Asymmetric bis(alkoxycarbonylation) reaction of cyclic olefins catalyzed by palladium in the presence of copper(I) Triflate

Article abstract of DOI:10.1246/bcsj.20120125

A palladium-catalyzed asymmetric bis(alkoxycarbonylation) reaction of 1,2-dihydronaphthalenes and related cyclic olefins in the presence of copper(I) triflate was achieved by using a chiral bioxazoline ligand under normal pressure of carbon monoxide and oxygen to give the corresponding optically active cis-dicarboxylates with enantioselectivities up to 94% ee. An asymmetric intra- and intermolecular bis(alkoxycarbonylation) reaction of a prochiral diol possessing dihydronaphthalene skeleton also proceeded enantioselectively by an appropriate selection of the substituent of bioxazoline ligand. The carbonylation product derived from 8-methoxy-1,2-dihydronaphthalene was applied to the synthesis of a biologically active hexahydrobenz[e]isoindole derivative.

Full text of DOI:10.1246/bcsj.20120125

© 2012 The Chemical Society of Japan
Bull. Chem. Soc. Jpn. Vol. 85, No. 11, 1225-1232 (2012) 1225
Asymmetric Bis(alkoxycarbonylation) Reaction of Cyclic Olefins
Catalyzed by Palladium in the Presence of Copper(I) Triflate
Takahiro Aratani, Kenji Tahara, Susumu Takeuchi, Satoko Kitamura, Moemi Murai,
Shuhei Fujinami, Katsuhiko Inomata, and Yutaka Ukaji*
Division of Material Sciences, Graduate School of Natural Science and Technology,
Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192
Received May 2, 2012; E-mail: ukaji@staff.kanazawa-u.ac.jp
A palladium-catalyzed asymmetric bis(alkoxycarbonylation) reaction of 1,2-dihydronaphthalenes and related cyclic
olefins in the presence of copper(I) triflate was achieved by using a chiral bioxazoline ligand under normal pressure of
carbon monoxide and oxygen to give the corresponding optically active cis-dicarboxylates with enantioselectivities up to
94% ee. An asymmetric intra- and intermolecular bis(alkoxycarbonylation) reaction of a prochiral diol possessing
dihydronaphthalene skeleton also proceeded enantioselectively by an appropriate selection of the substituent of
bioxazoline ligand. The carbonylation product derived from 8-methoxy-1,2-dihydronaphthalene was applied to the
synthesis of a biologically active hexahydrobenz[e]isoindole derivative.
Asymmetric carbonylation reactions catalyzed by transition
metals are important in organic synthesis to provide efficient
entries to a variety of useful carbon-homologated compounds
with oxygen-functional groups in optically active forms. Espe-
cially, carbonylation reaction of olefins provides a versatile
method for the functionalization of C=C double bond to
produce aldehydes, carboxylic acids, and esters,1 and intensive
research on asymmetric monocarbonylation has been re-
ported.1b,2 In contrast, reports on asymmetric dicarbonylation
which can introduce two carbonyl groups stereoselectively in
a single operation, have been limited.3 We have studied
palladium-catalyzed mono- and bis(alkoxycarbonylation)4,5 in
the presence of Cu(II) and Cu(I) salts, respectively, and already
reported an asymmetric bis(alkoxycarbonylation) reaction of
terminal olefins and homoallylic alcohols using a chiral
bioxazoline ligand, which gave the corresponding optically
active succinates and £-butyrolactones with moderate enantio-
selectivities.6 Herein, we wish to describe an asymmetric
bis(alkoxycarbonylation) reaction of cyclic olefins possess-
ing 1,2-dihydronaphthalene or related cyclic skeleton in the
presence of copper(I) triflate to give the corresponding optically
active cis-dicarboxylates with excellent enantioselectivities.7
Intra- and intermolecular version of asymmetric bis(alkoxy-
carbonylation) reaction of a prochiral diol possessing dihydro-
naphthalene skeleton is also reported.
diastereoselectivity in 32% yield. To our delight, the optical
yield of the obtained cis-diester 2a was determined to be 93% ee
by HPLC analysis (Table 1, Entry 1). In order to accelerate the
carbonylation, the reaction temperature was increased to 60 °C.
Within 2 d, 1,2-dihydronaphthalene (1a) almost disappeared
and the carbonylated product 2a was obtained in higher yield
without much decrease of enantioselectivity (Entry 2).9 Al-
though the reaction conditions for asymmetric bis(alkoxy-
carbonylation) reaction were previously investigated in the case
of styrene,6b the effect of palladium salt and copper salt to the
present bis(alkoxycarbonylation) reaction was examined. The
reaction by the use of allylpalladium chloride dimer proceeded
slower than that using PdCl2 to afford 2a with still high enan-
tioselectivity (Entry 3). Although the ratio of carbon monoxide
to oxygen did not influence enantioselectivity so much, employ-
ing almost equal volume of carbon monoxide and oxygen gave
better chemical yield and enantioselectivity (Entries 2, 4, and 5).
When CuCl and Cu(OTf)2 were employed as a copper salt, the
reactions afforded many unknown by-products and enantio-
selectivities of 2a were rather low (Entries 6 and 7).
