Mild, powerful, and robust methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively

Article abstract of DOI:10.1016/j.tet.2007.08.117

We developed two efficient practical methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively. The present mild and robust reaction was performed by two separate methods both by combining cheap and readily available amines, N-methylimidazole, and N,N,N′,N′-tetramethylethylenediamine (TMEDA). Method A uses catalytic N-methylimidazole and TMEDA with an equimolar amount of K₂CO₃, whereas Method B uses equimolar amounts of N-methylimidazole and TMEDA. The salient features are as follows. (i) With regard to reactivity, Method B was superior to Method A for esterification and thioesterification, whereas cost-effective Method A was superior to Method B for amide formation. (ii) Amide formation proceeded smoothly between acid chlorides and less nucleophilic and stereocongested amines such as 2,6-dichloroaniline. (iii) This protocol was applied to the successful synthesis of two agrochemicals, bromobutide and carpropamid.

Full text of DOI:10.1016/j.tet.2007.08.117

Tetrahedron 63 (2007) 12071–12080
Mild, powerful, and robust methods for esterification, amide
formation, and thioesterification between acid chlorides
and alcohols, amines, thiols, respectively
*
Hidefumi Nakatsuji, Mami Morimoto, Tomonori Misaki and Yoo Tanabe
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan
Received 25 July 2007; revised 24 August 2007; accepted 31 August 2007
Available online 12 September 2007
Abstract—We developed two efficient practical methods for esterification, amide formation, and thioesterification between acid chlorides
and alcohols, amines, thiols, respectively. The present mild and robust reaction was performed by two separate methods both by combining
cheap and readily available amines, N-methylimidazole, and N,N,N0,N0-tetramethylethylenediamine (TMEDA). Method A uses catalytic
N-methylimidazole and TMEDA with an equimolar amount of K2CO3, whereas Method B uses equimolar amounts of N-methylimidazole
and TMEDA. The salient features are as follows. (i) With regard to reactivity, Method B was superior to Method A for esterification and
thioesterification, whereas cost-effective Method Awas superior to Method B for amide formation. (ii) Amide formation proceeded smoothly
between acid chlorides and less nucleophilic and stereocongested amines such as 2,6-dichloroaniline. (iii) This protocol was applied to the
successful synthesis of two agrochemicals, bromobutide and carpropamid.
Ó 2007 Published by Elsevier Ltd.
1. Introduction
microfeeder apparatuses to strictly maintain a pH of around
11.5. Moreover, the reactivity is generally poor probably due
to the use of water media.
Esterification, amide formation, and thioesterification are
important unit processes frequently used for a wide range
of organic syntheses.1 These reactions between carboxylic
acid chlorides (the most popular activated acid derivative)
and alcohols, amines, and thiols are among the most general
and conventional synthetic methods available. These
methods generally require stoichiometric or excess amounts
of tertiary amines such as pyridine and Et3N as HCl scaven-
gers. These wasted organic amine reagent requires a large
quantity of biological and chemical oxygen demands
(BOD and COD) and is not suitable in terms of recent trends
in process chemistry.
2. Results and discussion
To solve these critical problems, we devised two mild,
powerful, and robust methods for esterification, amide for-
mation, and thioesterification between acid chlorides and
alcohols, amines, and thiols, respectively, in conventional
CH3CN or 1,2-dichlorobenzene solvent without using any
special techniques and apparatuses (Scheme 1).
Method A
In our continuing studies toward the development of mild,
practical, and cost-effective esterifications, amide forma-
tions, and thioesterification, we found that N-methylimida-
zole efficiently activates carboxylic acid derivatives.2
Recently, a water solvent Schotten–Baumann-type method
for esterification and amide formation between acid chlo-
rides and alcohols or amines was developed.3 This protocol
is cost-effective and environmentally benign for esterifica-
tion and amide formation from a green chemical standpoint,
however, it requires tedious procedures for many synthetic
chemists, because it has to handle both pH controller and
Me
N
N
R1CO2R2
or
R2OH
or
K2CO3
TMEDA
(0.1 eq.),
(1.5 eq.)
(0.1 eq.),
R1CONR2R3
or
+
NHR2R3
or
1
R COCl
/ CH3CN 0 - 5 °C, 1 h
R2SH
R1COSR2
Me
Method B
R1CO2R2
or
N
N
R2OH
or
TMEDA
(1.5 eq.)
(1.5 eq.),
2
3
1
R1CONR2R3
or
+
NHR R
R COCl
/ CH3CN 0 - 5 °C, 1 h
or
R1COSR2
R2SH
Scheme 1. Mild and powerful esterification, amide formation, and thioester-
ification by Methods A and B.
* Corresponding author. E-mail: tanabe@kwansei.ac.jp
0040–4020/$ - see front matter Ó 2007 Published by Elsevier Ltd.
doi:10.1016/j.tet.2007.08.117

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H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
The present reaction involves two methods; (i) Method A
uses K2CO3 functioning as the main base and a combination
of catalytic bases, N-methylimidazole and TMEDA, and
(ii) Method B uses a combination of equimolar amounts of
bases, N-methylimidazole and TMEDA (Scheme 1).
effective and process chemical standpoints, Method A
should precede Method B: when Method A produced dis-
appointing results, we switched to Method B. The salient
features are as follows. (i) The procedures are much sim-
pler and more robust than the water solvent method and
the yields are good to excellent.3 The reaction conditions
are mild and practical (0–5 ꢀC, 1 h; an additional
20–25 ꢀC, 1 h in some cases). (ii) Several primary alcohols
and less reactive phenols underwent smooth esterification
using PhCH2CH2COCl and 10-dodecenoyl chloride in
Method A (entries 1–10). (iii) Although Method A was
somewhat less efficient for secondary alcohols such as
L-menthol and 3-octanol, Method B was more successful
(entries 10, 12, 13, 16, 18, 20, 24, 26). (iv) t-BuOH did
not undergo the reaction (entry 14). (v) Stereocongested
t-BuCOCl underwent a smooth reaction using Method B
(entry 26). (vi) A double bond, a-phenoxy and a-chloro-
carbonyl cyclopropane carbonyl groups, was tolerated.
(vii) Two useful synthetic pyrethroids, chlovaporthrin and
permethrin,6 were successfully synthesized (entries 27
and 28). (viii) N-Benzyloxycarbonylproline chloride was
smoothly esterified with MeOH without any racemization
(entries 29 and 30).
2.1. Esterification using Methods A and B: B is superior
to A
The initial attempt was guided by more cost-effective Method
A for the reaction between PhCH2CH2COCl and 3-octanol
utilizing K2CO3 as the main base with representative and
available amine catalysts (Et3N, Me3N, BnNMe2, BuNMe2,
DMAP, TMEDA, and N-methylimidazole) (Table 1).
