Configurationally defined sexi- and octinaphthalene derivatives: Synthesis and optical properties

Article abstract of DOI:10.1016/j.tet.2004.03.055

The copper mediated oxidative coupling of optically active quaternaphthalenes having a 2-hydroxynaphthyl moiety gave configurationally defined optically active octinaphthalenes. The absolute configuration was determined by comparison with products of [6+2] coupling. The CD spectra of bi-, ter-, quater-, sexi- and octinaphthalenes suggested that the absolute configuration of the chiral axis could be deduced from the intensity of their Cotton effects.

Full text of DOI:10.1016/j.tet.2004.03.055

Tetrahedron 60 (2004) 4431–4441
Configurationally defined sexi- and octinaphthalene derivatives:
q
synthesis and optical properties
a
Takumi Furuta, Kiyoshi Tanaka, Kazunori Tsubaki and Kaoru Fuji
a
b
c,*
a
School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8414, Japan
b
c
Received 17 October 2003; revised 19 March 2004; accepted 19 March 2004
Abstract—The copper mediated oxidative coupling of optically active quaternaphthalenes having a 2-hydroxynaphthyl moiety gave
configurationally defined optically active octinaphthalenes. The absolute configuration was determined by comparison with products of
[6þ2] coupling. The CD spectra of bi-, ter-, quater-, sexi- and octinaphthalenes suggested that the absolute configuration of the chiral axis
could be deduced from the intensity of their Cotton effects.
q 2004 Published by Elsevier Ltd.
0
moieties are directly coupled each other, although the partial
1
. Introduction
connected at the 1,4-positions, in which the 1,1 -binaphthyl
0
0
Monodisperse, nanometer sized molecules having a unique
three-dimensional structure such as a helix have become of
great interest due to the possibility for their use as a specific
molecular device for material sciences as well as for the
incorporation of a 2,2 -difunctionalized 1,1 -binaphthyl into
2
a
a large molecule such as a polymer have been reported.
One example of monodisperse oligonaphthalene reported so
1
0,11
far was sexinaphthalene. Recently, we reported the
12a
preparation of stereochemically defined ter-, quarter- and
0
architectural beauty of their molecular shape. 2,2 -Difunc-
0
12b
tionalized 1,1 -binaphthalenes have been used not only as an
higher oligonaphthalenes
showed unique function as an organic zeolite (Fig. 1).
and quarternaphthalene 1
1
2c
excellent chiral inducer for asymmetric synthesis but also
for chiral recognition in host–guest chemistry. These
molecules possess a relatively rigid but flexible twisted
conformation around the axis between its aromatic rings.
Therefore, these molecules could be used as a key structural
element for introduction of a twisted conformation as well
as chirality into larger molecules. On the other hand, the
development of novel monodisperse p-conjugated oligo-
mers has recently attracted much attention due to their
Moreover, it has been reported that the meso-ternaphthalene
2 tethered by two crown ethers plays an interesting role as
a ditopic receptor for recognition of the length of
2
potential application in material sciences. Among them,
oligo(p-phenylene)s have received special attention and
3
have been used as backbones for artificial proton channels
4
and b-barrels and as rigid spacer units in an artificial
5
receptor of cyclic dipeptides. Oligo(p-phenylene)s are also
important model compounds for poly(p-phenylene)s since
some poly(p-phenylene)s are remarkable organic conduc-
6
7
tors upon doping and are also used as laser materials. The
8
,9
rod can contain 15 or even l6 phenyl rings. However, little
attention has been paid to rod-shaped naphthalenes
q
See Ref. 1.
Keywords: Sexinaphthalene; Octinaphthalene; Atropisomerism; Oxidative
coupling; CD spectra.
*
Corresponding author. Tel.: þ81-75-595-4727; fax: þ81-75-595-4775;
e-mail address: fuji@mb.kyoto-phu.ac.jp
Figure 1. Ter- and quaternaphthalenes.
0040–4020/$ - see front matter q 2004 Published by Elsevier Ltd.
doi:10.1016/j.tet.2004.03.055

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T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
1
3
a,v-diamines. It would be interesting to determine
whether higher oligonaphthalenes also show such specific
characteristics. We report here the synthesis of optically
active sexi- and octinaphthalenes as well as their CD
7 and 11, which were converted into the permethylated
derivatives 9 and 13, respectively. The only difference
of coupling products between 6 and 10 is the
absolute stereochemistry around the newly created
central bond, which was unambiguously determined
by synthesis via an alternative synthetic route that
included the [4þ2] construction of sexinaphthalenes
(Scheme 2).
1
spectra.
2
. Results and discussion
1
2a
2.1. Synthesis of oligonaphthalenes and determination of
their absolute configurations
Thus, the known quaternaphthalene (S,S,S)-14
was
methylated to give (S,S,S)-15, partial hydrolysis of which
afforded (S,S,S)-16 in 40% yield. In order to avoid
homocoupling of 16, the oxidative coupling between 16
The synthetic pathway to sexinaphthalenes, starting from
1
2a
12a
the optically active ternaphthalene 3,
is shown in
and (S)-17
was carried out in the presence of excess
Scheme 1. Methylation of (S,S)-3 afforded (S,S)-4, which
was converted into monohydroxyternaphthalene (S,S)-5 by
amount of 17 to give sexinaphthalenes (S,S,S,S,S)-18 and
(S,S,S,R,S)-19 in respective yields of 18 and l6%, along with
(S,S,S)-14 and its isomer with an R configuration at the
central bond. Methylation of 18 gave 7, which was identical
to one of the products of the homocoupling of 5, while
methylation of 19 gave 20, which is distinct from both 7
and 11. These findings clearly support the absolute
1
4
hydrogenolysis, in 82% overall yield. Oxidative coupling
of 5 in the presence of CuCl and racemic a-phenylethyl-
2
amine afforded sexinaphthalenes (S,S,S,S,S)-6 and its
diastereomer (S,S,R,S,S)-10 in 31 and 38% yield,
respectively. Methylation of 6 and 10 gave diastereomers
Scheme 1. The [3þ3] construction of sexinaphthalenes. Reagents: (a) CH
0 (38%); (d) K CO , MeOH.
3 2 3 2 2
I, K CO , 85%; (b) 10% Pd–C, H , 97%; (c) a-phenylethylamine, CuCl , 6 (31%),
1
2
3

T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
4433
Scheme 2. The [4þ2] construction of sexinaphthalenes. Reagents: (a) CH
16%).
3
I, K
2
CO
3
; (b) K
2
CO
3
, MeOH, 40%; (c) a-phenylethylamine, CuCl
2
, 18 (18%), 19
(
configurations of the coupling products 6, 10, 18 and 19 as
depicted in Schemes 1 and 2.
resulted in determination of the absolute configuration of the
products 30 and 31 as shown in Scheme 4.
A similar strategy to these transformations was used to
synthesize octinaphthalenes as well as to determine their
absolute stereochemistry (Schemes 3 and 4). Oxidative
coupling of quaternaphthalene (S,S,S)-16 gave
For the CD study described below, (S)-tetramethoxy-
binaphthalene 33 was also prepared from binaphthalene
34 of known absolute configuration by methylation
(Scheme 5).
1
2a
(
S,S,S,S,S,S,S)-21 (22%) and (S,S,S,R,S,S,S)-25 (30%).
Methylation of 21 followed by hydrolysis gave 23.