Then the asymmetric bis(alkoxycarbonylation) of several
cyclic olefins related to dihydronaphthalene was investigated by
the use of PdCl2 and CuOTf(C6H6)0.5 under carbon monoxide
and oxygen (ca. 1/1, v/v). The carbonylation reaction of indene
(1b) also afforded the corresponding dicarboxylate 2b with
excellent enantioselectivity (Entries 8 and 9). However, the
carbonylation of 7-membered cyclic olefin 1c was so sluggish
that yield was poor even at 60 °C (Entry 10). When the benzene
ring was substituted by an electron-withdrawing Br group,
the reaction was retarded (Entries 11 and 12). In these cases,
olefins 1c and 1d were not completely consumed. On the other
hand, the introduction of electron-donating MeO group at the
C7 position produced not only desired carbonylated product
2e with excellent enantioselectivity but also a mixture of
optically active cis- and trans-methoxycarbonylated products
Results and Discussion
First, an asymmetric bis(alkoxycarbonylation) reaction of
1,2-dihydronaphthalene (1a) was examined in the presence of
0.02 equivalents of PdCl2 and 0.5 equivalents of CuOTf-
(C6H6)0.5 under normal pressure of carbon monoxide and
oxygen (ca. 1/1, v/v) in MeOH/THF using (4S,4¤S)-4,4¤-
dibenzyl-4,4¤,5,5¤-tetrahydro-2,2¤-bioxazole (3A) as a chiral
ligand. The reaction proceeded very slowly to give dimethyl cis-
tetrahydronaphthalene-1,2-dicarboxylate (2a)8 with complete
Published on the web November 1, 2012; doi:10.1246/bcsj.20120125

1226 Bull. Chem. Soc. Jpn. Vol. 85, No. 11 (2012)
Asymmetric Bis(alkoxycarbonylation)
Table 1. Asymmetric Bis(alkoxycarbonylation) Reaction of Cyclic Olefins 1
PdCl2 (0.02 equiv)
Cu salt (0.5 equiv)
O
O
CO2Me
CO2Me
(0.04 equiv)
Bn
N
N
Bn
3A
R1
R1
CO/O2 (ca. 1/1)
MeOH/THF (1/1)
Temp, t d
n
n
R2
1
R2
2
(Bn = PhCH2)
Entry
n
R1
H
R2
H
Cu salt
Temp
t/d
Yield/%
ee/%a)
1
2
3b)
4c)
5d)
6
7
8
9
10
11
12
13
14
15
16
1
a
CuOTf(C6H6)0.5
rt
10
2
6
6
2
6
4
9
2
7
8
13
8
3
32
57
44
31
28
12
10
25
49
10
14
40
24f)
25g)
56
60
93
91
88
71
81
¹35e)
¹19e)
92
89
78
87
74
92
92
94
92
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
Cu(OTf)2
60 °C
60 °C
60 °C
60 °C
60 °C
60 °C
rt
60 °C
60 °C
rt
CuCl
0
H
H
b
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
CuOTf(C6H6)0.5
2
1
H
Br
H
H
c
d
60 °C
rt
60 °C
rt
1
1
MeO
H
H
e
MeO
f
11
2
60 °C
a) Enantioselectivities were determined by HPLC analysis (Daicel CHIRALPAK IA). b) Allylpalladium chloride
dimer (0.02 equiv as a monomer) was used instead of PdCl2. c) The ratio of CO/O2 was ca. 3/1. d) The ratio of
CO/O2 was ca. 1/3. e) Opposite enantiomer of 2a was preferentially obtained. f) Methoxycarbonylation products 4
(18% yield, 92% ee) and 5 (5% yield, 87% ee) were also produced. g) Methoxycarbonylation products 4 (24% yield,
87% ee) and 5 (11% yield, 87% ee) were also produced.
OMe
OMe
CO Me
2
CO Me
2
MeO
MeO
4
5
4 and 5 (Entries 13 and 14). MeO-substituted dihydronaph-
thalene at the C8 position 1f gave the product 2f in reasonable
yield with excellent enantioselectivity even at 60 °C (Entries 15
and 16).
£-Lactones possessing tetrahydronaphthalene skeleton have
been reported to have bioactivities such as antitumor activ-
ities.11 Previously we reported an intra- and intermolecular
asymmetric bis(alkoxycarbonylation) reaction of homoallylic
alcohols to produce the corresponding optically active £-
lactones.6a Therefore, an intra- and intermolecular bis(alkoxy-
carbonylation) reaction of a prochiral diol 8 possessing di-
hydronaphthalene skeleton was next performed using benzyl-
substituted bioxazoline ligand 3A at 60 °C to give a lactone 9
in 54% yield. However, its optical purity was disappointedly
low (Table 2, Entry 1). Then the intra- and intermolecular
bis(alkoxycarbonylation) reaction was examined using other
bioxazoline ligands. Although enantioselectivity was enhanced
by the use of isopropyl-substituted ligand 3C (Entry 3), more
bulky t-butyl-substituted ligand 3D showed less enantioselec-
tivity (Entry 4). It was found that phenyl-substituted ligand 3E
realized higher enantioselectivity of 87% ee (Entry 5). Ligand
10, in which aromatic ring was fused with oxazoline, showed
moderate selectivity (Entry 6).
Enantioselectivity of the present carbonylation of cyclic
olefins is higher than that in the case of terminal olefins:6b
Asymmetric bis(alkoxycarbonylation) reaction of (Z)-1-phenyl-
1-propene (6) was carried out. The reaction was sluggish to
give the corresponding succinate 7 with 74% ee, which was
slightly higher than that in the case of styrene but lower
than the cyclic olefins 1 (eq 1). This result suggested that
excellent enantioselectivity of the present bis(alkoxycarbonyl-
ation) reaction was mainly due to the rigid cyclic structure. In
addition, the planarity throughout an aromatic ring and a
double bond moiety (Car-CH=CH-C) might be also important
to realize high enantioselectivity.10
CO Me
2
PdCl (0.02 equiv)
2
CO Me
CuOTf(C H ) (0.5 equiv)
2
6
6 0.5
3A (0.04 equiv)
ð1Þ
The absolute configuration of the cis-diester 2f was deter-
mined to be R,R by chemical correlation as described later. The
CO/O (ca.1/1)
2
MeOH/THF (1/1), 60 °C, 2 d
21%
74% ee
6
7

T. Aratani et al.
Bull. Chem. Soc. Jpn. Vol. 85, No. 11 (2012) 1227
absolute configurations of other products 2a-2e were tenta-
tively determined to be also R,R.
bis(alkoxycarbonylation) reaction of 1a using benzyl-sub-
stituted ligand 3A is shown in Figure 2, based on the absolute
stereochemistry assigned above. The initial enantioselective
carbopalladation might proceed via T1 to avoid steric hindrance
between a benzyl group in 3A and aromatic ring in 1a found
in T2, resulting in furnishing (R,R)-diester 2a.12 The production
of MeO-substituted monocarbonylated compounds 4 and 5
from 1e with excellent enantioselectivity parallel to that of 2e
suggested the regioselective carbopalladation13 occurred to
give 12, followed by reductive elimination and subsequent
addition of MeOH as shown in 13 (Scheme 1).
In the case of intra- and intermolecular bis(alkoxycarbonyl-
ation) of 8, tethered alkoxycarbonyl moiety encounters the
steric hindrance between another benzyl group in ligand 3A as
depicted as T3 (Figure 3), which undermines the advantage of
T3 over T4 decreasing enantioselectivity. However, in the case
of phenyl-substituted ligand 3E,14 the phenyl group can twist to
release the congestion with alkoxycarbonyl moiety (T5), which
resulted in the effective stereodifferentiation over T6 to give the
lactone via T5 with high enantioselectivity.