No reaction occurred without the catalyst (entry 1). The use
of simple trialkylamines, such as Et3N (the most familiar
tertiary amine), Me3N (a sterically uncrowded and effective
sulfonylation reagent),4 and BuNMe2 had a small effect
(entries 2–5). Low to moderate yields were obtained when
DMAP (a super acylation catalyst),1 TMEDA (an effective
diamine for benzoylation),5 and N-methylimidazole (a new
acylation agent)2 were used (entries 6–8). The combined
use of different amine catalysts, however, exhibited syner-
gistic activity (entries 9–13). The increasing order of yield
for all six possible combinations was as follows. Method
A: (i) Et3N and TMEDA, (ii) DMAP and TMEDA, (iii)
Et3N and DMAP, (iv) Et3N and N-methylimidazole, (v)
DMAP and N-methylimidazole, and (vi) TMEDA and
N-methylimidazole (entry 14). Method B: (i), (iv), (ii),
(iii), (v), and (vi). The order was not necessarily the same
between Methods A and B, however, the best synergy effect
in both methods (joint action of amines) was obtained using
TMEDA and N-methylimidazole [entry 14, case (vi)]. This
result shows good agreement with the reported water solvent
method (see also Table 4).3 Eventually, we chose the com-
bined base catalysts, TMEDA and N-methylimidazole, for
the standard protocols.
2.2. Amide formation using Methods A and B: A is
superior to B
The present protocol was applied to amide formation. Table
3 lists the successful results. The salient features are as
follows. (i) In all cases examined, the reaction proceeded
successfully to give the desired amides in excellent yields
under mild and practical conditions (0–5 ꢀC, 1 h). (ii) Sur-
prisingly, Method A was superior to Method B, with respect
to the yield, especially for amide formation between
PhCH2CH2COCl and piperidine or Weinreb amine (entries
2 and 4). This tendency is in clear contrast to the esterifica-
tion mentioned above. (iii) The reaction using important
Weinreb amine, a water-soluble amine, and stereocongested
t-butylamine also proceeded smoothly (entries 4–6). (iv)
Using Method A, several types of acid chlorides produced
successful results (entries 7–16).
Table 2 lists the successful results of esterifications
between various acid chlorides and alcohols. From cost-
Table 1. Screening of amine catalysts during the esterification between PhCH2CH2COCl and 3-octanol using Methods A and B
Method A
Catalyst (0.1 eq.), K2CO3 (1.5 eq.)
/ CH3CN 0 - 5 °C, 1 h
OH
CO2
COCl
Ph
Ph
+
Catalyst (1.5 eq.)
(1.5 eq.)
/ CH3CN 0 - 5 °C, 1 h
Method B
Entry
Catalyst
Yielda/%
Method B
Entry
Catalyst
Yielda/%
Method A
Method A
Method B
1
2
3
4
5
6
7
None
Et3N
Me3N
BnNMe2
BuNMe2
DMAP
TMEDA
NR
37
16
15
—
38
19
40
45
43
49
8
9
N-Methylimidazole
Et3N, DMAP
Et3N, TMEDA
Et3N, N-methylimidazole
DMAP, TMEDA
49 (54b)
58
27
68
53
48
81
57
67
79
82
85c
10
11
12
13
14
23
54
DMAP, N-methylimidazole
N-methylimidazole, TMEDA
68
34 (45b)
77c
Determined by 1H NMR.
Catalyst of 0.2 equiv was used.
Isolated.
a
b
c

H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
12073
Table 2. Esterification of various substrates using Methods A and B
Method A
Me
N
N
(0.1 eq.), K2CO3 (1.5 eq.)
TMEDA (0.1 eq.),
/ CH3CN, 0 - 5 °C, 1 h
Me
R1CO2R2
R1COCl
(1.5 eq.)
R2OH
+
N
N
TMEDA (1.5 eq.),
(1.5 eq.)
/ CH3CN, 0 - 5 °C, 1 h
Method B
Entry
R1COCl
R2OH
Yield/%
Entry
R1COCl
R2OH
Yield/%
Method A (B)
Method A (B)
OH
OH
6
46a (89a)
99
Ph
1
2
3
95
98
90
16
17
18
COCl
4
COCl
OH
OH
7
6
OH
62a (94a)
Cl
OH
4
4
OH
OH
4
5
6
7
8
95
19
20
21
22
23
98
6
COCl
COCl
OH
OH
EtO2C
82
71a (98a)
94
4
4
OH
6
OH
99
PhO
O
OH
PhOH
Cl
85
76a (71a)a
4
COCl
OH
6
93 (96)
89
Cl
OH
Cl
OH
Cl
9
99 (98)
24
80a (97a)
OH
4
Cl
OH
OH
OH
6
COCl
COCl
10
11
12
69 (98)
91
25
26
27
84
Cl
OH
50a (95a)
6
Ph
OH
Cl
Cl
OH
COCl
77 (86)
94a
4
O
74 (95a)
Trace
28
29
92a
89b
HO
13
14
(ꢁ)-Menthol
t-BuOH
MeOH
N
COCI
Cbz
OH
6
15
BzCl
85
30
PhCH2OH
82b
a
Reaction conditions: 0–5 ꢀC for 1 h and 20–25 ꢀC for 1 h.
Without loss of optical purity.
b
2.3. Amide formation for weakly nucleophilic anilines
using Methods A and B, and an application to the
synthesis of two agrochemicals: A is far superior to B
chloroanilines, because there has been much demand for
this reaction from pharmaceutical and agrochemical indus-
tries. Nonetheless, it generally requires harsh reaction condi-
tions7 (high temperatures, excess amounts of acid chlorides,
or a use of specific TiCl4–AgOTf catalyst).7c Thus, we
evaluated the ability of the present amide formation using
We next focused our attention on the amide formation of
weakly nucleophilic arylamines such as nitroanilines and

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H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
Table 3. Amide formation of various substrates using Methods A and B
Method A
Me
N
N
(0.1 eq.), K2CO3 (1.5 eq.)
TMEDA (0.1 eq.),
/ CH3CN, 0 - 5 °C, 1 h
R1CONR2R3
R1COCl
(1.5 eq.)
+
NHR2R3
Me
N
N
TMEDA (1.5 eq.),
(1.5 eq.)
