Synthesis and properties of S,R-alternating octinaphthalenes

Article abstract of DOI:10.1016/j.tet.2009.05.040

(S,R,S,R,S,R,S)- and (S,R,S,S,S,R,S)-octinaphthalenes were synthesized by oxidative coupling of (S,R,S)-quaternaphthalene, and differences due to axis chirality of (S,R,S,R,S,R,S)-, (S,R,S,S,S,R,S)-, (S,S,S,R,S,S,S)-, and (S,S,S,S,S,S,S)-octinaphthalenes

Full text of DOI:10.1016/j.tet.2009.05.040

Tetrahedron 65 (2009) 6135–6140
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis and properties of S,R-alternating octinaphthalenes
,
Kazuto Takaishi a y, Daisuke Sue a, Shunsuke Kuwahara b, Nobuyuki Harada c,
,
Takeo Kawabata a, Kazunori Tsubaki d
*
a Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
b Faculty of Science, Toho University, Funabashi, Chiba 274-8510, Japan
c Department of Chemistry, Columbia University, 3000 Broadway, MC3152, New York, NY 10027, USA
d Graduate School of Life and Environmental Science, Kyoto Prefectural University, Sakyo, Kyoto 606-8522, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
(S,R,S,R,S,R,S)- and (S,R,S,S,S,R,S)-octinaphthalenes were synthesized by oxidative coupling of (S,R,S)-
quaternaphthalene, and differences due to axis chirality of (S,R,S,R,S,R,S)-, (S,R,S,S,S,R,S)-, (S,S,S,R,S,S,S)-,
and (S,S,S,S,S,S,S)-octinaphthalenes were compared using the Rf values on TLC, specific optical rotations,
1H NMR chemical shifts of the hydroxy groups, and CD spectra. A clear CD additivity was found in the D3
values of the 1La transition around 290 nm, which are proportional to the difference between the
numbers of S and R binaphthalene units.
Received 31 March 2009
Received in revised form 16 May 2009
Accepted 18 May 2009
Available online 23 May 2009
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
benzylation with 1.05 equiv of benzyl bromide to provide key
compound (S,R,S)-(þ)-4 in 43% yield. Table 1 summarizes the oxi-
In the field of materials science, rod shaped molecules1 such as
oligothiophene2 and oligophenylene3 have received much attention
due to the versatility of novel functions. We have been studying
oligonaphthalenes composed of a 2,3-dioxynaphthalene unit con-
tinuously connected at the 1,4-positions.4,5 In particular, we have
investigated the construction and function of homochiral oligo-
naphthalenes (thus, the axial chiralities are completely controlled,
either R or S) oligonaphthalenes. In homochiral oligonaphthalenes,
dioxy groups are arranged in a helical shape. In contrast, in S,R-al-
ternating oligonaphthalenes, the hydrophilic oxygen functional
groups are linearly aligned on one side of the molecule, and the
hydrophobic naphthalene rings are on the other side. In this paper,
we describe the synthesis of chiral octinaphthalenes (including the
S,R-alternating derivative), and compare their properties with those
of others having different axial chiralities.
dative coupling reactions of (S,R,S)-(þ)-4 to (S,R,S,R,S,R,S)-(þ)-5a
and (S,R,S,S,S,R,S)-(ꢀ)-5b under various conditions (discussed
below). The diastereomeric octinaphthalenes were separated by
column chromatography on SiO2. The introduction of tetraphenyl-
porphyrin carboxylic acid (TPPCO2H) under WSC/DMAP condi-
tions afforded (S,R,S,R,S,R,S)-(ꢀ)-6a and (S,R,S,S,S,R,S)-(ꢀ)-6b in
good yields. These were then used to determine the absolute
configuration. Compared to other diastereomeric octamers,
(S,R,S,R,S,R,S)-(þ)-5a was unstable in air or basic conditions, and
gradually tarnished to red-brown. Therefore, the central hydroxy
groups of (S,R,S,R,S,R,S)-(þ)-5a and (S,R,S,S,S,R,S)-(ꢀ)-5b were
protected by methyl groups in 40% and 93% yields, respectively.
Due to the chemical instability of (S,R,S,R,S,R,S)-(þ)-5a, the yield of
(S,R,S,R,S,R,S)-(þ)-7a was low.