To establish the absolute configuration of 9, it was converted
into the corresponding (S)-¡-methylbenzyl-substituted ure-
thane 11 as follows: The enantiomerically rich 9, obtained by
the use of (R,R)-phenyl-substituted bioxazoline ligand 3E, was
treated with (S)-(¡-methylbenzyl)isocyanate in the presence
of a catalytic amount of 4-(dimethylamino)pyridine to give
the corresponding urethane 11 (80%). Recrystallization gave
diastereomerically pure 11. The absolute stereochemistry of 11
was determined to be 3aR,4S,9aR by X-ray crystallographic
analysis of its single crystal (Figure 1). Thus, the absolute
configuration of 9 derived by using (4R,4¤R)-phenyl-substituted
bioxazoline ligand (R,R)-3E as a chiral ligand was assigned
to be 3aR,4S,9aS. This result suggests that (3aS,4R,9aR)-9
would be produced if (S,S)-3E was used as a chiral ligand, in
which the sense of chiral induction is similar to the bis(alkoxy-
carbonylation) reaction of 1,2-dihydronaphthalene (1a) using
(S,S)-3A.
Although the precise mechanism of the present reaction is
still an open question, a possible transition state of asymmetric
Optically active cis-1,2-disubstituted tetrahydronaphtha-
lenes have biological activities.15 For example, tricyclic hexa-
hydrobenz[e]isoindoles are reported to be ¡1A adrenoceptor
antagonists as potential agents for benign prostatic hyperplasia,
and a 6-MeO-substituted compound 18 with (R,R)-stereochem-
Table 2. Asymmetric Intra- and Intermolecular Bis(alkoxy-
carbonylation) Reaction of 8
PdCl (0.02 equiv)
2
CuOTf(C H ) (0.5 equiv)
6
6 0.5
O
O
MeO C
MeO C
2
4
2
S
O
O
MeO C
2
O
OCN
cat. DMAP
Ph
3a
R
(0.04 equiv)
R
N
N
O
O
3
R
R
9a
O
OH
OH
O
CH Cl
rt, 30 h
2
2
CO/O (ca. 1/1)
2
MeOH/THF (1/1)
OH
O
OH
9
N
S
11
80%
8
60 °C, t d
9
Ph
H
(3aR,4S,9aS)
(3aR,4S,9aR)
Entry
R
Ligand
t/d
Yield/%
ee/%a)
1
2
3
4
5
6
Bn
3A
3B
3C
3D
3Eb)
10
2
2
2
2
4
4
54
53
32
46
62
22
35
36
48
22
87c)
60
i-Bu
i-Pr
t-Bu
Ph
R
S
R
a) Enantioselectivities were determined by HPLC analysis
(Daicel CHIRALPAC IB). b) (R,R)-3E was used. c) Opposite
enantiomer of 9 was predominantly obtained.
S
O
O
N
N
10
Figure 1.
H
H
O
N
O
O
O
N
N
N
Me
Me
O
O
O
H
Pd
Pd
H
H
H
H
O
H
T
T
2
1
Figure 2.

1228 Bull. Chem. Soc. Jpn. Vol. 85, No. 11 (2012)
Asymmetric Bis(alkoxycarbonylation)
Pd+
MeO H
O
C
CO2Me
OMe
4,5
− H+
− Pd(0)
MeO
MeO
12
13
Scheme 1.
H
H
O
O
O
O
N
N
N
N
O
O
H
Pd
Pd
H
H
H
H
O
O
H HO
HO
T3
T4
H
H
O
O
O
O
N
N
N
N
O
O
H
Pd
Pd
H
H
H
H
O
O
H HO
T5
T6
HO
Figure 3.
istry of the ring junction of the benz[e]isoindole is most
effective.15d The present bis(alkoxycarbonylation) could pro-
vide two vicinal substituents with cis-relationship at once in
an enantioselective manner, and the products might be good
precursors for cis-1,2-disubstituted tetrahydronaphthalenes.
Thus, the construction of a hexahydrobenz[e]isoindole skeleton
from the carbonylated product 2f was performed (Scheme 2).
Reduction of 2f (93% ee) by LiAlH4 gave a cis-diol 14. Toward
the construction of pyrrolidine ring, conversion of diol 14 to the
corresponding disulfonate was first tried by treatment with
methanesulfonyl chloride or trifluoromethanesulfonic anhy-
dride in the presence of an amine base.16 However, the corre-
sponding tetrahydrofuran was directly produced and the desired
disulfonate was obtained as a minor product. After several
experiments, the diol could be transformed into the correspond-
ing cyclic sulfonate 15 in good yield.17 The cyclic sulfonate 15
was treated with benzylamine, followed by addition of a base to
form a hexahydrobenz[e]isoindole skeleton 16. Hydrogenolysis
of 16 catalyzed by Pd(OH)2/C furnished a debenzylated amine
17 as a precursor of 18.15d The absolute configuration of the
amine 17 was determined to be R,R by a comparison of its
action of 1,2-dihydronaphthalenes and related cyclic olefins to
form the optically active cis-diesters with excellent enantio-
selectivities. The intra- and intermolecular version of the bis-
(alkoxycarbonylation) was also realized to furnish the corre-
sponding optically active £-lactone. This carbonylation method
provides a useful route to synthesize chiral polycyclic com-
pounds, such as hexahydrobenz[e]isoindoles.
Experimental
1
The H NMR spectra were recorded on JEOL Lambda 400
and ECS 400 NMR (400 MHz) spectrometers. The chemical
shifts were determined in the ¤-scale relative to TMS (¤ = 0
ppm) as an internal standard. The IR spectra were measured on
a JASCO FT/IR-230 spectrometer. Elemental analyses were
carried out on a Yanaco CHN Corder MT-5 elemental analyzer.
The MS spectra were recorded with JEOL JMS-SX102A and
JMS-700 mass spectrometers. THF and Et2O were freshly
distilled over sodium diphenyl ketyl. All other solvents were
distilled and stored over drying agents. Merck silica gel 60
PF254 (Art. 7749), Cica silica gel 60N spherical neutral
(37563-84), and JAIGL-SIL (s-043-15) were used for thin-layer
chromatography (TLC), flash column chromatography, and
recycle HPLC, respectively. All of the melting points were
determined with a micro melting apparatus (Yanagimoto-
Seisakusho) and are uncorrected.
25
specific rotation (½¡ꢀD ¹21 (c 0.34, MeOH) with the reported
20
one [(R,R)-isomer: ½¡ꢀD ¹22.0 (c 1.39, MeOH)].15d Accord-
ingly, the absolute stereochemistry of bis(alkoxycarbonylation)
product 2f was also confirmed to be R,R.
As described above, we have developed the enantioselective
palladium-catalyzed asymmetric bis(alkoxycarbonylation) re-
Chiral ligands 3A-3D,18a 3E,18b and 1018c were prepared by
the methods reported in the literature.