/ CH3CN, 0 - 5 °C, 1 h
Method B
Entry
R1COCl
NHR2R3
Yield/%
Method A
Entry
R1COCl
PhCOCl
NHR2R3
Yield/%
Method B
96
Method A
Ph
1
2
PhNH2
98
7
8
PhNH2
97
99
COCl
Piperidine
COCl
Piperidine
97
17a
77
9
10
11
PhNH2
97
99
99
Piperidine
PhNH2
3
4
99
Ph
NH2
COCl
12
13
Piperidine
PhNH2
99
99
Me
NH HCl
99b
27a,c
.
PhO
COCl
COCl
MeO
MeO
NH2
5
6
86
84
14
15
PhNH2
99
89
OMe
tBuNH2
Cl
99d
88d
Piperidine
Cl
Cl
COCl
16
PhNH2
99
Determined by 1H NMR.
K2CO3 (2.5 equiv) was used.
TMEDA (2.5 equiv) was used.
Reaction conditions: 0–5 ꢀC for 1 h and 20–25 ꢀC for 1 h.
a
b
c
d
such less nucleophilic anilines. All six possible combina-
tions for both Methods A and B using different amine
catalysts were re-checked by the amide formation between
PhCH2CH2COCl or c-HexCOCl and very weakly nucleo-
philic 2,6-dichloroaniline (Table 4). The best synergy effect
was obtained using TMEDA and N-methylimidazole (entry
6). Note that N-methylimidazole is superior to DMAP in
a couple of comparable cases (entries 1 and 3, 5 and 6).
Table 5 lists the successful results of amide formation using
weakly nucleophilic anilines using Method A. It should be
noted that Method A was far superior to Method B in every
case examined. In general, systems using a main inorganic
base such as K2CO3, KOH, etc.,—and catalytic amine bases
are cost-effective, but inferior to conventional systems using
main amine bases with regard to reaction speed and yield.4a,b
Table 4. Comparable experiments of amine catalysts during the amide
formation between PhCH2CH2COCl or cyclohexanoyl chloride and 2,6-
dichloroaniline
1
(1.5 eq.)
R COCl
K2CO3
Catalyst
Cl
+
O
(1.5 eq.)
(0.1 eq.),
We propose a plausible mechanism to account for this
unique relationship reversal of amide formation that Method
A is superior to Method B (Scheme 2).
Cl
R1
N
/ CH3CN 0 -5 °C, 1 h
H
H2N
Cl
Cl
Method A. Two different roles of N-methylimidazole and
TMEDA are assumed. An N-methylimidazole catalyst cap-
tures an acid chloride (R1COCl) to form a highly reactive
acylimidazolium chloride intermediate A, which in turn
condenses with an amine (R1R2NH) to produce the desired
amide (R1CONR2R3), while releasing TMEDA$HCl B. In
B, TMEDA might chelate with a proton through bidentate
hydrogen bonds. K2CO3 immediately neutralizes B to
reform TMEDA while releasing KHCO3 and KCl for com-
pleting the catalytic cycle. Note that (i) HCl is eventually
Entry Catalyst
Yielda/%
R1¼PhCH2CH2 R1¼c-Hex
1
2
3
4
5
6
Et3N, DMAP
Et3N, TMEDA
Et3N, N-methylimidazole
DMAP, TMEDA
DMAP, N-methylimidazole
62
57
64
50
60
27)
20
34)
33*
29
N-methylimidazole, TMEDA 82
57*
Determined by 1H NMR.
a

H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
12075
Table 5. Amide formation between several acid chlorides and weakly nucleophilic anilines using Methods A and B
Method A
Me
N
N
(0.1 eq.), K2CO3 (1.5 eq.)
TMEDA (0.1 eq.),
/ CH3CN, 0 - 5 °C, 1 h
Me
+
RCOCl
(1.5 eq.)
ArNH2
RCONHAr
N
N
(Ar = less
(1.5 eq.)
TMEDA (1.5 eq.),
/ CH3CN, 0 - 5 °C, 1 h
nucleophilic)
Method B
Entry
R1COCl
ArNH2
Yield/%
Entry
R1COCl
PhCOCl
R2NH2
Yield/%
Method A
Method B
Method A
Cl
NH2
Cl
NH2
Cl
Ph
1
82
Trace
6
99
COCl
NH2
COCl
2
3
95
92
26a
14a
7
8
89b
94
O2N
NH2
NH2
Cl
COCl
COCl
NO2
NH2
4
91
39a
12a
9
94
93
Cl
Cl
Cl
NH2
5
99
10
PhO
COCl
Cl
Reaction conditions: 0–5 ꢀC for 1 h and 20–25 ꢀC for 1 h.
Determined by 1H NMR.
a
b
transformed to inert inorganic salts, KHCO3 and KCl, by
the action of K2CO3 and (ii) the two amines have different
roles: N-methylimidazole activates acyl chloride, whereas
TMEDA acts as an HCl scavenger. A previous report of
the water solvent method describes the 1H NMR characteri-
zation for the formation of intermediate A.3
Method B. The formation of A and B is similar to Method A.
The most crucial feature is that B is progressively accumu-
lated in the system and reacts with R2R3NH by the equilib-
rium to form less reactive R2R3NH$HCl. This side reaction
significantly retards the desired amide formation.
We next compare the performance of the present method
with the water solvent method.3 Clear contrast is shown in
Table 6; the present method using 2,6-dichloroaniline was
much more powerful than the water solvent method with
or without amine catalysts.
Method A
R1CONR2R3
Me
+
N
N
H
Cl-
R1COCl
N
O
N
The present amide formation of Method A is demonstrated
by the synthesis of couple of commercial agrochemicals,
bromobutide (herbicide)8 and carpropamid (fungicide),9 as
shown in Scheme 3. The desired reactions using bulky
substrates, between 2-bromo-3,3-dimethylbutanoyl chloride
B
K2CO3
KHCO3+ KCl
TMEDA
R2R3NH
R1CN
Me
N
Cl-
+
A
Table 6. Comparison of Method A with the water solvent method
Cl
Method B
Cl
CONH
NH2
Cl
R2R3NH
TMEDA
Ph
+
Ph
COCl
(1.5 eq.)
Me
N
N
Cl
R1COCl
A
R1CONR2R3
Entry
Conditions
Yield/%
1
2
K2CO3 (1.5 equiv)/H2O (pH w11.5), 20 ꢀC, 1 h
TMEDA (0.1 equiv), N-methylimidazole/H2O
(pH w11.5), 20 ꢀC, 1 h
TMEDA (0.1 equiv), N-methylimidazole,
K2CO3 (1.5 equiv)/CH3CN, 0–5 ꢀC, 1 h
Trace
Trace
B
side
+
3
2
Cl-
B
R2R3NH
+
TMEDA
R R N H
+
reaction
3
82
Scheme 2. Proposed mechanism for Methods A and B.