The coupling conditions of (S,R,S)-(þ)-4 were optimized using
1H NMR measurements (Fig. 1). Thus, the ratio of desired
(S,R,S,R,S,R,S)-(þ)-5a,(S,R,S,S,S,R,S)-(ꢀ)-5b, and recovered (S,R,S)-
(þ)-4 was estimated by integrating the corresponding central hy-
droxy protons for 5a,b and the bottom hydroxy proton of 4. Prior
to measuring the NMR of the reaction mixture, we confirmed (1)
the chemical shifts of the hydroxy protons of (S,R,S)-
(þ)-4,(S,R,S,R,S,R,S)-(þ)-5a, and (S,R,S,S,S,R,S)-(ꢀ)-5b, which were
observed near 6.22, 6.09, and 6.44 ppm, respectively, and de-
termined (2) that the influence of sample concentration on the
chemical shifts of the OH protons was negligible.
2. Results and discussion
Scheme 1 outlines the synthetic route to chiral octinaphtha-
lenes. The central hydroxy groups of (S,R,S)-(þ)-15f were methyl-
ated under MeI/K2CO3 conditions to give (S,R,S)-(þ)-2 in 98% yield.
Both benzyl groups on the top and bottom naphthalenes were
removed with Pd/C and hydrogen (92%) followed by mono-
For the copper promoted oxidative coupling reaction of naphthols,
several groups have reported isomerization of a newly formed axis
along with a bond forming reaction.6 We also found that the coupling
reactions of chiral binaphthyls exhibited some degree of chiral
* Corresponding author. Tel./fax: þ81 75 703 5902.
E-mail address: tsubaki@kpu.ac.jp (K. Tsubaki).
Present address: Supramolecular Science Laboratory, RIKEN (The Institute of
y
Physical and Chemical Research), Wako, Saitama 351-0198, Japan.
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.05.040

6136
K. Takaishi et al. / Tetrahedron 65 (2009) 6135–6140
OBn
OBu
OBn
OBu
OBn
OBu
OBn
OR1
OBu
OBu
OBu
OBu
OBu
OMe
OMe
OMe
OMe
OBu
OBu
OBu
OBu
(b)
(a)
(d)
OBu
OBu
OH
OH
OMe
OMe
OMe
OMe
Table 1
98%
92%
OBu
OBu
OBu
OBu
OBu
OBu
OR3
OR3
3
R
O
R3
O
OBu
OBu
OR2
(S,R,S)-(+)-3: R1= R2= H
BuO
BuO
OBn
OBn
(S,R,S)-(+)-1
(S,R,S)-(+)-2
(c) 43%
MeO
MeO
(S,R,S)-(+)-4: R1= Bn, R2=H
OMe
OMe
Ph
OBu
OBu
BuO
BuO
O
NH
N
N
-COTPP
Ph
HN
BnO
OBn
(S,R,S,S,S,R,S)-(-)-5b: R3=H
(a) 96%
Ph
(S,R,S,R,S,R,S)-(+)-5a: R3=H
(e) 97%
(S,R,S,R,S,R,S)-(-)-6a: R3=COTPP
(S,R,S,S,S,R,S)-(-)-6b: R3=COTPP
(e) 93%
(S,R,S,S,S,R,S)-(-)-7b: R3=Me
(a) 40%
(S,R,S,R,S,R,S)-(+)-7a: R3=Me
Scheme 1. Synthetic route for the octinaphthalenes. Conditions: (a) MeI, K2CO3; (b) Pd/C, H2; (c) BnBr, K2CO3; (d) see Table 1; (e) TPPCO2H, WSC, DMAP.
induction, and the substituent on the side chain controls the chirality.5f
Thus,(1) when the all side chains were methoxy groups except top and
bottom groups, the product was obtained through precipitation along
with epimerization of the newly formed axis,(2) when n-butoxy groups
or tert-butyl ester groups were present on the side chain, the homo-
chiral product was generated under thermodynamic control, but (3) the
kinetically controlled product was obtained for the substrate with an
amide side chain. In all cases, quaternaphthalenes with homochiralities
predominate over heterochiral derivatives.
