H
Cl
R1
β
δ
γ
R2=H
γ
CH2R2
S(O)Tol
CH2R2
MgX
CH3
15
13
t
t
CH2COO Bu
CH2COO Bu
H
H
R1
γ
Cl
H
1,2-CH insertion
R1
R2
H
R2
δ
H
MgX
H
16
14
Scheme 2.
or 12 were obtained by 1,2-CH insertion or stereospecific 1,2-CC
insertion reaction, respectively.15 On the other hand, treatment of 13
with Grignard reagent afforded magnesium carbenoid intermediates
addition reaction proceeded in a highly stereospecific manner, as
reported in the previous papers,14b,16 and the structure of 19a and
20a was determined to be (3S
*
,4R
*
*
,SS )-tert-butyl 4-chloro-3-(2-
14, from which
16 were obtained by 1,2-CH insertion. These procedures offer a novel
method for a synthesis of -unsaturated esters. Details of this study
and the mechanisms and stereochemistry of this reaction are
described.
b
,
g
-unsaturated esters 15, and
g
,
d
-unsaturated esters
phenylethyl)-4-(p-tolylsulfinyl)butyrate and (3R
respectively, as shown in Table 1.
*
,4R
*
,SS )-isomer,
*
b
,
g
Based on our experiences,13 the adduct 19a was first treated
with 1.7 equiv of i-PrMgCl in toluene at room temperature; how-
ever, the treatment gave the expected olefin 21a in only 5% yield
with several unknown products. The treatment of 20a with
i-PrMgCl gave only a complex mixture. We tried to find the opti-
mized conditions (Grignard reagent, solvent, temperature) for
obtaining the desired 21a and finally i-PrMgBr in toluene at room
temperature was the conditions of choice for this reaction. Thus,
quite interestingly, treatment of adduct 19a with i-PrMgBr
2. Results and discussion
2.1. A synthesis of b,g-unsaturated esters from aldehydes
with chloromethyl p-tolyl sulfoxide and tert-butyl acetate
At first,1-chloro-4-phenyl-1-(p-tolylsulfinyl)-1-butenes 17a and
18a (R¼PhCH2CH2) were synthesized from 3-phenylpropanal and
chloromethyl p-tolyl sulfoxide in two steps in high overall yield14b
(see Table 1). The two geometrical isomers were separately treated
with lithium enolate of tert-butyl acetate to afford the adducts (19a
and 20a), each in quantitative yield as a single diastereomer.14b The
(1.7 equiv) gave the desired
(entry 1). The treatment of 20a with i-PrMgBr also gave the desired
-unsaturated ester 21a as the main product; however, the yield
was worse compared with that from 19a (entry 2). At present, we
still find it difficult to propose the reason why i-PrMgBr, not
i-PrMgCl, gave the good results.
b,g-unsaturated ester 21a in 85% yield
b,g

H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
615
Table 1
Synthesis of
b
,g
-unsaturated esters 21 from the adducts of 1-chlorovinyl p-tolyl sulfoxides with lithium enolate of tert-butyl acetate 19 and 20
t
CH2COO Bu
H
t
H
R
LiCH2COO Bu
Cl
H
S(O)Tol
R
THF, -78 °C
t
Cl
CH2COO Bu
S(O)Tol
i-PrMgBr (1.7 eq)
17
19
H
Toluene, r. t.
R
H
t
CH2COO Bu
H
H
R
t
Cl
LiCH2COO Bu
Cl
H
R
21
THF, -78 °C
S(O)Tol
S(O)Tol
18
20
Entry
19 and 20
21
R
Yielda/%
CH2CH2
1
2
19a
20a
21a
21a
85
41
3
4
19b
20b
CH3(CH2)5
CH3(CH2)5
21b
21b
65
50
5
6
19c
20c
21c
21c
56b
44
7
8
19d
20d
(CH3)3C
(CH3)3C
21d
21d
70
64
9
10
19e
20e
21e
21e
88
50
11
12
19f
20f
21f
21f
5
45
13
14
19g
20g
21g
21g
47
40
NC
a
The yield of the reaction of adducts 19 and 20 with i-PrMgBr.
b
Cyclopropane 22 was obtained as an inseparable by-product in 35% yield (calculated from the 1H NMR spectrum).
t
CH2COO Bu
22
Because we assured that this would become a useful method for
a synthesis of -unsaturated esters, we studied generality of this
aldehyde, p-anisaldehyde (Table 2). The addition reaction of
1-chlorovinyl p-tolyl sulfoxide 23 with lithium enolate of tert-
butyl acetate gave adduct 24 as a single isomer in a quantitative
yield. Quite interestingly, treatment of 24 with i-PrMgBr gave
b,g
reaction starting from various aldehydes and the results are
summarized in Table 1. n-Heptanal, cyclohexanecarboxaldehyde,
pivalaldehyde, benzaldehyde, 1-naphthaldehyde, and 4-cyano-
benzaldehyde were selected as the representative aldehydes. As
mentioned above, 1-chlorovinyl p-tolyl sulfoxides 17 and 18 were
synthesized from the aldehydes in two steps in high overall
yields.14 Addition reaction of vinyl sulfoxides 17 and 18 with lith-
ium enolate of tert-butyl acetate gave almost quantitative yields of
adducts 19 and 20, respectively. Finally, treatment of 19 and 20 with
i-PrMgBr (1.7 equiv) in toluene at room temperature for 10 min
three
b,g-unsaturated esters 25 (49%, by 1,2-CH insertion), 26
Table 2
Investigation for the best conditions of the reaction of 24 with Grignard reagent to
give (Z)- -unsaturated ester 26 through the magnesium carbenoid 1,2-CC
b,g
insertion reaction
H
t
CH2COO Bu
H
PMP
S(O)Tol
t
Cl
H
LiCH2COO Bu
Grignard reagent
toluene, 0 °C,
30 min
Cl
THF, -78 °C
gave moderate to good yields of the desired
b,
g-unsaturated esters
MeO
S(O)Tol
23
24
21a to 21g bearing a substituent R at the
b-position except one
example (entry 11). Obviously, the products 21 were derived
through the 1,2-CH insertion of the magnesium carbenoid in-
termediates. One example (entry 11) gave quite complex mixture
and the desired product 21f could be obtained in only 5% yield. Only
the case of cyclohexyl group as R gave cyclopropane 22 as a by-
product by 1,3-CH insertion17 (entry 5). Although the reason is not
clear at present, in all examples, except one case (entries 11 and 12),
the yields were better when the reaction was conducted with the
isomer 19. It is worth noting that migration of the double bond at
t
t
t
CH2COO Bu
PMP
CH2COO Bu
H
CH2COO Bu
H
+
+
H
H
PMP
PMP = p-Methoxyphenyl
H
H
PMP
26
25
27
Entry
Grignard reagent
25
Yielda/%
26
27
1
2
3
4
i-PrMgBr
i-PrMgCl
MeMgCl
EtMgCl
49
Trace
2
21
64
46
80
16
5
22
6
the
b,g-position to the a,b-position under these conditions was
never observed throughout this study.
Next, we investigated the above-mentioned reactions with
1-chlorovinyl p-tolyl sulfoxide derived from electron-rich aromatic
0
a
The yield of the reaction of adduct 24 with Grignard reagent.

616
H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
(21%, by 1,2-CC insertion), and 27 (16%, by 1,2-CC insertion) as
shown in entry 1 of Table 2. When i-PrMgCl was used in this
reaction, b,g-unsaturated ester 26 became the main product with
the geometrical isomer 27 (entry 2). MeMgCl gave the products 26
and 27 through the magnesium carbenoid 1,2-CC insertion re-
action; however, the selectivity between them was low (entry 3).
Finally, EtMgCl was found to be the best Grignard reagent for this
proposed in the previous communication.15 Although the reason is
not clear at present, the yields were always better when adducts 30
derived from (Z)-1-chlorovinyl p-tolyl sulfoxide 28 were used (see
entries 2–9).
2.2. A synthesis of b,g-unsaturated esters from aldehydes
with chloromethyl p-tolyl sulfoxide, tert-butyl acetate, and
reaction and (Z)-
b
,g
-unsaturated ester 26 was obtained in highly
iodomethane
selective manner (entry 4). We still find it very difficult to propose
a rational explanation why EtMgCl is the best reagent in this
reaction; however, by the discovery mentioned above, we expec-
It is well known that the intermediates of the conjugate addition
reaction of carbon nucleophiles to a,b-unsaturated sulfoxides are
ted that we could obtain
electron-rich aromatic ring at the
aromatic aldehydes.
b
,
g
-unsaturated butyl esters bearing an
a-sulfinyl carbanions and they can be trapped with several elec-
g-position from electron-rich
trophiles.18 Indeed, in our case, addition reaction of 1-chlorovinyl
p-tolyl sulfoxide 28e with lithium enolate of tert-butyl acetate
followed by treatment of iodomethane gave methylated adducts 36
Examples for the synthesis of b,g-unsaturated esters 33 and 34
starting from electron-rich aromatic aldehydes (4-(dimethylami-
no)benzaldehyde, 4-(methylthio)benzaldehyde, piperonal, furfural,
and 2-formylthiophene) through 1-chlorovinyl p-tolyl sulfoxides
(28 and 29) and the adducts with lithium enolate of tert-butyl
acetates (30 and 31) are summarized in Table 3. Quite interestingly,
as shown in Table 3, adducts 30 derived from (Z)-1-chlorovinyl
and 37 in 80% and 19% yields, respectively, via the lithium a-sulfinyl
carbanion 35 (Scheme 3). The same treatment of the geometrical
isomer 29e afforded methylated adducts 41 and 42 in 75% and 24%
yields, respectively, through the lithium
Treatment of the main methylated adduct 36 with EtMgCl in
toluene at 0 ꢁC for 30 min gave
-unsaturated ester with the
thiophene ring at the -position 38 in 85% yield via the magnesium
a-sulfinyl carbanion 40.
b,g
p-tolyl sulfoxides 28 gave (Z)-
electron-rich aromatic ring at the
adducts 31 derived from (E)-1-chlorovinyl p-tolyl sulfoxides 29
gave (E)- -unsaturated esters bearing an electron-rich aromatic
ring at the -position 34. From these results, it is obvious that this
b
,g
-unsaturated esters bearing an
b
g
-position 33. On the other hand,
carbenoid 1,2-CH insertion. No product through the magnesium
carbenoid 1,2-CC insertion was obtained. Quite interestingly, only
Z-isomer was obtained and no E-isomer was observed. The same
treatment of 37 gave 38 as one of the products. In this case
desulfinylated product 39 (45%) was the main product. It is worthy
of note that these magnesium carbenoid 1,2-CH insertions are
highly selective reactions.
b,g
g
magnesium carbenoid 1,2-CC insertion reaction is a highly stereo-
specific reaction. A plausible mechanism for this highly stereo-
specific magnesium carbenoid 1,2-CC insertion reaction has been
The treatment of 41 with EtMgCl gave
b,g-unsaturated ester
with the thiophene ring at the -position 38 in 78% yield via the
magnesium carbenoid 1,2-CH insertion. Very interestingly, the 1,2-
CH insertion of the magnesium carbenoid intermediates derived
b
Table 3
Synthesis of b,g-unsaturated esters 33 and 34 by treatment of adducts 30 and 31,
derived from electron-rich aromatic aldehydes, with EtMgCl
from 36 and 41 gave the same
tive manner. Again the reaction of the minor adduct 42 gave several
unknown products with the same
product in only 28% yield.
b,g-unsaturated 38 in highly selec-
t
H
CH2COO Bu
t
H
Ar
LiCH2COO Bu
S(O)Tol
Cl
H
Ar
b,g-unsaturated 38 as the main
THF, -78 °C
Cl
S(O)Tol
EtMgCl (1.7 eq)
Toluene, 0 °C
28
30
In order to present a plausible mechanism of these highly
stereoselective reactions, we first have to confirm the stereo-
chemistry of the methylated adducts (36, 37, 41, and 42). From our
cumulative examination, the relative stereochemistry of C-3 and
the sulfinyl group is obvious as depicted in Scheme 3.14b,16 Stereo-
chemistry of the carbons bearing the sulfinyl and the methyl groups
was determined from the cyclopropanes derived from the meth-
ylated adducts. For example, the methylated adduct 36 was treated
with LDA to afford cyclopropane 43 in moderate yield and the
stereochemistry was determined from its NOESY spectrum. As the
stereochemistry of the methyl group and the hydrogen on the cy-
clopropane ring was established to be cis, as depicted in Scheme 3,
t
CH2COO Bu
H
H
Ar
t
LiCH2COO Bu
Cl
Cl
H
Ar
THF, -78 °C
S(O)Tol
S(O)Tol
29
31
t
t
t
CH2COO Bu
CH2COO Bu
CH2COO Bu
Ar
+
H
+
H
H
H
Ar
H
H
32
Ar
34
33
Entry
1
30 and 31
32
33
34
the configuration of methylated adduct 36 is determined to be 3R
4S ,sS . In a similar manner, the stereochemistry of 41 and 42 was
determined from the stereochemistry of cyclopropane 44.
*
,
Ar
Yielda/%
*
*
30ab
0
50
0
All the stereochemistry of the methylated adducts in hand, we
propose the plausible mechanism of this highly stereoselective 1,2-
CH insertion as shown in Figure 1. Because the sulfoxide-magne-
sium exchange reaction is known to take place with retention of the
configuration of the carbon bearing the sulfinyl group,19 treatment
of 36, 37, 41, and 42 with EtMgCl gave the magnesium carbenoids
having retained configuration (A–D) as shown in Fig 1. The mag-
nesium and carbonyl oxygen atom of the ester group is supposed to
make chair like six-membered conformation A–D, in which the
bulkiest tert-butoxy group would occupy the equatorial position.16
In these intermediates, C–H bond of the carbon bearing the thio-
phene ring attacks the chlorine atom from its back side to give 38.
This type of reaction is expected to occur smoothly when the
chlorine and the hydrogen are in anti periplaner geometry.
(CH3)2N
2
3
30b
31b
3
17
80
8
8
42
CH3S
O
4
5
30c
31c
0
12
95
0
0
83
O
O
6
7
30d
31d
0
0
92
0
0
75
8
9
30e
31e
0
92
0
0
72
S
Trace
a
The yield of the reaction of 30 and 31 with EtMgCl.