Treatment of 23 with CH I/K CO in acetone converted
2.2. Conformation of oligonaphthalenes
3
2
3
2
3 into 24, which has a methoxy group as a uniform
One of the most interesting aspects of oligonaphthalenes is
their molecular shape, which is reminiscent of the banisters
of a spiral staircase, and their p-system, which is totally
substituent. The diastereomer 25 was transformed to 28
through the same sequence of reactions as those for 21
1
5
(
Scheme 3). The [6þ2] construction of octinaphthalenes is
different from that of helicenes. An interesting question is
how many naphthyl rings are required to complete a full
turn of the helix. An X-ray crystal structural analysis of a
quaternaphthalene 1 revealed that four naphthyl units are
also shown in Scheme 4. Partial hydrolysis of (S,S,S,S,S)-7
gave (S,S,S,S,S)-29, which was then subjected to the
oxidative coupling in the presence of 5 equiv. of (S)-17 to
give (S,S,S,S,S,S,S)-30 (13%) and (S,S,S,S,S,R,S)-31 (22%).
Methylation of 30 gave 22, while that of 31 gave 32, which
l2a
insufficient. Since none of the sexi- or octinaphthalenes
gave fruitful crystals for X-ray analysis, the most stable

4434
T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
2 3 2 3 2 3
Scheme 3. The [4þ4] construction of octinaphthalenes. Reagents: (a) a-phenylethylamine, CuCl , 21 (22%), 25 (30%); (b) CH I, K CO ; (c) K CO , MeOH.
conformation of 24 was calculated by MacroModel/MM2
version 6.0). The calculation results indicated that at least
five to six naphthyls are necessary for a turn (Fig. 2a). The
results suggest an additivity relationship between the
intensity of Cotton effect and the number of naphthalene
chromophores.
(
dihedral angles between each naphthyl unit are nearly 808
and the length of molecule including hydrogen atoms is
˚
Taking this hypothesis into account, the CD spectra of
12a
3
quaternaphthalene 1, in which the dihedral angles between
5 A. These results are consistent with the X-ray analysis of
quater-, sexi-, and octinaphthalenes 37,
13 and 28
possessing aR configuration at the central axis were
measured and compared with the spectra of their dia-
stereomers 36, 9 and 24, respectively. The quaternaphthal-
ene 37 showed a smaller positive Cotton effect (D1 27.7) at
233.7 nm than that of its isomer 36 (Fig. 4a). Also, the
sexinaphthalene 13 exhibited a smaller positive Cotton
effect (D1 86.4) at 239.9 nm than that of 9 (Fig. 4b). The
same tendency was observed in octinaphthalenes (Fig. 4c).
Moreover, the intensity of Cotton effect of 13 around
240 nm is similar to that of 36. This could be explained by
the partial cancellation of Cotton effect owing to R axis of
13. The same relationship was observed between 9 and 28.
These results clearly showed that the intensity of Cotton
effect depends on the absolute configuration due to each
axis. Therefore, it could be concluded that the intensity of
Cotton effect could be useful informative source for the
determination of the absolute configuration of such kinds of
oligonaphthalenes.
1
2a
each naphthalene are 74.7, 79.7 and 113.08. The top view
of 24 showed the cylindrical shape of molecule having
˚
around 9 A diameter (Fig. 2b). The calculation for the
corresponding 24-mer revealed that the helix repeated a full
turn every five to six naphthyls (Fig. 2c). The central eight
naphthalene units of the 24-mer were extracted and
compared with octinaphthalene 24 (Fig. 2a and d). While
the two conformations are quite similar, a slight lag was
observed for a turn.
2
.3. CD spectra of oligonaphthalenes
The CD spectra of permethylated, configurationally defined
12a
12a
bi-, ter-, quater-, sexi- and octinaphthalenes 33, 35, 36,
and 24, possessing aS configuration around each axis,
were taken (Fig. 3 and Table 1). All compounds showed
9
1
6
strong split Cotton effects of positive exciton chirality.
The intensity of their Cotton effect around 240 nm are
obviously increased in accordance with the increase of
the number of naphthyl units, D1 12.8, 68.8, 83.8, 102.7,
The development of specific functions and the further study
of optical properties of synthesized oligonaphthalenes are
currently under investigation.
1
36.8 for 33, 35, 36, 9 and 24, respectively (Table 1). These

T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
4435
Scheme 4. The [6þ2] construction of octinaphthalenes. Reagents: (a) K
2 3 2 3 2 3
CO , MeOH; (b) a-phenylethylamine, CuCl , 30 (13%), 31 (22%); (c) CH I, K CO .
3. Experimental
3.1. General
Melting points are uncorrected. Nuclear magnetic resonance
NMR) spectra were taken in CDC1 at 200 or 400 MHz for
(
3
1
13
H NMR and at 50 MHz for C NMR, with chemical shifts
being reported as d ppm from tetramethylsilane as an
internal standard. FT-IR, UV and CD spectra were obtained
Scheme 5. Preparation of tetramethoxybinaphthalene.
(a)
(b)
(d)
(c)
Figure 2. (a) The most stable conformation of octinaphthalene 24 calculated by MacroModel (version 6.0). (b) The top view of octinaphthalene 24. (c) The
most stable conformation of the 24-mer calculated by MacroModel (version 6.0). (d) The central eight naphthalenes of the 24-mer.

4436
T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
was refluxed for 2 h. After cooling, the reaction mixture was
evaporated under reduced pressure, and the residue was
added to a mixture of ethyl acetate and aq. 2 N HCl. The
organic layer was separated, dried and then evaporated in
vacuo to give a residue. The residue was purified by column
chromatography (SiO , n-hexane/EtOAc¼2/1) to afford
2
(S,S)-4 as colorless powder (445 mg, 85%), which was
recrystallized from CH Cl /EtOAc/pet. ether to give color-
2
2
2
0
less prisms. Mp 206–208 8C; [a] ¼2113.7 (c 2.3, CHCl );
D
3
1
H NMR (200 MHz, CDCl ): d 8.0–7.1 (m, 19H), 5.37 (s,
3
2
2
1
H), 3.79 (s, 3H), 3.67 (s, 3H), 3.64 (s, 3H), 3.60 (s, 3H),
.42 (s, 3H); IR (CHCl ): 3063, 3029, 3010, 2940, 1766,
3
597, 1503, 1467, 1016 cm2 ; EI MS m/z 664 (M ). Anal.
1
þ
Calcd for C H O : C, 77.69; H, 5.46. Found: C, 77.39; H,
3 36 7
4
5.45.
3.1.2. (S,S)-Ternaphthalene 5. To a suspension of
palladium on carbon (10%, 296 mg) in CHCl , a solution
3
of (S,S)-4 (320 mg, 0.48 mmol) in CHCl3 (15 mL) and
AcOH (0.75 mL) was added. The mixture was stirred at
room temperature for 29 h under hydrogen. After the
catalyst was filtered off, the filtrate was evaporated under
reduced pressure to give a residue, which was purified by
the recrystallization from CH Cl /EtOAc/pet. ether to give
2
2
(
S,S)-5 as colorless plates (268 mg, 97%). Mp 161–162 8C;
2
0
D
1
[
a] ¼273.4 (c 0.6, CHCl ); H NMR (200 MHz, CDCl ):
3
3
d 8.0–7.1 (m, 14H), 6.18 (s, 1H), 3.65 (s, 3H), 3.63 (s, 3H),
3.62 (s, 3H), 3.60 (s, 3H), 2.43 (s, 3H); IR (CHCl ): 3522,
3
2
1
3
5
009, 3010, 2941, 1631, 1506, 1468, 1221 cm ; EI MS m/z
þ þ
74 (M ); HRMS m/z Calcd for C H O (M ) 574.1992.
36 30 7
Figure 3. CD spectra of oligonaphthalenes in 0.4% dioxane–MeOH.
Table 1. CD Spectral data of oligonaphthalenes
Found 574.2007.