T. Aratani et al.
Bull. Chem. Soc. Jpn. Vol. 85, No. 11 (2012) 1229
OH
O
SO2
O
OH
SOCl2
LiAlH4
90%
2f
then NaIO4
cat. RuCl3·nH2O
78%
MeO
14
MeO
15
Ph
N
NH
H2
cat. Pd(OH)2/C
BnNH2
then NaH
88%
76%
16
17
MeO
MeO
O
S
N
N
N
R
known
O
R
N
Cl
18
MeO
Scheme 2.
1
A Representative Procedure for the Asymmetric Bis(alk-
oxycarbonylation) Reaction of 1f (Table 1, Entry 16).
Under an Ar atmosphere, CuOTf(C6H6)0.5 (186 mg, 0.74 mmol)
was placed in a flask and a MeOH (6 mL) solution of 1f
(235 mg, 1.47 mmol) and a THF (6 mL) solution of 3A (19 mg,
0.059 mmol) were added. To the mixture, PdCl2 (5.32 mg,
0.030 mmol) was added. The Ar atmosphere was replaced with
CO/O2 (ca. 1/1, v/v) and the reaction mixture was stirred for
2 d at 60 °C. A saturated aqueous solution of NaHCO3 was
added to the reaction mixture at rt, and the insoluble substance
was filtered off. After the filtrate was extracted with AcOEt,
the combined extracts were washed with water and brine,
dried over Na2SO4, and condensed in vacuo. The residue was
purified by column chromatography (CHCl3/hexane = 1/1 and
then with CHCl3/AcOEt = 100/1, v/v) and further recycle
HPLC (hexane/AcOEt = 3/1, v/v) to give 2f (245 mg, 60%).
The optical purity was determined to be 92% ee by HPLC
analysis (Daicel CHIRALPAK IA©2, hexane/EtOH = 50/1).
In a similar manner, diester 2a-2e, 7, and lactone 9 were
prepared from the corresponding olefins 1a-1e, 6, and diol 8,
respectively.
984, 933, 762 cm¹1. H NMR (CDCl3): ¤ 3.12-3.22 (m, 1H),
3.50-3.62 (m, 2H), 3.63 (s, 3H), 3.73 (s, 3H), 4.31 (d, J =
8.29 Hz, 1H), 7.16-7.27 (m, 3H), 7.35 (d, J = 7.08 Hz, 1H).
HRMS (EI+) (M+), Found: m/z 234.08866. Calcd for
C13H14O4: 234.08921.
Dimethyl (5R,6R)-6,7,8,9-Tetrahydro-5H-benzo[7]annu-
lene-5,6-dicarboxylate (2c):
EtOH, 78% ee). IR (neat): 3057, 3020, 2950, 2855, 1736, 1436,
1304, 1223, 1011, 954, 752 cm¹1. H NMR (CDCl3): ¤ 1.34-
1.45 (m, 1H), 1.97-2.07 (m, 1H), 2.20 (dddd, J = 14.64, 12.44,
12.20, 3.42 Hz, 1H), 2.32-2.40 (m, 1H), 2.64-2.79 (m, 3H),
3.65 (s, 3H), 3.75 (s, 3H), 4.55 (d, J = 2.20 Hz, 1H), 7.09-7.22
(m, 4H). HRMS (EI+) (M+), Found: m/z 262.12065. Calcd for
C15H18O4: 262.12051.
Dimethyl (1R,2R)-6-Bromo-1,2,3,4-tetrahydronaphtha-
lene-1,2-dicarboxylate (2d):
EtOH, 87% ee). IR (neat): 2952, 2841, 1731, 1590, 1482,
1456, 1435, 1224, 1160, 1012, 988, 824, 803 cm¹1. H NMR
(CDCl3): ¤ 2.28-2.34 (m, 1H), 2.37 (dddd, J = 13.42, 12.20,
11.95, 5.86 Hz, 1H), 2.72-2.78 (m, 1H), 2.81 (ddd, J = 17.08,
11.95, 7.07 Hz, 1H), 2.93 (ddd, J = 17.08, 5.86, 2.20 Hz, 1H),
3.66 (s, 3H), 3.74 (s, 3H), 4.18 (d, J = 5.12 Hz, 1H), 7.23-7.29
(m, 3H). HRMS (EI+) (M+), Found: m/z 326.0154. Calcd for
C14H15O479Br: 326.0154. Found: m/z 328.0128. Calcd for
C14H15O481Br: 328.0133.
25
An oil. ½¡ꢀD ¹50 (c 0.10,
1
25
An oil. ½¡ꢀD +44 (c 0.17,
1
Dimethyl (1R,2R)-1,2,3,4-Tetrahydronaphthalene-1,2-di-
25
carboxylate (2a): An oil. ½¡ꢀD +66 (c 0.45, EtOH, 93% ee).
IR (neat): 2952, 1735, 1491, 1434, 1298, 1223, 1158, 1051,
1
1010, 989, 781, 747 cm¹1. H NMR (CDCl3): ¤ 2.28-2.34 (m,
1H), 2.42 (dddd, J = 12.44, 12.20, 11.71, 6.10 Hz, 1H), 2.80
(ddd, J = 12.44, 5.37, 3.66 Hz, 1H), 2.84 (ddd, J = 17.32,
11.71, 6.59 Hz, 1H), 2.97 (ddd, J = 17.32, 6.10, 2.20 Hz, 1H),
3.66 (s, 3H), 3.74 (s, 3H), 4.23 (d, J = 5.37 Hz, 1H), 7.12-7.21
(m, 3H), 7.37 (d, J = 8.05 Hz, 1H). HRMS (EI+) (M+), Found:
m/z 248.10426. Calcd for C14H16O4: 248.10486.
Dimethyl (1R,2R)-6-Methoxy-1,2,3,4-tetrahydronaphtha-
lene-1,2-dicarboxylate (2e): An oil. ½¡ꢀ2D5 +61 (c 0.35, EtOH,
92% ee). IR (neat): 2951, 2839, 1732, 1609, 1503, 1434, 1263,
1223, 1158, 1128, 1038, 990, 834, 786 cm¹1. 1H NMR (CDCl3):
¤ 2.25-2.32 (m, 1H), 2.40 (dddd, J = 13.42, 12.44, 11.95,
5.86 Hz, 1H), 2.78 (ddd, J = 12.44, 5.12, 3.42 Hz, 1H), 2.82
(ddd, J = 17.32, 11.95, 6.59 Hz, 1H), 2.93 (ddd, J = 17.32,
5.86, 1.95 Hz, 1H), 3.65 (s, 3H), 3.74 (s, 3H), 3.77 (s, 3H),
4.17 (d, J = 5.12 Hz, 1H), 6.65 (d, J = 2.68 Hz, 1H), 6.73
Dimethyl (1R,2R)-2,3-Dihydro-1H-indene-1,2-dicarbox-
25
ylate (2b): An oil. ½¡ꢀD +15 (c 0.28, EtOH, 92% ee). IR
(neat): 2952, 2849, 1735, 1436, 1339, 1222, 1118, 1076, 1035,

1230 Bull. Chem. Soc. Jpn. Vol. 85, No. 11 (2012)
Asymmetric Bis(alkoxycarbonylation)
(dd, J = 8.54, 2.68 Hz, 1H), 7.27 (d, J = 8.54 Hz, 1H). HRMS
(EI+) (M+), Found: m/z 278.11599. Calcd for C15H18O5:
278.11542.