2.0 equiv of CuCl2, and 2.5 equiv of amine in MeOH/CH2Cl2 (1.0 ml/
1.0 ml) at 0 ꢁC for 7 h. We initially investigated the effect of amines
on the diastereoselectivity of coupling reactions of (S,R,S)-(þ)-4
(Table 1, entries 1–5). Despite the type of amine, (S,R,S,S,S,R,S)-(ꢀ)-5b
prevailed over (S,R,S,R,S,R,S)-(þ)-5a, indicating that the proximal axis
from the reaction site induced the same absolute configuration at the
newly formed axis ((S)-chirality brings (S)-chirality). Although the
highest diastereoselectivity of S,R-alternating octinaphthalene was
observed using di-iso-propylamine (entry 4), the reaction was too
slow to apply to practical syntheses. Therefore, we chose di-n-pro-
pylamine as an amine (entry 5). This reaction was extremely sensi-
tive to temperature; the reaction was negligible at ꢀ20 ꢁC (entry 8),
but at 20 ꢁC (entry 6) the reaction proceeded smoothly without
generating the desired S,R-alternating octamer, suggesting that the
epimerization of the axis occurs easily and (S,R,S,S,S,R,S)-(ꢀ)-5b is
the thermodynamically favored product. A longer reaction time and
Based on previous conditions, the coupling reaction was in-
vestigated under the following conditions: (S,R,S)-(þ)-4 (100 mg),
Table 1
The oxidative coupling conditions of (S,R,S)-(þ)-4
Entry
Amine
Ratioa of 4:5ab: 5bc
Temp (ꢁC)
Time (h)
1
2
3
4
5
6
7
8
iso-Propylamine
(S)-1-Phenylethylamine
n-Propylamine
43:14:43
90:2:8
100:0:0
86:7:7
36:25:39
1:0:99
16:20:64
100:0:0
32:28:40
32:20:48
81:1:18
45:21:34
0
0
0
0
0
7
7
7
7
7
7
24
7
7
7
Di-iso-propylamine
Di-n-propylamine
Di-n-propylamine
Di-n-propylamine
Di-n-propylamine
Di-n-propylamine
Di-n-propylamine
Di-n-propylamine
Di-n-propylamine
(S,R,S)-(+)-4
20
0
ꢀ20
(S,R,S,R,S,R,S)-(+)-5a
(S,R,S,S,S,R,S)-(-)-5b
9d
10e
11f
12g
0
0
0
0
7
1.5
The reactions were carried out under following conditions: (S,R,S)-(þ)-4 (100 mg),
CuCl2 (2.0 equiv), and amine (2.5 equiv) in MeOH/CH2Cl2 (1.0 ml/1.0 ml).
a
Based on 1H NMR measurements.
b
reaction mixture
Compound (S,R,S,R,S,R,S)-(þ)-5a.
c
Compound (S,R,S,S,S,R,S)-(ꢀ)-5b.
d
6.6
6.4
6.2
6.0
(δ/ppm)
MeOH/CH2Cl2 (0.5 ml/0.5 ml).
e
MeOH/CH2Cl2 (0.67 ml/1.33 ml).
MeOH/CH2Cl2 (1.33 ml/0.67 ml).
CuCl2 (10.0 equiv) and di-n-propylamine (12.5 equiv).
f
Figure 1. Partial 1H NMR (400 MHz) spectra of oligonaphthalenes with the hydroxy
groups in CDCl3 at 20 ꢁC (concentration of pure material is 2.56 mM).
g

K. Takaishi et al. / Tetrahedron 65 (2009) 6135–6140
6137
As the number of R configuration axes in octinaphthalenes in-
creased, the Rf values decreased. Considering the polarities of each
naphthalene unit, this tendencycan be explained using (S,R,S,R,S,R,S)-
(þ)-7a as an example (Fig. 3). The dipole moments of the top naph-
thalene ring and that of the third naphthalene ring were parallel and
coincident, and six parallel interactions were observed in this mole-
cule. On the other hand, the six antiparallel interactions of the dipole
moment occurred between every other naphthalene ring; therefore,
(S,S,S,S,S,S,S)-(ꢀ)-7d had a small polarity and showed a high Rf value.
With regard to the specific optical rotation of the octinaphthalenes, as
the number of S configuration axes increased, the specific optical
rotation became more negative.
(a) CD
(S,R,S,R,S,R,S)-(-)-6a
(S,R,S,S,S,R,S)-(-)-6b
200
0
1.0
0.5
-200
(b) UV-vis
Finally, we investigated the CD and UV spectra of chiral octi-
naphthalenes 7a–d (Fig. 4); Table 3 lists the spectral data (wave-
length of maximum absorption (
l
), molar absorption coefficient (
3),
molar absorption coefficient per naphthalene unit (
3
/unit), molar
CD (D3), and molar CD per the difference between the numbers of S
and R binaphthalene units (D3/(SꢀR))).