3.1.3. Oxidative coupling to sexinaphthalenes (S,S,S,
S,S)-6 and (S,S,R,S,S)-10. A mixture of CuCl (126 mg,
Compound
lext (nm) (D1)
2
0.94 mmol) and a-phenylethylamine (0.30 mL, 2.4 mmol)
in MeOH (0.5 mL) was stirred for 20 min, to which was
3
3
3
9
2
3
1
2
3
5
6
286.1 (24.4), 240.3 (12.8), 208.2 (216.0)
286.3 (211.3), 240.3 (68.8), 208.2 (230.7)
288.9 (218.3), 239.6 (83.8), 207.4 (243.7)
291.9 (236.8), 239.5 (102.7), 207.4 (279.8)
291.6 (248.8), 239.2 (136.8), 206.9 (2119.4)
285.7 (26.9), 245.5 (215.0), 233.7 (27.7), 209.3 (227.9)
292.6 (221.2), 239.9 (86.4), 207.7 (263.4)
291.9 (230.7), 239.5 (108.8), 207.1 (284.0)
added a solution of (S,S)-5 (268 mg, 0.47 mmol) in CH Cl
2
2
(20 mL). After being stirred for 23 h under nitrogen, the
reaction mixture was acidified with conc. HCl, concen-
trated, and extracted with EtOAc. The organic layer was
washed with water, dried, and evaporated to give a residue.
The residue was purified by column chromatography (SiO2,
n-hexane/CH Cl /EtOAc¼8/5/1) to afford (S,S,S,S,S)-6
4
7
3
8
2
2
(83 mg, 31%) and (S,S,R,S,S)-10 (102 mg, 38%).
Compound (S,S,S,S,S)-6. Mp .300 8C; colorless powder
2
0
(
CHCl ); H NMR (200 MHz, CDCl ): d 7.92 (d, 2H,
from CH Cl /Et O/pet. ether); [a] ¼2190.6 (c 0.4,
2
2
2
D
1
3 3
J¼8.4 Hz), 7.79 (s, 2H), 7.6–7.1 (m, 22H), 6.33 (s, 2H),
3.79 (s, 6H), 3.74 (s, 12H), 3.67 (s, 6H), 2.45 (s, 6H); IR
(
1
CHCl ): 3511, 3009, 2941, 1767, 1507, 1453, 1391, 1237,
3
201, 1014 cm2 ; FAB MS m/z 1147 (MþH) . Anal. Calcd
1
þ
on a JASCO FT/IR-300, Shimadzu UV-2200 and JASCO
J-720W, respectively. All extractive organic solutions were
dried over anhydrous MgSO . Flash column chromato-
graphy was carried out with silica gel 60 spherical
(150–325 mesh) and Kiesel gel 60 F254 plates (Merck)
were used for preparative TLC (pTLC).
for C72
H
58
O14: C, 75.38; H, 5.10. Found: C, 75.15; H, 5.05.
Compound (S,S,R,S,S)-10. Mp .300 8C; colorless prisms
4
2
0
1
(from benzene); [a]
(200 MHz, CDCl
): d 7.93 (d, 2H, J¼8.4 Hz), 7.79 (s, 2H),
7.6–7.1 (m, 22H), 6.23 (s, 2H), 3.78 (s, 6H), 3.76 (s, 6H),
¼2117.0 (c 0.3, CHCl
); H NMR
D
3
3
3.72 (s, 6H), 3.68 (s, 6H), 2.45 (s, 6H); IR (CHCl ): 3518,
3010, 2941, 1766, 1602, 1453, 1393, 1350, 1014 cm
3
2
1
3
(
1
.1.1. (S,S)-Ternaphthalene 4. To a mixture of (S,S)-3
500 mg, 0.79 mmol) and potassium carbonate (1.6 g,
2 mmol) in acetone (15 mL) was added dropwise methyl
iodide (1.0 mL, 16 mmol) at room temperature. The mixture
;
þ
FAB MS m/z 1147 (MþH) . Anal. Calcd for C72
H
O. Anal. Calcd for C, 74.79; H, 5.14. Found: C,
-
58
O
14·1/2H
2
74.78; H, 5.09.

T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
4437
Figure 4. (a) CD spectra of quaternaphthalenes 36 and 37 in 0.4% dioxane–MeOH. (b) CD spectra of sexinaphthalenes 9 and 13 in 0.4% dioxane–MeOH. (c)
CD spectra of octinaphthalenes 24 and 28 in 0.4% dioxane–MeOH.
3.1.4. (S,S,S,S,S)-Sexinaphthalene 7. Following the
procedure for the preparation of 4, (S,S,S,S,S)-6 (73 mg,
0.37 mmol) and methyl iodide (63 mL, 1.0 mmol) in
acetone (10 mL) for 2 h. After extraction with CH Cl , the
2
2
6
0
4 mmol) was treated with potassium carbonate (128 mg,
.93 mmol) and methyl iodide (82 mL, 1.3 mmol) in
organic layer was dried and evaporated to give a residue,
which was subjected to column chromatography on silica
gel. Elution with n-hexane/CH Cl /EtOAc (6/3/1) gave
acetone (10 mL) for 2 h. After extraction with CH Cl , the
2
2
2
2
organic layer was dried and evaporated to give a residue,
which was subjected to column chromatography on silica
gel. Elution with n-hexane/CH Cl /EtOAc (6/3/1) gave
(S,S,S,S,S)-9 (19 mg, 64%). Mp .300 8C; colorless powder
0
2
D
(from CH Cl /Et O/pet. ether); [a] ¼2194.9 (c 0.9,
2
2
2
1
CHCl ); H NMR (200 MHz, CDCl ): d 7.86 (d, 2H,
3
2
2
3
(
(
S,S,S,S,S)-7 (74 mg, 98%). Mp .300 8C; colorless powder
2
J¼8.1 Hz), 7.5–7.1 (m, 24H), 4.12 (s, 6H), 3.90 (s, 6H),
21
0
D
from CH Cl /Et O/pet. ether); [a] ¼2196.7 (c 0.3,
3.88 (s, 6H), 3.85 (s, 6H), 3.77 (s, 6H), 3.76 (s, 6H); IR
(CHCl ): 3062, 3010, 2939, 1463, 1390, 1346, 1019 cm
2
2
2
1
CHCl ); H NMR (200 MHz, CDCl ): d 7.91 (d, 2H,
3
;
CD (0.4% dioxane in MeOH): see Table 1; UV (0.4%
3
3
J¼8.1 Hz), 7.78 (s, 2H), 7.6–7.2 (m, 22H), 3.90 (s, 12H),
1
3
3
NMR (50 MHz, CDCl ): d 169.5, 151.0, 150.9, 150.8,
.83 (s, 6H), 3.77 (s, 6H), 3.65 (s, 6H), 2.44 (s, 6H);
C
dioxane in MeOH) lmax 302.6 nm (1 40187), 230.8
(301685); FAB MS m/z 1119 (MþH) . Anal. Calcd for
þ
C H O : C, 77.26; H, 5.58. Found: C, 77.14; H, 5.49.
3
1
1
1
3
1
49.2, 143.6, 132.4, 131.2, 131.1, 131.0, 130.7, 127.9,
7
2 62 12
27.0, 126.7, 126.5, 126.3, 126.1, 125.9, 125.7, 125.6,
25.4, 120.9, 77.2, 61.1, 60.8, 60.7, 20.7; IR (CHCl ): 3062,
010, 2940, 2828, 1766, 1504, 1453, 1390, 1347, 1239,
3.1.7. (S,S,R,S,S)-Sexinaphthalene 11. Following the
procedure for the preparation of 4, (S,S,R,S,S)-10 (92 mg,
81 mmol) was treated with potassium carbonate (158 mg,
1.1 mmol) and methyl iodide (0.1 mL, 1.6 mmol) in acetone
(20 mL) for 2 h. After extraction with CH Cl , the organic
3
220, 1210, 1016 cm2 ; FAB MS m/z 1175 (MþH) . Anal.