2952, 2844, 1734, 1496, 1435, 1254, 1199, 1167, 1012, 752,
1
739 cm¹1. H NMR (CDCl3): ¤ 1.88 (dddd, J = 13.28, 10.53,
10.07, 5.50 Hz, 1H), 2.31 (dddd, J = 13.28, 5.04, 5.04, 3.66
Hz, 1H), 2.85 (ddd, J = 16.48, 10.07, 5.04 Hz, 1H), 2.92 (ddd,
J = 16.48, 5.50, 5.04 Hz, 1H), 3.25 (ddd, J = 10.53, 8.70,
3.66 Hz, 1H), 3.72 (s, 3H), 3.77 (s, 3H), 4.19 (d, J = 8.70 Hz,
1H), 7.12-7.21 (m, 3H), 7.37 (d, J = 8.05 Hz, 1H). HRMS
(EI+) (M+), Found: m/z 248.1054. Calcd for C14H16O4:
248.1049.
Methyl (1R,2R)-1,6-Dimethoxy-1,2,3,4-tetrahydronaph-
25
thalene-2-carboxylate (4): An oil. ½¡ꢀD +94 (c 0.30, EtOH,
87% ee). IR (neat): 2948, 2836, 1740, 1609, 1578, 1503, 1456,
1434, 1374, 1316, 1284, 1265, 1242, 1220, 1155, 1106, 1081,
1
1037, 943, 911, 866, 834, 809, 765 cm¹1. H NMR (CDCl3): ¤
2.07 (dddd, J = 13.42, 6.59, 3.42, 2.20 Hz, 1H), 2.26 (dddd,
J = 13.42, 12.69, 11.71, 6.34 Hz, 1H), 2.71 (ddd, J = 12.69,
3.42, 2.93 Hz, 1H), 2.75 (ddd, J = 17.32, 11.71, 6.59 Hz, 1H),
2.96 (ddd, J = 17.32, 6.34, 2.20 Hz, 1H), 3.31 (s, 3H), 3.77
(s, 3H), 3.78 (s, 3H), 4.55 (d, J = 2.93 Hz, 1H), 6.69 (d, J =
2.68 Hz, 1H), 6.73 (dd, J = 8.29, 2.68 Hz, 1H), 7.17 (d, J =
8.29 Hz, 1H). HRMS (EI+) (M+), Found: m/z 250.12117.
Calcd for C14H18O4: 250.12051.
(2-Hydroxymethyl-1,2-dihydronaphthalen-2-yl)methanol
(8). To a suspension of LiAlH4 (964 mg, 25.3 mmol) in THF
(20 mL) was added dropwise 1,2-dihydronaphthalene-2,2-di-
carboxylic acid19 (1.843 g, 8.4 mmol) in THF (20 mL) at 0 °C
under N2 atmosphere. The resulting mixture was stirred for 10 h
at rt, and then refluxed for 2 h. The resulting reaction mixture
was treated with a saturated aqueous Na2SO4 solution (17 mL).
The insoluble substance was filtered off, followed by washing
with AcOEt, and the filtrate was concentrated in vacuo.
Separation of the residue by column chromatography (hexane/
AcOEt = 3/1, v/v) afforded the diol 8. The obtained diol was
recrystallized from AcOEt/hexane to give pure 8 (638 mg)
in 40% yield. Mp 115.0-116.0 °C (from AcOEt/hexane). IR
(KBr): 3333, 2933, 2872, 1482, 1447, 1087, 1048, 1027,
788 cm¹1. 1H NMR (CDCl3): ¤ 2.13 (br, 2H), 2.85 (s, 2H), 3.65
(d, J = 10.56 Hz, 2H), 3.72 (d, J = 10.56 Hz, 2H), 5.76 (d,
J = 9.64 Hz, 1H), 6.56 (d, J = 9.64 Hz, 1H), 7.04-7.19 (m,
4H). HRMS (EI+) (M+), Found: m/z 190.09935. Calcd for
C12H14O2: 191.09938.
Methyl (1S,2R)-1,6-Dimethoxy-1,2,3,4-tetrahydronaph-
25
thalene-2-carboxylate (5): An oil. ½¡ꢀD ¹18 (c 0.12, EtOH,
87% ee). IR (neat): 2946, 1732, 1608, 1504, 1434, 1268, 1240,
1
1159, 1081, 1037, 844 cm¹1. H NMR (CDCl3): ¤ 2.03 (dddd,
J = 13.42, 8.54, 7.56, 6.34 Hz, 1H), 2.16 (dddd, J = 13.42,
6.34, 6.10, 3.90 Hz, 1H), 2.77-2.82 (m, 2H), 2.99 (ddd,
J = 8.54, 6.59, 3.90 Hz, 1H), 3.39 (s, 3H), 3.70 (s, 3H), 3.78 (s,
3H), 4.72 (d, J = 6.59 Hz, 1H), 6.61 (d, J = 2.68 Hz, 1H), 6.76
(dd, J = 8.54, 2.68 Hz, 1H), 7.29 (d, J = 8.54 Hz, 1H). HRMS
(EI+) (M+), Found: m/z 250.12114. Calcd for C14H18O4:
250.12051.
Dimethyl (1R,2R)-5-Methoxy-1,2,3,4-tetrahydronaphtha-
25
lene-1,2-dicarboxylate (2f):
An oil. ½¡ꢀD +86 (c 0.89,
Methyl (3aR,4S,9aS)-9a-(Hydroxymethyl)-3-oxo-1,3,3a,
4,9,9a-hexahydronaphtho[2,3-c]furan-4-carboxylate (9):
EtOH, 94% ee). IR (neat): 2952, 2839, 1737, 1588, 1469, 1434,
25
1346, 1260, 1222, 1158, 1092, 1077, 1051, 995, 894, 820, 767,
Mp 98.5-99.5 °C (from EtOH/hexane). ½¡ꢀD +126 (c 0.47,
1
729 cm¹1. H NMR (CDCl3): ¤ 2.30-2.37 (m, 2H), 2.48-2.58
EtOH, 87% ee obtained by the use of (R,R)-3E). IR (KBr):
(m, 1H), 2.76 (ddd, J = 8.78, 7.56, 5.37 Hz, 1H), 3.02 (ddd,
J = 17.81, 3.90, 3.66 Hz, 1H), 3.66 (s, 3H), 3.74 (s, 3H), 3.81
(s, 3H), 4.21 (d, J = 5.12 Hz, 1H), 6.71 (d, J = 8.05 Hz, 1H),
6.98 (d, J = 7.81 Hz, 1H), 7.13 (dd, J = 8.05, 7.81 Hz, 1H).