Only Z-isomer could be synthesized from 4-(dimethylamino)benzaldehyde.
b

H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
617
t
CH2COO Bu
H
t
LiCH2COO Bu
CH3I
-78 °C, 10 min
S
S
S
S(O)Tol
S(O)Tol
Li
THF, -78 °C
Cl
Cl
28e
35
t
t
t
CH2COO Bu
CH2COO Bu
CH2COO Bu
H
H
S(O)Tol
Cl
S(O)Tol
S
H
EtMgCl
S
+
t
CH2COO Bu
toluene, 0 °C,
30 min
Cl
CH3
H
CH3
H
CH3
S
38
36 (3R*,4S*,sS*; 80%)
37 (3R*,4R*,sS*; 19%)
Cl
85% from 36
12% from 37
CH3
39
t
CH2COO Bu
H
t
S
H
S
CH3I
-78 °C, 10 min
Cl
LiCH2COO Bu
S(O)Tol
Li
THF, -78 °C
S(O)Tol
Cl
29e
40
t
t
t
CH2COO Bu
CH2COO Bu
CH2COO Bu
H
S(O)Tol
Cl
S
H
S(O)Tol
S
S
+
EtMgCl
toluene, 0 °C, 30 min
Cl
CH3
CH3
41 (3S*,4R*,sS*; 75%)
CH3
38
42 (3S*,4S*,sS*; 24%)
78% from 41
28% from 42
NOE
COOtBu
S
H
COOtBu
LDA / THF
LDA / THF
-78 °C ~ 0 °C
S
CH3
36
42
CH3
-78 °C ~ 0 °C
H
S(O)Tol
S(O)Tol
43 (53%)
44 (44%)
Scheme 3.
Cl
Cl
t
CH2COO Bu
H
O
CH3
Mg
EtMgCl
toluene
S
S(O)Tol
O
S
H3C Cl
H
A
36
CH3
Cl
t
Cl
CH2COO Bu
H
O
O
Mg
S
S(O)Tol
S
H
H3C Cl
B
37
CH3
H
S
t
Cl
CH2COO Bu
t
H
CH2COO Bu
S(O)Tol
Cl
Mg
38
O
O
S
H3C
single isomer
H3C
Cl
S
H
41
C
t
H
CH2COO Bu
S(O)Tol
CH3
Cl
S
O
O
Cl
Mg
H3C
Cl
S
H
42
D
Figure 1.
As mentioned above, compounds 36 and 41 gave smoothly 38 in
good yields, respectively. The conformation of the magnesium
carbenoid intermediate derived from 36 and 41 is expected to be A
and C, respectively, from which the 1,2-CH insertion takes place
smoothly. At the same time, it is explained that why the same (Z)-
tert-butyl 4-methyl-3-thienyl-3-pentenoate 38 was obtained from
36 and 41 in highly stereoselective manner. We can also explain the
reason why the magnesium carbenoid intermediates B and D

618
H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
Table 4
Synthesis of tri-substituted
b,
g-unsaturated esters 46 by treatment of adducts 45, which were derived from aromatic aldehydes via 1-chlorovinyl p-tolyl sulfoxides
t
t
CH2COO Bu
CH2COO Bu
H
t
LiCH2COO Bu
CH3I
-78 °C,
10 min
EtMgCl
toluene
0 °C, 30 min
S(O)Tol
H3C Cl
45
S(O)Tol
H
R
R
R
THF, -78 °C
CH3
Cl
46
1-chlorovinyl p-tolyl sulfoxide
Entry
1
1-Chlorovinyl p-tolyl sulfoxide
45
Yielda/% (diastereomeric ratio)
46
R
(Configuration)
Yield/%
23 (Z)
45a
99 (81:19)
46a
77
H3CO
O
2
3
28c (Z)
29c (E)
45b
45b
99 (86:14)
99 (68:32)
46b
46b
76
66
O
4
5
19e (Z)
20e (E)
45c
45c
99 (91:9)
99 (69:31)
46c
46c
63
69
6
7
19a (Z)
20a (E)
45d
45d
99 (61:39)
99 (76:24)
46d
46d
63
42
CH2CH2
a
A mixture of two diastereomers was used in the next reaction.
derived from 37 and 42, respectively, did not give good yield of the
olefin but a rather complex mixture from the conformers depicted
in Figure 1.
with EtMgCl in toluene at 0 ꢁC for 30 min to give the desired 46 in
moderate to good yields. In this case, again, only Z-isomers were
obtained.
As we recognized that this is a good way for a synthesis of
b,g-unsaturated esters by combination of four components, alde-
Finally, this procedure was extended with iodoalkanes other
than iodomethane and the results are summarized in Table 5. As
shown in Table 5, trapping the intermediates 35 and 40, derived
from 28e and 29e, respectively, with iodoethane and allyl iodide
gave 47a and 47b in high to quantitative yields as a mixture of two
diastereomers. Treatment of 47 with EtMgCl smoothly afforded
hyde, chloromethyl p-tolyl sulfoxide, tert-butyl acetate, and iodo-
methane, generality of this procedure was investigated and the
results are summarized in Table 4. Addition reaction of 1-chloro-
vinyl p-tolyl sulfoxides with lithium enolate of tert-butyl acetate
followed by treatment with iodomethane gave the methylated
adduct 45 as a mixture of two diastereomers in quantitative yields.
Without separation of the diastereomers, the mixture was treated
olefins; however, the products were not the expected
unsaturated esters but -unsaturated esters 48. Moreover, the
products were mixture of two geometrical isomers.
b,g-
g,d
Table 5
Synthesis of g,d-unsaturated esters 48 from 1-chlorovinyl p-tolyl sulfoxide 28e and 29e via adduct 47
t
CH2COO Bu
H
t
LiCH2COO Bu
S
S
S(O)Tol
S(O)Tol
LDA / THF
-78 °C
Li
Cl
Cl
35, 40
28e (Z), 29e (E)
t
CH2COO Bu
Electrophile
Temp., Time
EtMgCl
S
S(O)Tol
Products 48
E
Cl
47
Entry
Electrophile
Temp/ꢁC
Time/min
47/Yield %
(diastereomeric ratio)
Product 48
Yield/%
t
CH2COO Bu
1a
2a
3
28e
29e
28e
CH3CH2I
CH3CH2I
ꢀ78 to –0
ꢀ78 to –0
ꢀ78
120
120
30
47a
47a
47b
83 (79:21)
81b
87c
66d
S
H
84 (73:27)
99 (81:19)
H
48a
S
I
I
t
CH2COO Bu
H
4
29e
ꢀ78
30
47b
99 (79:21)
51e
H
48b
a
equivHMPA (8 equiv) was added as an additive.
b
c
A 2:5 mixture of two diastereomers determined from 1H NMR.
A 3:2 mixture of two diastereomers determined from 1H NMR.
A 1:1 mixture of two diastereomers determined from 1H NMR.
A 11:6 mixture of two diastereomers determined from 1H NMR.
d
e

H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
619
In conclusion, we found that magnesium carbenoids 10, derived
from the adduct of 1-chlorovinyl p-tolyl sulfoxides 7 with lithium
enolate of tert-butyl acetate, take place 1,2-CH or 1,2-CC insertion
Calcd for C15H19ClOS: C, 63.70; H, 6.77; Cl, 12.53; S, 11.34. Found: C,
63.79; H, 6.77; Cl, 12.32; S, 11.28.
reaction to give
b,
g-unsaturated esters 11 or 12 depending on the
3.6. (Z)-1-Chloro-3,3-dimethyl-1-(p-tolylsulfinyl)-
nature of the substituent R1. It was also found that the 1,2-CC
insertion reaction is highly stereospecific. The intermediate of the
reaction of 7 with lithium enolate of tert-butyl acetate (8) was found
to be able to be trapped with iodoalkanes to give 13 in high yields.
When R2¼H, treatment of 13 with EtMgCl resulted in the highly
1-butene (17d)
Colorless crystals; mp 74.5–75 ꢁC (hexane/AcOEt); IR (KBr)
2959, 1593, 1473, 1363, 1198, 1087, 1056, 869, 804 cmꢀ1 1H NMR
;
d
1.25 (9H, s), 2.42 (3H, s), 6.76 (1H, s), 7.31 (2H, d, J¼8.1 Hz), 7.55
stereoselective magnesium carbenoid 1,2-CH insertion to afford
b,
g-
(2H, d, J¼8.1 Hz). Anal. Calcd for C13H17ClOS: C, 60.80; H, 6.67; Cl,
unsaturated esters 15. The reactions mentioned in this paper con-
13.81; S, 12.49. Found: C, 60.67; H, 6.66; Cl, 14.2; S, 12.38.
siderablycontribute to a synthesis of various
b,g-unsaturated esters.
3.7. (E)-1-Chloro-3,3-dimethyl-1-(p-tolylsulfinyl)-
3. Experimental
1-butene (18d)
3.1. General
Colorless oil; IR (neat) 2964, 1597, 1477, 1365, 1250, 1203, 1088,
946, 859, 809, 622 cmꢀ1 1H NMR
; d 1.39 (9H, s), 2.42 (3H, s), 6.45
All melting points were measured on a Yanaco MP-S3 apparatus
and are uncorrected. 1H NMR spectra were measured in a CDCl3
solution with JEOL JNM-LA 300, 500, BRUKER DPX 400, and AV 600
spectrometer. Electron-impact mass spectra (MS) were obtained at
70 eV by direct insertion by HITACHI M-80B mass spectrometer. IR
spectra were recorded on a Perkin–Elmer Spectrum One FTIR in-
strument. Silica gel 60 N 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 irradia-
tion. In experiment requiring a dry solvent and reagent, HMPA and
diisopropylamine and toluene were distilled from CaH2, and THF
was distilled form diphenylketyl. Compounds 17a,20 17e,20 18a,20
18e,20 19a,14b 20a,14b are known.
(1H, s), 7.33 (2H, d, J¼8.1 Hz), 7.53 (2H, d, J¼8.1 Hz). MS m/z (%) 256
(Mþ, 15), 158 (14), 140 (100), 123 (19), 92 (30), 77 (10), 57 (45). Calcd
for C13H17ClOS: M, 256.0688. Found: m/z 256.0688.
3.8. (Z)-1-Chloro-2-(1-napthyl)-1-(p-tolylsulfinyl)ethene (17f)
Colorless crystals; mp 90–90.5 ꢁC (hexane/AcOEt); IR (KBr)
3038, 1591, 1490, 1444, 1393, 1344, 1282, 1087, 1061, 925, 896,
773 cmꢀ1; 1H NMR
d
2.44 (3H, s), 7.36 (2H, d, J¼8.2 Hz), 7.49 (1H, t,
J¼7.7 Hz), 7.53–7.61 (2H, m), 7.73 (2H, d, J¼8.2 Hz), 7.81 (1H, d,
J¼7.1 Hz), 7.87–7.89 (2H, m), 8.03 (1H, d, J¼8.0 Hz), 8.32 (1H, s).
Anal. Calcd for C19H15ClOS: C, 69.82; H, 4.63; Cl, 10.85; S, 9.81.
Found: C, 69.83; H, 4.47; Cl, 10.71; S, 9.72.
3.2. (Z)-1-Chloro-1-(p-tolylsulfinyl)-1-octene (17b)
3.9. (E)-1-Chloro-2-(1-naphethyl)-1-(p-tolylsulfinyl)-
ethene (18f)
Colorless oil; IR (neat) 2928, 2857, 1492, 1458, 1089, 1062,
807 cmꢀ1; 1H NMR
d
0.88 (3H, t, J¼6.9 Hz), 1.25–1.35 (6H, m), 1.46–
Colorless crystals; mp 154–154.5 ꢁC (hexane/AcOEt); IR (KBr)
1.52 (2H, m), 2.34 (2H, q, J¼7.3 Hz), 2.42 (3H, s), 6.78 (1H, t, J¼7.3 Hz),
7.31 (2H, d, J¼8.1 Hz), 7.56 (2H, d, J¼8.1 Hz). MS m/z (%) 284 (Mþ, 22),
267(24), 236 (23),158 (29),140 (100),123 (49), 92(33), 91 (23). Calcd
for C15H21ClOS: M, 284.1002. Found: m/z 284.0997.
3007, 1590, 1491, 1447, 1396, 1083, 1052, 1013, 903, 802, 776 cmꢀ1
;
1H NMR
d
2.40 (3H, s), 7.26–7.28 (2H, m), 7.39 (2H, d, J¼8.3 Hz),
7.54–7.62 (3H, m), 7.67 (1H, d, J¼7.1 Hz), 7.82 (1H, s), 7.86–7.88 (1H,
m), 7.93–7.96 (2H, m). Anal. Calcd for C19H15ClOS: C, 69.82; H, 4.63;
Cl, 10.85; S, 9.81. Found: C, 69.79; H, 4.48; Cl, 10.85; S, 9.84.
3.3. (E)-1-Chloro-1-(p-tolylsulfinyl)-1-octene (18b)
3.10. (Z)-1-Chloro-2-(4-cyanophenyl)-1-(p-tolylsulfinyl)-
Colorless oil; IR (neat) 2928, 2858, 1493, 1458, 1089, 1064,
ethene (17g)
808 cmꢀ1; 1H NMR
d
0.91 (3H, t, J¼6.9 Hz), 1.29–1.34 (4H, m), 1.35–
1.42 (2H, m), 1.50–1.56 (2H, m), 2.42 (3H, s), 2.60 (1H, dt, J¼14.5,
7.6 Hz), 2.72 (1H, dt, J¼14.8, 8.6 Hz), 6.31 (1H, dd, J¼8.6, 7.6 Hz), 7.32
(2H, d, J¼8.0 Hz), 7.51 (2H, d, J¼8.0 Hz). MS m/z (%) 284 (Mþ, 12),
267 (100),197 (37),161 (17),139 (19),123 (15), 91 (15), 65 (7), 41 (7).
Calcd for C15H21ClOS: M, 284.1002. Found: m/z 284.1001.
Colorless crystals; mp 170–170.5 ꢁC (hexane/AcOEt); IR (KBr)
3007, 2226 (CN), 1603, 1492, 1409, 1089, 1060, 920, 832, 808 cmꢀ1
;
1H NMR
d
2.43 (3H, s), 7.31 (1H, s), 7.33 (2H, d, J¼8.3 Hz), 7.45 (2H, d,
J¼8.3 Hz), 7.63 (2H, d, J¼8.5 Hz), 7.75 (2H, d, J¼8.5 Hz). Anal. Calcd
for C16H12ClNOS: C, 63.68; H, 4.01; N, 4.64; Cl,11.75; S,10.62. Found:
C, 63.58; H, 3.71; N, 4.41; Cl, 11.56; S, 10.60.