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H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
Method A
to esterification, functionalized or stereocongested acid
chlorides produced satisfactory results using Method B
(entries 7–10).
Me
COCl
N
N
K2CO3
O
TMEDA
Br
+
(1.5 eq.)
(0.1 eq.),
(0.1 eq.),
N
H
Ph
3. Conclusions
/ Chlorobenzene,
20 - 25 °C, 2 h
Br
94%
H2N
Me
Ph
bromobutide
We presented two mild, powerful, and robust methods,
Method A (cat. N-methylimidazole and TMEDA–K2CO3)
and Method B (N-methylimidazole and TMEDA) for ester-
ification, amide formation, and thioesterification. Method B
produced higher yields than Method A for esterification and
thioesterification, whereas the more cost-effective Method A
showed considerably higher yield for amide formation
including the use of important but less nucleophilic anilines.
This amide formation was applied to an efficient synthesis of
two agrochemicals, bromobutide and carpropamid. Because
of the high efficiency and generality, the present protocol,
particularly amide formation, will provide a new avenue
for practical, cost-effective, and environmentally benign
process chemistry for such acylation reactions.
O
O
Et
N
H
C6H4(p-Cl)
93%
Cl Cl
+
Et
/ CH3CN, 0 - 5 °C, 1 h
Cl Cl
carpropamid
H2N
C6H4(p-Cl)
Scheme 3. Synthesis of bromobutide and carpropamid.
and a,a-dimethylbenzylamine, between 1-ethyl-2,2-
dichloro-3-methylcyclopropanecarbonyl chloride and 1-
(4-chlorophenyl)ethylamine,proceededsmoothlyundermuch
milder conditions to give bromobutide and carpropamid,
respectively, in both excellent yields.
4. Experimental and references
4.1. General
2.4. Thioesterification using Methods A and B: B is
superior to A
Melting points were determined on a hot stage microscope
apparatus (Yanagimoto) and were uncorrected. NMR spectra
were recorded on a JEOL DELTA300 spectrometer, operat-
Finally, the present protocol was applied to thioesterifica-
tion. Table 7 lists the successful results. The salient features
are as follows. (i) In every case examined, the desired
reaction proceeded smoothly using several aromatic and
aliphatic thiols, and acid chlorides under mild and practical
conditions (0–5 ꢀC, 1 h and 20–25 ꢀC, 1 h) (entries 1–12).
(ii) Method B produced slightly better results with
regard to yield compared to Method A. This tendency
resembles the esterification described in Table 1. Similar
1
ing at 300 MHz for H NMR and 100 MHz for 13C NMR.
Chemical shift (d ppm) were reported downfield from tetra-
methylsilane (0 ppm) for 1H NMR and were reported in the
scale relative to CDCl3 (77.00 ppm) for 13C NMR. IR spec-
tra were recorded on JASCO FT/IR-8000 and/or FT/IR-5300
spectrophotometer. Mass spectra were measured on a JEOL
JMS-T100LC spectrometer.
Table 7. Thioesterification of several substrates using Methods A and B
Method A
Me
N
N
(0.1 eq.), K2CO3 (1.5 eq.)
TMEDA (0.1 eq.),
/ CH3CN, 0 - 5 °C, 1 h
R1COCl
(1.5 eq.)
R1COSR2
R2SH
(1.0 eq.)
+
Me
N
N
(1.5 eq.)
TMEDA (1.5 eq.),
/ CH3CN, 0 - 5 °C, 1 h
Method B
Entry
R1COCl
R2SH
Yield/%
Entry
R1COCl
R2SH
Yield/%
Method A (B)
Method A (B)
COCl
Ph
SH
SH
1
2
89
6
7
87
COCl
6
6
98
83
Ph
PhSH
SH
COCl
3
4
92
8
9
86
95
PhO
COCl
COCl
SH
SH
81 (94)
Cl
COCl
5
BzCl
88
10
67 (99)
6

H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
12077
The following esters and amides obtained in this paper are
4.3. A typical procedure of esterification (Method B)
(Table 2, entry 12)
known compounds: 1-octyl 3-phenylpropanoate,10 9-de-
cene-1-yl 3-phenylpropanoate,11 6-chlorohexyl 3-phenyl-
propanoate,11 2-hexyn-1-yl 3-phenylpropanoate,11 ethyl
6-(3-phenylpropanoyloxy)hexanoate,11 furfuryl 3-phenyl-
propanoate,3 phenyl 3-phenylpropanoate,12 1-octyl 2-chloro-
benzoate (commercially available: AKos Screening
Library), 1-octyl 2,4-dichlorobenzoate (commercially avail-
able: AKos Screening Library), 1-phenylethyl 3-phenyl-
propanoate,13 3-octyl 3-phenylpropanoate,3 1-menthyl
3-phenylpropanoate,11 tert-butyl 3-phenylpropionate,14
1-octyl benzoate,11 3-octyl benzoate,15 1-octyl cyclohexane-
carboxylate,10 3-octyl cyclohexanecarboxylate,3 1-octyl
10-undecenoate,16 1-octyl phenoxyacetoate,17 1-octyl 2-
chloropropanoate,18 1-octyl methacrylate,19 1-octyl 2,2-
dimethylpropanoate,11 1-ethynyl-2-methyl-2-pentenyl 3-
(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate
(chlovaporthrin: vaporthrin analog),20 m-phenoxybenzyl 3-
(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,21
N-carbobenzoxy-L-proline methyl ester,22 N-carbobenzoxy-
L-proline phenylmethyl ester,23 N-phenyl-3-phenylpropiao-
PhCH2CH2COCl (252 mg, 1.5 mmol) was added to a stirred
suspension of 3-octanol (130 mg, 1 mmol), N-methylimida-
zole (123 mg, 1.5 mmol), and TMEDA (174 mg, 1.5 mmol)
in CH3CN (1 mL) at 0–5 ꢀC under an Ar atmosphere, and the
mixture was stirred at the same temperature for 1 h. Water
was added to the stirred mixture, which was extracted with
EtOAc. The organic phase was washed with water and brine,
dried (Na2SO4), and concentrated. The obtained crude
product was purified by silica gel column chromatography
(hexane/EtOAc¼25:1) to give 1-octyl 3-phenylpropanonate
(224 mg, 86%).