0.0
Although, octinaphthalenes 7a–d have similar shapes and in-
tensities in the UV–vis spectra (Fig. 4b and Table 3, UV–vis), they
display distinct differences in the CD spectra (Fig. 4a and Table 3,
CD). As the number of S binaphthalene units increased, the in-
tensity of the positive Cotton effect near 230 nm, which is as-
cribed to the positive exciton coupling between the transition
moments parallel to the long axes of the naphthalene rings (1Bb),
increased with a slight red shift in wavelength of l1 (235 nm/
239 nm). However, the intensity of the negative Cotton effect near
290 nm, which is generated by the negative exciton coupling
between the transition moments parallel to the short axes of
naphthalene rings (1La) and those parallel to the long axes of
adjacent naphthalene rings (1Bb), increased without a shift in
wavelength. As shown in Table 3, the values of D32/(SꢀR) are al-
most constant (ꢀ6.1 to ꢀ6.3) indicating that the CDs of S and R
binaphthalene units cancel each other, and the observed CD re-
flects the remaining chirality of the binaphthalene unit. For ex-
ample, in the case of (S,R,S,R,S,R,S)-7a, the CD of three S and three
R binaphthalene units cancel one another and therefore, the
remaining one S binaphthalene unit governs the observed CD at
290 nm. The other isomer (S,R,S,S,S,R,S)-7b has five S units and
two R units, and hence the observed spectrum reflects the CD of
the remaining three S units, i.e., three times stronger Cotton effect.
The CDs of 7c and 7d can be similarly analyzed. The additivity
correlation was thus clearly observed in the CDs of 1La transition.
On the other hand, the CD spectra of 1Bb transition around
230 nm do not show any additivity correlation (Table 3).
200
400
wavelength (nm)
600
Figure 2. CD (a) and UV–vis (b) spectra of (S,R,S,R,S,R,S)-(ꢀ)-6a (red) and (S,R,S,S,S,R,S)-
(ꢀ)-6b (blue). Conditions: CH2Cl2, 1.0ꢂ10ꢀ5 M, 25 ꢁC, light path length¼0.1 cm.
higher reaction concentration provided a high reaction conversion
with a low selectivity of desired (S,R,S,R,S,R,S)-(þ)-5a (entries 7 and
9). Even in the presence of a large excess of CuCl2 (10 equiv) and di-n-
propylamine (12.5 equiv), the diastereoselectivity did not improve
(entry 12). Additionally, changing the proportion of mixed solvent
was ineffective (entries 10 and 11). Hence, both thermodynamically
and kinetically, the reaction provides (S,R,S,S,S,R,S) over (S,R,S,R,S,R,S)
derivatives.
The absolute configuration of the binaphthalene moiety around
the newly formed bond was unambiguously determined by the
exciton-coupled CD method using two TPPs (tetraphenylporphyr-
ins) as powerful excitons.7 Figure 2 shows the UV and CD spectra of
diastereomeric TPP-octinaphthalenes. The UV–vis spectra of
(S,R,S,R,S,R,S)-(ꢀ)-6a and (S,R,S,S,S,R,S)-(ꢀ)-6b had nearly identical
shapes and intensities. However, clear split Cotton effects due to
chiral exciton coupling between the two TPPs were present in the
CD spectra. The absolute configuration of the target axis of (ꢀ)-6a,
which displayed negative first and positive second Cotton effects,
was R. On the other hand, TPP ester (ꢀ)-6b shows positive first and
negative second Cotton effects leading to the S absolute configu-
ration of the newly formed axis.
In conclusion, we synthesized (S,R,S,R,S,R,S)- and (S,R,S,S,S,R,S)-
octinaphthalenes via oxidative coupling of (S,R,S)-quaternaph-
thalene, and compared their Rf values on TLC, specific optical
rotations, the 1H NMR chemical shifts of the hydroxy groups, and CD
spectra. A clear CD additivity between the intensity of the Cotton
effect near 290 nm and the axial chirality of the binaphthalene units
was observed. We are currently investigating the CD mechanism of
these chiral oligonaphthalenes to clarify why the additivity corre-
lation is observed for the 1La transition, but not for the 1Bb transition.
Moreover, we are also studying new functions of these chiral
compounds, including selective solubilization of carbon nanotubes.
We next investigated the properties of (S,R,S,R,S,R,S)- and (S,R,S,-
S,S,R,S)-octinaphthalenes as well as (S,S,S,R,S,S,S)- and (S,S,S,S,S,S,S)-
octinaphthalenes, which were synthesized in our previous
studies.5f,i Table 2 summarizes the Rf values on TLC, [ ]D, and 1H
a
NMR chemical shifts of the central hydroxy groups.