3.4. (Z)-1-Chloro-2-cyclohexyl-1-(p-tolylsulfinyl)ethene (17c)
3.11. (E)-1-Chloro-2-(4-cyanophenyl)-1-(p-tolylsulfinyl)-
Colorless oil; IR (neat) 2927, 1596, 1493, 1449, 1087, 967, 898,
ethene (18g)
809 cmꢀ1; 1H NMR
d 1.22–1.33 (5H, m), 1.65–1.78 (5H, m), 2.42 (3H,
s), 2.53–2.61 (1H, m), 6.63 (1H, d, J¼9.2 Hz), 7.31 (2H, d, J¼8.0 Hz),
7.54 (2H, d, J¼8.0 Hz). MS m/z (%) 282 (Mþ, 31), 265 (14), 234 (31),
152 (31), 140 (100), 123 (25), 92 (31), 79 (14). Calcd for C15H19ClOS:
M, 282.0845. Found: m/z 282.0838.
Colorless crystals; mp 120.5–121 ꢁC (hexane/AcOEt); IR (KBr)
3014, 2232 (CN), 1604, 1500, 1083, 1069, 900, 822 cmꢀ1 1H NMR
;
d
2.43 (3H, s), 7.34 (2H, d, J¼8.1 Hz), 7.65 (2H, d, J¼8.1 Hz), 7.66 (1H,
s), 7.69 (2H, d, J¼8.4 Hz), 7.83 (2H, d, J¼8.4 Hz). Anal. Calcd for
C16H12ClNOS: C, 63.68; H, 4.01; N, 4.64; Cl, 11.75; S, 10.62. Found: C,
63.63; H, 3.81; N, 4.42; Cl, 11.60; S, 10.60.
3.5. (E)-1-Chloro-2-cyclohexyl-1-(p-tolylsulfinyl)ethene (18c)
Colorless crystals; mp 69.5–70 ꢁC (hexane/AcOEt); IR (KBr) 2921,
3.12. (3S
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-hexyl-4-(p-tolylsul-
*
1444, 1394, 1089, 1060, 906, 861, 806 cmꢀ1
;
1H NMR
d
1.20–1.28
finyl)butyrate (19b)
(3H, m), 1.32–1.44 (2H, m), 1.70–1.74 (2H, m), 1.76–1.83 (2H, m),
1.88–1.93 (1H, m), 2.42 (3H, s), 3.06 (1H, tq, J¼11.0, 3.8 Hz), 6.16 (1H,
d, J¼11.0 Hz), 7.33 (2H, d, J¼8.3 Hz), 7.50 (2H, d, J¼8.3 Hz). Anal.
tert-Butyl acetate (0.73 mL, 5.4 mmol) was added to a solution of
LDA (5.4 mmol) in 12 mL of dry THF at ꢀ78 ꢁC with stirring. The

620
H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
solution was stirred for 10 min and then a solution of 17b (300 mg,
1.1 mmol) in THF (3 mL) was added with stirring. The reaction
mixture was stirred for 5 min, then the reaction was quenched by
adding satd aq NH4Cl. The whole was extracted with CHCl3. The
extract was washed with brine and the organic layer was dried over
MgSO4 and the solvent was evaporated. The residue was purified by
silica gel column chromatography to afford 19b (429 mg, 99%) as
colorless oil. IR (neat) 2931, 1728 (CO), 1462, 1365, 1219, 1154, 1084,
NMR
d
0.95 (9H, s), 1.49 (9H, s), 2.39 (1H, dd, J¼16.9, 6.9 Hz), 2.43
(3H, s), 2.51 (1H, dd, J¼16.9, 4.4 Hz), 3.06 (1H, ddd, J¼6.9, 4.4,
0.8 Hz), 4.57 (1H, d, J¼0.8 Hz), 7.32 (2H, d, J¼8.1 Hz), 7.67 (2H, d,
J¼8.1 Hz). Anal. Calcd for C19H29ClO3S: C, 61.19; H, 7.84; Cl, 9.51; S,
8.60. Found: C, 61.33; H, 7.87; Cl, 9.42; S, 8.57.
3.18. (3R
(p-tolylsulfinyl)butyrate (19e)
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-phenyl-4-
*
808 cmꢀ1; 1H NMR
d
0.90 (3H, t, J¼6.9 Hz), 1.30–1.33 (6H, m), 1.40–
1.48 (4H, m), 1.44 (9H, s), 2.36 (1H, dd, J¼16.0, 9.3 Hz), 2.43 (3H, s),
2.51 (1H, dd, J¼16.0, 4.7 Hz), 2.96–3.02 (1H, m), 4.64 (1H,
d, J¼2.2 Hz), 7.32 (2H, d, J¼8.0 Hz), 7.68 (2H, d, J¼8.0 Hz). MS (FAB)
m/z (%) 401 ([MþH]þ, 18), 345 (100), 327 (23), 293 (4), 140 (22), 123
(22), 109 (14), 57 (12). Calcd for C21H34ClO3S: M, 401.1918. Found:
m/z 401.1917.
Colorless crystals; mp 129.5–130 ꢁC (hexane/AcOEt); IR (KBr)
2979, 1724 (CO), 1455, 1369, 1274, 1243, 1152, 1049, 976, 817,
732 cmꢀ1; 1H NMR
d
1.30 (9H, s), 2.42 (3H, s), 2.83 (1H, dd, J¼15.8,
8.0 Hz), 2.88 (1H, dd, J¼15.8, 8.0 Hz), 4.41 (1H, dt, J¼8.0, 3.0 Hz),
4.67 (1H, d, J¼3.0 Hz), 7.30 (2H, d, J¼8.1 Hz), 7.35–7.41 (3H, m),
7.51–7.54 (2H, m), 7.63 (2H, d, J¼8.1 Hz). Anal. Calcd for
C21H25ClO3S: C, 64.19; H, 6.41; Cl, 9.02; S, 8.16. Found: C, 64.20; H,
6.22; Cl, 8.93; S, 8.34.
3.13. (3R
*
,4R
*
*
,sS )-tert-Butyl 4-chloro-3-hexyl-4-
(p-tolylsulfinyl)butyrate (20b)
3.19. (3S
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-phenyl-4-
*
Colorless oil; IR (neat) 2930, 1732 (CO), 1456, 1368, 1258, 1152,
1057, 812 cmꢀ1; 1H NMR
d
0.90 (3H, t, J¼6.9 Hz),1.22–1.32 (10H, m),
(p-tolylsulfinyl)butyrate (20e)
1.48 (9H, s), 2.31 (1H, dd, J¼15.9, 6.4 Hz), 2.44 (3H, s), 2.81 (1H, dd,
J¼15.9, 3.7 Hz), 2.95–3.02 (1H, m), 4.43 (1H, d, J¼2.1 Hz), 7.34 (2H,
d, J¼8.3 Hz), 7.66 (2H, d, J¼8.3 Hz). MS (FAB) m/z (%) 401 ([MþH]þ,
17), 345 (100), 327 (39), 293 (4), 140 (20), 123 (18), 109 (11), 57 (10).
Calcd for C21H34ClO3S: M, 401.1917. Found: m/z 401.1920.
Colorless crystals; mp 75.5–76 ꢁC (hexane/AcOEt); IR (KBr)
2978, 1725 (CO), 1495, 1455, 1369, 1270, 1154, 1041, 965, 809,
702 cmꢀ1; 1H NMR
d
1.24 (9H, s), 2.42 (3H, s), 3.00 (1H, dd, J¼15.9,
10.7 Hz), 3.08 (1H, dd, J¼15.9, 4.9 Hz), 4.21 (1H, ddd, J¼10.7, 4.9,
3.0 Hz), 4.51 (1H, d, J¼3.0 Hz), 7.26–7.36 (7H, m), 7.65 (2H, d,
J¼8.2 Hz). Anal. Calcd for C21H25ClO3S: C, 64.19; H, 6.41; Cl, 9.02; S,
8.16. Found: C, 64.00; H, 6.22; Cl, 9.00; S, 8.15.
3.14. (3R
*
,4R
*
*
,sS )-tert-Butyl 4-chloro-3-cyclohexyl-4-
(p-tolylsulfinyl)butyrate (19c)
Colorless crystals; mp 117.5–118 ꢁC (hexane/AcOEt); IR (KBr)
3.20. (3R
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-(1-naphthyl)-4-
*
2931, 1721 (CO), 1447, 1366, 1235, 1154, 1049, 815 cmꢀ1 1H NMR
;
d
(p-tolylsulfinyl)butyrate (19f)
1.03 (1H, dq, J¼12.4, 3.3 Hz), 1.08–1.18 (1H, m), 1.24–1.36 (3H, m),
Colorless crystals; mp 147–147.5 ꢁC (hexane/AcOEt); IR (KBr)
1.45 (9H, s), 1.66–1.69 (1H, m), 1.74–1.79 (2H, m), 1.86–1.95 (3H, m),
2.43 (3H, s), 2.48 (1H, dd, J¼16.2, 8.7 Hz), 2.56 (1H, dd, J¼16.2, 4.9 Hz),
2.79–2.84 (1H, m), 4.68 (1H, d, J¼3.6 Hz), 7.33 (2H, d, J¼8.3 Hz), 7.69
(2H, d, J¼8.3 Hz). Anal. Calcd for C21H31ClO3S: C, 63.22; H, 7.83; Cl,
8.89; S, 8.04. Found: C, 63.35; H, 7.77; Cl, 8.81; S, 8.02.
2978, 1732 (CO), 1597, 1499, 1363, 1267, 1147, 1039, 785 cmꢀ1 1H
;
NMR d 1.12 (9H, s), 2.41 (3H, s), 2.98–3.11 (2H, m), 4.82 (1H, s), 5.22
(1H, s), 7.29 (2H, d, J¼8.0 Hz), 7.47–7.53 (2H, m), 7.59–7.63 (3H, m),
7.70 (1H, d, J¼7.3 Hz), 7.83–7.88 (2H, m), 8.52 (1H, d, J¼8.2 Hz).
Anal. Calcd for C25H27ClO3S: C, 67.78; H, 6.14; Cl, 8.00; S, 7.24.
Found: C, 67.82; H, 6.05; Cl, 7.90; S, 7.22.
3.15. (3S
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-cyclohexyl-4-
*
(p-tolylsulfinyl)butyrate (20c)
3.21. (3S
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-(1-naphthyl)-4-
*
Colorless oil; IR (neat) 2928, 1732 (CO), 1450, 1367, 1288, 1152,
(p-tolylsulfinyl)butyrate (20f)
1057, 956, 813 cmꢀ1; 1H NMR
d 1.00–1.27 (6H, m), 1.48 (9H, s), 1.70–
1.78 (5H, m), 2.38 (1H, dd, J¼16.6, 8.0 Hz), 2.43 (3H, s), 2.69 (1H, dd,
J¼16.6, 3.6 Hz), 2.91–2.96 (1H, m), 4.48 (1H, d, J¼1.8 Hz), 7.33 (2H,
d, J¼8.1 Hz), 7.66 (2H, d, J¼8.1 Hz). MS (FAB) m/z (%) 399 ([MþH]þ,
18), 343 (100), 325 (37), 167 (10), 140 (15), 123 (14), 83 (7), 57 (8).
Calcd for C21H32ClO3S: M, 399.1761. Found: m/z 399.1763.
Colorless oil; IR (neat) 2978, 1732 (CO), 1640, 1598, 1455, 1368,
1287, 1149, 1052, 969, 782 cmꢀ1; 1H NMR
d 1.09 (9H, s), 2.40 (3H, s),
3.26 (2H, d, J¼7.8 Hz), 4.55 (1H, d, J¼2.0 Hz), 5.34–5.38 (1H, m), 7.29
(2H, d, J¼8.1 Hz), 7.43 (1H, t, J¼7.6 Hz), 7.49–7.53 (2H, m), 7.58–7.62
(1H, m), 7.67 (2H, d, J¼8.1 Hz), 7.78 (1H, d, J¼8.1 Hz), 7.86 (1H, d,
J¼8.1 Hz), 8.23 (1H, d, J¼8.5 Hz). MS m/z (%) 442 (Mþ, 4), 369 (13),
302 (5), 247 (44), 229 (46), 211 (73), 165 (86), 140 (100), 139 (16), 92
(14), 57 (78). Calcd for C25H27ClO3S: M, 442.1369. Found: m/z
442.1367.
3.16. (3R
*
,4R
*
*
,sS )-tert-Butyl 4-chloro-3-(1,1-dimethylethyl)-
4-(p-tolylsulfinyl)butyrate (19d)
Colorless oil; IR (neat) 2969, 1732 (CO), 1480, 1369, 1305, 1258,
1148, 1056, 956, 812 cmꢀ1; 1H NMR
d 1.17 (9H, s), 1.47 (9H, s), 2.42
(3H, s), 2.47 (1H, dd, J¼15.9, 9.9 Hz), 2.54 (1H, dd, J¼15.9, 3.5 Hz),
3.00 (1H, ddd, J¼9.9, 3.5, 1.7 Hz), 4.62 (1H, d, J¼1.7 Hz), 7.31 (2H, d,
J¼8.1 Hz), 7.69 (2H, d, J¼8.1 Hz). MS m/z (%) 372 (Mþ, 5), 299 (20),
259 (5), 177 (15), 140 (100), 139 (13), 92 (10), 57 (53). Calcd for
C19H29ClO3S: M, 372.1526. Found: m/z 372.1525.
3.22. (3R
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-(4-cyanophenyl)-4-
*
(p-tolylsulfinyl)butyrate (19g)
Colorless crystals; mp 143.5–144 ꢁC (hexane/AcOEt); IR (KBr)
2985, 2229 (CN), 1722 (CO), 1370, 1268, 1142, 1043, 843, 813 cmꢀ1
;
1H NMR
d
1.31 (9H, s), 2.43 (3H, s), 2.83 (1H, dd, J¼16.2, 7.7 Hz), 2.89
3.17. (3S
*
,4R
*
*
,sS )-tert-Butyl 4-chloro-3-(1,1-dimethylethyl)-4-
(1H, dd, J¼16.2, 8.3 Hz), 4.48 (1H, dt, J¼7.7, 2.9 Hz), 4.66 (1H, d,
J¼2.9 Hz), 7.32 (2H, d, J¼8.1 Hz), 7.62 (2H, d, J¼8.1 Hz), 7.66 (2H, d,
J¼8.5 Hz), 7.69 (2H, d, J¼8.5 Hz). Anal. Calcd for C22H24ClNO3S: C,
63.22; H, 5.79; N, 3.35; Cl, 8.48; S, 7.67. Found: C, 63.30; H, 5.57; N,
3.00; Cl, 8.24; S, 7.63.
