Double-Helical Oligo Esters: Chiral Twist of Two Aromatic Ester Chains

Full text of DOI:10.1002/(sici)1521-3773(19980202)37:1/2<131::aid-anie131>3.0.co;2-k

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Experimental Section
Double-Helical Oligo Esters: Chiral Twist of
Two Aromatic Ester Chains
X-ray structure analysis: Crystal dimensions 0.020 Â 0.015 Â 0.015 mm.
Monoclinic, space group C2/c, a ˆ 13.056(2), b ˆ 7.2941(9), c ˆ 15.162(2) Š,
Kyoko Nozaki,* Takakiyo Terakawa, Hidemasa
Takaya, and Tamejiro Hiyama
3
� 1
b ˆ 103.575(2)8, Vˆ 1403.6(3) Š , Z ˆ 4,
M
w
ˆ 784.2 gmol
,
1
calcd
ˆ
�
3
3
2
.711 gcm , F(000) ˆ 1,464. CCD Siemens diffractometer (sealed tube,
� 1
.4 kW), l(MoKa) ˆ 0.71073 Š, mKa ˆ 14.87 mm ; of 2611 reflections meas-
ured, 1002 were independent (Rint ˆ 0.0547), 2 < q < 23.58. Structure
The double-helical structure is often found in nature, and
artificial double-helical molecules are also of interest; for
instance, in 1991 Lehn and co-workers prepared a double-
helical structure by utilizing the coordination of nitrogen
[25]
determination and refinement software SHELXTL. All the hydrogen
atoms were located in the difference Fourier maps. The 114 variables were
refined by full-matrix least-squares with anisotropic thermal parameters for
all non-hydrogen atoms and isotropic for hydrogen atoms. The final
[1]
atoms of two chains to copper ions. In another example, two
chains are bound by hydrogen bonds of an oligopeptide.[
However, in contrast to these approaches based on self-
assembly, covalent bonds have been used less frequently in
the synthesis of such molecules. Here we report the prepar-
ation of oligo esters 2 and 3. In these molecules, biphenyl
groups are sandwiched between two chiral binaphthyl groups.
Through this ªchiral twistº, the originally achiral biphenyl
groups are fixed in the same absolute configuration as the two
binaphthyl groups on both ends. As a result, the two oligo
ester chains in one molecule (green and red in 1 ± 3) are
twisted to form a double-helical structure.[
residuals were R
F
ˆ 0.024 for F > 4s(F) and 0.027 for all data, GOF(F) ˆ
2]
1.167. Further details of crystal structure investigation may be obtained
from the Fachinformationszentrum, Karlsruhe, D-76344, Eggenstein-Leo-
poldshargen (Germany), on quoting the depository number CSD-407222.
Patent Registry No. (NH
4
)
2
Ge
7
O
15 9700705.
Received: July 4, 1997 [Z10637IE]
German version: Angew. Chem. 1998, 110, 135 ± 138
Keywords: germanium ´ solid-state structures ´ microporos-
ity ´ zeolite analogues
3]
[
[
[
1] R. M. Barrer, Hydrothermal Chemistry of Zeolites, Academic Press,
London, 1982.
2] Adsorption and Ion Exchange with Synthetic Zeolites, Principle and
Practice (Ed.: W. H. Flank), ACS Symp. Ser. 1980, 135).
3] Zeolites and Related Microporous Materials: State of the Art 1994,
Proceedings of the 10th International Zeolite Conference, Vol. 84 (Eds.:
J. Weitkamp, H. G. Karge, H. Pfeifer, W. Hölderich), Elsevier,
Amsterdam, 1994.
[
[
[
4] A. Corma, Chem. Rev. 1995, 95, 559.
5] G. D. Stucky, Prog. Inorg. Chem. 1992, 40.
6] S. J. Weigel, J. C. Gabriel, E. Gutierrez Puebla, A. Monge Bravo, N. J.
Henson, L. M. Bull, A. K. Cheetham, J. Am. Chem. Soc. 1996, 118,
2427.
[
[
[
7] S. T. Wilson, B. M. Lok, C. A. Messina, T. R. Cannan, E. M. Flanigen,
J. Am. Chem. Soc. 1982, 108, 1146.
8] R. H. Jones, J. M. Thomas, R. Xu, Q. Huo, A. K. Cheetham, A. V.
Powell, J. Chem. Soc. Chem. Commun. 1991, 1266.