1
þ
Calcd for C H O : C, 75.62; H, 5.32. Found: C, 75.75; H,
7
5
4 62 14
.26.
2
2
layer was dried and evaporated to give a residue, which was
subjected to column chromatography on silica gel. Elution
with n-hexane/CH Cl /EtOAc (6/3/1) gave (S,S,R,S,S)-11
3
.1.5. (S,S,S,S,S)-Sexinaphthalene 8. To a mixture of
S,S,S,S,S)-7 (43 mg, 37 mmol) and potassium carbonate
(
(
(
2
2
73 mg, 0.53 mmol) in CH Cl (5 mL) was added MeOH
2
0.20 mL) at room temperature. After being stirred for 4 h,
(84 mg, 89%). Mp .300 8C; colorless prisms (recrystal-
2
2
0
lized from n-hexane/CH Cl /EtOAc); [a] ¼295.0 (c 1.4,
2
2
D
1
3 3
the reaction mixture was concentrated under reduced
pressure, and then acidified with aq. 2 N HCl. The mixture
was extracted with CH Cl , dried and evaporated in vacuo
CHCl ); H NMR (200 MHz, CDCl ): d 7.95 (d, 2H,
J¼8.2 Hz), 7.82 (s, 2H), 7.6–7.2 (m, 22H), 3.95 (s, 6H),
3.86 (s, 6H), 3.77 (s, 12H), 3.70 (s, 6H), 2.48 (s, 6H); IR
2
2
2
1
to give a residue. The residue was purified by column
chromatography (SiO , n-hexane/CH Cl /EtOAc¼6/3/1) to
(CHCl ): 3063, 3013, 2940, 1766, 1453, 1390, 1015 cm
3
;
þ
75.62; H, 5.32. Found: C, 75.55; H, 5.31.
FAB MS m/z 1175 (MþH) . Anal. Calcd for C H O : C,
74 62 14
2
2
2
afford (S,S,S,S,S)-8 (38 mg, 95%). Mp .300 8C; orange
0
2
D
powder (from CH Cl /Et O/pet. ether); [a] ¼2146.5 (c
2
2
2
1
1
.2, CHCl ); H NMR (200 MHz, CDCl ): d 7.84 (d, 2H,
3
3.1.8. (S,S,R,S,S)-Sexinaphthalene 12. Following the
procedure for the preparation of 8, (S,S,R,S,S)-11 (65 mg,
56 mmol) was treated with potassium carbonate (109 mg,
0.79 mmol) and MeOH (0.2 mL) in CH Cl (5 mL) for 7 h.
3
J¼8.1 Hz), 7.54 (s, 2H), 7.56–7.2 (m, 22H), 6.22 (s, 2H),
.911 (s, 6H), 3.907 (s, 6H), 3.82 (s, 6H), 3.75 (s, 6H), 3.64
s, 6H); IR (CHCl ): 3520, 3009, 2938, 2854, 1766, 1507,
3
(
3
2
2
2
1
1
(
1
452, 1390, 1348, 1112, 1017 cm ; FAB MS m/z 1091
þ
091.4007. Found 1091.3986.
After extraction with CH Cl , the organic layer was dried
2 2
MþH) ; HRMS m/z Calcd for C H O (MþH)þ
and evaporated to give a residue, which was subjected to
column chromatography on silica gel. Elution with
n-hexane/EtOAc (2/1) gave (S,S,R,S,S)-12 (58 mg, 95%).
Mp .300 8C; orange powder (from n-hexane/EtOAc);
7
0 59 12
3
.1.6. (S,S,S,S,S)-Sexinaphthalene 9. Following the pro-
2
0
1
cedure for the preparation of 4, (S,S,S,S,S)-8 (29 mg,
6 mmol) was treated with potassium carbonate (52 mg,
[a] ¼263.8 (c 1.4, CHCl ); H NMR (200 MHz,
D
3
2
CDCl ): d 7.83 (d, 2H, J¼8.0 Hz), 7.6–7.1 (m, 24H), 6.22
3

4438
T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
(
s, 2H), 3.92 (s, 6H), 3.82 (s, 6H), 3.72 (s, 12H), 3.65 (s,
a solution of (S,S,S)-16 (96 mg, 0.13 mmol) and (S)-17
(252 mg, 0.65 mmol) in CH Cl (12 mL). After being
6
1
1
5
H); IR (CHCl ): 3520, 3008, 2940, 2359, 1631, 1579,
3
2
2
2
1
507, 1452, 1390, 1111, 1017, 908 cm ; FAB MS m/z
091 (MþH) . Anal. Calcd for C H O : C, 77.05; H,
stirred for 27 h under nitrogen, the reaction mixture was
acidified with conc. HCl, concentrated, and extracted with
EtOAc. The organic layer was washed with water, dried,
and evaporated to give a residue, which was subjected to
column chromatography. Elution with n-hexane/CH Cl /
þ
.36. Found: C, 76.81; H, 5.09.
7
0 58 12
3.1.9. (S,S,R,S,S)-Sexinaphthalene 13. Following the
procedure for the preparation of 4, (S,S,R,S,S)-12 (39 mg,
3
0
2
2
EtOAc (4/5/1) gave (S,S,S)-14 (66 mg), its isomer
possessing (S,R,S)-configuration (51 mg) and a separable
mixture of 18 and 19, from which 18 (27 mg, 18%) and 19
(24 mg, 16%) were afforded after pTLC with n-hexane/
acetone (3/2).
6 mmol) was treated with potassium carbonate (71 mg,
.51 mmol) and methyl iodide (90 mL, 1.4 mmol) in
acetone (20 mL) for 2 h. After extraction with CH Cl , the
2
2
organic layer was dried and evaporated to give a residue,
which was subjected to column chromatography on silica
gel. Elution with n-hexane/CH Cl /EtOAc (6/3/1) gave
2
0
Compound (S,S,S,S,S)-18. Amorphous; [a] ¼2144.1 (c
2
2
D
1
(
S,S,R,S,S)-13 (35 mg, 87%). Mp .300 8C; colorless
2
1.2, CHCl ); H NMR (200 MHz, CDCl ): d 7.92 (d, 2H,
3
3
0
D
powder (from n-hexane/CH Cl /EtOAc); [a] ¼289.3 (c
J¼8.8 Hz), 7.80 (s, 1H), 7.78 (s, 1H), 7.6–7.1 (m, 22H),
6.34 (s, 2H), 3.87 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.78 (s,
3H), 3.73 (s, 3H), 3.65 (s, 3H), 3.57 (s, 3H), 3.54 (s, 3H),
2
2
1
0
.4, CHCl ); H NMR (200 MHz, CDCl ): d 7.86 (d, 2H,
3 3
J¼8.1 Hz), 7.6–7.1 (m, 24H), 4.13 (s, 6H), 3.89 (s, 6H),
3
.82 (s, 6H), 3.78 (s, 6H), 3.75 (s, 6H), 3.73 (s, 6H); IR
2.45 (s, 6H); IR (CHCl ): 3508, 3063, 3009, 2940, 2854,
3
21
21
( ;
CD (0.4% dioxane in MeOH): see Table 1; UV (0.4%
CHCl ): 3063, 3010, 2939, 1463, 1391, 1350, 1019 cm
1766, 1506, 1454, 1392, 1348, 1014 cm ; FAB MS m/z
þ
1147.3905. Found 1147.3885.
3
1147 (MþH) ; HRMS m/z Calcd for C H O (MþH)þ
7
2 59 14
dioxane in MeOH) lmax 302.6 nm (1 42700), 230.8
302330); FAB MS m/z 1119 (MþH) . Anal. Calcd for
þ
C H O ·1/2H O: C, 76.65; H, 5.63. Found: C, 76.69; H,
(
2
0
Compound (S,S,S,R,S)-19. Amorphous; [a] ¼295.8 (c 0.5,
7
2
62 12
2
D
1
5
.61.