(p-tolylsulfinyl)butyrate (20d)
Colorless crystals; mp 79–79.5 ꢁC (hexane/AcOEt); IR (KBr)
2975, 1729 (CO), 1481, 1370, 1294, 1147, 1050, 809, 774 cmꢀ1 1H
;

H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
621
3.23. (3S ,4R
* *
,sS
*
)-tert-Butyl 4-chloro-3-(4-cyanophenyl)-4-
3.29. tert-Butyl 3-(1-naphethyl)-3-butenoate (21f)
(p-tolylsulfinyl)butyrate (20g)
Colorless oil; IR (neat) 2978, 1729 (CO), 1638, 1509, 1454, 1368,
1289, 1255, 1150, 964, 779 cmꢀ1; 1H NMR
1.26 (9H, s), 3.45 (2H, s),
Colorless crystals; mp 132–132.5 ꢁC (hexane/AcOEt); IR (KBr)
d
2978, 2229 (CN), 1728 (CO), 1368, 1260, 1145, 1049, 845, 818 cmꢀ1
;
5.82 (1H, d, J¼1.4 Hz), 5.58 (1H, d, J¼1.4 Hz), 7.36 (1H, dd, J¼7.1,
1.3 Hz), 7.41–7.45 (1H, m), 7.46–7.49 (2H, m), 7.77 (1H, d, J¼8.2 Hz),
7.83–7.86 (1H, m), 8.06–8.09 (1H, m). MS m/z (%) 268 (Mþ, 19), 212
(82), 195 (22), 165 (68), 152 (100), 57 (77), 41 (24), 28 (16). Calcd for
C18H20O2: M, 268.1462. Found: m/z 268.1464.
1H NMR
d
1.27 (9H, s), 2.42 (3H, s), 3.05 (1H, dd, J¼16.3, 10.8 Hz),
3.13 (1H, dd, J¼16.3, 4.7 Hz), 4.23 (1H, ddd, J¼10.8, 4.7, 2.5 Hz), 4.39
(1H, d, J¼2.5 Hz), 7.33 (2H, d, J¼8.0 Hz), 7.48 (2H, d, J¼8.3 Hz), 7.63
(2H, d, J¼8.3 Hz), 7.64 (2H, d, J¼8.0 Hz). Anal. Calcd for
C22H24ClNO3S: C, 63.22; H, 5.79; N, 3.35; Cl, 8.48; S, 7.67. Found: C,
63.27; H, 5.71; N, 3.24; Cl, 8.39; S, 7.69.
3.30. tert-Butyl 3-(4-cyanophenyl)-3-butenoate (21g)
Colorless oil; IR (neat) 2979, 2228 (CN), 1729 (CO), 1607, 1369,
3.24. tert-Butyl 3-methylidene-5-phenylpentanoate (21a)
1258, 1150, 847 cmꢀ1; 1H NMR
d
1.35 (9H, s), 3.44 (2H, d, J¼1.0 Hz),
5.37 (1H, s), 5.59 (1H, s), 7.52 (2H, d, J¼8.7 Hz), 7.62 (2H, d,
J¼8.7 Hz). MS m/z (%) 243 (Mþ, 7), 228 (5), 187 (75), 159 (23), 142
(46), 140 (20), 115 (17), 57 (100). Calcd for C15H17 NO2: M, 243.1259.
Found: m/z 243.1256.
i-PrMgBr (0.76 M solution in THF, 0.27 mL, 0.21 mmol) was
added to dry toluene (1.9 mL) in a flame-dried flask at room
temperature. A solution of 19a (50 mg, 0.12 mmol) in toluene
(0.5 mL) was added dropwise to the solution of i-PrMgBr and the
reaction mixture was stirred at room temperature for 10 min. The
reaction was quenched by adding satd aq NH4Cl. The whole was
extracted with CHCl3. The extract was washed with brine and the
organic layer was dried over MgSO4 and the solvent was evap-
orated. The residue was purified by silica gel column chroma-
tography to give 24.9 mg (85%) of 21a as colorless oil. IR (neat)
3.31. (Z)-1-Chloro-2-(4-methoxyphenyl)-1-(p-tolylsul-
finyl)ethene (23)
Colorless crystals; mp 80–80.5 ꢁC (hexane/AcOEt); IR (KBr)
2936, 1605, 1514, 1308, 1256, 1177, 1068, 897, 826, 749 cmꢀ1 1H
;
NMR
d
2.42 (3H, s), 3.84 (3H, s), 6.93 (2H, d, J¼8.8 Hz), 7.31 (2H, d,
2979, 1732 (CO), 1455, 1368, 1256, 1146, 899, 699 cmꢀ1
;
1H NMR
J¼8.1 Hz), 7.55 (1H, s), 7.62 (2H, d, J¼8.1 Hz), 7.75 (2H, d, J¼8.8 Hz).
Anal. Calcd for C16H15ClO2S: C, 62.64; H, 4.93; Cl, 11.56; S, 10.45.
Found: C, 62.57; H, 4.68; Cl, 11.29; S, 10.41.
d
1.46 (9H, s), 2.39–2.43 (2H, m), 2.76–2.80 (2H, m), 2.99 (2H, s),
4.92 (1H, m), 4.94 (1H, m), 7.16–7.20 (3H, m), 7.26–7.30 (2H, m).
MS m/z (%) 246 (Mþ, 5), 190 (28), 173 (22), 145 (27), 130 (100), 91
(82), 57 (85). Calcd for C16H22O2: M, 246.1620. Found: m/z
246.1617.
3.32. (3R
*
,4R
*
*
,sS )-tert-Butyl 4-chloro-3-(4-methoxyphenyl)-
4-(p-tolylsulfinyl)butanoate (24)
3.25. tert-Butyl 3-methylidenenonanoate (21b)
tert-Butyl acetate (0.88 mL, 6.52 mmol) was added to a solution
of LDA (6.52 mmol) in 28 mL of dry THF at ꢀ78 ꢁC with stirring. The
solution was stirred for 10 min and then a solution of 23 (500 mg,
1.63 mmol) in THF (5 mL) was added. The reaction mixture was
stirred for 5 min and the reaction was quenched by adding satd aq
NH4Cl. The whole was extracted with CHCl3. The extract was
washed with brine and the organic layer was dried over MgSO4. The
solvent was evaporated to give a residue, which was purified by
silica gel column chromatography to give 644 mg (93%) of 24 as
colorless crystals. Mp 99–99.5 ꢁC (hexane/AcOEt); IR (neat) 2979,
Colorless oil; IR (neat) 2928, 1732 (CO), 1457, 1368, 1256,
1145 cmꢀ1; 1H NMR
(9H, s), 2.08 (2H, t, J¼7.5 Hz), 2.93 (2H, s), 4.86 (1H, m), 4.88 (1H, m).
MS m/z (%) 226 (Mþ, 2), 211 (14), 170 (14), 110 (31), 69 (13), 57 (100).
Calcd for C14H26O2: M, 226.1933. Found: m/z 226.1932.
d
0.88 (3H, t, J¼6.7 Hz), 1.28–1.31 (8H, m), 1.45
3.26. tert-Butyl 3-cyclohexyl-3-butenoate (21c)
1729 (CO), 1611, 1515, 1456, 1368, 1252, 1149, 1051, 839, 756 cmꢀ1
1H NMR
;
Colorless oil; IR (neat) 2928, 1732 (CO), 1643, 1450, 1368, 1257,
1144, 966, 890, 752 cmꢀ1; 1H NMR
d 1.10–1.29 (5H, m), 1.45 (9H, s),
d
1.32 (9H, s), 2.41 (3H, s), 2.78 (1H, dd, J¼15.7, 7.8 Hz), 2.83
(1H, dd, J¼15.7, 8.0 Hz), 3.83 (3H, s), 4.37 (1H, dt, J¼7.8, 2.9 Hz), 4.65
(1H, d, J¼2.9 Hz), 6.91 (2H, d, J¼8.8 Hz), 7.30 (2H, d, J¼8.1 Hz), 7.44
(2H, d, J¼8.8 Hz), 7.63 (2H, d, J¼8.1 Hz). Anal. Calcd for C22H27ClO4S:
C, 62.47; H, 6.43; Cl, 8.38; S, 7.58. Found: C, 62.50; H, 6.38; Cl, 8.32;
S, 7.47.
1.67–1.69 (1H, m), 1.75–1.82 (4H, m), 1.90–1.96 (1H, m), 2.95 (2H, s),
4.86 (1H, m), 4.89 (1H, m). MS m/z (%) 224 (Mþ, 4), 168 (86), 150
(27), 123 (18), 108 (100), 81 (32), 67 (18), 57 (83). Calcd for
C14H24O2: M, 224.1776. Found: m/z 224.1776.
3.27. tert-Butyl 4,4-dimethyl-3-methylidenepentanoate (21d)
3.33. (Z)-tert-Butyl 4-(4-Methoxyphenyl)-3-butenoate (26)
and E-isomer (27)
Colorless oil; IR (neat) 2961, 1731 (CO),1367, 1257, 1137 cmꢀ1; 1H
NMR
d
1.07 (9H, s), 1.45 (9H, s), 2.96 (2H, d, J¼1.0 Hz), 4.87 (1H, d,
EtMgCl (2.0 M solution in diethyl ether, 0.1 mL, 0.20 mmol) was
added to dry toluene (1.9 mL) at 0 ꢁC, and then a solution of 24
(50 mg 0.118 mmol) in toluene (0.5 mL) was added dropwise to the
solution of EtMgCl. The reaction mixture was stirred at 0 ꢁC for
30 min. The reaction was quenched by adding satd aq NH4Cl. The
whole was extracted with CHCl3 and the extract was washed with
brine and the organic layer was dried over MgSO4 and the solvent
was evaporated. The residue was purified by silica gel column
chromatography to give 23.4 mg (80%) of 26 and 1.76 mg (6%) of 27
both as colorless oil. Compound 26: IR (neat) 2978, 1730 (CO), 1608,
J¼0.9 Hz), 5.03 (1H, d, J¼0.9 Hz). MS m/z (%) 198 (Mþ, 3), 142 (94),
125 (48), 97 (52), 83 (96), 57 (100). Calcd for C12H22O2: M, 198.1620.
Found: m/z 198.1622.
3.28. tert-Butyl 3-phenyl-3-butenoate (21e)
Colorless oil; IR (neat) 2979, 1732 (CO), 1368, 1258, 1148 cmꢀ1
1H NMR
5.50 (1H, d, J¼0.8 Hz), 7.26–7.28 (1H, m), 7.31–7.34 (2H, m), 7.42–
7.44 (2H, m). MS m/z (%) 218 (Mþ, 2), 162 (79), 145 (15), 134 (31), 117
(35), 91 (18), 57 (100). Calcd for C14H18O2: M, 218.1305. Found: m/z
218.1314.
;
d
1.35 (9H, s), 3.43 (2H, d, J¼1.1 Hz), 5.21 (1H, d, J¼1.1 Hz),
1511, 1459, 1368, 1254 (COC), 1148, 1034, 843 cmꢀ1; 1H NMR
d 1.46
(9H, s), 3.24 (2H, dd, J¼7.3, 1.9 Hz), 3.82 (3H, s), 5.78 (1H, dt, J¼11.5,
7.3 Hz), 6.54 (1H, d, J¼11.5 Hz), 6.88 (2H, d, J¼8.7 Hz), 7.22 (2H, d,

622
H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
J¼8.7 Hz). MS m/z (%) 248 (Mþ, 22), 175 (18), 147 (86), 115 (10), 103
(12), 91 (10), 57 (100). Calcd for C15H20O3: M, 248.1412. Found: m/z
248.1412. Compound 27: IR (neat) 2978, 1730 (CO), 1608, 1513, 1368,
3.40. (Z)-1-Chloro-2-(2-furyl)-1-(p-tolylsulfinyl)ethene (28d)
Colorless crystals; mp 100–100.5 ꢁC (hexane/AcOEt); IR (KBr)
3128, 3023, 1610, 1494, 1470, 1397, 1323, 1307, 1085, 1060, 1018, 903,
1250 (COC), 1148, 1035, 839 cmꢀ1; 1H NMR
d 1.47 (9H, s), 3.13 (2H,
dd, J¼7.2, 5.7 Hz), 3.80 (3H, s), 6.14 (1H, dt, J¼16.0, 7.2 Hz), 6.40 (1H,
d, J¼16.0 Hz), 6.84 (2H, d, J¼8.7 Hz), 7.30 (2H, d, J¼8.7 Hz). MS m/z
(%) 248 (Mþ, 31), 192 (20), 147 (100), 131 (10), 103 (13), 91 (10), 57
(70), 41 (12). Calcd for C15H20O3: M, 248.1413. Found: m/z 248.1415.
816, 751 cmꢀ1; 1HNMR
(1H, d, J¼3.4 Hz), 7.32 (2H, d, J¼8.1 Hz), 7.53 (1H, d, J¼1.8 Hz), 7.57
(1H, s), 7.61 (2H, d, J¼8.1 Hz). Anal. Calcd for C13H11ClO2S: C, 58.54; H,
4.16; Cl, 13.29; S, 12.02. Found: C, 58.52; H, 3.94; Cl, 13.28; S, 12.20.
d
2.42(3H, s), 6.52(1H, dd, J¼3.4,1.8 Hz), 7.02
3.34. tert-Butyl 3-(4-methoxyphenyl)-3-butenoate (25)
3.41. (E)-1-Chloro-2-(2-furyl)-1-(p-tolylsulfinyl)ethene (29d)
Colorless oil; IR (neat) 2978, 1725 (CO), 1608, 1513, 1459, 1368,
Colorless crystals; mp 103–103.5 ꢁC (hexane/AcOEt); IR (KBr)
3139, 3031, 1621, 1480, 1383, 1275, 1149, 1085, 1063, 1018, 959, 876,
1249 (COC),1147,1034, 836 cmꢀ1; 1H NMR
d 1.36 (9H, s), 3.40 (2H, d,
J¼0.9 Hz), 3.81 (3H, s), 5.11 (1H, d, J¼0.9 Hz), 5.42 (1H, d, J¼0.9 Hz),
6.85 (2H, d, J¼8.9 Hz), 7.37 (2H, d, J¼8.9 Hz). MS m/z (%) 248 (Mþ, 9),
192 (100), 175 (15), 147 (21), 133 (19), 115 (11), 57 (68). Calcd for
C15H20O3: M, 248.1410. Found: m/z 248.1401.
813, 753 cmꢀ1
;
1H NMR
d
2.41 (3H, s), 6.54 (1H, dd, J¼3.4, 1.8 Hz),
6.69 (1H, d, J¼3.4 Hz), 6.92 (1H, s), 7.30 (2H, d, J¼8.1 Hz), 7.60 (1H,
s), 7.61 (2H, d, J¼8.1 Hz). Anal. Calcd for C13H11ClO2S: C, 58.54; H,
4.16; Cl, 13.29; S, 12.02. Found: C, 58.47; H, 3.93; Cl, 13.10; S, 11.93.