4.3.1. 1-Octyl 2,6-chlorobenzoate (Table 2, entry 10). Col-
orless oil; 1H NMR (300 MHz, CDCl3) d 2.96–3.05 (2H, m),
3.09–3.17 (2H, m), 7.07–7.16 (1H, m), 7.19–7.38 (8H, m);
13C NMR (75 MHz, CDCl3) d 30.7, 35.1, 126.4, 127.1,
128.3, 128.6, 128.9, 139.8, 144.0, 169.2; IR (neat) 3030,
2957, 2184, 1773, 1564, 1451, 1354, 1284 cmꢁ1; HRMS
(ESI) calcd for C15H20Cl2O2 (M+Na+) 317.0112, found
317.0112.
namide,24
N-(2,6-dichlorophenyl)-3-phenylpropanamide
(commercially available: Aurora Screening Library),
N-(2,6-dichlorophenyl)cyclohexamide (commercially avail-
able: Aurora Screening Library), N-(3-phenylpropanoyl)-
piperidine,11 N-[(S)-1-phenylethyl]-3-phenylpropanamide,11
N-methoxy-N-methyl-3-phenylpropanamide,25 N-(2,2-di-
methoxyethyl)-3-phenylpropanamide,26 N-(1,1-dimethyl-
4.3.2. 3-Octyl 10-undecenoate (Table 2, entry 20). Color-
less oil; H NMR (300 MHz, CDCl3) d 0.80–0.92 (6H, m),
1
1.19–1.69 (22H, m), 1.97–2.08 (2H, m), 2.29 (2H, t,
J¼7.6 Hz), 4.82 (1H, quin, J¼6.2 Hz), 4.87–5.06 (2H, m),
5.81 (1H, ddt, J¼6.9, 10.0, 17.5 Hz); 13C NMR (75 MHz,
CDCl3) d 9.6, 14.0, 22.5, 25.0, 25.1, 26.9, 28.9, 29.0, 29.2,
29.3, 31.7, 33.6, 33.7, 34.7, 75.1, 114.1, 139.1, 173.7; IR
(neat) 3073, 2930, 2857, 1734, 1644, 1462, 1370,
1242 cmꢁ1; HRMS (ESI) calcd for C19H36O2 (M+Na+)
319.2613, found 319.2613.
ethyl)-3-phenylpropanamide,11
N-phenylbenzamide,27
N-benzoylpiperidine,11 N-phenylcyclohexamide,28 N-cyclo-
hexanecarbonyl piperidine,11 N-phenyl-10-undecenoyl-
amide,29
10-undecenecarbonylpiperidine,30
N-phenyl
phenoxyacetyl amide,31 N-phenyl-2-chloropropanoylamide,32
2-chloropropanoylpiperidine,33 N-phenyl-3-(2,2-dichloro-
vinyl)-2,2-dimethylcyclopropanamide,34
N-(4-nitro-
N-(2-nitrophenyl)-3-
phenyl)-3-phenylpropanamide,35
4.3.3. 3-Octyl phenoxyacetoate (Table 2, entry 22). Color-
less oil; H NMR (300 MHz, CDCl3) d 0.78–0.96 (6H, m),
1
phenylpropanamide (commercially available: Aurora
Screening Library), N-(2-chlorophenyl)-3-phenylpropan-
amide,36 N-(2,4-dichloro)-3-phenylpropanamide (commer-
cially available: Aurora Screening Library), N-(2-
chlorophenyl)benzamide,37 N-(2-chlorophenyl)cyclohex-
1.15–1.39 (6H, m), 1.46–1.67 (4H, m), 4.62 (2H, s), 4.95
(1H, quin, J¼6.5 Hz), 6.85–7.03 (3H, m), 7.21–7.34 (2H,
m); 13C NMR (75 MHz, CDCl3) d 9.6, 14.1, 22.6, 25.0,
27.0, 31.7, 33.6, 65.4, 77.6, 114.6, 121.7, 129.6, 158.0,
169.0; IR (neat) 2934, 2863, 1759, 1732, 1601, 1497,
1460, 1383, 1285 cmꢁ1; HRMS (ESI) calcd for C16H24O3
(M+Na+) 287.1623, found 287.1623.
amide,38
N-(2-chlorophenyl)-10-undecenoyl
amide,39
N-(2-chlorophenyl)phenoxyacetyl amide,40 N-(2-chloro-
phenyl)-2-chloropropanoyl amide,41 S-1-octyl 3-phenylpro-
panthioate,2 S-benzyl 3-phenylpropanthioate,2 S-phenyl
3-phenylpropanthioate,2 S-cyclohexyl 3-phenylpropan-
thioate,2 S-1-octyl cyclohexanthioate,2 S-1-octyl 2,2-dime-
thylpropanthioate.42
4.3.4. 3-Octyl 2-chloropropanoate (Table 2, entry 24).
Colorless oil; 1H NMR (300 MHz, CDCl3) d 0.79–0.97
(6H, m), 1.19–1.41 (6H, m), 1.48–1.69 (4H, m), 1.74 (3H,
d, J¼6.9 Hz), 4.40 (1H, q, J¼6.9 Hz), 4.88 (1H, quin,
J¼6.2 Hz); 13C NMR (75 MHz, CDCl3) d 9.5, 14.0, 21.5,
22.5, 24.8, 24.9, 26.9, 31.6, 33.4, 52.9, 77.5, 169.9, 191.3;
IR (neat) 2934, 2863, 1742, 1460, 1379, 1335, 1275,
1246 cmꢁ1; HRMS (ESI) calcd for C11H21Cl1O2 (M+Na+)
243.2231, found 243.1128.
4.2. A typical procedure of esterification (Method A)
(Table 2, entry 1)
PhCH2CH2COCl (252 mg, 1.5 mmol) was added to a stirred
suspension of 1-octanol (130 mg, 1 mmol), N-methylimid-
azole (8 mg, 0.1 mmol), TMEDA (12 mg, 0.1 mmol), and
K2CO3 (207 mg, 1.5 mmol) in CH3CN (1 mL) at 0–5 ꢀC
under an Ar atmosphere, and the mixture was stirred at the
same temperature for 1 h. Water was added to the stirred mix-
ture, which was extracted with EtOAc. The organic phase
was washed with water and brine, dried (Na2SO4), and con-
centrated. The obtained crude product was purified by silica
gel column chromatography (hexane/EtOAc¼25:1) to give
1-octyl 3-phenylpropanonate (248 mg, 95%).