CHCl ); H NMR (200 MHz, CDCl ): d 7.93 (d, 2H,
3
3
J¼7.0 Hz), 7.80 (s, 1H), 7.79 (s, 1H), 7.6–7.1 (m, 22H),
6.27 (s, 2H), 3.86 (s, 3H), 3.85 (s, 6H), 3.78 (s, 3H), 3.75 (s,
3H), 3.65 (s, 3H), 3.59 (s, 3H), 3.57 (s, 3H), 2.45 (s, 3H),
3.1.10. (S,S,S)-Quaternaphthalene 15. Following the
procedure for the preparation of 4, (S,S,S)-14 (203 mg,
0
1
.26 mmol) was treated with potassium carbonate (257 mg,
.9 mmol) and methyl iodide (0.33 mL, 5.2 mmol) in
2.44 (s, 3H); IR (CHCl ): 3517, 3063, 3026, 3009, 2941,
3
2
1
2855, 1766, 1731, 1504, 1453, 1391, 1014 cm ; FAB MS
þ
acetone (7.0 mL) for 1.5 h. After extraction with EtOAc,
the organic layer was dried and evaporated to give a residue.
The residue was purified by recrystallization from n-hexane/
CH Cl /Et O to give (S,S,S)-15 as colorless plates (177 mg,
m/z 1147 (MþH) ; HRMS m/z Calcd for C H O
7
2 59 14
þ
(MþH) 1147.3905. Found 1147.3915.
3.1.13. Methylation of (S,S,S,S,S)-18 to (S,S,S,S,S)-7.
Following the procedure for the preparation of 4,
(S,S,S,S,S)-18 (23 mg, 20 mmol) was treated with potassium
carbonate (40 mg, 0.30 mmol) and methyl iodide (0.13 mL,
2.0 mmol) in acetone (15 mL) for 2 h. After extraction with
CH Cl , the organic layer was dried and evaporated to give
2
2
2
2
0
1
8
5%). Mp 298–300 8C; [a] ¼2131.0 (c 0.8, CHCl ); H
D
3
NMR (200 MHz, CDCl ): d 7.91 (d, 2H, J¼7.8 Hz), 7.77 (s,
3
2
6
H), 7.6–7.1 (m, 14H), 3.80 (s, 6H), 3.75 (s, 6H), 3.62 (s,
H), 2.44 (s, 6H); IR (CHCl ): 3062, 3011, 2941, 1766,
3
2
1
1
504, 1466, 1453, 1370, 1155, 1105, 1015 cm ; EI MS m/z
2
2
þ
Found: C, 74.63; H, 5.16.
8
02 (M ). Anal. Calcd for C H O : C, 74.80; H, 5.27.
50 42 10
a residue, which was subjected to column chromatography
on silica gel. Elution with n-hexane/CH Cl /EtOAc (4/5/1)
2
2
gave (S,S,S,S,S)-7 (13 mg, 55%), which was identical with
the product obtained from the methylation of (S,S,S,S,S)-6 in
terms of the spectroscopic data as well as the retention time
in HPLC analysis with chiral stationary phase (Chiralpak
3.1.11. (S,S,S)-Quaternaphthalene 16. Following the
procedure for the preparation of 8, (S,S,S)-15 (30 mg,
3
5
7 mmol) was treated with potassium carbonate (7.4 mg,
4 mmol) and MeOH (0.13 mL) in CH Cl (5 mL) for 8 h.
AS, 14% i-PrOH/n-hexane, 0.7 mL/min, t ¼23.9 min).
2
2
R
After extraction with EtOAc, the organic layer was dried
and evaporated to give a residue, which was subjected to
pTLC. Developing with n-hexane/CH Cl /EtOAc (4/5/1)
3.1.14. (S,S,S,R,S)-Sexinaphthalene 20. Following the
procedure for the preparation of 4, (S,S,S,R,S)-19 (10 mg,
8.7 mmol) was treated with potassium carbonate (17 mg,
0.12 mmol) and methyl iodide (0.11 mL, 1.7 mmol) in
acetone (10 mL) for 2 h. After extraction with CH Cl , the
2
2
gave (S,S,S)-16 (11 mg, 40%). Mp 170–171 8C; colorless
needles (recrystallized from CH Cl /EtOAc/Et O/pet.
2
2
2
2
0
1
ether); [a] ¼2129.9 (c 0.6, CHCl3); H
200 MHz, CDCl ): d 8.0–7.2 (m, 18H), 6.21 (s, 1H),
NMR
D
2
2
(
organic layer was dried and evaporated to give a residue,
which was subjected to pTLC. Developing with n-hexane/
CH Cl /EtOAc (4/5/1) gave (S,S,S,R,S)-20 (7.9 mg, 77%).
3
3
3
2
1
.81 (s, 3H), 3.79 (s, 3H), 3.76 (s, 3H), 3.73 (s, 3H), 3.63 (s,
H), 3.61 (s, 3H), 2.44 (s, 3H); IR (CHCl ): 3522, 3010,
3
2
2
940, 1767, 1602, 1467, 1453, 1390, 1155, 1110,
1
Mp .300 8C; colorless powder (from CH Cl /benzene);
2 2
016 cm2 ; EI MS m/z 760 (M ). Anal. Calcd for
þ
[a] ¼291.6 (c 0.3, CHCl ); H NMR (200 MHz, CDCl ):
20
1
D
3
3
C H O : C, 75.78; H, 5.30. Found: C, 75.61; H, 5.44.
48 40 9
d 7.92 (d, 2H, J¼8.0 Hz), 7.78 (s, 2H), 7.6–7.2 (m, 22H),
3.91 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.81 (s, 3H), 3.80 (s,
3H), 3.78 (s, 3H), 3.77 (s, 3H), 3.76 (s, 3H), 3.64 (s, 3H),
3.1.12. Oxidative coupling to sexinaphthalenes (S,S,S,
S,S)-18 and (S,S,S,R,S)-19. A mixture of CuCl (210 mg,
3.56 (s, 3H), 2.45 (s, 3H), 2.44 (s, 3H); IR (CHCl ): 3063,
3
2
1.6 mmol) and a-phenylethylamine (0.25 mL, 2.0 mmol) in
MeOH (0.6 mL) was stirred for 20 min, to which was added
3009, 2940, 2854, 1766, 1729, 1577, 1502, 1466, 1453,
1390, 1016 cm2 ; FAB MS m/z 1175 (MþH) ; HRMS m/z
1
þ

T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
4439
Calcd for C H O
2 63 14
(MþH)þ 1175.4218. Found
to column chromatography on silica gel. Elution with
n-hexane/CH Cl /EtOAc (4/5/1) gave (S,S,S,S,S,S,S)-23
7
1
175.4221.