Table 2
The Rf values on TLC, [a
]D, and 1H NMR chemical shifts
Rf valuea
[
a
]
D
(ꢁC)
d
(ppm)c
b
(S,R,S,R,S,R,S)-(þ)-5a
(S,R,S,S,S,R,S)-(ꢀ)-5b
(S,S,S,R,S,S,S)-(ꢀ)-5c
(S,S,S,S,S,S,S)-(ꢀ)-5d
0.19
0.24
0.32
0.47
þ21 (20)
ꢀ2 (20)
6.09
6.44
6.04
6.36
ꢀ81 (18)
3. Experimental
ꢀ146 (18)
(S,R,S,R,S,R,S)-(þ)-7a
(S,R,S,S,S,R,S)-(ꢀ)-7b
(S,S,S,R,S,S,S)-(ꢀ)-7c
(S,S,S,S,S,S,S)-(ꢀ)-7d
0.30
0.43
0.49
0.65
þ29 (20)
ꢀ22 (20)
ꢀ82 (20)
ꢀ137 (20)
d
d
d
d
3.1. Compound (S,R,S)-(D)-2
A
suspension of (S,R,S)-(þ)-15f (20.0 g, 19.2 mmol), K2CO3
(7.0 g, 50 mmol, 2.6 equiv), and methyl iodide (5.2 ml, 84 mmol,
4.4 equiv) in DMF (70 ml) was stirred for 3 h at 70 ꢁC. The reaction
mixture was then poured into a mixed solvent of ethyl acetate
and water. The organic layer was separated and washed
a
TLC on silica gel 60 F254 plates (0.25 mm, Merck, CHCl3/Et2O¼100:1).
b
c
For concentration, see Experimental section.
1H NMR chemical shifts of the central hydroxy groups; 2.56 mM in CDCl3 at
20 ꢁC.

6138
K. Takaishi et al. / Tetrahedron 65 (2009) 6135–6140
OBn
OBu
OBn
OBu
OBn
OBu
OBn
OBu
OBu
OBu
OBu
OMe
OBu
OMe
O
O
O
X
O
X
X
X
OMe
OMe
OMe
OMe
MeO
BuO
MeO
BuO
O
X
X
X
X
X
O
X
O
O
O
OBu
OBu
OBu
OBu
BuO
MeO
MeO
BuO
O
MeO
OMe
OMe
OMe
MeO
BuO
OMe
OBu
OBu
OMe
BuO
BuO
OBu
OBu
BuO
X
X
O
MeO
MeO
MeO
OMe
OMe
OMe
OBu
OBu
MeO
O
OBu
OBu
BuO
BuO
BuO
BuO
BnO
(S,R,S,S,S,R,S)-(-)-7b
BnO
(S,S,S,S,S,S,S)-(-)-7d
OBn
(S,S,S,R,S,S,S)-(-)-7c
OBn
(S,R,S,R,S,R,S)-(+)-7a
Figure 3. The dipole moments of each naphthalene units. The B denotes a parallel and ꢂ denotes an antiparallel between two naphthalenes.
successively with a hydrochloric acid solution, water (twice), and
brine. After drying over magnesium sulfate, the solvent was
evaporated in vacuo to give a residue, which was purified by
3.2. Compound (S,R,S)-(D)-35e
A
suspension of dibenzyl ether of (S,R,S)-(þ)-2 (150 mg,
column
chromatography
(SiO2
hexane/chloroform/ethyl
0.141 mmol) and 10% Pd/C (7.5 mg) in THF (5 ml) was stirred at
room temperature for 21 h under a H2 balloon. The Pd/C was re-
moved by filtration, and the solvent was evaporated in vacuo to
afford crude of (S,R,S)-3 as a white powder (124 mg, 99% yield).
Crude (S,R,S)-(þ)-3 was directly used for the next step without
further purification.
acetate¼20:3:1) to afford (S,R,S)-(þ)-2 (20.2 g, 98%): yellow
20
powder; mp¼131 ꢁC; [
a
]
þ30 (c 0.91, CHCl3); IR (KBr) 2957,
D
1455, 1371, 1246 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d
0.55 (t, J¼7.2,
6H), 0.61 (t, J¼7.2 Hz, 6H), 0.7–1.5 (m, 16H), 3.73 (s, 6H), 3.6–3.9
(m, 4H), 4.0–4.3 (m, 4H), 5.35 (s, 4H), 7.10–7.55 (m, 22H), 7.57 (d,
J¼7.8 Hz, 4H), 7.81 (d, J¼8.2 Hz, 2H); HRMS calcd for C72H74O8:
1066.5384. Found: 1066.5389. Anal. Calcd for C72H74O8: C, 81.02;
H, 6.99. Found: C, 80.88; H, 7.13.