9] Q. Gao, S. Li, R. Xu, J. Chem. Soc. Chem. Commun. 1994, 1465.
[
[
[
10] Q. Huo, R. Xu, J. Chem. Soc. Chem. Commun. 1992, 1391.
11] J. B. Parise, J. Chem. Soc. Chem. Commun. 1985, 606.
For the synthesis of these compounds (S)-1,1'-binaphthyl-
,2'-dicarbonyl dichloride was initially treated with biphenyl-
,2',6,6'-tetrol (Scheme 1), which gave the 1:1 coupling
2
2
12] M. P. Attfield, R. E. Morris, E.Guti e rrez Puebla, A. Monge Bravo,
A. K. Cheetham, J. Chem. Soc. Chem. Commun. 1995, 843.
13] M. A. Roberts, A. N. Fitch, J. Phys. Chem. Solids 1991, 52, 1209.
14] J. Cheng, R. Xu, J. Chem. Soc. Chem. Commun. 1991, 483.
15] S. Feng, M. Greenblatt, Chem. Mater. 1992, 4, 462.
16] S. Feng, M. Tsai, S. P. Szu, M. Greenblatt, Chem. Mater. 1992, 4, 468.
17] S. Feng, M. Tsai, M. Greenblatt, Chem. Mater. 1992, 4, 388.
18] B. Bialek, V. Gramlich, Z. Kristallogr. 1992, 198, 67.
[
[
[
[
[
[
[
product 4a and the 2:1 product 2 in 41% and 54% yield,
respectively. It is noteworthy that 4a was obtained as a single
diastereomer although two diastereomers 4a and 4b could
have formed. Biphenyl-2,2',6,6'-tetrol itself is an achiral
molecule. After the first esterification of the 2-hydroxy group,
the two hydroxy groups at the 2'- and 6'-positions are
diastereotopic. Thus the second esterification step proceeds
exclusively at one of these two hydroxy groups.
The absolute configuration of the biphenyl group was
determined by the following method: The two hydroxy groups
of 4a were protected as methyl ethers, and then the compound
was hydrolyzed to give the 2,2'-dimethoxybiphenyl-6,6'-diol
19] M. A. Roberts, A. N. Fitch, A. V. Chadwick, J. Phys. Chem. Solids
1995, 56, 1353.
[
[
[
20] M. A. Roberts, A. N. Fitch, Z. Kristallogr. 1996, 211, 378.
21] J. Cheng, R. Xu, G. Yang, J. Chem. Soc. Dalton Trans. 1991, 1537.
22] R. H. Jones, J. Chen, J. M. Thomas, A. George, M. B. Hurthouse, R.
Xu, S. Li, Y. Lu, G. Yang, Chem. Mater. 1992, 4, 808.
23] N. Ingri, G. Lundgren, Acta Chem. Scand. 1963, 17, 590.
24] W. L. Roth, F. Reidinger, S. J. La Placa, Superionic Conductors,
Plenum, New York, 1976.
[
[
(
5) and 1,1'-binaphthyl-2,2'-dicarboxylic acid (Scheme 2). The
[
25] SHELXTL, Siemens Energy & Automation Inc., Analytical Instru-
mentation, 1996.
[‡]
[
*] Dr. K. Nozaki, T. Terakawa, Prof. Dr. H. Takaya,
Prof. Dr. T. Hiyama
Department of Material Chemistry
Graduate School of Engineering, Kyoto University
Yoshida, Sakyo-ku, Kyoto, 606-01 (Japan)
Fax: Int. code ‡ (81)75761-8846
e-mail: nozaki@npc05.kuic.kyoto-u.ac.jp
‡
[
] Deceased October 4, 1997.
Angew. Chem. Int. Ed. 1998, 37, No. 1/2
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1433-7851/98/3701-0131 $ 17.50+.50/0
131

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each other at their 2-positions to form a (R)-biphenyl
group.[ In the 1:2 condensation product 2 (Scheme 1), one
biphenyl group is sandwiched between the two binaphthyl
groups. Only one diastereomer was formed. The absolute
configuration of the central biphenyl group is assigned to be S
on the basis of the above result. An optimized space-filling
model of the oligo ester 2 is shown in Figure 1. In this model,
O
7, 8]
Et3N
Cl HO
+
OH
Cl HO
OH THF/CH Cl
2
2
O
rt, 17 h
O
O
OH
OH
O
Cl HO
diastereo-
topic
O
O
O
O
O
OH
OH
O
O
OH
OH
+
+
2
Figure 1. A model of 2 optimized with an MM2 force field (CAChe
O
system). One ester chain, ªnaphthyl-C(ˆO)OC
6
H
OC(ˆO)C
6 3
H -naph-
3
thylº, is depicted in light gray and the other in dark gray. The two chains
form a double-helical structure.