2
2
(
9.7 mg, 66%). Mp .300 8C; orange powder (from
0
2
D
3
.1.15. Oxidative coupling to octinaphthalenes (S,S,S,
n-hexane/CH Cl /EtOAc); [a] ¼2190.3 (c 0.5, CHCl );
2
2
3
1
S,S,S,S)-21 and (S,S,S,R,S,S,S)-25. A mixture of CuCl2
135 mg, 1.0 mmol) and a-phenylethylamine (0.16 mL,
.3 mmol) in MeOH (0.4 mL) was stirred for 20 min, to
which was added a solution of (S,S,S)-16 (383 mg,
.50 mmol) in CH Cl (8 mL). After being stirred for 36 h
H NMR (200 MHz, CDCl ): d 7.84 (d, 2H, J¼8.3 Hz),
3
(
1
7.6–7.1 (m, 32H), 6.23 (s, 2H), 3.94 (s, 6H), 3.92 (s, 18H),
3.83 (s, 6H), 3.76 (s, 6H), 3.65 (s, 6H); IR (CHCl ): 3521,
3
2
1
3017, 2939, 2854, 1452, 1389, 1221, 1210 cm ; FAB MS
þ
0
m/z 1463 (MþH) ; HRMS m/z Calcd for C H O
94 79 16
2
2
þ
under nitrogen, the reaction mixture was acidified with
conc. HCl, concentrated, and extracted with EtOAc. The
organic layer was washed with water, dried, and evaporated
to give a residue. The residue was purified by column
chromatography (SiO , n-hexane/CH Cl /EtOAc¼4/5/1) to
(MþH) 1463.5368. Found 1463.5372.
3.1.18. (S,S,S,S,S,S,S)-Octinaphthalene 24. Following the
procedure for the preparation of 4, (S,S,S,S,S,S,S)-23
(12 mg, 8.1 mmol) was treated with potassium carbonate
(32 mg, 0.23 mmol) and methyl iodide (0.10 mL, 1.6 mmol)
in acetone (5 mL) for 2 h. After extraction with CH Cl , the
2
2
2
afford (S,S,S,S,S,S,S)-21 (84 mg, 22%) and (S,S,S,R,S,S,S)-
2
5 (114 mg, 30%).
2
2
organic layer was dried and evaporated to give a residue,
which was subjected to column chromatography on silica
gel. Elution with n-hexane/CH Cl /EtOAc (4/5/1) gave
Compound (S,S,S,S,S,S,S)-21. Mp .300 8C; pale yellow
0
2
D
powder (from CH Cl /Et O); [a] ¼2155.7 (c 0.4, CHCl );
2
2
2
3
2
2
1
H NMR (200 MHz, CDCl ): d 7.93 (d, 2H, J¼7.9 Hz), 7.79
(S,S,S,S,S,S,S)-24 (12 mg, 100%). Mp .300 8C; colorless
3
2
0
(
s, 2H), 7.7–7.1 (m, 30H), 6.37 (s, 2H), 3.89 (s, 6H), 3.88 (s,
powder (from CH Cl /Et O/pet. ether); [a] ¼2177.8 (c
0.1, CHCl ); H NMR (400 MHz, CDCl ): d 7.86 (d, 2H,
3 3
2
2
2
D
1
6
2
2
(
1
H), 3.86 (s, 6H), 3.79 (s, 6H), 3.76 (s, 6H), 3.66 (s, 6H),
.45 (s, 6H); IR (CHCl ): 3510, 3063, 3009, 2940, 2854,
J¼8.1 Hz), 7.5–7.1 (m, 32H), 4.13 (s, 6H), 3.92 (s, 6H),
3
2
1
360, 2341, 1766, 1155, 1111 cm ; FAB MS m/z 1519
þ
519.5266. Found 1519.5240.
3.914 (s, 6H), 3.912 (s, 6H), 3.88 (s, 6H), 3.85 (s, 6H), 3.77
(s, 6H), 3.76 (s, 6H); IR (CHCl ): 3008, 2935, 2854, 1454,
MþH) ; HRMS m/z Calcd for C H O (MþH)þ
9
6
79 18
3
1389, 1115, 1019 cm2 ; CD (0.4% dioxane in MeOH): see
Table 1; UV (0.4% dioxane in MeOH) lmax 305.4 nm (1
1
þ
Calcd for C H O : C, 77.30; H, 5.54. Found: C, 77.07; H,
5.43.
Compound (S,S,S,R,S,S,S)-25. Mp .300 8C; colorless
1
72533), 229.8 (407143); FAB MS m/z 1491 (MþH) . Anal.
2
0
powder (from toluene); [a] ¼2150.6 (c 2.2, CHCl ); H
D
3
96 82 16
NMR (200 MHz, CDCl ): d 7.96 (d, 2H, J¼8.0 Hz), 7.83 (s,
3
2
1
3
H), 7.7–7.1 (m, 30H), 6.34 (s, 2H), 3.92 (s, 6H), 3.90 (s,
2H), 3.82 (s, 12H), 3.69 (s, 6H), 2.49 (s, 6H); IR (CHCl ):
3.1.19. (S,S,S,R,S,S,S)-Octinaphthalene 26. Following the
procedure for the preparation of 4, (S,S,S,R,S,S,S)-25
(14 mg, 9.2 mmol) was treated with potassium carbonate
(37 mg, 0.26 mmol) and methyl iodide (0.23 mL, 3.7 mmol)
in acetone (10 mL) for 2 h. After extraction with CH Cl ,
3
2
1
519, 3009, 2940, 2854, 1766, 1155, 1110 cm ; FAB MS
þ
m/z 1519 (MþH) ; HRMS m/z Calcd for C H O
9
6 79 18
þ
(
MþH) 1519.5266. Found 1519.5259.
2
2
3.1.16. (S,S,S,S,S,S,S)-Octinaphthalene 22. Following the
procedure for the preparation of 4, (S,S,S,S,S,S,S)-21
the organic layer was dried and evaporated to give a residue,
which was subjected to pTLC. Developing with n-hexane/
CH Cl /EtOAc (4/5/1) gave (S,S,S,R,S,S,S)-26 (12 mg,
(
(
6.0 mg, 4.0 mmol) was treated with potassium carbonate
16 mg, 0.12 mmol) and methyl iodide (0.10 mL, 1.6 mmol)
2
2
86%). Mp .300 8C; colorless prisms (from n-hexane/
0
2
1
in acetone (5 mL) for 2 h. After extraction with CH Cl , the
2
CH Cl /EtOAc); [a] ¼2139.2 (c 1.5, CHCl ); H NMR
2
2
2
D
3
organic layer was dried and evaporated to give a residue,
which was subjected to column chromatography on silica
gel. Elution with n-hexane/CH Cl /EtOAc (4/5/1) gave
(200 MHz, CDCl ): d 7.92 (d, 2H, J¼8.1 Hz), 7.79 (s, 2H),
3
7.6–7.1 (m, 30H), 3.93 (s, 6H), 3.88 (s, 6H), 3.859 (s, 6H),
3.856 (s, 6H), 3.83 (s, 6H), 3.79 (s, 6H), 3.65 (s, 6H), 2.45 (s,
6H); IR (CHCl ): 3063, 3010, 2940, 2854, 1766, 1577,
2
2
(
S,S,S,S,S,S,S)-22 (3.0 mg, 49%). Mp .300 8C; colorless
2
3
0
D
21
þ
powder (from CH Cl /Et O/pet. ether); [a] ¼2215.7 (c
1504, 1453, 1390, 1017 cm ; FAB MS m/z 1547 (MþH) .
2
2
2
1
0
.4, CHCl ); H NMR (200 MHz, CDCl ): d 7.92 (d, 2H,
3
Anal. Calcd for C H O : C, 76.05; H, 5.34. Found: C,
98 82 18
3
J¼7.9 Hz), 7.79 (s, 2H), 7.6–7.1 (m, 30H), 3.93 (s, 12H),
76.09; H, 5.41.