HRMS (EI+) (M+), Found: m/z 278.11568. Calcd for
C15H18O5: 278.11542.
3446, 2953, 2919, 1765, 1734, 1457, 1437, 1348, 1281, 1214,
1
1028, 762 cm¹1. H NMR (CDCl3): ¤ 2.07 (br, 1H), 2.58 (d,
J = 6.60 Hz, 1H), 2.89 (s, 2H), 3.34 (s, 2H), 3.63 (s, 3H), 4.38
(d, J = 6.60 Hz, 1H), 4.39 (d, J = 8.79 Hz, 1H), 4.63 (d,
J = 8.79 Hz, 1H), 7.11-7.17 (m, 1H), 7.25-7.28 (m, 2H), 7.34-
7.37 (m, 1H). Found: C, 65.06; H, 5.90%. Calcd for C15H16O5:
C, 65.21; H, 5.84%.
Dimethyl (2R,3R)-2-Methyl-3-phenylsuccinate (7): An
25
oil. ½¡ꢀD ¹80° (c 0.25, EtOH, 74% ee). IR (neat): 3062, 3032,
Methyl (3aR,4S,9aR)-3-Oxo-9a-[(S)-(¡-methylbenzyl)car-
bamoyloxy]methyl-1,3,3a,4,9,9a-hexahydronaphtho[2,3-c]-
furan-4-carboxylate (11). A CH2Cl2 (0.5 mL) solution of
(S)-(¡-methylbenzyl)isocyanate (32 mg, 0.22 mmol) was added
to the lactone 9 (30 mg, 0.11 mmol, 83% ee) and 4-(dimethyl-
amino)pyridine (0.1 mg) at rt under a nitrogen atmosphere and
the mixture was stirred for 30 h at rt. After quenching the
reaction by the addition of water, the mixture was extracted
with AcOEt. The combined extracts were washed with brine,
dried over Na2SO4. The solvent was evaporated and the residue
was separated by TLC on SiO2 (hexane/AcOEt = 1/1, v/v) to
afford 11 (41 mg) in 80% yield as a solid. Diastereomerically
pure 11 was obtained by recrystallization twice (AcOEt/
2958, 2850, 1730, 1455, 1436, 1375, 1323, 1295, 1195, 1155,
1060, 1000, 907, 854, 728, 698 cm¹1. 1H NMR (CDCl3): ¤ 0.96
(d, J = 7.32 Hz, 3H), 3.18 (dq, J = 11.22, 7.32 Hz, 1H), 3.63
(s, 3H), 3.73 (s, 3H), 3.78 (d, J = 11.22 Hz, 1H), 7.25-7.35 (m,
5H). HRMS (EI+) (M+), Found: m/z 236.10433. Calcd for
C13H16O4: 236.10486.
Isomerization of 2a to trans-Isomer.8 To a MeOH (2 mL)
solution of 2a (169 mg, 0.68 mmol) was added NaOMe (0.1 M
in MeOH, 1.4 mL, 0.14 mmol) and the reaction mixture was
heated at 60 °C for 6 h. A saturated aqueous solution of NH4Cl
was added at rt and the mixture was extracted with AcOEt. The
combined extracts were washed with water and brine, dried
over Na2SO4, and condensed in vacuo to give a crude 3/1
mixture of trans-isomer of 2a and recovered 2a. A part of
the crude mixture was separated by TLC on SiO2 (hexane/
AcOEt = 5/1) and further recycle HPLC (hexane/AcOEt =
5/1) to isolate trans-isomer of 2a.
25
hexane). Mp 122-123 °C (from hexane/AcOEt). ½¡ꢀD +40 (c
0.1, EtOH). IR (KBr): 3342, 2920, 1773, 1724, 1523, 1234,
1
1211, 1079, 1056, 1035, 767, 697 cm¹1. H NMR (CDCl3): ¤
1.43 (d, J = 6.88 Hz, 3H), 2.68 (d, J = 6.44 Hz, 1H), 2.73 (d,
J = 15.12 Hz, 1H), 2.96 (d, J = 15.12 Hz, 1H), 3.62 (s, 3H),
3.77 (d, J = 10.56 Hz, 1H), 3.87 (d, J = 10.56 Hz, 1H), 4.38 (d,
J = 6.40 Hz, 1H), 4.41 (d, J = 8.68 Hz, 1H), 4.49 (d, J = 8.68
Dimethyl (1S*,2R*)-1,2,3,4-Tetrahydronaphthalene-1,2-
dicarboxylate (trans-Isomer of 2a): An oil. IR (neat): 3022,

T. Aratani et al.
Bull. Chem. Soc. Jpn. Vol. 85, No. 11 (2012) 1231
Hz, 1H), 4.72-4.79 (m, 1H), 5.04 (d, J = 7.80 Hz, 1H), 7.08 (d,
J = 5.96 Hz, 1H), 7.22-7.36 (m, 8H). HRMS (EI+) (M+),
Found: m/z 423.16822. Calcd for C22H25NO6: 423.16819.
Crystal data: C24H25NO6, Mr = 423.46, monoclinic, P21, a =
6.74 (d, J = 8.30 Hz, 1H), 6.77 (d, J = 7.81 Hz, 1H), 7.18 (dd,
J = 8.30, 7.81 Hz, 1H). Found: C, 54.74; H, 5.60%. Calcd for
C13H16O5S: C, 54.91; H, 5.67%.