3.35. (Z)-1-Chloro-2-(4-dimethylaminophenyl)-
1-(p-tolylsulfinyl)ethene (28a)
3.42. (Z)-1-Chloro-2-(2-thienyl)-1-(p-tolylsulfinyl)-
ethene (28e)
Colorless crystals; mp 131.5–132 ꢁC (hexane/AcOEt); IR (KBr)
Colorless crystals; mp 104–104.5 ꢁC (hexane/AcOEt); IR (KBr)
2917, 1607, 1526, 1374 (CN), 1194, 1085, 1064, 910, 807 cmꢀ1
;
1H
3080, 1595, 1417, 1217, 1018, 1049, 904, 816, 733 cmꢀ1 1H NMR
;
NMR
d
2.41 (3H, s), 3.02 (6H, s), 6.68 (2H, d, J¼9.0 Hz), 7.30 (2H, d,
d
2.42 (3H, s), 7.12 (1H, dd, J¼5.1, 3.7 Hz), 7.32 (2H, d, J¼8.1 Hz), 7.46
J¼8.1 Hz), 7.48 (1H, s), 7.60 (2H, d, J¼8.1 Hz), 7.72 (2H, d, J¼9.0 Hz).
Anal. Calcd for C17H18ClNOS: C, 63.84; H, 5.67; N, 4.38; Cl, 11.08; S,
10.03. Found: C, 63.86; H, 5.56; N, 4.36; Cl, 10.90; S, 9.97.
(1H, d, J¼3.7 Hz), 7.50 (1H, d, J¼5.1 Hz), 7.62 (2H, d, J¼8.1 Hz), 7.85
(1H, s). Anal. Calcd for C13H11ClOS2: C, 55.21; H, 3.92; Cl, 12.54; S,
22.68. Found: C, 55.24; H, 3.80; Cl, 12.40; S, 22.78.
3.36. (Z)-1-Chloro-2-(4-methylthiophenyl)-
1-(p-tolylsulfinyl)ethene (28b)
3.43. (E)-1-Chloro-2-(2-thienyl)-1-(p-tolylsulfinyl)-
ethene (29e)
Colorless crystals; mp 97.5–98 ꢁC (hexane/AcOEt); IR (KBr) 1592,
Colorless crystals; mp 122.5–123 ꢁC (hexane/AcOEt); IR (KBr)
1492, 1403, 1326, 1190, 1086, 1069, 895, 884, 823, 810 cmꢀ1
;
1H
3082, 1587, 1493, 1422, 1211, 1085, 1059, 906, 812, 723 cmꢀ1 1H
;
NMR
d
2.42 (3H, s), 2.50 (3H, s), 7.25 (2H, d, J¼8.5 Hz), 7.32 (2H, d,
NMR
d
2.42 (3H, s), 7.08 (1H, dd, J¼5.2, 3.6 Hz), 7.26 (1H, d,
J¼8.1 Hz), 7.56 (1H, s), 7.63 (2H, d, J¼8.1 Hz), 7.69 (2H, d, J¼8.5 Hz).
Anal. Calcd for C16H15ClOS2: C, 59.52; H, 4.68; Cl, 10.98; S, 19.86.
Found: C, 59.39; H, 4.60; Cl, 10.98; S, 19.66.
J¼3.6 Hz), 7.30 (1H, s), 7.31 (2H, d, J¼8.3 Hz), 7.50 (1H, d, J¼5.2 Hz),
7.61 (2H, d, J¼8.3 Hz). Anal. Calcd for C13H11ClOS2: C, 55.21; H, 3.92;
Cl, 12.54; S, 22.68. Found: C, 55.10; H, 3.88; Cl, 12.51; S, 22.81.
3.37. (E)-1-Chloro-2-(4-methylthiophenyl)-
1-(p-tolylsulfinyl)ethene (29b)
3.44. (3R
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-(4-dimethyl-
*
aminophenyl)-4-(p-tolylsulfinyl)butanoate (30a)
Colorless crystals; mp 102.5–103 ꢁC (hexane/AcOEt); IR (KBr)
Colorless crystals; mp 143–143.5 ꢁC (hexane/AcOEt); IR (KBr)
2965, 1707 (CO), 1615, 1523, 1366 (CN), 1296, 1163, 1054, 969,
1589, 1490, 1434, 1401, 1094, 1083, 1052, 890, 826, 808 cmꢀ1 1H
;
NMR
d
2.42 (3H, s), 2.53 (3H, s), 7.26 (1H, s), 7.28 (2H, d, J¼8.3 Hz),
821 cmꢀ1; 1H NMR
d
1.33 (9H, s), 2.41 (3H, s), 2.80 (2H, d, J¼7.8 Hz),
7.31 (2H, d, J¼8.2 Hz), 7.46 (2H, d, J¼8.2 Hz), 7.49 (2H, d, J¼8.3 Hz).
Anal. Calcd for C16H15ClOS2: C, 59.52; H, 4.68; Cl, 10.98; S, 19.86.
Found: C, 59.56; H, 4.61; Cl, 10.70; S, 19.94.
2.96 (6H, s), 4.32 (1H, dt, J¼7.8, 2.8 Hz), 4.67 (1H, d, J¼2.8 Hz), 6.72
(2H, d, J¼8.0 Hz), 7.29 (2H, d, J¼8.9 Hz), 7.37 (2H, d, J¼8.9 Hz), 7.63
(2H, d, J¼8.0 Hz). Anal. Calcd for C23H30ClNO3S: C, 63.36; H, 6.94; N,
3.21; Cl, 8.13; S, 7.35. Found: C, 63.31; H, 6.94; N, 3.17; Cl, 8.18; S, 7.31.
3.38. (Z)-1-Chloro-2-piperonyl-1-(p-tolylsulfinyl)ethene (28c)
3.45. (3R
*
,4R
*
*
,sS )-tert-Butyl 4-chloro-3-(4-methylsulfanyl-
Colorless crystals; mp 113–113.5 ꢁC (hexane/AcOEt); IR (KBr)
phenyl)-4-(p-tolylsulfinyl)butanoate (30b)
2900, 1622, 1503, 1448, 1264, 1067, 928, 815 cmꢀ1 1H NMR
; d 2.42
(3H, s), 6.01 (2H, s), 6.84 (1H, d, J¼8.1 Hz), 7.20 (1H, dd, J¼8.1,
1.7 Hz), 7.32 (2H, d, J¼8.1 Hz), 7.42 (1H, d, J¼1.7 Hz), 7.51 (1H, s),
7.62 (2H, d, J¼8.1 Hz). Anal. Calcd for C16H13ClO3S: C, 59.91; H, 4.08;
Cl, 11.05; S, 10.00. Found: C, 59.83; H, 4.02; Cl, 10.87; S, 10.03.
Colorless oil; IR (neat) 2978, 1728 (CO), 1598, 1495, 1368, 1258,
1150, 1052, 959, 812, 749 cmꢀ1; 1H NMR
d 1.32 (9H, s), 2.42 (3H, s),
2.77 (3H, s), 2.82 (1H, dd, J¼15.8, 7.8 Hz), 2.84 (1H, dd, J¼15.8,
7.8 Hz), 4.37 (1H, dt, J¼7.8, 2.8 Hz), 4.66 (1H, d, J¼2.8 Hz), 7.26 (2H,
d, J¼8.4 Hz), 7.30 (2H, d, J¼8.1 Hz), 7.44 (2H, d, J¼8.4 Hz), 7.63 (2H,
d, J¼8.1 Hz). MS m/z (%) 438 (Mþ, 8), 365 (18), 298 (12), 243 (70),
242 (50), 206 (70), 178 (18), 140 (100), 139 (25), 115 (23), 57 (84).
Calcd for C22H27ClO3S2: M, 438.1090. Found: m/z 438.1088.
3.39. (E)-1-Chloro-2-piperonyl-1-(p-tolylsulfinyl)ethene (29c)
Colorless crystals; mp 119.5–120 ꢁC (hexane/AcOEt); IR (KBr)
2917, 1585, 1489, 1447, 1258, 1092, 1031, 924, 885, 811 cmꢀ1 1H
;
NMR
d
2.42 (3H, s), 6.05 (2H, s), 6.86 (1H, d, J¼8.0 Hz), 7.00 (1H, dd,
3.46. (3S
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-(4-methyl-
*
J¼8.0, 1.7 Hz), 7.10 (1H, d, J¼1.7 Hz), 7.22 (1H, s), 7.32 (2H, d,
J¼8.1 Hz), 7.51 (2H, d, J¼8.1 Hz). Anal. Calcd for C16H13ClO3S: C,
59.91; H, 4.08; Cl, 11.05; S, 10.00. Found: C, 59.84; H, 3.98; Cl, 10.72;
S, 9.81.
sulfanylphenyl)-4-(p-tolylsulfinyl)butanoate (31b)
Colorless oil; IR (neat) 2979, 1728 (CO), 1597, 1495, 1368, 1259,
1151, 1085, 1052, 1016, 956, 812, 756 cmꢀ1 1H NMR
; d 1.27 (9H, s),

H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
623
2.42 (3H, s), 2.46 (3H, s), 2.97 (1H, dd, J¼16.0, 10.8 Hz), 3.07 (1H,
dd, J¼16.0, 4.8 Hz), 4.17 (1H, ddd, J¼10.8, 4.8, 3.0 Hz), 4.48 (1H, d,
J¼3.0 Hz), 7.20 (2H, d, J¼8.5 Hz), 7.27 (2H, d, J¼8.5 Hz), 7.31 (2H, d,
J¼8.1 Hz), 7.64 (2H, d, J¼8.1 Hz). MS m/z (%) 438 (Mþ, 5), 365 (25),
299 (14), 243 (100), 242 (37), 206 (50),184 (18),140 (94),115 (22), 57
(90). Calcd for C22H27ClO3S2: M, 438.1090. Found: m/z 438.1090.
J¼8.2 Hz). Anal. Calcd for C19H23ClO3S2: C, 57.20; H, 5.81; Cl, 8.89; S,
16.07. Found: C, 57.27; H, 5.76; Cl, 8.77; S, 16.11.
3.52. (3S
*
,4R
*
*
,sS )-tert-Butyl 4-chloro-3-(2-thienyl)-4-
(p-tolylsulfinyl)butanoate (31e)
Colorless oil; IR (neat) 2979, 1732 (CO), 1597, 1494, 1456, 1368,
3.47. (3R
*
,4R
*
,sS
*
)-tert-Butyl 4-chloro-3-(2-piperonyl)-4-
1291, 1258, 1152, 1053, 972, 846, 756, 701 cmꢀ1; 1H NMR
d 1.33 (9H,
(p-tolylsulfinyl)butanoate (30c)
s), 2.43 (3H, s), 2.92 (1H, dd, J¼15.9, 10.5 Hz), 3.10 (1H, dd, J¼15.9,
4.2 Hz), 4.53 (1H, ddd, J¼10.5, 4.2, 2.8 Hz), 4.56 (1H, d, J¼2.8 Hz),
6.96 (1H, dd, J¼5.1, 1.1 Hz), 7.06 (1H, d, J¼3.5 Hz), 7.22 (1H, dd, J¼5.1,
1.1 Hz), 7.33 (2H, d, J¼8.2 Hz), 7.67 (2H, d, J¼8.2 Hz). MS m/z (%) 398
(Mþ, 5), 325 (21), 203 (29), 185 (12), 166 (18), 140 (100), 139 (18),
123 (13), 57 (73). Calcd for C19H23ClO3S2: M, 398.0777. Found: m/z
398.0780.
Colorless amorphous; IR (neat) 2979, 1727 (CO),1491, 1368, 1253
(COC),1151,1042 (SO), 934 cmꢀ1; 1H NMR
d 1.34 (9H, s), 2.42 (3H, s),
2.78 (1H, dd, J¼16.0, 8.0 Hz), 2.79 (1H, dd, J¼16.0, 8.0 Hz), 4.34 (1H,
dt, J¼7.8, 2.9 Hz), 4.63 (1H, d, J¼3.0 Hz), 5.98 (2H, s), 6.83 (1H, dd,
J¼7.2, 1.4 Hz), 7.01 (1H, s), 7.02 (1H, dd, J¼7.2, 1.8 Hz), 7.30 (2H, d,
J¼8.2 Hz), 7.63 (2H, d, J¼8.2 Hz). MS m/z (%) 436 (Mþ, 12), 363 (12),
241 (40), 240 (36), 204 (42), 140 (100), 139 (22), 91 (13), 57 (79).
Calcd for C22H25ClO5S: M, 436.1112. Found: m/z 436.1107.
3.53. (Z)-tert-Butyl 4-(4-dimethylaminophenyl)-
3-butenoate (33a)
3.48. (3S
*
,4R
*
,sS
*
)-tert-Butyl 4-chloro-3-(2-piperonyl)-4-
Colorless oil; IR (neat) 2978, 1732 (CO), 1611, 1523, 1446, 1393,
(p-tolylsulfinyl)butanoate (31c)
1367 (CN), 1256, 1147, 948, 829 cmꢀ1 1H NMR
; d 1.46 (9H, s), 2.96
(6H, s), 3.28 (2H, dd, J¼7.3, 1.9 Hz), 5.69 (1H, dt, J¼11.6, 7.3 Hz), 6.49
(1H, d, J¼11.6 Hz), 6.71 (2H, d, J¼8.5 Hz), 7.20 (2H, d, J¼8.5 Hz). MS
m/z (%) 261 (Mþ, 45), 205 (40), 188 (11), 160 (100), 144 (13), 116 (10),
115 (12), 57 (19). Calcd for C16H23 NO2: M, 261.1729. Found: m/z
261.1726.
Colorless amorphous; IR (neat) 2977, 2929, 1733 (CO), 1504,
1488, 1368, 1242 (COC), 1149, 1040 (SO), 935 cmꢀ1 1H NMR
; d 1.30
(9H, s), 2.42 (3H, s), 2.92 (1H, dd, J¼16.0, 10.8 Hz), 3.04 (1H, dd,
J¼16.0, 4.7 Hz), 4.12 (1H, ddd, J¼7.6, 4.5, 3.1 Hz), 4.48 (1H, d,
J¼2.9 Hz), 5.94 (2H, s), 6.76 (1H, d, J¼8.0 Hz), 6.81 (1H, dd, J¼8.1,
1.7 Hz), 6.85 (1H, d, J¼1.7 Hz), 7.32 (2H, d, J¼8.3 Hz), 7.64 (2H, d,
J¼8.3 Hz). MS m/z (%) 436 (Mþ, 7), 363 (12), 241 (46), 205 (65), 204
(39), 182 (16), 140 (100), 139 (22), 91 (16), 57 (96). Calcd for
C22H25ClO5S: M, 436.1111. Found: m/z 436.1112.