3.3. Compound (S,R,S)-(D)-4
A mixture of (S,R,S)-(þ)-3 (20.0 g, 23.2 mmol), benzyl bro-
mide (2.9 ml, 24.4 mmol, 1.05 equiv), and K2CO3 (3.85 g,
24.4 mmol, 1.05 equiv) in DMF (200 ml) was stirred for 22 h at
70 ꢁC. The reaction mixture was poured into a mixed solvent of
ethyl acetate and water. The organic layer was separated and
washed successively with a hydrochloric acid solution, water
(twice), and brine. After drying over magnesium sulfate, the
solvent was evaporated in vacuo to give a residue, which was
(a) CD
7d
7a
7c
7b
200
7b
7c
7a
7d
Table 3
UV–vis and CD data of octinaphthalenes 7a–d
0
UV–vis
l1 (nm) 31
31/unita l2 (nm) 32
32/unita
69,200 8650
68,700 8590
4
(S,R,S,R,S,R,S)-(þ)-7a 234
(S,R,S,S,S,R,S)-(ꢀ)-7b 234
431,000 53,900
308
307
307
306
429,000 53,600
435,000 54,400
434,000 54,300
(S,S,S,R,S,S,S)-(ꢀ)-7c
(S,S,S,S,S,S,S)-(ꢀ)-7d
234
234
68,700 8590
66,000 8250
-200
2
CD
l1 (nm) D31
D31/(SꢀR)b l2 (nm) D32
D32/(SꢀR)b
(b) UV-vis
(S,R,S,R,S,R,S)-(þ)-7a 235
(S,R,S,S,S,R,S)-(ꢀ)-7b 236
(S,S,S,R,S,S,S)-(ꢀ)-7c 239
(S,S,S,S,S,S,S)-(ꢀ)-7d 239
þ168 þ168
293
292
292
293
ꢀ6.3 ꢀ6.3
þ231 þ77
þ293 þ59
þ330 þ47
ꢀ19 ꢀ6.3
0
ꢀ31 ꢀ6.2
220
260
300
340
ꢀ43 ꢀ6.1
wavelength (nm)
Conditions: Dioxane/CH2Cl2¼200:1, 20 ꢁC, light path length¼10 mm.
a
Unit: number of naphthalene units.
Figure 4. CD (a) and UV–vis (b) spectra of octinaphthalenes 7a–d. Conditions: Di-
oxane/CH2Cl2¼200:1, 20 ꢁC, light path length¼1.0 cm.
b
(SꢀR): number of S binaphthalene unitsꢀnumber of R binaphthalene units.

K. Takaishi et al. / Tetrahedron 65 (2009) 6135–6140
6139
purified by column chromatography (SiO2, hexane/chloroform/
3.6. Compound (S,R,S,S,S,R,S)-(L)-6b
ethyl acetate¼15:1:1) to afford (S,R,S)-(þ)-4 (9.7 g, 43%), over-
reacted (S,R,S)-(þ)-2 (4.1 g 17%), and recovered (S,R,S)-(þ)-3
TPP ester (ꢀ)-6b was similarly synthesized: 98% yield; purple
20
(5.6 g, 28%).
solid; mp¼232 ꢁC; [
a
]
ꢀ3872 (c 0.43, CHCl3); IR (KBr) 2954, 1744,
Compound (S,R,S)-(þ)-4: yellow solid; mp¼74 ꢁC; [
a]
þ37 (c
1597, 1348, 1243 cmꢀ1D
;
1H NMR (400 MHz, CDCl3)
d
ꢀ2.81 (s, 4H),
20
D
0.92, CHCl3); IR (KBr) 3434, 2957, 1441, 1376, 1245 cmꢀ1
;
1H NMR
0.59 (t, J¼7.3 Hz, 6H), 0.59 (t, J¼7.3 Hz, 6H), 0.66 (t, J¼7.3 Hz, 6H),
0.66 (t, J¼7.3 Hz, 6H), 0.8–1.6 (m, 32H), 3.6–4.1 (m, 14H), 3.84 (s,
6H), 3.84 (s, 6H), 4.39 (m, 2H), 5.38 (s, 4H), 6.75–7.0 (br, 2H), 7.3–7.9
(m, 62H), 8.15–8.25 (m, 14H), 8.35 (d, J¼8.0 Hz, 4H), 8.42 (brs, 4H),
8.55 (m, 4H), 8.72 (m, 4H), 8.9–9.0 (m, 8H); MS (FABþ) m/z 3232
(MþHþ). Anal. Calcd for C220H190N8O18$2CH2Cl2: C, 78.34; H, 5.74;
N, 3.29. Found: C, 78.35; H, 5.72; N, 3.33.