4.4. A typical procedure of amide formation (Method A)
(Table 3, entry 1)
PhCH2CH2COCl (252 mg, 1.5 mmol) was added to a stirred
suspension of aniline (93 mg, 1 mmol), N-methylimidazole
(8 mg, 0.1 mmol), TMEDA (12 mg, 0.1 mmol), and K2CO3
(207 mg, 1.5 mmol) in CH3CN (1 mL) at 0–5 ꢀC under an
Ar atmosphere, and the mixture was stirred at the same

12078
H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
temperature for 1 h. Water was added to the stirred mixture,
which was extracted with EtOAc. The organic phase was
washed with water and brine, dried (Na2SO4), and concen-
trated. The obtained crude product was purified by silica
gel column chromatography (hexane/EtOAc¼25:1) to give
N-phenyl 3-phenylpropanamide (220 mg, 98%).
suspension of 1-(4-chlorophenyl)ethylamine (156 mg,
1 mmol), N-methylimidazole (8 mg, 0.1 mmol), TMEDA
(12 mg, 0.1 mmol), and K2CO3 (207 mg, 1.5 mmol) in
CH3CN (1 mL) at 0–5 ꢀC under an Ar atmosphere, and the
mixture was stirred at the same temperature for 1 h. Water
was added to the stirred mixture, which was extracted with
EtOAc. The organic phase was washed with water and brine,
dried (Na2SO4), and concentrated to give the crude product.
The obtained crude product was washed with hexane (ca.
5 mL) to give bromobutide (311 mg, 93%).
4.5. A typical procedure of amide formation (Method B)
(Table 3, entry 1)
PhCH2CH2COCl (252 mg, 1.5 mmol) was added to a stirred
suspension of aniline (93 mg, 1 mmol), N-methylimidazole
(123 mg, 1.5 mmol), and TMEDA (174 mg, 1.5 mmol) in
CH3CN (1 mL) at 0–5 ꢀC under an Ar atmosphere, and the
mixture was stirred at the same temperature for 1 h. Water
was added to the stirred mixture, which was extracted with
EtOAc. The organic phase was washed with water and brine,
dried (Na2SO4), and concentrated. The obtained crude prod-
uct was purified by silica gel column chromatography (hex-
ane/EtOAc¼25:1) to give N-phenyl 3-phenylpropiaonamide
(216 mg, 96%).
Colorless crystals; mp 169.0–169.5 ꢀC; 1H NMR (300 MHz,
CDCl3) d 0.89 (3Hꢂ2/3, t, J¼7.6 Hz), 0.99 (3Hꢂ1/3, t,
J¼7.6 Hz), 1.17–1.22 (3H, m), 1.49–1.59 (4H, m), 1.83–
2.01 (1H, m), 2.21 (1H, q, J¼6.5 Hz), 5.17 (1H, quin,
J¼7.2 Hz), 5.85 (1H, br), 7.28–7.34 (4H, m); 13C NMR
(75 MHz, CDCl3) d 8.6, 10.8, 10.9, 21.2, 21.3, 22.0, 29.6,
43.2, 48.7, 66.6, 127.6, 127.9, 128.7, 128.8, 133.2, 141.0,
141.4, 167.2, 167.4; IR (KBr) 3270, 3057, 2878, 1644,
1530, 1493, 1456, 1414 cmꢁ1
.
4.7. A typical procedure of thioesterification (Method A)
(Table 7, entry 1)
4.6. A typical procedure of amide formation using
a weakly nucleophilic aniline (Method A)
(Table 5, entry 1)
PhCH2CH2COCl (252 mg, 1.5 mmol) was added to a stirred
suspension of 1-octanthiol (146 mg, 1 mmol), N-methylimi-
dazole (8 mg, 0.1 mmol), TMEDA (12 mg, 0.1 mmol), and
K2CO3 (207 mg, 1.5 mmol) in CH3CN (1 mL) at 0–5 ꢀC un-
der an Ar atmosphere, and the mixture was stirred at the
same temperature for 1 h, and at 20–25 ꢀC for 1 h. Water
was added to the stirred mixture, which was extracted with
EtOAc. The organic phase was washed with water and brine,
dried (Na2SO4), and concentrated. The obtained crude prod-
uct was purified by silica gel column chromatography (hex-
ane/EtOAc¼25:1) to give S-1-octyl 3-phenylpropanthioate
(247 mg, 89%).
PhCH2CH2COCl (252 mg, 1.5 mmol) was added to a stirred
suspension of 2,6-dichloroaniline (162 mg, 1 mmol), N-
methylimidazole (8 mg, 0.1 mmol), TMEDA (12 mg,
0.1 mmol), and K2CO3 (207 mg, 1.5 mmol) in CH3CN
(1 mL) at 0–5 ꢀC under an Ar atmosphere, and the mixture
was stirred at the same temperature for 1 h, and at 20–
25 ꢀC for 1 h. Water was added to the stirred mixture, which
was extracted with EtOAc. The organic phase was washed
with water and brine, dried (Na2SO4), and concentrated.
The obtained crude product was purified by silica gel
column chromatography (hexane/EtOAc¼5:1) to give N-
(2,6-dichlorophenyl) 3-phenylpropanamide (242 mg, 82%).
4.8. A typical procedure of thioesterification (Method B)
(Table 7, entry 10)
4.6.1. Synthesis of bromobutide8 using Method A (Scheme
3). 3,3-Dimethyl-2-bromobutanoyl chloride (320 mg,
1.5 mmol) was added to a stirred suspension of a,a-dime-
thylbenzylamine (135 mg, 1 mmol), N-methylimidazole
(8 mg, 0.1 mmol), TMEDA (12 mg, 0.1 mmol), and
K2CO3 (207 mg, 1.5 mmol) in chlorobenzene (1 mL) at 0–
5 ꢀC under an Ar atmosphere, and the mixture was stirred
at 20–25 ꢀC for 2 h. Water was added to the stirred mixture,
which was extracted with EtOAc. The organic phase was
washed with water and brine, dried (Na2SO4), and concen-
trated to give the crude product. The obtained crude product
was washed with hexane (ca. 5 mL) to give bromobutide
(294 mg, 94%).
t-BuCOCl (252 mg, 1.5 mmol) was added to a stirred sus-
pension of 1-octanthiol (146 mg, 1 mmol), N-methylimida-
zole (123 mg, 1.5 mmol), and TMEDA (174 mg,
1.5 mmol) in CH3CN (1 mL) at 0–5 ꢀC under an Ar atmo-
sphere, and the mixture was stirred at the same temperature
for 1 h, and at 20–25 ꢀC for 1 h. Water was added to the
stirred mixture, which was extracted with EtOAc. The
organic phase was washed with water and brine, dried
(Na2SO4), and concentrated. The obtained crude product
was purified by silica gel column chromatography (hex-
ane/EtOAc¼25:1) to give S-1-octyl 2,2-dimethylpropan-
thioate (230 mg, 99%).