3.54. tert-Butyl 3-(4-methylsulfanylphenyl)-
3-butenoate (32b)
Colorless oil; IR (neat) 2978, 1732 (CO), 1596, 1496, 1368, 1257,
1148, 967, 829 cmꢀ1; 1H NMR
d 1.36 (9H, s), 2.48 (3H, s), 3.40 (2H, d,
3.49. (3R
*
,4R
*
,sS
*
)-tert-Butyl 4-chloro-3-(2-furyl)-4-
J¼1.0 Hz), 5.17 (1H, d, J¼1.0 Hz), 5.49 (1H, d, J¼0.7 Hz), 7.21 (2H, d,
J¼8.6 Hz), 7.36 (2H, d, J¼8.6 Hz). MS m/z (%) 264 (Mþ,16), 208 (100),
191 (15), 163 (8), 149 (12), 115 (24), 57 (52). Calcd for C15H20O2S: M,
264.1183. Found: m/z 264.1183.
(p-tolylsulfinyl)butanoate (30d)
Colorless crystals; mp 89–89.5 ꢁC (hexane/AcOEt); IR (KBr)
2979, 1732 (CO), 1596, 1494, 1368, 1291, 1152, 1055, 913, 813,
738 cmꢀ1; 1H NMR
d
1.39 (9H, s), 2.43 (3H, s), 2.77 (1H, dd, J¼16.1,
3.55. (Z)-tert-Butyl 4-(4-methylsulfanylphenyl)-
3-butenoate (33b)
7.7 Hz), 2.91 (1H, dd, J¼16.1, 7.7 Hz), 4.52 (1H, dt, J¼7.7, 2.8 Hz), 4.59
(1H, d, J¼2.8 Hz), 6.40 (1H, dd, J¼3.2, 1.8 Hz), 6.45 (1H, d, J¼3.2 Hz),
7.32 (2H, d, J¼8.1 Hz), 7.46 (1H, d, J¼1.8 Hz), 7.67 (2H, d, J¼8.1 Hz).
Anal. Calcd for C19H23ClO4S: C, 59.60; H, 6.05; Cl, 9.26; S, 8.37.
Found: C, 59.31; H, 5.69; Cl, 8.95; S, 8.43.
Colorless oil; IR (neat) 2978, 1729 (CO), 1596, 1494, 1368, 1329,
1257, 1148, 955, 840 cmꢀ1; 1H NMR
d 1.46 (9H, s), 2.49 (3H, s), 3.24
(2H, dd, J¼7.4, 1.8 Hz), 5.85 (1H, dt, J¼11.6, 7.4 Hz), 6.54 (1H, dt,
J¼11.6, 1.8 Hz), 7.21 (2H, d, J¼8.8 Hz), 7.23 (2H, d, J¼8.8 Hz). MS m/z
(%) 264 (Mþ, 40), 208 (12), 191 (13), 163 (45), 147 (8), 115 (39), 57
(100). Calcd for C15H20O2S: M, 264.1182. Found: m/z 264.1179.
3.50. (3S
*
,4R
*
,sS )-tert-Butyl 4-chloro-3-(2-furyl)-4-
*
(p-tolylsulfinyl)butanoate (31d)
Colorless oil; IR (neat) 2978, 1739 (CO), 1595, 1501, 1451, 1369,
3.56. (E)-tert-Butyl 4-(4-methylsulfanylphenyl)-
3-butenoate (34b)
1264, 1151, 1042, 947, 850, 747 cmꢀ1
;
1H NMR
d
1.37 (9H, s), 2.43
(3H, s), 2.87 (1H, dd, J¼16.0, 10.8 Hz), 3.02 (1H, dd, J¼16.0, 4.1 Hz),
4.26 (1H, dt, J¼10.8, 4.1 Hz), 4.72 (1H, d, J¼3.7 Hz), 6.26 (1H, d,
J¼3.3 Hz), 6.33 (1H, dd, J¼3.3, 1.8 Hz), 7.34 (2H, d, J¼8.2 Hz), 7.36
(1H, d, J¼1.8 Hz), 7.67 (2H, d, J¼8.2 Hz). MS m/z (%) 382 (Mþ, 5), 309
(32), 243 (7), 187 (36), 150 (14), 140 (100), 123 (11), 92 (14), 77 (12),
57 (73), 41 (8). Calcd for C19H23ClO4S: M, 382.1006. Found: m/z
382.1015.
Colorless oil; IR (neat) 2978, 1726 (CO), 1596, 1494, 1393, 1368,
1257, 1147, 968, 846 cmꢀ1; 1H NMR
d 1.47 (9H, s), 2.48 (3H, s), 3.14
(2H, dd, J¼7.0, 1.4 Hz), 6.25 (1H, dt, J¼15.9, 7.0 Hz), 6.40 (1H, d,
J¼15.9 Hz), 7.19 (2H, d, J¼8.4 Hz), 7.29 (2H, d, J¼8.4 Hz). MS m/z (%)
264 (Mþ, 44), 208 (14), 163 (72), 147 (8), 115 (39), 57 (100). Calcd for
C15H20O2S: M, 264.1183. Found: m/z 264.1190.
3.51. (3R
*
,4R
*
,sS
*
)-tert-Butyl 4-chloro-3-(2-thienyl)-4-
3.57. tert-Butyl 3-(2-piperonyl)-3-butenoate (32c)
(p-tolylsulfinyl)butanoate (30e)
Colorless oil; IR (neat) 2922, 1732 (CO), 1505, 1493, 1445, 1368,
Colorless crystals; mp 105.5–106 ꢁC (hexane/AcOEt); IR (KBr)
2979, 1723 (CO), 1452, 1396, 1368, 1265, 1166, 1043, 851, 815,
1235 (COC), 1146, 1040, 937, 813 cmꢀ1; 1H NMR
d 1.38 (9H, s), 3.37
(2H, d, J¼1.0 Hz), 5.12 (1H, d, J¼0.9 Hz), 5.40 (1H, d, J¼0.9 Hz), 5.95
(2H, s), 6.76 (1H, d, J¼8.1 Hz), 6.90 (1H, dd, J¼8.1, 1.8 Hz), 6.95 (1H,
d, J¼1.8 Hz). MS m/z (%) 262 (Mþ, 17), 206 (100), 189 (16), 178 (16),
103 (14), 57 (26). Calcd for C15H18O4: M, 262.1205. Found: m/z
262.1204.
717 cmꢀ1; 1H NMR
d
1.36 (9H, s), 2.42 (3H, s), 2.81 (1H, dd, J¼16.0,
7.8 Hz), 2.85 (1H, dd, J¼16.0, 7.8 Hz), 4.67 (1H, d, J¼2.8 Hz), 4.75
(1H, dt, J¼7.8, 2.8 Hz), 7.05 (1H, dd, J¼5.1, 3.5 Hz), 7.26 (1H, d,
J¼3.5 Hz), 7.31 (2H, d, J¼8.2 Hz), 7.33 (1H, d, J¼5.1 Hz), 7.65 (2H, d,

624
H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
3.58. (Z)-tert-Butyl 4-(2-piperonyl)-3-butenoate (33c)
and the whole was extracted with CHCl3 and the organic layer was
dried over MgSO4. The solvent was evaporated to give a residue,
which was purified by silica gel column chromatography to give
224 mg (80%) of 36 as colorless crystals and 55 mg (19%) of 37 as
colorless crystals. Compound 36: mp 127.5–128 ꢁC (hexane/AcOEt);
IR (KBr) 2975, 1723 (CO), 1432, 1366, 1285, 1157, 1056, 849, 813,
Colorless oil; IR (neat) 2978, 1731 (CO), 1490, 1442, 1368, 1237
(COC), 1147, 1040, 846, 820 cmꢀ1 1H NMR
; d 1.47 (9H, s), 3.23 (2H,
dd, J¼7.3, 1.9 Hz), 5.79 (1H, dt, J¼11.6, 7.3 Hz), 5.96 (2H, s), 6.50 (1H,
dt, J¼11.5, 1.8 Hz), 6.75 (1H, dd, J¼8.1, 1.5 Hz), 6.78 (1H, d, J¼7.4 Hz),
6.80 (1H, d, J¼1.9 Hz). MS m/z (%) 262 (Mþ, 100), 189 (55), 161 (77),
131 (90), 103 (40), 57 (86). Calcd for C15H18O4: M, 262.1205. Found:
m/z 262.1207.
714 cmꢀ1; 1H NMR
d 1.27 (9H, s), 1.41 (3H, s), 2.44 (3H, s), 2.83 (1H,
dd, J¼15.3, 11.8 Hz), 3.17 (1H, dd, J¼15.3, 3.3 Hz), 4.15 (1H, dd,
J¼11.8, 3.3 Hz), 6.96 (1H, dd, J¼4.8, 3.6 Hz), 7.06 (1H, d, J¼3.6 Hz),
7.26 (1H, d, J¼4.8 Hz), 7.33 (2H, d, J¼8.1 Hz), 7.59 (2H, d, J¼8.1 Hz).
Anal. Calcd for C20H25ClO3S2: C, 58.17; H, 6.10; Cl, 8.58; S, 15.53.
Found: C, 58.16; H, 6.00; Cl, 8.55; S, 15.57. Compound 37: mp 111–
111.5 ꢁC (hexane/AcOEt); IR (KBr) 2977, 1731 (CO), 1371, 1355, 1251,
3.59. (E)-tert-Butyl 4-(2-piperonyl)-3-butenoate (34c)
Colorless oil; IR (neat) 2978, 1731 (CO), 1490, 1446, 1368, 1250
(COC), 1147, 1040, 964, 937, 801 cmꢀ1
;
1H NMR
d
1.47 (9H, s), 3.12
1153, 1051, 851, 809 cmꢀ1 1H NMR
; d 1.27 (9H, s), 1.54 (3H, s), 2.41
(2H, dd, J¼7.2, 1.5 Hz), 5.95 (2H, s), 6.11 (1H, dt, J¼15.8, 7.2 Hz), 6.37
(1H, d, J¼15.8 Hz), 6.73 (1H, d, J¼8.0 Hz), 6.78 (1H, dd, J¼8.0,1.6 Hz),
6.92 (1H, d, J¼1.6 Hz). MS m/z (%) 262 (Mþ, 88), 206 (54), 161 (100),
131 (93), 103 (44), 57 (93). Calcd for C15H18O4: M, 262.1205. Found:
m/z 262.1207.
(3H, s), 2.84 (1H, dd, J¼15.0, 10.0 Hz), 2.88 (1H, dd, J¼15.0, 5.2 Hz),
4.34 (1H, dd, J¼10.0, 5.2 Hz), 7.01 (1H, dd, J¼5.0, 3.5 Hz), 7.26–7.30
(3H, m), 7.32 (1H, d, J¼5.0 Hz), 7.59 (2H, d, J¼8.3 Hz). Anal. Calcd for
C20H25ClO3S2: C, 58.17; H, 6.10. Found: C, 58.16; H, 6.00.
3.65. (3S
*
,4R
*
,sS
*
)-tert-Butyl 4-chloro-3-(2-thienyl)-4-(p-tolyl-
,4S ,sS )-isomer (42)
3.60. (Z)-tert-Butyl 4-(2-furyl)-3-butenoate (33d)
sulfinyl)pentanoate (41) and (3S
*
*
*
Colorless oil; IR (neat) 2980, 1732 (CO), 1490, 1369, 1277, 1150,
Compound 41: colorless crystals; mp 121–121.5 ꢁC (hexane/
1013, 961, 735 cmꢀ1
;
1H NMR
d
1.47 (9H, s), 3.47 (2H, dd, J¼7.0,
AcOEt); IR (KBr) 2976, 1715 (CO), 1478, 1437, 1368, 1292, 1148, 1055,
853, 701 cmꢀ1; 1H NMR
d 1.25 (3H, s), 1.28 (9H, s), 2.43 (3H, s), 2.95
1.9 Hz), 5.76 (1H, dt, J¼11.6, 7.0 Hz), 6.29 (1H, d, J¼3.4 Hz), 6.31 (1H,
dt, J¼11.6, 1.8 Hz), 6.39 (1H, dd, J¼3.4, 1.8 Hz), 7.40 (1H, d, J¼1.8 Hz),
MS m/z (%) 208 (Mþ, 15), 152 (8), 135 (8), 108 (8), 107 (45), 77 (17),
57 (100). Calcd for C12H16O3: M, 208.1098. Found: m/z 208.1098.
(1H, dd, J¼15.3, 11.6 Hz), 3.34 (1H, dd, J¼15.3, 3.6 Hz), 4.33 (1H, dd,
J¼11.6, 3.6 Hz), 6.96 (1H, dd, J¼5.1, 3.6 Hz), 7.04 (1H, dd, J¼3.6,
1.0 Hz), 7.23 (1H, dd, J¼5.1, 1.0 Hz), 7.33 (2H, d, J¼8.3 Hz), 7.66 (2H,
d, J¼8.3 Hz). Anal. Calcd for C20H25ClO3S2: C, 58.17; H, 6.10; Cl, 8.58;
S, 15.53. Found: C, 58.29; H, 6.11; Cl, 8.51; S, 15.50. Compound 42:
colorless oil; IR (neat) 2979, 1732 (CO), 1597, 1456, 1369, 1287, 1152,
3.61. (E)-tert-Butyl 4-(2-furyl)-3-butenoate (34d)
1057, 844, 759, 702 cmꢀ1 1H NMR
; d 1.24 (9H, s), 1.65 (3H, s), 2.43
Colorless oil; IR (neat) 2980, 1732 (CO), 1458, 1393, 1369, 1331,
1257, 1150, 1013, 732 cmꢀ1 1H NMR
; d 1.46 (9H, s), 3.11 (2H, d,
(3H, s), 2.84 (1H, dd, J¼15.6, 11.7 Hz), 3.37 (1H, dd, J¼15.6, 3.4 Hz),
4.00 (1H, dd, J¼11.7, 3.4 Hz), 6.96 (1H, dd, J¼5.1, 3.6 Hz), 7.01 (1H,
dd, J¼3.6, 1.0 Hz), 7.25 (1H, dd, J¼5.1, 1.0 Hz), 7.33 (2H, d, J¼8.1 Hz),
7.61 (2H, d, J¼8.1 Hz). MS (FAB) m/z (%) 413 ([MþH]þ, 37), 357 (100),
339 (7), 321 (5), 217 (27), 181 (76), 139 (16), 123 (13), 57 (18). Calcd
for C20H26ClO3S2: M, 413.1012. Found: m/z 413.1010.
J¼6.5 Hz), 6.19 (1H, d, J¼3.3 Hz), 6.20 (1H, dt, J¼15.8, 6.5 Hz), 6.29
(1H, d, J¼15.8 Hz), 6.35 (1H, dd, J¼3.3, 1.6 Hz), 7.33 (1H, d, J¼1.6 Hz),
MS m/z (%) 208 (Mþ, 18),152 (11),108 (8), 107 (53), 77 (15), 57 (100),
41 (18), 28 (31). Calcd for C12H16O3: M, 208.1099. Found: m/z
208.1108.