(3aR,9bR)-2-Benzyl-6-methoxy-2,3,3a,4,5,9b-hexahydro-
1H-benzo[e]isoindole (16). To a THF (2 mL) solution of
the cyclic sulfonate 15 (57 mg, 0.20 mmol) was added a THF
(2 mL) solution of benzylamine (64 mg, 0.060 mmol), and the
reaction mixture was refluxed for 7 d. After cooling to rt, NaH
(60% dispersion in mineral oil, 24 mg, 0.60 mmol) was added
and the mixture was stirred for 2 h until getting clear. Water
was added and the solution was partitioned between AcOEt
and water. The combined organic extracts were successively
washed with water and brine, dried over Na2SO4, and con-
densed in vacuo. The residue was purified by TLC on SiO2
8.964(2), b = 8.639(1), c = 13.874(2) ¡, V = 1045.4(3) ¡3,
¹3
¢ = 103.353(4)°, Z = 2,
Dcalcd = 1.345 g cm , R = 0.046
(Rw = 0.048) for 3348 reflections with I > 3.00·(I) and 281
variable parameters. Crystallographic data for 11 have been
deposited with Cambridge Crystallographic Data Centre as
supplementary publication No. CCDC 869665. Copies of the
data can be obtained free of charge via www.ccdc.cam.ac.uk/
conts/retrieving.html.
(1R,2R)-5-Methoxy-1,2,3,4-tetrahydronaphthalene-1,2-
dimethanol (14).
To a suspension of LiAlH4 (382 mg,
25
10.1 mmol) in Et2O (15 mL) was added dropwise an Et2O
(3 mL) solution of dimethyl (1R,2R)-5-methoxy-1,2,3,4-tetra-
hydronaphthalene-1,2-dicarboxylate (2f) (800 mg, 2.87 mmol,
93% ee) at 0 °C under N2 atmosphere. The resulting mixture
was gradually warmed to rt and stirred for 18 h at rt, and then
treated with a saturated aqueous Na2SO4 solution (2.9 mL). The
insoluble substance was filtered off, followed by washing with
AcOEt, and the filtrate was concentrated in vacuo. Separation
of the residue by column chromatography (hexane/AcOEt =
3/1 to 1/1, v/v) afforded the corresponding diol 14 (574 mg,
(hexane/AcOEt = 5/1) to give 16 (52 mg, 88%). An oil. ½¡ꢀD
+19 (c 0.51, EtOH). IR (neat): 2922, 2853, 2833, 2784, 1584,
1468, 1338, 1258, 1098, 1077, 777, 729, 699 cm¹1. H NMR
1
(CDCl3): ¤ 1.52 (dddd, J = 12.93, 8.54, 8.29, 4.15 Hz, 1H),
1.73 (dddd, J = 12.93, 7.32, 5.37, 4.39 Hz, 1H), 2.18 (dd,
J = 9.51, 9.27 Hz, 1H), 2.21 (dd, J = 9.51, 6.83 Hz, 1H), 2.53-
2.63 (m, 2H), 2.68 (ddd, J = 16.59, 7.32, 4.18 Hz, 1H), 3.22
(dd, J = 9.03, 7.81 Hz, 1H), 3.28 (m, 1H), 3.40-3.44 (m, 1H),
3.58 (d, J = 12.69 Hz, 1H), 3.64 (d, J = 12.69 Hz, 1H), 3.81 (s,
3H), 6.67 (d, J = 8.30 Hz, 1H), 6.70 (d, J = 7.56 Hz, 1H), 7.08
(dd, J = 8.30, 7.56 Hz, 1H), 7.22-7.34 (m, 5H). HRMS (FAB+)
(M+ + 1), Found: m/z 294.18629. Calcd for C20H24NO:
294.18579.
25
90%). An oil. ½¡ꢀD +45° (c 2.30, EtOH). IR (neat): 3337,
2925, 1585, 1466, 1437, 1345, 1260, 1107, 1069, 971, 941,
1
776, 715 cm¹1. H NMR (CDCl3): ¤ 1.67-1.74 (m, 2H), 2.05-
2.14 (m, 1H), 2.52 (ddd, J = 18.05, 9.51, 9.03 Hz, 1H), 2.85
(ddd, J = 18.05, 4.64, 4.39 Hz, 1H), 3.13-3.17 (m, 1H), 3.71
(dd, J = 11.22, 3.17 Hz, 1H), 3.74-3.82 (m, 2H), 3.79 (s, 3H),
3.89 (dd, J = 11.22, 9.51 Hz, 1H), 4.09-4.14 (br, 2H), 6.66 (d,
J = 7.56 Hz, 1H), 6.82 (d, J = 7.81 Hz, 1H), 7.11 (dd, J =
7.81, 7.56 Hz, 1H). HRMS (EI+) (M+), Found: m/z 222.12521.
Calcd for C13H18O3: 222.12560.
(3aR,9bR)-6-Methoxy-2,3,3a,4,5,9b-hexahydro-1H-ben-
zo[e]isoindole (17).15d To a solution of 16 (48 mg, 0.16 mmol)
in EtOH (3 mL) was added 68 mg of 20% Pd(OH)2/C (10 mg).
The resulting mixture was stirred for 1 h under normal pressure
of a H2 atmosphere at 60 °C, and then the catalyst was filtered
off. The solvent of the filtrate was removed in vacuo to give
the almost pure amine (28 mg) in 76% yield. The residue was
dissolved in MeOH and aqueous HCl solution was added.
The solution was condensed in vacuo to give the HCl salt of
the amine. Recrystallization of the salt from MeOH/AcOEt/
hexane gave the purified salt, which was neutralized by the
treatment with aqueous NaOH solution and the purified free
4-Methoxy-5,6,6a,7,11,11a-hexahydro-8,10-dioxa-9-thia-
cyclohepta[a]naphthalene 9,9-Dioxide (15). To a CH2Cl2
(10 mL) solution of 14 (483 mg, 2.17 mmol) was added thionyl
chloride (0.19 mL, 2.61 mmol), and the reaction mixture was
stirred for 10 min at rt. An excess thionyl chloride was
evaporated to give a solid (544 mg). The resulting solid was
dissolved in CH3CN (3 mL) and CCl4 (3 mL), and H2O (4.5
mL) was further added to the solution. After the mixture was
cooled to 0 °C, solid NaIO4 (867 mg, 4.05 mmol) and RuCl3¢
nH2O (2 mg, 0.01 mmol) was added to the reaction mixture.17
After stirring for 1 h at rt, Et2O and water were added, and
insoluble substance was filtered off. The filtrate was extracted
with AcOEt, and the combined extracts were successively
washed with water and brine, dried over Na2SO4, and con-
densed in vacuo. The resulting solid was recrystallized from
EtOH to give 15 (480 mg) in 78% yield. Mp 161-162 °C (from
25
amine 17 was re-extracted with AcOEt. An oil. ½¡ꢀD ¹21 (c
0.34, MeOH). [lit:15d ¹22° (c 1.39, MeOH)]. IR (HCl salt)
(KBr): 2906, 2742, 2594, 2491, 2421, 2359, 1586, 1472, 1462,
1
1259, 1098, 1085, 781 cm¹1. H NMR (HCl salt, CD3OD): ¤
1.59 (ddt, J = 13.42, 4.88, 11.22 Hz, 1H), 1.94 (ddd, J =
13.42, 9.27, 4.64 Hz, 1H), 2.52 (ddd, J = 17.56, 10.73, 5.12
Hz, 1H), 2.62-2.71 (m, 1H), 2.87 (dt, J = 17.56, 4.64 Hz, 1H),
3.09 (t, J = 10.73 Hz, 1H), 3.22 (dd, J = 11.95, 3.66 Hz, 1H),
3.54-3.66 (m, 3H), 3.81 (s, 3H), 6.79 (d, J = 8.05 Hz, 1H),
6.81 (d, J = 8.05 Hz, 1H), 7.16 (t, J = 8.05 Hz, 1H).