Colorless crystals; mp 176.0–176.5 ꢀC; 1H NMR (300 MHz,
CDCl3) d 1.50 (9H, s), 1.69 (3H, s), 1.74 (3H, s), 4.03 (1H, s),
6.32 (1H, br), 7.30–7.45 (5H, m); 13C NMR (75 MHz,
CDCl3) d 26.9, 27.6, 28.1, 29.2, 35.1, 56.3, 64.7, 124.6,
126.8, 128.4, 146.3, 166.7; IR (KBr) 3319, 3059, 2968,
4.8.1. S-1-Octyl 10-undecenthioate (Table 7, entry 7).
Colorless oil; H NMR (300 MHz, CDCl3) d 0.88 (3H, t,
1
J¼6.9 Hz), 1.16–1.41 (20H, m), 1.48–1.71 (4H, m), 2.02
(2H, q, J¼6.9 Hz), 2.53 (2H, t, J¼7.6 Hz), 2.86 (2H, t,
J¼7.6 Hz), 4.88–5.04 (1H, m), 5.81 (1H, ddt, J¼6.6, 10.3,
17.2 Hz); 13C NMR (75 MHz, CDCl3) d 14.1, 22.6, 25.7,
28.8, 28.9, 28.9, 29.0, 29.1, 29.1, 29.2, 29.2, 29.6, 31.8,
33.8, 44.1, 114.1, 139.1, 199.8; IR (neat) 2926, 2855,
1744, 1694, 1642, 1462, 1414, 1238 cmꢁ1; HRMS (ESI)
calcd for C19H36O1S1 (M+Na+) 335.2385, found 335.2383.
1820, 1678, 1541, 1367, 1199 cmꢁ1
.
4.6.2. Synthesis of carpropamid9 using Method A (Scheme
3). 2,2-Dichloro-1-ethyl-3-methylcyclopropanecarbonyl
chloride (321 mg, 1.5 mmol) was added to a stirred

H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
12079
N. F. Pyrethrum, The Natural Insecticides; Academic:
New York, NY, 1973.
4.8.2. S-1-Octyl phenoxyacetothioate (Table 7, entry 8).
Colorless oil; H NMR (300 MHz, CDCl3) d 0.88 (3H, t,
1
7. (a) Ley, S. V.; Woodward, P. R. Tetrahedron Lett. 1987, 28,
3019; (b) Rao, C. S.; Rambabu, M.; Srinivasan, P. S.
Indian J. Chem., Sect. B 1987, 26B, 407; (c) Miyashita, M.;
Shiina, I.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1994,
67, 210.
8. (a) Kirino, O.; Furuzawa, K.; Takayama, C.; Matsumoto, H.;
Mine, A. J. Pesticide Sci. 1983, 8, 301; (b) Kirino, O.;
Hashimoto, S.; Furuzawa, K.; Takayama, C.; Ohshio, H.
J. Pesticide Sci. 1983, 8, 315; (c) Kirino, O.; Furuzawa, K.;
Takayama, C.; Mizutani, T. J. Pesticide Sci. 1984, 9, 181; (d)
Watanabe, T.; Suzuki, Y.; Hirai, H. Japan Patent 57,203,049,
1982; Chem. Abstr. 1983, 99, 22141t.
9. (a) Kurahashi, Y.; Kagabu, S.; Sakawa, S.; Matsumoto, N.;
Yamada, T. Japan Patent 62,201,855, 1987; Chem. Abstr.
1988, 108, 167121a; (b) Kurahashi, Y.; Kagabu, S.;
Matsumoto, N.; Yamada, T.; Wada, K.; Kondo, T. Japan
Patent 54 349, 1998; Chem. Abstr. 1998, 109, 190038h.
10. Xiang, J.; Orita, A.; Otera, J. Adv. Synth. Catal. 2002,
344, 84.
J¼7.2 Hz), 1.18–1.42 (10H, m), 1.51–1.65 (2H, m), 2.93
(2H, t, J¼7.2 Hz), 4.68 (2H, s), 6.88–7.05 (3H, m), 7.23–
7.35 (2H, m); 13C NMR (75 MHz, CDCl3) d 14.0, 22.5,
28.0, 28.7, 29.0, 29.0, 29.2, 31.7, 72.8, 114.7, 121.9,
129.5, 157.7, 198.2; IR (neat) 2928, 2855, 1682, 1599,
1495, 1458, 1435, 1302, 1244 cmꢁ1; HRMS (ESI) calcd
for C15H24O1S1 (M+Na+) 275.1446, found 275.1446.
4.8.3. S-1-Octyl 2-chloropropanthioate (Table 7, entry 9).
Colorless oil; H NMR (300 MHz, CDCl3) d: 0.88 (3H, t,
1
J¼6.9 Hz), 1.19–1.43 (10H, m), 1.51–1.65 (2H, m), 1.71
(3H, d, J¼6.9 Hz), 2.91 (2H, t, J¼7.2 Hz), 4.47 (1H, q,
J¼6.9 Hz); 13C NMR (75 MHz, CDCl3) d 14.0, 22.1, 22.6,
28.8, 29.0, 29.1, 29.5, 31.7, 59.8, 197.8; IR (neat) 2928,
2857, 1674, 1451, 1412, 1375, 1275, 1235 cmꢁ1; HRMS
(ESI) calcd for C11H21O1S1 (M+Na+) 259.0899, found
259.0895.
11. (a) Wakasugi, K.; Nakamura, A.; Tanabe, Y. Tetrahedron Lett.
2001, 42, 7427; (b) Wakasugi, K.; Nakamura, A.; Iida, A.;
Nishii, Y.; Nakatani, N.; Fukushima, S.; Tanabe, Y.
Tetrahedron 2003, 59, 5337.
12. Mukaiyama, T.; Ichikawa, J.; Asami, M. Chem. Lett. 1983, 293.
13. Savile, C. K.; Kazlauskas, R. J. J. Am. Chem. Soc. 2005, 127,
12228.
14. Orsini, F.; Pelizzoni, F. Synth. Commun. 1984, 14, 805.
15. Katritzky, A. R.; El-Mowafy, A. J. Org. Chem. 1982, 47, 3511.
16. Yu, A.; Sun, B. Food Chem. 2005, 89, 227.
Acknowledgements
This research was partially supported by Grant-in-Aids for
Scientific Research on Basic Areas (B) ‘18350056’, Priority
Areas (A) ‘17035087’ and ‘18037068’, and Exploratory
Research ‘17655045’ from the Ministry of Education,
Culture, Sports, Science and Technology (MEXT). We thank
Kuraray Co. Limited, for generous gift of methyl dichloro-
vinylcrysanthemate.
17. Hashimoto, T.; Sugimoto, Y.; Yokoyama, Y.; Inanaga, J. J. Org.
Chem. 1996, 61, 4491.