(400 MHz, CDCl3)
d
0.5–0.65 (m, 9H), 0.71 (t, J¼7.4 Hz, 3H), 0.7–1.5
(m, 16H), 3.5–4.2 (m, 8H), 3.72 (s, 3H), 3.72 (s, 3H), 5.36 (s, 2H), 6.22
(s,1H), 7.1–7.5 (m,19H), 7.58 (d, J¼7.3 Hz, 2H), 7.81 (d, J¼8.2 Hz,1H),
7.82 (d, J¼7.8 Hz, 1H); HRMS calcd for C65H68O8: 976.4914. Found:
976.4879. Anal. Calcd for C65H68O8$0.5H2O: C, 79.16; H, 7.05. Found:
C, 79.03; H, 7.02.
3.7. Compound (S,R,S,R,S,R,S)-(D)-7a
3.4. Compounds (S,R,S,R,S,R,S)-(D)-5a and
(S,R,S,S,S,R,S)-(L)-5b
Compound (þ)-5a was methylated with K2CO3 and methyl io-
dide in DMF to yield (þ)-7a: 40% yield; yellow solid; mp¼n.d.
To a solution of CuCl2 (83 mg, 0.61 mmol) in methanol (3.0 ml),
iso-propylamine (65 ml, 0.77 mmol) was added under an argon at-
20
(decomp.); [
a
]
D
þ29 (c 0.75, CHCl3); IR (KBr) 2935, 1453, 1375,
1244 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
0.49 (t, J¼7.3 Hz, 6H), 0.56
mosphere in an ice bath. After 1 h, a solution of (S,R,S)-(þ)-4
(300 mg, 0.31 mmol) in dichloromethane (3.0 ml) was added, and
subsequently stirred for 10 h. The reaction mixture was poured into
a mixed solvent of 0.1 M hydrochloric acid solution, and chloro-
form. The organic layer was washed with a sodium hydrogen car-
bonate solution, water, and brine. It was then dried over sodium
sulfate and evaporated to give a residue, which was purified by
column chromatography (SiO2, hexane/chloroform/ethyl acet-
ate¼8:3:1 then chloroform/diethyl ether¼100:1) to successively
afford to (S,R,S,R,S,R,S)-(þ)-5a (50 mg, 17%) and (S,R,S,S,S,R,S)-
(ꢀ)-5b (203 mg, 68%).
(t, J¼7.3 Hz, 6H), 0.63 (t, J¼7.3 Hz, 6H), 0.64 (t, J¼7.3 Hz, 6H), 0.7–1.5
(m, 32H), 3.6–4.2 (m, 16H), 3.70 (s, 6H), 3.71 (s, 6H), 3.74 (s, 6H),
5.30 (s, 4H), 7.10–7.55 (m, 32H), 7.52 (d, J¼7.6 Hz, 4H), 7.76 (d,
J¼8.2 Hz, 2H); MS (FABþ) m/z 1979 (Mþ). Anal. Calcd for
C132H138O16$H2O: C, 79.33; H, 7.06. Found: C, 79.21; H, 7.11.