3
6
1
1
1
3
.92 (s, 12H), 3.84 (s, 6H), 3.78 (s, 6H), 3.66 (s, 6H), 2.45 (s,
H); C NMR (50 MHz, CDCl ): d 169.6, 151.0, 150.9,
1
3
3.1.20. (S,S,S,R,S,S,S)-Octinaphthalene 27. Following the
procedure for the preparation of 8, (S,S,S,R,S,S,S)-26
(36 mg, 23 mmol) was treated with potassium carbonate
(91 mg, 0.66 mmol) and MeOH (0.4 mL) in CH Cl (5 mL)
3
49.2, 143.6, 132.5, 131.3, 131.2, 131.1, 130.7, 127.9,
27.1, 126.8, 126.7, 126.6, 126.3, 126.1, 126.0, 125.7,
25.5, 121.0, 61.1, 60.9, 60.7, 20.8; IR (CHCl ): 3063,
3
2
2
2
1
009, 2938, 1765, 1453, 1389, 1222, 1017 cm ; FAB MS
for 25 h. After extraction with CH Cl , the organic layer
2 2
þ
.34. Found: C, 75.79; H, 5.24.
m/z 1547 (MþH) . Anal. Calcd for C H O : C, 76.05; H,
was dried and evaporated to give a residue, which was
subjected to column chromatography on silica gel. Elution
with n-hexane/CH Cl /EtOAc (6/3/1) gave (S,S,S,R,S,S,S)-
9
8 82 18
5
2
2
3.1.17. (S,S,S,S,S,S,S)-Octinaphthalene 23. Following the
procedure for the preparation of 8, (S,S,S,S,S,S,S)-22
27 (30 mg, 90%). Mp .300 8C; orange powder (from
2
0
D
1
CH Cl /EtOAc); [a] ¼2115.4 (c 1.0, CHCl ); H NMR
2
2
3
(
16 mg, 10 mmol) was treated with potassium carbonate
(200 MHz, CDCl ): d 7.84 (d, 2H, J¼8.1 Hz), 7.6–7.1 (m,
3
(
for 3 h. After extraction with CH Cl , the organic layer was
60 mg, 0.43 mmol) and MeOH (0.4 mL) in CH Cl (5 mL)
32H), 6.23 (s, 2H), 3.94 (s, 6H), 3.89 (s, 6H), 3.86 (s, 6H),
3.84 (s, 12H), 3.77 (s, 6H), 3.64 (s, 6H); IR (CHCl ): 3521,
3063, 3009, 2940, 2853, 1507, 1467, 1452, 1389, 1111,
2
2
2
2
3
dried and evaporated to give a residue, which was subjected

4440
T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
1
þ
1
071 cm2 ; FAB MS m/z 1463 (MþH) ; HRMS m/z Calcd
(CHCl ): 3693, 3510, 3063, 3026, 3009, 2940, 2854, 1766,
3
þ
21
for C H O (MþH) 1463.5368. Found 1463.5370.
1505, 1453, 1390, 1347, 1016 cm ; FAB MS m/z 1519
þ
9
4 79 16
(
1519.5266. Found 1519.5251.
MþH) ; HRMS m/z Calcd for C H O (MþH)þ
9
6 79 18
3.1.21. (S,S,S,R,S,S,S)-Octinaphthalene 28. Following the
procedure for the preparation of 4, (S,S,S,R,S,S,S)-27
20 mg, 14 mmol) was treated with potassium carbonate
(55 mg, 0.40 mmol) and methyl iodide (0.17 mL, 2.8 mmol)
in acetone (4 mL) for 2 h. After extraction with CH Cl , the
organic layer was dried and evaporated to give a residue,
which was subjected to column chromatography on silica
gel. Elution with n-hexane/CH Cl /EtOAc (4/5/1) gave
2
0
(
Compound (S,S,S,S,S,R,S)-31. Amorphous; [a] ¼2186.8
D
1
(c 0.3, CHCl ); H NMR (200 MHz, CDCl ): d 7.95 (d, 2H,
3
3
J¼8.5 Hz), 7.82 (s, 1H), 7.81 (s, 1H), 7.6–7.2 (m, 30H),
6.27 (brs, 2H), 3.97 (s, 3H), 3.95 (s, 3H), 3.94 (s, 3H), 3.93
(s, 3H), 3.90 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.79 (s, 6H),
3.67 (s, 3H), 3.62 (s, 3H), 3.60 (s, 3H), 2.47 (s, 3H), 2.46 (s,
2
2
2
2
(
S,S,S,R,S,S,S)-28 (12 mg, 58%). Mp .300 8C; colorless
0
3H); IR (CHCl ): 3673, 3518, 3023, 3009, 2940, 1731,
3
2
D
21
powder (from CH Cl /EtOAc); [a] ¼2129.6 (c 0.7,
1505, 1453, 1389, 1374, 1249, 1045, 1015 cm ; FAB MS
þ
2
2
1
CHCl ); H NMR (400 MHz, CDCl ): d 7.86 (d, 2H,
3
m/z 1519 (MþH) ; HRMS m/z Calcd for C H O
96 79 18
3
þ
J¼8.0 Hz), 7.6–7.1 (m, 32H), 4.13 (s, 6H), 3.93 (s, 6H),
(MþH) 1519.5266. Found 1519.5245.
3
.87 (s, 6H), 3.85 (s, 12H), 3.82 (s, 6H), 3.772 (s, 6H), 3.768
2
1
(
s, 6H); IR (CHCl ): 3017, 2939, 1390, 1221 cm ; CD
3
3.1.24. Methylation of (S,S,S,S,S,S,S)-30 to (S,S,S,
S,S,S,S)-22. Following the procedure for the preparation
of 4, (S,S,S,S,S,S,S)-30 (5.1 mg, 3.4 mmol) was treated with
potassium carbonate (14 mg, 0.10 mmol) and methyl iodide
(85 mL, 1.4 mmol) in acetone (10 mL) for 2 h. After
extraction with CH Cl , the organic layer was dried and
(0.4% dioxane in MeOH): see Table 1; UV (0.4% dioxane in
MeOH) lmax 305.2 nm (1 72244), 230.6 (392756); FAB MS
þ
.54. Found: C, 77.43; H, 5.52.
m/z 1491 (MþH) . Anal. Calcd for C H O : C, 77.30; H,
9
6 82 16
5
2
2
3.1.22. (S,S,S,S,S)-Sexinaphthalene 29. Following the
procedure for the preparation of 8, (S,S,S,S,S)-7 (40 mg,
evaporated to give a residue, which was subjected to column
chromatography on silica gel. Elution with n-hexane/
CH Cl /EtOAc (4/5/1) gave (S,S,S,S,S,S,S)-22 (4.8 mg,
91%), which was identical with the product obtained from
the methylation of (S,S,S,S,S,S,S)-21 in terms of the
spectroscopic data as well as the retention time in HPLC
analysis with chiral stationary phase (Chiralpak AS, 25%
3
7
4 mmol) was treated with potassium carbonate (9.9 mg,
2 mmol) and MeOH (0.44 mL) in CH Cl (5 mL) for 5 h.
2
2
2
2
After extraction with CH Cl , the organic layer was dried
2
2
and evaporated to give a residue, which was subjected to
pTLC. Developing with n-hexane/CH Cl /EtOAc (4/5/1)
2
2
gave
(S,S,S,S,S)-29
(15 mg,
38%).
Amorphous;
i-PrOH/n-hexane, 0.8 mL/min, t ¼32.0 min).