References and notes
18. Komarek, K.; Churacek, J.; Jaroslav, K.; Tesarik, K.
J. Chromatogr. 1986, 357, 273.
1. (a) Smith, M. B.; March, J. March’s Advanced Organic
Chemistry Reactions, Mechanisms, and Structure, 6th ed.;
Wiley: New York, NY, 2007; p 1411, 1425, 1427; (b) Greene,
T. W.; Wuts, P. G. Protective Groups in Organic Synthesis,
4th ed.; Wiley: New York, NY, 2007; p 538; (c) Benz, G.
Comprehensive Organic Synthesis; Trost, B. M., Fleming, I.,
Eds.; Pergamon: Oxford, 1991; Vol. 6, p 323; (d) Otera, J.
Esterification; Wiley-VCH: Weinheim, 2003.
19. Inanaga, J.; Handa, Y.; Tabuchi, T.; Otsubo, K.; Yamaguchi,
M.; Hanamoto, T. Tetrahedron Lett. 1991, 32, 6557.
20. Kitamura, S.; Itaya, N.; Okuno, Y.; Ohno, N.; Matsuo, T.;
Hirano, M.; Mizutani, T.; Takeda, H. German Patent
2,418,950, 1974; Chem. Abstr. 1975, 82, 72566e.
21. Elliott, M.; Farham, A. W.; Janes, N. F.; Needham, P. H.;
Pulman, D. A. Nature 1974, 284, 710.
2. (a) Wakasugi, K.; Iida, A.; Misaki, T.; Nishii, Y.; Tanabe, Y.
Adv. Synth. Catal. 2003, 345, 1209; (b) Misaki, T.; Nagase,
R.; Matsumoto, K.; Tanabe, Y. J. Am. Chem. Soc. 2005, 127,
2854; (c) Iida, A.; Nakazawa, S.; Okabayashi, T.; Horii, A.;
Misaki, T.; Tanabe, Y. Org. Lett. 2006, 8, 5215.
22. Yamada, T.; Isono, N.; Inui, A.; Miyazawa, T.; Kuwata, S.;
Watanabe, H. Bull. Chem. Soc. Jpn. 1978, 51, 1897.
23. Hattori, K.; Sajiki, H.; Hirota, K. Tetrahedron 2000, 56, 8433.
24. Tozawa, T.; Yamane, Y.; Mukaiyama, T. Chem. Lett. 2005,
734.
3. Nakatsuji, H.; Morita, J.; Misaki, T.; Tanabe, Y. Adv. Synth.
Catal. 2006, 348, 2057.
25. Murphy, J. A.; Commeureuc, A. G. J.; Snaddon, T. N.;
McGuire, T. M.; Khan, T. A.; Hisler, K.; Dewis, M. L.;
Carling, R. Org. Lett. 2005, 7, 1427.
26. Hanzlik, P. R.; Jacober, P. S.; Zygmunt, J. Biochim. Biophys.
Acta, Gen. Subj. 1991, 1073, 33.
27. Ishihara, K.; Yano, T. Org. Lett. 2004, 6, 1983.
4. (a) Tanabe, Y.; Yamamoto, H.; Yoshida, Y.; Miyawaki, T.;
Utsumi, N. Bull. Chem. Soc. Jpn. 1995, 68, 297; (b) Yoshida,
Y.; Sakakura, Y.; Aso, N.; Okada, S.; Tanabe, Y. Tetrahedron
1999, 55, 2183; (c) Yoshida, Y.; Shimonishi, K.; Sakakura,
Y.; Okada, S.; Aso, N.; Tanabe, Y. Synthesis 1999, 1633; (d)
Morita, J.; Nakatsuji, H.; Misaki, T.; Tanabe, Y. Green Chem.
2005, 7, 711.
5. (a) Sano, T.; Ohashi, K.; Oriyama, T. Synthesis 1999, 1141; (b)
Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999,
265.
˚
28. Itsenko, O.; Kihlberg, T.; Langstrom, B. J. Org. Chem. 2004,
€
69, 4356.
29. Bergmann, D. J.; Campi, E. M.; Jackson, W. R.; Patti, A. F.;
Saylik, D. Aust. J. Chem. 2000, 53, 835.
30. Coan, S. B.; Papa, D. J. Am. Chem. Soc. 1955, 77, 2402.
31. Govande, V. V.; Deshmukh, A. R. A. S. Tetrahedron Lett. 2004,
45, 6563.
32. Cho, S.; Park, Y.; Kim, J.; Lee, S.; Ma, C.; Song, S.; Joo, W.;
Falck, J. R.; Shiro, M.; Shin, D.; Yoon, Y. J. Org. Chem.
2003, 68, 7918.
6. (a) Naumann, K. Synthetic Pyrethroid Insecticides. Chemistry
of Plant Protection; Springer: Berlin, 1990; Vol. 5; (b)
Matsui, M.; Yamamoto, I. Naturally Occurring Insecticides;
Marcel Dekker: New York, NY, 1971; (c) Elliot, M.; Janes,

12080
H. Nakatsuji et al. / Tetrahedron 63 (2007) 12071–12080
33. Ma, C.; Cho, S.; Falck, J. R.; Shin, D. Synth. Commun. 2004,
34, 1399.
38. Park, Y.; Kim, M.; Kwak, Y.; Lee, J.; Yoh, S.; Kim, W.
J. Photosci. 2000, 7, 135.
34. Fuchs, R.; Hoffmann, H.; Schroeder, R.; Hammann, I.;
Homeyer, B., German Patent 2,944,849, 1981; Chem. Abstr.
1981, 95, 150170f.
35. Barton, D. H. R.; Ozbalik, N,; Vacher, B. Tetrahedron 1988, 44,
3501.
36. Kikugawa, Y.; Mitsui, K. Chem. Lett. 1993, 1369.
37. Wan, W.; Ma, Z.; Li, B.; Zhang, K.; Cao, S.; Zhang, S.; Shi, Z.
J. Am. Chem. Soc. 2006, 128, 7416.
39. Vig, O. P.; Trehan, I. R.; Kad, G. L.; Dhawan, R. K.; Grewal,
M. S. Indian J. Chem., Sect. B 1980, 19B, 688.
40. Kodama, Y.; Ori, M.; Nishio, T. Helv. Chim. Acta 2005,
88, 187.
41. Sonawane, H. R.; Pol, A. V.; Nanjundiah, B. S.; Sudalai, A.
J. Chem. Res., Synop. 1998, 90.
42. Funatomi, T.; Wakasugi, K.; Misaki, T.; Tanabe, Y. Green
Chem. 2006, 8, 1022.