3.8. Compound (S,R,S,S,S,R,S)-(L)-7b
Compound (ꢀ)-7b was similarly prepared from (ꢀ)-5b: 93%
20
yield; yellow solid; mp¼128 ꢁC; [
a
]
ꢀ22 (c 1.17, CHCl3); IR (KBr)
D
2934, 1442, 1375, 1238 cmꢀ1 1H NMR (400 MHz, CDCl3)
; d 0.5–0.8
Compound (S,R,S,R,S,R,S)-(þ)-5a: yellow solid; mp¼276 ꢁC;
20
[
a
]
þ21 (c 0.75, CHCl3); IR (KBr) 3513, 2956, 1596, 1375 cmꢀ1
;
(m, 18H), 0.7–1.5 (m, 32H), 3.6–4.2 (m, 16H), 3.78 (s, 6H), 3.78 (s,
6H), 3.78 (s, 6H), 5.37 (s, 4H), 7.10–7.55 (m, 32H), 7.59 (d, J¼7.3 Hz,
4H), 7.82 (d, J¼7.8 Hz, 2H); MS (FABþ) m/z 1979 (Mþ). Anal. Calcd for
D
1H NMR (400 MHz, CDCl3)
d
0.57 (t, J¼7.3 Hz, 6H), 0.6–0.7 (m,
12H), 0.72 (t, J¼7.3 Hz, 6H), 0.8–1.5 (m, 32H), 3.70–4.35 (m, 16H),
3.78 (s, 6H), 3.81 (s, 6H), 5.37 (s, 4H), 6.09 (s, 2H), 7.15–7.65 (m,
42H), 7.82 (d, J¼8.2 Hz, 2H); MS (FABþ) m/z 1951 (Mþ). Anal.
C132H138O16$H2O: C, 79.33; H, 7.06. Found: C, 79.34; H, 7.05.
Calcd for C130H134
H, 6.44.
O
16$2CHCl3: C, 74.70; H, 6.55. Found: C, 74.92;
3.9. Compound (S,S,S,R,S,S,S)-(L)-7c
20
Compound (S,R,S,S,S,R,S)-(ꢀ)-5b: yellow solid; mp¼118 ꢁC; [
a
;
]
ꢀ2 (c 0.90, CHCl3); IR (KBr) 3504, 2956, 1441, 1375, 1237 cmꢀ1
1DH
Compound (ꢀ)-7c was similarly prepared from the corre-
20
sponding precursor: 97%; white solid; mp¼112 ꢁC; [
a
]
ꢀ82 (c
D
1.08, CHCl3); IR (KBr) 2956, 1442, 1375, 1240 cmꢀ1 1H NMR
;
NMR (400 MHz, CDCl3)
d
0.58 (t, J¼7.8 Hz, 6H), 0.6–1.6 (m, 50H),
3.70–3.90 (m, 8H), 3.78 (s, 6H), 3.81 (s, 6H), 4.0–4.3 (m, 8H), 5.38 (s,
(400 MHz, CDCl3)
d
0.55 (t, J¼7.3 Hz, 6H), 0.69 (t, J¼7.3 Hz, 6H), 0.6–
4H), 6.44 (s, 2H), 7.1–7.65 (m, 42H), 7.83 (d, J¼8.2 Hz, 2H); MS
1.6 (m, 44H), 3.6–4.2 (m, 16H), 3.83 (s, 6H), 3.85 (s, 6H), 3.86 (s, 6H),
5.38 (s, 4H), 7.1–7.55 (m, 38H), 7.60 (d, J¼7.3 Hz, 4H), 7.82 (d,
J¼7.8 Hz, 2H); MS (FABþ) m/z 1979 (Mþ). Anal. Calcd for
(FABþ) m/z 1951 (Mþ). Anal. Calcd for C130H134
O16$2CHCl3: C, 74.70;
H, 6.55. Found: C, 75.04; H, 6.31.
C132H138O16$1.5H2O: C, 78.97; H, 7.08. Found: C, 79.00; H, 7.12.
3.5. Compound (S,R,S,R,S,R,S)-(L)-6a
Acknowledgements
To a solution of (S,R,S,R,S,R,S)-(þ)-5a (25 mg, 0.013 mmol) in
CH2Cl2 (2.0 ml), TPPCO2H (42 mg, 0.064 mmol), WSC$HCl (192 mg,
0.13 mmol), and DMAP (31 mg, 0.27 mmol) were added and stirred
at room temperature for 19 h. The reaction mixture was quenched
with water, extracted with chloroform, washed successively with
a 0.1 M hydrochloric acid solution, water, and brine. It was then
dried over MgSO4 and evaporated to give a residue, which was
purified by recycling preparative HPLC (Japan Analytical Industry
Co., Ltd. LC-908) connected to JAIGEL-1H (20ꢂ600 mm) and JAI-
GEL-2H (20ꢂ600 mm) under a 3.5 ml/min of flow rate with CHCl3
The authors are sincerely grateful to Mr. Kazuhiro Hayashi
(Kyoto University) for the dipole calculations. This study was partly
supported by Grant-in-Aid for Scientific Research (KAKENHI)
(17659004) and the Japan Securities Scholarship Foundation (JSSF).
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20
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