3.62. (Z)-tert-Butyl 4-(2-thienyl)-3-butenoate (33e)
3.66. (Z)-tert-Butyl 3-(2-thienyl)-3-pentenoate (38)
Colorless oil; IR (neat) 2979, 1732 (CO), 1393, 1368, 1330, 1258,
1149, 847, 697 cmꢀ1
;
1H NMR
d
1.48 (9H, s), 3.37 (2H, dd, J¼7.0,
EtMgCl (2.0 M solution in diethyl ether, 0.1 mL, 0.2 mmol) was
added to dry toluene (1.9 mL) at 0 ꢁC. A solution of 36 (50 mg,
0.12 mmol) in toluene (0.5 mL) was added dropwise to the solution
of EtMgCl and the reaction mixture was stirred at 0 ꢁC for 30 min.
The reaction was quenched by adding satd aq NH4Cl. The whole was
extracted with CHCl3 and the organic layer was dried over MgSO4
and the solvent was evaporated. The residue was purified by silica
gel column chromatography to give 24.5 mg (85%) of 38 as colorless
oil. IR (neat) 2978, 1732 (CO), 1455, 1392, 1368, 1329, 1256, 1146,
2.0 Hz), 5.82 (1H, dt, J¼11.6, 7.0 Hz), 6.67 (1H, dt, J¼11.6, 2.0 Hz),
7.02 (2H, d, J¼3.6 Hz), 7.28 (1H, d, J¼3.6 Hz). MS m/z (%) 224 (Mþ,
24), 168 (3), 151 (14), 123 (67), 121 (7), 97 (6), 79 (8), 57 (100). Calcd
for C12H16O2S: M, 224.0871. Found: m/z 224.0871.
3.63. (E)-tert-Butyl 4-(2-thienyl)-3-butenoate (34e)
Colorless oil; IR (neat) 2978, 1729 (CO), 1392, 1368, 1336, 1256,
843, 696 cmꢀ1
;
1H NMR
d
1.37 (9H, s), 1.89 (3H, d, J¼7.1 Hz), 3.30
1207, 1147, 955, 851, 696 cmꢀ1; 1H NMR
d 1.47 (9H, s), 3.12 (2H, dd,
(2H, t, J¼1.0 Hz), 5.74 (1H, q, J¼7.1 Hz), 6.99 (1H, dd, J¼3.6, 1.3 Hz),
7.01 (1H, dd, J¼5.0, 3.6 Hz), 7.26 (1H, dd, J¼5.0, 1.0 Hz). MS m/z (%)
238 (Mþ, 6), 183 (10), 182 (100), 154 (16), 137 (29), 123 (25), 111 (5),
97 (17), 57 (37). Calcd for C13H18O2S: M, 238.1027. Found: m/z
238.1027.
J¼7.2, 1.4 Hz), 6.12 (1H, dt, J¼15.6, 7.2 Hz), 6.58 (1H, d, J¼15.6, Hz),
6.91–6.96 (2H, m), 7.13 (1H, d, J¼5.0 Hz). MS m/z (%) 224 (Mþ, 24),
168 (10), 123 (80), 121 (7), 97 (7), 79 (8), 77 (6), 57 (100). Calcd for
C12H16O2S: M, 224.0871. Found: m/z 224.0871.
3.64. (3R
*
,4S
*
*
,sS )-tert-Butyl 4-chloro-3-(2-thienyl)-4-(p-tolyl-
sulfinyl)pentanoate (36) and (3R
*
,4R ,sS )-isomer (37)
*
*
3.67. tert-Butyl 4-chloro-3-(2-thienyl)pentanoate (39)
tert-Butyl acetate (0.38 mL, 2.83 mmol) was added to a solution
of LDA (2.83 mmol) in 12 mL of dry THF at ꢀ78 ꢁC with stirring. The
solution was stirred for 10 min and then a solution of 28e (200 mg,
0.71 mmol) in THF (2 mL) was added. The reaction mixture was
stirred for 5 min and CH3I (0.44 mL, 7.07 mmol) was added and
stirred for 5 min. The reaction was quenched with satd aq NH4Cl
Colorless oil; IR (neat) 2978, 1732 (CO), 1455, 1368, 1281, 1258,
1150, 846 cmꢀ1
;
1H NMR
d
1.31 (9H, s), 1.43 (3H, d, J¼6.6 Hz), 2.62
(1H, dd, J¼15.5,10.1 Hz), 3.04 (1H, dd, J¼15.5, 4.7 Hz), 3.61 (1H, ddd,
J¼10.1, 7.5, 6.6 Hz), 4.15 (1H, dq, J¼7.5, 6.6 Hz), 6.91 (1H, dd, J¼3.5,
1.2 Hz), 6.94 (1H, dd, J¼5.0, 3.5 Hz), 7.19 (1H, dd, J¼5.0, 1.2 Hz). MS
(ESI) m/z (%) 275 ([MþH]þ, 17), 261 (100), 249 (39), 239 (13), 185

H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
625
(25), 137 (8). Calcd for C13H20ClO2S: M, 275.0870. Found: m/z
275.0867.
6.75–6.79 (2H, m), 6.83 (1H, d, J¼1.3 Hz), 7.33 (2H, d, J¼8.1 Hz), 7.60
(2H, d, J¼8.1 Hz). Anal. Calcd for C23H27ClO5S: C, 61.26; H, 6.03; Cl,
7.86; S, 7.11. Found: C, 61.30; H, 6.02.
3.68. (Z)-tert-Butyl 2-methyl-3-(2-thienyl)-2-
(p-tolylsulfinyl)cyclopropanecarboxylate (43)
3.73. tert-Butyl 4-chloro-3-phenyl-4-(p-tolylsulfinyl)-
pentanoate (45c)
A solution of 36 (100 mg, 0.24 mmol) in 1 mL of dry THF was
added to a solution of LDA (0.29 mmol) in 4 mL of THF at ꢀ78 ꢁC
with stirring. The reaction mixture was slowly allowed to warm to
0 ꢁC and the reaction was quenched by adding satd aq NH4Cl. The
whole was extracted with CHCl3 and the organic layer was dried
over MgSO4. The solvent was evaporated to give a residue, which
was purified by silica gel column chromatography to give 48 mg
(53%) of 43 as colorless crystals. Colorless crystals; mp 144.5–145 ꢁC
(hexane/AcOEt); IR (KBr) 2978, 1727 (CO), 1455, 1412, 1369, 1215,
Isolable main product derived from 19e: colorless crystals; mp
159–159.5 ꢁC (hexane/AcOEt); IR (KBr) 2977, 1717 (CO), 1366, 1293,
1155, 1055, 814, 757 cmꢀ1; 1H NMR
d 1.19 (9H, s), 1.31 (3H, s), 2.44
(3H, s), 2.94 (1H, dd, J¼15.3, 11.7 Hz), 3.12 (1H, dd, J¼15.3, 3.7 Hz),
3.83 (1H, dd, J¼11.7, 3.7 Hz), 7.29–7.35 (7H, m), 7.59 (2H, d,
J¼8.2 Hz). Anal. Calcd for C22H27ClO3S: C, 64.93; H, 6.69. Found: C,
64.76; H, 6.75.
1152, 1091, 1052, 809, 703 cmꢀ1; 1H NMR
d
1.27 (3H, s), 1.40 (9H, s),
3.74. tert-Butyl 4-chloro-3-phenyl-4-(p-tolylsulfinyl)-
2.41 (3H, s), 2.68 (1H, d, J¼6.3 Hz), 3.12 (1H, dd, J¼6.3, 0.8 Hz), 7.00
(1H, dd, J¼5.1, 3.5 Hz), 7.16 (1H, dt, J¼3.5, 1.1 Hz), 7.27 (1H, dd, J¼5.1,
1.1 Hz), 7.30 (2H, d, J¼8.1 Hz), 7.55 (2H, d, J¼8.1 Hz). Anal. Calcd for
C20H24O3S2: C, 63.80; H, 6.42; S, 17.03. Found: C, 63.78; H, 6.26; S,
16.95.
pentanoate (45c)
Isolable main product derived from 20e: colorless crystals; mp
126.0–126.5 ꢁC (hexane/AcOEt); IR (KBr) 2980, 1711 (CO), 1370,
1301, 1146, 1087, 1057, 812, 701 cmꢀ1 1H NMR
; d 1.15 (9H, s), 1.57
(3H, s), 2.43 (3H, s), 3.00 (1H, dd, J¼15.6, 12.2 Hz), 3.42 (1H, dd,
J¼15.6, 3.8 Hz), 3.77 (1H, dd, J¼12.2, 3.8 Hz), 7.29–7.34 (7H, m), 7.61
(2H, d, J¼8.2 Hz). Anal. Calcd for C22H27ClO3S: C, 64.93; H, 6.69.
Found: C, 64.68; H, 6.79.
3.69. (E)-tert-Butyl 2-methyl-3-(2-thienyl)-2-(p-tolylsulfinyl)-
cyclopropanecarboxylate (44)
Colorless crystals; mp 131.5–132 ꢁC (hexane/AcOEt); IR (KBr)
2984, 1716 (CO), 1459, 1412, 1366, 1260, 1153, 1033, 809, 692 cmꢀ1
;
3.75. tert-Butyl 4-chloro-3-(2-phenylethyl)-4-(p-tolyl-
sulfinyl)pentanoate (45d)
1H NMR
d
0.97 (3H, s), 1.55 (9H, s), 2.30 (1H, d, J¼6.6 Hz), 2.42 (3H,
s), 3.74 (1H, dd, J¼6.6, 1.0 Hz), 6.91 (1H, dt, J¼3.5, 1.1 Hz), 6.95 (1H,
dd, J¼5.1, 3.5 Hz), 7.20 (1H, dd, J¼5.1, 1.1 Hz), 7.31 (2H, d, J¼8.2 Hz),
7.52 (2H, d, J¼8.2 Hz). Anal. Calcd for C20H24O3S2: C, 63.80; H, 6.42;
S, 17.03. Found: C, 63.82; H, 6.42; S, 16.85.
Isolable main product derived from 19a: colorless crystals; mp
131–131.5 ꢁC (hexane/AcOEt); IR (KBr) 2972, 1718 (CO), 1597, 1495,
1372, 1281, 1214, 1145, 1061, 811, 702 cmꢀ1; 1H NMR
d 1.48 (9H, s),
1.49 (3H, s), 1.65–1.72 (1H, m), 2.07–2.14 (1H, m), 2.44 (3H, s), 2.45
(1H, dd, J¼16.3, 8.3 Hz), 2.51–2.69 (3H, m), 2.96 (1H, dd, J¼16.3,
3.1 Hz), 7.14 (2H, d, J¼7.6 Hz), 7.18 (1H, t, J¼7.3 Hz), 7.24–7.27 (2H,
m), 7.33 (2H, d, J¼8.1 Hz), 7.63 (2H, d, J¼8.1 Hz). Anal. Calcd for
C24H31ClO3S: C, 66.26; H, 7.18; Cl, 8.15; S, 7.37. Found: C, 65.95; H,
7.12.
3.70. tert-Butyl 4-chloro-3-(4-methoxyphenyl)-4-(p-tolyl-
sulfinyl)pentanoate (45a)
Isolable main product: colorless crystals; mp 151–151.5 ꢁC
(hexane/AcOEt); IR (KBr) 2973, 1717 (CO), 1610, 1515, 1365, 1290,
1254, 1156, 1055, 811 cmꢀ1; 1H NMR
d 1.21 (9H, s), 1.31 (3H, s), 2.43
(3H, s), 2.89 (1H, dd, J¼15.2, 11.8 Hz), 3.10 (1H, dd, J¼15.2, 3.8 Hz),
3.79 (3H, s), 3.81 (1H, dd, J¼11.8, 3.8 Hz), 6.85 (2H, d, J¼8.8 Hz), 7.26
(2H, d, J¼8.8 Hz), 7.32 (2H, d, J¼8.1 Hz), 7.58 (2H, d, J¼8.1 Hz). Anal.
Calcd for C23H29ClO4S: C, 63.22; H, 6.69; Cl, 8.11; S, 7.34. Found: C,
63.24; H, 6.61; Cl, 8.08; S, 7.37.
3.76. tert-Butyl 4-chloro-3-(2-phenylethyl)-4-(p-tolyl-
sulfinyl)pentanoate (45d)
Isolable main product derived from 20a: colorless oil; IR (neat)
2978, 1723 (CO), 1598, 1456, 1368, 1259, 1151, 1085, 1049, 754 cmꢀ1
;
1H NMR
d 1.39 (9H, s), 1.51 (3H, s), 1.78–1.91 (1H, m), 2.19–2.30 (1H,
3.71. tert-Butyl 4-chloro-3-(2-piperonyl)-4-(p-tolylsulfinyl)-
pentanoate (45b)
m), 2.35–2.48 (2H, m), 2.44 (3H, s), 2.56 (1H, ddd, J¼13.8, 9.8,
6.8 Hz), 2.73–2.81 (1H, m), 2.83–2.90 (1H, m), 7.20–7.27 (5H, m),
7.31–7.36 (4H, m). MS m/z (%) 435 (Mþ, 33), 379 (78), 361 (5), 325
(10), 239 (7), 203 (100), 143 (53), 140 (21), 91 (25), 57 (23). Calcd for
C24H31ClO3S: M, 435.1760. Found: m/z 435.1763.
Isolable main product derived from 28c: colorless crystals; mp
153.5–154 ꢁC (hexane/AcOEt); IR (KBr) 2974, 1715 (CO), 1492, 1447,
1367, 1291, 1249, 1155, 1054, 933, 811 cmꢀ1; 1H NMR
d 1.26 (9H, s),
1.31 (3H, s), 2.44 (3H, s), 2.84 (1H, dd, J¼15.3, 11.8 Hz), 3.07 (1H, dd,
J¼15.3, 3.6 Hz), 3.75 (1H, dd, J¼11.8, 3.6 Hz), 5.95 (2H, s), 6.74 (1H, d,
J¼8.1 Hz), 6.78 (1H, dd, J¼8.1, 1.6 Hz), 6.87 (1H, d, J¼1.6 Hz), 7.33
(2H, d, J¼8.2 Hz), 7.58 (2H, d, J¼8.2 Hz). Anal. Calcd for C23H27ClO5S:
C, 61.26; H, 6.03; Cl, 7.86; S, 7.11. Found: C, 61.18; H, 5.95; Cl, 7.82; S,
7.10.