R
20
1
[
CDCl ): d 8.0–7.8 (m, 3H), 7.6–7.2 (m, 23H), 6.27 (s,
a] ¼2191.6 (c 0.3, CHCl ); H NMR (200 MHz,
D
3
3.1.25. (S,S,S,S,S,R,S)-Octinaphthalene 32. Following the
procedure for the preparation of 4, (S,S,S,S,S,R,S)-31
(5.0 mg, 3.3 mmol) was treated with potassium carbonate
(13 mg, 94 mmol) and methyl iodide (81 mL, 1.3 mmol) in
acetone (5 mL) for 2 h. After extraction with CH Cl , the
3
1
3
3
1
H), 3.94 (s, 12H), 3.93 (s, 12H), 3.86 (s, 3H), 3.85 (s, 3H),
.80 (s, 3H), 3.78 (s, 3H), 3.68 (s, 3H), 3.67 (s, 3H), 2.48 (s,
H); IR (CHCl ): 3521, 3063, 3010, 2939, 2854, 1766,
505, 1467, 1452, 1389, 1347, 1240, 1017 cm ; FAB MS
þ
3
2
1
2
2
m/z 1133 (MþH) ; HRMS m/z Calcd for C H O
organic layer was dried and evaporated to give a residue,
which was subjected to column chromatography on silica
gel. Elution with n-hexane/CH Cl /EtOAc (4/5/1) gave
7
2 61 13
þ
(
MþH) 1133.4112. Found 1133.4086.
2
2
3
.1.23. Oxidative coupling to octinaphthalenes (S,S,S,
(S,S,S,S,S,R,S)-32 (5.1 mg, 100%). Mp .300 8C; colorless
2
0
D
S,S,S,S)-30 and (S,S,S,S,S,R,S)-31. A mixture of CuCl2
51 mg, 0.38 mmol) and a-phenylethylamine (61 mL,
.47 mmol) in MeOH (0.4 mL) was stirred for 20 min, to
which was added a solution of (S,S,S,S,S)-29 (35 mg,
1 mmol) and (S)-17 (61 mg, 0.16 mmol) in CH Cl
powder (from CH Cl /benzene); [a] ¼2113.0 (c 0.2,
2
2
1
3 3
(
0
CHCl ); H NMR (200 MHz, CDCl ): d 7.95 (d, 2H,
J¼8.0 Hz), 7.81 (s, 2H), 7.6–7.2 (m, 30H), 3.97 (s, 3H),
3.96 (s, 3H), 3.95 (s, 3H), 3.94 (s, 3H), 3.93 (s, 3H), 3.91 (s,
3H), 3.86 (s, 3H), 3.84 (s, 6H), 3.80 (s, 6H), 3.79 (s, 3H),
3.68 (s, 3H), 3.59 (s, 3H), 2.47 (s, 3H), 2.46 (s, 3H); IR
3
2
2
(
15 mL). After being stirred for 16 h under nitrogen, the
reaction mixture was acidified with conc. HCl, concen-
trated, and extracted with EtOAc. The organic layer was
washed with water, dried, and evaporated to give a residue,
which was subjected to pTLC. Developing with n-hexane/
acetone (3/2) afforded a mixture of 30 and 31 as a polar
fraction and 14 and its isomer as less polar fraction. From a
polar and less polar fractions, 30 (6.2 mg, 13%) and 31
(CHCl ): 3062, 3007, 2939, 2854, 1766, 1728, 1577, 1503,
3
2
1
1453, 1390, 1349, 1239, 1017, 909 cm ; FAB MS m/z
1547 (MþH) ; HRMS m/z Calcd for C H O (MþH)þ
þ
1547.5579. Found 1547.5582.
9
8 83 18
0
0
0
3.1.26. (S)-2,3,2 ,3 -Tetramethoxy-1,1 -binaphthalene
(33). Following the procedure for the preparation of 4,
(S)-34 (551 mg, 1.6 mmol) was treated with potassium
carbonate (3.2 g, 23 mmol) and methyl iodide (2.0 mL,
32 mmol) in acetone (25 mL) for 1.5 h. After extraction
with EtOAc, the organic layer was dried and evaporated to
give a residue, which was purified by recrystallization from
EtOAc to give (S)-33 as colorless prisms (230 mg, 38%).
(
11 mg, 22%), and 14 (15 mg) and its isomer (18 mg) were
isolated, respectively, after the second separation by pTLC
with n-hexane/CH Cl /EtOAc (4/5/1).
2
2
2
0
Compound (S,S,S,S,S,S,S)-30. Amorphous; [a] ¼2254.9
D
1
(
c 0.1, CHCl ); H NMR (200 MHz, CDCl ): d 7.95 (d, 2H,
3
3
2
0
1
J¼8.8 Hz), 7.83 (s, 1H), 7.81 (s, 1H), 7.7–7.1 (m, 30H),
Mp 204–206 8C; [a] ¼252.2 (c 1.0, CHCl ); H NMR
D
3
6
3
3
.40 (s, 1H), 6.38 (s, 1H), 3.97 (s, 3H), 3.95 (s, 6H), 3.94 (s,
H), 3.91 (s, 6H), 3.86 (s, 3H), 3.80 (s, 3H), 3.78 (s, 3H),
.68 (s, 3H), 3.61 (s, 3H), 3.57 (s, 3H), 2.48 (s, 6H); IR
(200 MHz, CDCl ): d 7.80 (d, 2H, J¼8.3 Hz), 7.5–7.0 (m,
3
8H), 4.08 (s, 6H), 3.63 (s, 6H); IR (CHCl ): 3011, 2940,
3
1597, 1464, 1420, 1251, 1117 cm2 ; CD (0.4% dioxane in
1

T. Furuta et al. / Tetrahedron 60 (2004) 4431–4441
4441
MeOH): see Table 1; UV (0.4% dioxane in MeOH) lmax
25.6 nm (1 5193), 290.6 (10559), 280.2 (11193), 232.0
119248). Anal. Calcd for C H O : C, 76.99; H, 5.92.
9. Liess, P.; Hensel, V.; Schl u¨ ter, A.-D. Liebigs Ann. 1996,
l037–1040.
3
(
10. Koch, K.-H.; M u¨ llen, K. Chem. Ber. 1991, 124, 2091–2100.
11. Optically active polynaphthalenes connected at 1.4-positions
were reported. See: (a) Habaue, S.; Seko, T.; Okamoto, Y.
Macromolecules 2002, 35, 2437–2439. (b) Habaue, S.; Seko,
T.; Okamoto, Y. Macromolecules 2003, 36, 2604–2608. A
2
4 22 4
Found: C, 76.89; H, 5.89.
3.2. Molecular modeling of octinaphthalene 24 and
corresponding 24-mer
9
-mer of naphthalene connected at 1.5-positions was also
reported. See: (c) Marin, G. H.; Horak, V. J. Org. Chem. 1994,
9, 4267–4271.
The lowest energy conformations of octinaphthalene 24 and
corresponding 24-mer were obtained by MacroModel
5
(
version. 6.0) using MM2 force field. The calculations
1
2. (a) Tanaka, K.; Furuta, T.; Fuji, K.; Miwa, Y.; Taga, T.
Tetrahedron: Asymmetry 1996, 7, 2199–2202. (b) Tsubaki,
K.; Miura, M.; Morikawa, H.; Tanaka, H.; Kawabata, T.;
Furuta, T.; Tanaka, K.; Fuji, K. J. Am. Chem. Soc. 2003, 125,
were started from the structures 24 and 24-mer, in which the
absolute configuration of each axis was prefixed as aS.
1
6200–16201. (c) Fuji, K.; Furuta, T.; Otsubo, T.; Tanaka, K.
References and notes
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1
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2
. A preliminary communication of part of this work has been
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3
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(
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8