4a
4b
41%
not detected
54%
Scheme 1.
two ester chains, whcih are depicted in light gray and dark
gray in Figure 1, form the double-helical structure. The two
chains are bound to each other by the covalent bond between
the two benzene rings of each biaryl group.
O
MeI, K2CO3
DMF
O
O
OMe
OMe
4a
35 °C, 5 h
The longer biphenyl ester 3 was synthesized from 4a and
biphenyl-2,2',6,6'-tetracarbonyl tetrachloride (Scheme 3).
Again, a single coupling product was obtained. The product
O
O
KOH
Cl
Cl
HO
HO
OMe
OMe
+
EtOH aq.
reflux, 6 h
O
O
O
O
O
NEt3
Cl CH Cl
Cl
Cl
Cl
(
S)-5
4a
+
3
2
2
quantitative
95% ee
48%
rt, 22 h
>
Scheme 2.
Scheme 3.
enantiomeic excess of 5 was determined to be >95% by
was assigned as the aromatic oligo ester 3 with three S
configured biphenyl groups and two binaphthyl groups.
The specific rotations of esters 1 ± 3 [a]D (c ˆ
HPLC on a chiral column. By comparison of the optical
[
4]
rotation value of 5 to that in the literature, this compound
was assigned the absolute configuration S. This indicates that
the absolute configuration of the biphenyl group is controlled
by that of the binaphthyl group. The 1,1'-binaphthyl-2,2'-
dicarboxylic acid was recovered without racemization. Thus,
the present method provides a novel synthetic route to
�
1
1.00 g100 mL ) are shown in Table 1. The greater the number
of biphenyl groups in the molecule, the more the specific
rotation increases. This increase in specific rotation can be
attributed to the double-helical structures of 1 ± 3. The CD
absorption of the biaryl group at around 250 ± 260 nm also
increases in the series 1 !2 !3. This is a further indication
that all biphenyl groups in 3 are S configured. Unlike common
[
5]
optically active biphenyl compounds.
The following experiments also suggest that the biphenyl
group in such cyclic esters prefers to adopt the same absolute
configuration as the binaphthyl group. The condensation of
Table 1. Optical rotation and CD-spectroscopic data of the oligo esters
(
S)-1,1'-binaphthyl-2,2'-diol with (S)-1,1'-binaphthyl-2,2'-di-
1 ± 3.
carboxylic acid dichloride gave the cyclic ester 1 as a single
product in 92% yield, while a complex mixture of products
was obtained from (R)-1,1'-binaphthyl-2,2'-diol and (S)-1,1'-
binaphthyl-2,2'-dicarbonyl dichloride. In addition, Miyano
and co-workers reported the asymmetric synthesis of a
biphenyl group. In their work, two benzoic acid derivatives
were linked to (R)-1,1'-binaphthyl-2,2'-diol through ester
bonds, and then the two phenyl groups were connected to
25
D
CD[c]
Ester No. of
biphenyl groups
[a]
lmax
emax
[
a]
1
2
3
0
1
3
� 553
� 589
� 821
260
254
252
2
[a]
[b]
� 131
[
d]
� 286
[
6]
. [c] 2.05 Â 10� m in 1,4-
5
[a] c ˆ 1.00 in CHCl
3
. [b] c ˆ 1.00 in CH
2
Cl
2
dioxane. [d] Because of the low solubility of 3, other solvents that were
clear at <240 nm were not used.
1
32
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Angew. Chem. Int. Ed. 1998, 37, No. 1/2

COMMUNICATIONS
macrocyclic compounds, the conformation of the cyclic oligo
esters 2 and 3 is much more restricted because the binaphthyl
groups are not allowed to rotate around the 1,1' axis because
of steric repulsion between the 8- and 8'-hydrogen atoms.
Thus once the configuration of the biphenyl groups is
regulated in 2 and 3, the conformation of the whole molecule
is restricted unequivocally except for the small changes in the
torsion angles of the biaryl groups. Accordingly, a double-
helical structure similar to that of 2 is suggested for 3.