3.77. (Z)-tert-Butyl 3-(4-methoxyphenyl)-3-pentenoate (46a)
Colorless oil; IR (neat) 2979, 1732 (CO), 1610, 1513, 1456, 1367,
1289, 1248, 1148, 1036, 837 cmꢀ1 1H NMR
; d 1.31 (9H, s), 1.64 (3H,
dt, J¼6.9, 1.1 Hz), 3.23 (2H, t, J¼1.1 Hz), 3.81 (3H, s), 5.65 (1H, tq,
J¼6.9, 1.1 Hz), 6.86 (2H, d, J¼8.9 Hz), 7.13 (2H, d, J¼8.9 Hz). MS m/z
(%) 262 (Mþ, 12), 206 (100), 189 (8), 161 (25), 147 (55), 121 (15), 115
(6), 91 (7), 57 (31). Calcd for C16H22O3: M, 262.1569. Found: m/z
262.1570.
3.72. tert-Butyl 4-chloro-3-(2-piperonyl)-4-(p-tolylsulfinyl)-
pentanoate (45b)
Isolable main product derived from 29c: colorless crystals; mp
3.78. (Z)-tert-Butyl 3-(2-piperonyl)-3-pentenoate (46b)
125–125.5 ꢁC (hexane/AcOEt); IR (KBr) 2981, 1708 (CO), 1491, 1445,
1369, 1300, 1237, 1148, 1052, 1034, 929, 806 cmꢀ1
;
1H NMR
d
1.22
Colorless oil; IR (neat) 2978, 1732 (CO), 1489, 1435, 1367, 1331,
(9H, s), 1.56 (3H, s), 2.43 (3H, s), 2.90 (1H, dd, J¼15.7, 12.1 Hz), 3.38
1240, 1155, 1040, 938, 814 cmꢀ1; 1H NMR
d
1.34 (9H, s), 1.63 (3H, dt,
(1H, dd, J¼15.7, 3.7 Hz), 3.67 (1H, dd, J¼12.1, 3.7 Hz), 5.96 (2H, s),
J¼6.8, 1.1 Hz), 3.20 (2H, t, J¼1.1 Hz), 5.65 (1H, tq, J¼6.8, 1.1 Hz), 5.94

626
H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
(2H, s), 6.66 (1H, dd, J¼7.8, 1.7 Hz), 6.70 (1H, d, J¼1.7 Hz), 6.77 (1H,
d, J¼7.8 Hz). MS m/z (%) 276 (Mþ, 15), 220 (100), 203 (13), 175 (14),
161 (27), 145 (13), 131 (23), 115 (11), 103 (5), 57 (31). Calcd for
C16H20O4: M, 276.1361. Found: m/z 276.1361.
3.84. tert-Butyl 4-chloro-3-(2-thienyl)-4-(p-tolylsulfinyl)-6-
heptenoate (47b)
Isolable main product derived from 29e: colorless oil; IR (neat)
2979, 1732 (CO), 1640, 1597, 1429, 1368, 1256, 1153, 1051, 927, 812,
757 cmꢀ1 1H NMR
; d 1.23 (9H, s), 2.45 (3H, s), 2.68–2.84 (2H, m),
3.79. (Z)-tert-Butyl 3-phenyl-3-pentenoate (46c)
2.91 (1H, dd, J¼16.1, 12.0 Hz), 3.62 (1H, dd, J¼16.1, 3.0 Hz), 3.92 (1H,
dd, J¼12.0, 3.0 Hz), 5.33 (1H, dd, J¼5.5, 1.6 Hz), 5.37 (1H, d,
J¼0.9 Hz), 5.99 (1H, m), 6.94 (1H, dd, J¼5.0, 3.6 Hz), 6.97 (1H, dd,
J¼3.6, 1.2 Hz), 7.23 (1H, dd, J¼5.0, 1.2 Hz), 7.35 (2H, d, J¼8.1 Hz), 7.68
(2H, d, J¼8.1 Hz). MS (FAB) m/z (%) 439 ([MþH]þ, 36), 383 (100), 365
(11), 263 (8), 243 (34), 207 (81), 161 (25), 159 (36), 140 (28), 123
(22), 57 (48). Calcd for C22H28ClO3S2: M, 439.1168. Found: m/z
439.1163.
Colorless oil; IR (neat) 2979, 1732 (CO), 1455, 1392, 1368, 1257,
1148, 701 cmꢀ1
;
1H NMR
d
1.30 (9H, s), 1.64 (3H, d, J¼6.9 Hz), 3.26
(2H, t, J¼1.1 Hz), 5.69 (1H, tq, J¼6.9, 1.1 Hz), 7.19–7.25 (3H, m), 7.31–
7.34 (2H, m). MS m/z (%) 232 (Mþ, 2), 176 (100),159 (9), 148 (10), 131
(42), 117 (23), 115 (22), 91 (26), 77 (8), 57 (92). Calcd for C15H20O2:
M, 232.1463. Found: m/z 232.1465.
3.80. (E)-tert-Butyl 3-(2-phenylethyl)-3-pentenoate (46d)
3.85. tert-Butyl 3-(2-thienyl)-4-hexenoate (48a)
Colorless oil; IR (neat) 2978, 1732 (CO), 1496, 1455, 1368, 1257,
Colorless oil (5:2 mixture of two diastereomers); IR (neat) 2978,
1732 (CO), 1456, 1393, 1368, 1255, 1151, 964, 848, 764, 695 cmꢀ1; 1H
1148, 747, 699 cmꢀ1
;
1H NMR
d
1.46 (9H, s), 1.54 (3H, d, J¼6.7 Hz),
2.40–2.43 (2H, m), 2.66–2.69 (2H, m), 2.92 (2H, s), 5.39 (1H, q,
J¼6.7 Hz), 7.17–7.20 (3H, m), 7.25–7.29 (2H, m). MS m/z (%) 260 (Mþ,
10), 204 (100), 187 (14), 175 (16), 144 (75), 143 (23), 117 (25), 104
(35), 91 (97), 57 (80). Calcd for C17H24O2: M, 260.1777 Found: m/z
260.1776.
NMR
d 1.39 (2.6H, s), 1.40 (6.4H, s), 1.67–1.68 (0.9H, m), 1.73 (2.1H,
dd, J¼6.6, 1.5 Hz), 2.53 (0.7H, dd, J¼14.6, 8.6 Hz), 2.59 (0.3H, dd,
J¼14.7, 8.4 Hz), 2.67 (0.3H, dd, J¼14.7, 7.0 Hz), 2.72 (0.7H, dd, J¼14.6,
6.4 Hz), 4.00–4.05 (0.3H, m), 4.37–4.44 (0.7H, m), 5.47–5.62 (2H,
m), 6.81 (0.3H, dt, J¼3.5, 1.0 Hz), 6.83 (0.7H, dt, J¼3.5, 1.2 Hz), 6.91
(0.7H, dd, J¼5.1, 3.5 Hz), 6.92 (0.3H, dd, J¼5.1, 3.5 Hz), 7.13 (0.7H, dd,
J¼5.1, 1.2 Hz), 7.14 (0.3H, dd, J¼5.1, 1.0 Hz). MS m/z (%) 252 (Mþ, 3),
196 (62), 195 (122), 179 (4), 149 (11), 137 (100), 135 (22), 97 (10), 57
(18). Calcd for C14H20O2S: M, 252.1184. Found: m/z 252.1187.
3.81. tert-Butyl 4-chloro-3-(2-thienyl)-4-(p-tolylsulfinyl)-
hexanoate (47a)
Isolable main product derived from 28e: colorless oil; IR (neat)
3.86. tert-Butyl 3-(2-thienyl)-4,6-heptadienoate (48b)
2978, 1732 (CO), 1597, 1456, 1368, 1255, 1151, 1058, 848, 756,
702 cmꢀ1; 1H NMR
d
0.90 (3H, t, J¼7.4 Hz), 1.27 (9H, s), 1.57 (1H, q,
Colorless oil (1:1 mixture of two diastereomers); IR (neat) 2978,
J¼7.5 Hz), 1.98 (1H, q, J¼7.5 Hz), 2.44 (3H, s), 2.71 (1H, dd, J¼15.7,
10.0 Hz), 2.77 (1H, dd, J¼15.7, 4.5 Hz), 4.30 (1H, dd, J¼10.0, 4.5 Hz),
6.93 (1H, dd, J¼5.1, 3.5 Hz), 7.00 (1H, dd, J¼3.5, 0.8 Hz), 7.22 (1H, dd,
J¼5.1, 0.8 Hz), 7.34 (2H, d, J¼8.1 Hz), 7.70 (2H, d, J¼8.1 Hz). MS (FAB)
m/z (%) 427 ([MþH]þ, 22), 371 (43), 353 (7), 317 (7), 263 (11), 231
(57), 195 (100), 194 (22), 140 (19), 139 (17), 57 (29). Calcd for
C21H28ClO3S2: M, 427.1169. Found: m/z 427.1166.
2930, 1729 (CO), 1456, 1368, 1256, 1152, 1040, 847, 699 cmꢀ1 1H
;
NMR
d
1.39 (4.5H, s), 1.40 (4.5H, s), 2.56 (0.5H, dd, J¼14.7, 8.7 Hz),
2.65 (0.5H, dd, J¼14.8, 8.4 Hz), 2.72 (0.5H, dd, J¼14.8, 7.0 Hz), 2.77
(0.5H, dd, J¼14.7, 6.3 Hz), 4.09–4.17 (0.5H, m), 4.52–4.58 (0.5H, m),
5.03–5.29 (2H, m), 5.52 (0.5H, t, J¼10.4 Hz), 5.81 (0.5H, dd, J¼15.1,
7.9 Hz), 6.08 (0.5H, t, J¼10.8 Hz), 6.13 (0.5H, dd, J¼15.1, 10.4 Hz),
6.39 (0.5H, dt, J¼16.9,10.4 Hz), 6.76 (0.5H, dt, J¼16.8,10.8 Hz), 6.83–
6.84 (1H, m), 6.91–6.94 (1H, m), 7.14–7.17 (1H, m). MS m/z (%) 264
(Mþ, 9), 208 (61), 191 (11), 162 (14), 149 (100), 148 (61), 115 (25), 97
(12), 57 (31). Calcd for C15H20O2S: M, 264.1184. Found: m/z
264.1185.
3.82. tert-Butyl 4-chloro-3-(2-thienyl)-4-(p-tolylsulfinyl)-
hexanoate (47a)
Isolable main product derived from 29e: colorless oil; IR (neat)
2979, 1732 (CO), 1597, 1456, 1368, 1286, 1256, 1154, 1050, 848,
Acknowledgements
756 cmꢀ1
;
1H NMR
d
1.22 (9H, s), 1.25 (3H, t, J¼7.6 Hz), 2.01–2.16
(2H, m), 2.45 (3H, s), 2.91 (1H, dd, J¼16.2, 12.2 Hz), 3.59 (1H, dd,
J¼16.2, 2.9 Hz), 3.91 (1H, dd, J¼12.2, 2.9 Hz), 6.91–6.96 (2H, m), 7.21
(1H, dd, J¼4.8, 1.5 Hz), 7.35 (2H, d, J¼8.1 Hz), 7.70 (2H, d, J¼8.1 Hz).
MS (FAB) m/z (%) 427 ([MþH]þ, 44), 371 (80), 353 (8), 317 (7), 231
(48), 195 (100), 154 (14), 140 (17), 123 (12), 57 (20). Calcd for
C21H28ClO3S2: M, 427.1169. Found: m/z 427.1168.
This work was supported by a Grant-in-Aid for Scientific Re-
search No. 19590018 from the Ministry of Education, Culture,
Sports, Science, and Technology, Japan, which is gratefully
acknowledged.
References and notes
1. Some monographs for the chemistry of carboxylic acids and their de-
rivatives: (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,
1992; Parts 1 and 2.
3.83. tert-Butyl 4-chloro-3-(2-thienyl)-4-(p-tolylsulfinyl)-6-
heptenoate (47b)
Isolable main product derived from 28e: colorless oil; IR (neat)
2979, 1728 (CO), 1641, 1596, 1434, 1393, 1256, 1152, 1044, 845, 756,
703 cmꢀ1 1H NMR
; d 1.24 (9H, s), 2.42 (3H, s), 2.58–2.80 (2H, m),
2. For example: (a) Chemistry and Biochemistry of the Amino Acids; Barrett, G. C.,
Ed.; Chapmann and Hall: London, 1985; (b) Williams, R. M. Synthesis of Optically
2.81 (1H, dd, J¼14.7, 11.3 Hz), 2.91 (1H, dd, J¼14.7, 3.9 Hz), 4.54 (1H,
dd, J¼11.3, 3.9 Hz), 5.09 (1H, dd, J¼17.0, 1.4 Hz), 5.16 (1H, dd, J¼10.2,
1.4 Hz), 6.08 (1H, dddd, J¼17.0, 10.2, 8.4, 5.9 Hz), 7.02 (1H, dd, J¼5.1,
3.9 Hz), 7.29–7.35 (4H, m), 7.65 (2H, d, J¼8.2 Hz). MS (FAB) m/z (%)
439 ([MþH]þ, 49), 383 (100), 365 (10), 263 (29), 243 (69), 207 (95),
161 (29), 159 (48), 140 (36), 123 (21), 57 (53). Calcd for
C22H28ClO3S2: M, 439.1169. Found: m/z 439.1171.
Active
a-Amino Acids; Pergamon: Oxford, 1989; (c) Enantioselective Synthesis of
b-Amino Acids; Juaristi, E., Ed.; Wiley-VCH: New York, NY, 1997.
3. For example: (a) Trost, B. M.; Salzmann, T. N.; Hiroi, K. J. Am. Chem. Soc. 1976, 98,
4887; (b) Clive, D. L. Tetrahedron 1978, 34, 1049.
4. (a) Wadsworth, W. S., Jr. Org. React. 1977, 25, 73; (b) Maryanoff, B. E.; Reitz, A. B.
Chem. Rev. 1989, 89, 863; (c) Shen, Y. Acc. Chem. Res. 1998, 31, 584; (d) Ando, K.
J. Synth. Org. Chem. Jpn. 2000, 58, 869; (e) Hassner, A.;Stumer, C. Organic Synthesis

H. Yamashita, T. Satoh / Tetrahedron 65 (2009) 613–627
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Based on Name Reactions; Pergamon: Amsterdam, 2002; (f) Mundy, B. P.; Ellerd,
M. G.; Favaloro, F. G., Jr. Name reactions and Reagents in Organic Synthesis,
2nd ed.; Wiley-Interscience: Hoboken, NJ, 2005; (g) Li, J. J. Name Reactions,
3rd ed.; Springer: Berlin, 2006.
5. (a) Kowalski, C. J.; Haque, M. S.; Fields, K. J. Am. Chem. Soc. 1985, 107, 1429; (b)
Kowalski, C. J.; Reddy, R. J. Org. Chem. 1992, 57, 7194; (c) Satoh, T.; Nakamura, A.;
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