25
EtOH). ½¡ꢀD +16 (c 0.35, CHCl3). IR (KBr): 2938, 2848,
The present work was financially supported in part by
a Grant-in-Aid for Scientific Research on Priority Areas
“Advanced Molecular Transformations of Carbon Resources”
from The Ministry of Education, Culture, Sports, Science and
Technology (MEXT) and a Grant-in-Aid for Scientific Re-
search from Japan Society for the Promotion of Science (JSPS).
We also thank Mr. Tomoki Furuya for his contribution to
detailed experiments in the asymmetric bis(alkoxycarbonyl-
ation) reaction of 1a.
1587, 1462, 1437, 1392, 1364, 1344, 1257, 1199, 1078, 1043,
1017, 990, 957, 920, 895, 856, 815, 798, 783, 759, 736,
1
713 cm¹1. H NMR (CDCl3): ¤ 1.88-1.94 (m, 1H), 1.98-2.10
(m, 1H), 2.18-2.30 (m, 1H), 2.54 (ddd, J = 17.81, 11.95,
6.59 Hz, 1H), 3.01 (ddd, J = 17.81, 5.61, 1.46 Hz, 1H), 3.45
(ddd, J = 10.98, 3.42, 3.17 Hz, 1H), 3.82 (s, 3H), 4.31 (dd,
J = 12.44, 3.42 Hz, 1H), 4.35 (dd, J = 12.44, 3.17 Hz, 1H),
4.59 (dd, J = 12.20, 11.59 Hz, 1H), 4.80 (d, J = 12.20 Hz, 1H),

1232 Bull. Chem. Soc. Jpn. Vol. 85, No. 11 (2012)
References
Asymmetric Bis(alkoxycarbonylation)
produced. After purification by column chromatography, 2a was
obtained in 68% yield, however, HPLC analysis still showed
several other peaks of impurities. Further purification by recycle
HPLC gave the pure 2a in 57% yield.
10 On the basis of our investigation of the CPK molecular
model, both carbons of aromatic ring and double bond moiety
(Car-CH=CH-C) almost lie in the same plane in the case of 1,2-
dihydronaphthalene (1a) and indene (1b). In contrast, those of 1c
and 6 do not.20
11 C. Canel, R. M. Moraes, F. E. Dayan, D. Ferreira,
Phytochemistry 2000, 54, 115; M. C. Clasby, S. Chackalamannil,
M. Czarniecki, D. Doller, K. Eagen, W. J. Greenlee, Y. Lin, J. R.
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M. Chintala, Y. Hsieh, A. T. McPhail, Bioorg. Med. Chem. Lett.
2007, 17, 3647, and references cited therein.
12 Asymmetric bis(alkoxycarbonylation) reaction of 1a using
phenyl-substituted ligand (R,R)-3E was examined at 60 °C for 2 d
to give (1S,2S)-2a in 35% yield with enantioselectivity of 75% ee.
This result revealed that benzyl-substituted ligand 3A was more
effective for asymmetric bis(alkoxycarbonylation) reaction of 1a
than phenyl-substituted ligand 3E.
1
a) H. M. Colquhoun, D. J. Thompson, M. V. Twigg,
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A. Gsponer, B. Milani, G. Consiglio, Helv. Chim. Acta
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S. C. A. Nefkens, M. Sperrle, G. Consiglio, Angew. Chem.,
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13 Benzylic Pd intermediate might be dominated over its
regioisomer because of the contribution of η3-character in the
resonance with aromatic ring: An example of η3-character of
benzylic Pd species. A. M. Johns, M. Utsunomiya, C. D. Incarvito,
J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 1828.
14 Transition states T5 and T6 represent the reaction using
(S,S)-3E although the actual examination was carried out using
(R,R)-3E.
4
K. Inomata, S. Toda, H. Kinoshita, Chem. Lett. 1990, 1567;
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5
Related alkoxycarbonylation: Y. Tamaru, M. Hojo, Z.
Yoshida, J. Org. Chem. 1991, 56, 1099; M. Sperrle, G. Consiglio,
Chem. Ber. 1997, 130, 1557; T. Yokota, S. Sakaguchi, Y. Ishii,
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Wakita, T. Arai, H. Sasai, Tetrahedron Lett. 2003, 44, 711; K.
Kato, C. Matsuba, T. Kusakabe, H. Takayama, S. Yamamura, T.
Mochida, H. Akita, T. A. Peganova, N. V. Vologdin, O. V. Gusev,
Tetrahedron 2006, 62, 9988; L. F. Tietze, J. Zinngrebe, D. A.
Spiegl, F. Stecker, Heterocycles 2007, 74, 473.
16 C. Mazzini, J. Lebreton, V. Alphand, R. Furstoss, J. Org.
Chem. 1997, 62, 5215.
6
a) Y. Ukaji, M. Miyamoto, M. Mikuni, S. Takeuchi, K.
17 K. T. Sprott, E. J. Corey, Org. Lett. 2003, 5, 2465.
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7
Preliminary results have been reported: T. Aratani, K.
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1328.
8
The treatment of 2a with NaOMe in MeOH at 60 °C gave
19 B. A. Hathaway, D. E. Nichols, M. B. Nichols, G. K. W.
Yim, J. Med. Chem. 1982, 25, 535.
20 References listed below support the nonplanar conforma-
tion of 1c and 6: T. Schaefer, R. Sebastian, G. H. Penner, Can. J.
Chem. 1988, 66, 584; F. D. Lewis, X. Zuo, J. Am. Chem. Soc.
2003, 125, 8806.
the corresponding isomerized trans-diester. The relative stereo-
chemistry of 2a was confirmed to be cis by NMR spectra in
comparison of the coupling constants J1-2 5.37 Hz for 2a (cis) with
8.70 Hz for trans-isomer. See experimental section.
9
In the 1H NMR spectrum of the crude products, it was
observed that most of 1a was consumed and 2a was predominantly