[8] T. Sugimura, H. Yamada, S. Inoue, A. Tai, Tetrahedron: Asymmetry
1
997, 8, 649.
9] G. Lindsten, O. Wennerström, R. Isaksson, J. Org. Chem. 1987, 52, 547.
10] T. Ohta, M. Ito, K. Inagaki, H. Takaya, Tetrahedron Lett. 1993, 34,
615.
[
[
1
[11] E. A. Coulson, J. Chem. Soc. 1937, 1298.
From Molecular to One-Dimensional
Experimental Section
Polychalcogenides: Preparation, Structure,
and Reactivity of NaNbS , the First Ternary
6
2
and 4a. A solution of biphenyl-2,2',6,6'-tetrol (1.10 mmol) in THF[9] was
Alkali Metal Niobium Polychalcogenide
Exhibiting Infinite Anionic Chains**
added to a solution of the acid chloride derived from (S)-1,1'-binaphthyl-
10]
2
,2'-dicarboxylic acid[ (1.00 mmol) in CH
2 2
Cl , and the resulting mixture
was stirred at 208C for 22 h. Aqueous work-up followed by purification by
silica-gel column chromatography (CH Cl /EtOAc, 9/1) gave 4a (41%
Wolfgang Bensch,* Christian Näther, and
Peter Dürichen
2
2
yield) and 2 (54% yield) as colorless solids. 4a: Sublimed above 206.08C;
1
H NMR (CDCl
3
): d ˆ 7.95 ± 7.89 (m, 4H), 7.81 (d, 2H, J ˆ 8.58 Hz), 7.52 (t,
2
H, J ˆ 6.93 Hz), 7.30 ± 7.03 (m, 6H), 6.79 (d, 2H, J ˆ 8.25 Hz), 6.60 (d, 2H,
The preparation of multinary transition metal chalcoge-
nides in reactive alkali polychalcogenide melts at temper-
atures between 250 and 5008C is a fast-growing area of
inorganic solid state chemistry.[ Owing to the relatively low
13
J ˆ 8.25 Hz); C NMR (CDCl
3
): d ˆ 166.76, 154.16, 149.27, 136.95, 134.39,
1
1
33.01, 129.60, 129.49, 128.57, 128.17, 127.71, 127.53, 127.22, 124.56, 115.44,
13.98, 111.32. 2: M.p. (CH Cl /hexane) 274.3 ± 274.98C; H NMR (CDCl ):
2 2 3
1
1,2]
d ˆ 7.97 ± 7.91 (m, 8H), 7.81 (d, 4H, J ˆ 8.58 Hz), 7.52 (t, 4H, J ˆ 6.93 Hz),
1
3
2�
7
(
1
[
.31 ± 7.24 (m, 4H), 7.05 ± 6.99 (m, 6H), 6.75 (d, 4H, J ˆ 7.92); C NMR
CDCl
): d ˆ 166.34, 149.00, 136.35, 134.29, 132.96, 129.58, 128.57, 128.37,
28.18, 127.63, 127.42, 127.26, 124.56, 119.37, 116.17; HR-MS: m/z found for
reaction temperatures, compounds containing large Qx ions
3
(
x > 1) are accessible which cannot be obtained with classical
high-temperature syntheses.
‡
M‡H] : 831.1975; calcd.: 831.2017.
: Biphenyl-2,2',6,6'-tetracarboxylic acid (0.21 mmol) was converted into
Recently we investigated new polychalcogenide com-
pounds of niobium. There are only a few examples of such
compounds prepared by the
[11]
3
the corresponding acid chloride and condensed with 4a (0.41 mmol) in the
presence of triethylamine (21 mmol). Work-up followed by purification by
2
Cl
2
) gave 3 (48% yield) as fine needles:
Cl
): d ˆ 8.02 ± 7.78 (m, 16H), 7.58
reactive flux method.[ Sys-
3]
column chromatography (CH
Sublimed above 470.08C. H NMR (CD
1
2
2
tematic variation of the
(
t, 4H, J ˆ 7.92 Hz), 7.47 (t, 2H, J ˆ 8.24 Hz), 7.32 (t, 4H, J ˆ 8.24 Hz),
13
preparation
conditions
7.21 ± 7.02 (m, 12H), 6.79 (d, 4H, J ˆ 8.25 Hz); C NMR (CD
2
Cl
2
): d ˆ
yielded several novel niobi-
um chalcogenides, all con-
1
1
1
1
66.54, 165.35, 149.65, 149.14, 137.39, 136.80, 134.77, 133.46, 133.40, 131.75,
29.88, 129.04, 128.77, 128.68, 128.52, 128.21, 127.71, 127.65, 124.63, 120.39,
‡
20.14, 116.33; HR-MS: m/z found for [M‡H] : 1307.2607; calcd.:
4�
taining molecular [Nb Q ]
subunits
2
11
307.2548.
(Figure 1).[
4±7]
These units occur as isolated
anions, as in K Nb S , or
4 2 11
Received: June 3, 1997 [Z10506IE]
German version: Angew. Chem. 1998, 110, 138 ± 140
[4]
4�
11
Figure 1. View of the [Nb
unit (Nb ˆ *
2
Q ]
are connected through ter-
minal sulfur ligands, as in
, Q ˆ ).
Keywords: chirality ´ configuration determination ´ helical
structures ´ oligomers
[5]
2�
Rb Nb S or Cs Nb S . Incorporation of additional S3
6
4
22
6
4 22
fragments, which are present under the preparation condi-
4
�
tions, can lead to an expansion of the [Nb Q ] subunits. In
2
11
[
[
[
1] W. Zarges, J. Hall, J.-M. Lehn, C. Bolm, Helv. Chim. Acta 1991, 74,
843.
2] M. Mascal, C. M. Moody, A. I. Morrell, A. M. Z. Slawin, D. J.
Williams, J. Am. Chem. Soc. 1993, 115, 814.
3] The construction of ªsingle helicalº polymers has been intensively
studied by Pu et al. by utilizing the chirality of 1,1'-binaphthyl groups:
a) L. Ma, Q.-S. Hu, D. Vitharana, C. Wu, C. M. S. Kwan, L. Pu,
Macromolecules 1997, 30, 204; b) W.-S. Huang, Q.-S. Hu, X.-F. Zheng,
J. Anderson, L. Pu, J. Am. Chem. Soc. 1997, 119, 4313; c) L. Ma, Q.-S.
Hu, D. Vitharana, C. Wu, C. M. S. Kwan, L. Pu, Macromolecules 1997,
[6]
2�
K Nb S
the S3 ion acts as a terminal ligand, and in
it connects two units to form the novel complex
1
4
2
14
[
7]
K Nb S
6 4
25
6�
[
Nb S ] ion.
4 25
By extending the synthetic conditions used for preparing
the novel niobium compounds to sodium polysulfide melts, we
succeeded in synthesizing transparent, orange-red needles.[
All crystals investigated were grown together, and a twin
8]
[9]
refinement had to be performed. Here we report on the
3
0, 204.
synthesis, crystal structure, optical behavior, and reactivity of
4] [a]2
5
ˆ � 146 (c ˆ 0.89, CHCl
) for the sample of >95% ee (deter-
ˆ � 144
) has been reported for (S)-5. H. Moorlag, A. I.
Meyers, Tetrahedron Lett. 1993, 34, 6993.
[
D
3
NaNbS , the first ternary niobium chalcogenide containing
mined by HPLC with CHIRALCEL OD). A value of [a]
c ˆ 0.77, CHCl
D
6
(
3
one-dimensional anionic polymeric chains.
[
*] Prof. Dr. W. Bensch, Dr. C. Näther, Dipl.-Chem. P. Dürichen
Institut für Anorganische Chemie der Universität
Olshausenstrasse 40, D-24098 Kiel (Germany)
Fax: Int. code ‡ (49)431-8801520
[
5] Asymmetric synthesis of 5 other than that given in ref. [3] see: a) T.
Harada, T. Yoshida, A. Inoue, M. Takeuchi, A. Oku, Synlett 1995, 283;
b) G. Deglogu, D. Fabbri, Tetrahedron: Asymmetry 1997, 8, 759.
6] S. Miyano, H. Fukushima, S. Handa, H. Ito, H. Hashimoto, Bull.
Chem. Soc. Jpn. 1988, 61, 3249.
[
[
e-mail: wbensch@ac.uni-kiel.de
7] A similar Ullmann coupling is used for the synthesis of 1. S. Miyano, S.
Handa, M. Tobita, H. Hashimoto, Bull. Chem. Soc. Jpn. 1986, 59, 235.
[**] This work was supported by the Deutsche Forschungsgemeinschaft
(DFG).
Angew. Chem. Int. Ed. 1998, 37, No. 1/2
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
1433-7851/98/3701-0133 $ 17.50+.50/0
133