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Separation of the Enantiomers of 2 2-Dihydroxy-1 1-binaphthyl and 10 10-Dihydroxy-9 9-biphenanthryl by Complexation with N-Alkylcinchonidinium Halides.

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Separation of the Enantiomers of
2,2'-Dihydroxy-l, 1'-binaph thy1 and 10,lO'Dihydroxy-9,Y-biphenanthryl by Complexation
with N-Alkylcinchonidinium Halides**
By Koichi Tanaka, Toru Okada, and Fuumio Toda*
The enantiomers of 2,2'-dihydroxy-I ,l'-binaphthyl 1 are
important C, symmetrical, chiral compounds, whose use is
not only limited to asymmetric syntheses."] They are also
used for the separation of racemates by the formation of
inclusion complexes['] and as chiral shift reagents.13] The
are alenantiomers of 10,1O-dihydroxy-9,9-biphenanthryl3
so important chiral host compounds.f41
Several methods for the separation of the enantiomers
and 3L6]have been reported. One of the most effecof 1[5.6]
tive of these methods is the formation of inclusion complexes
with optically active (R,R)-(
+)-2,3-dimethoxy-N,N,N',N'tetramethylsuccinamide (4) and (R,R)-(
+ )-N,N,N',N'-tetramethyl-2,2-dimethyl- 3,3-dioxolane- rrans-4,5-dicarboxamide (5), respectively.[6]One disadvantage of this method,
R = PhCH,; X
b: R = nBu; X = Br
Prof. F. Toda, Associate Prof. K. Tanaka, T. Okada
Department of Applied Chemistry, Faculty of Engineering
Ehime University, Matsuyama, Ehime 790 (Japan)
Telefax: Int. code (899)230672
[**] This work was supported by the Japanese Ministry of Education, Science,
and Culture (Grant-in-Aid for Scientific Research (B), no. 04453 102).
A w e > < >Chem.
In!. Ed. EngI. 1993,32. No. 8
however, is that the amide host compounds (4 and 5)"l are
not commerically available, and must be synthesized from
tartaric acid prior to the resolution experiment.
Recently we have found that commercially available Nalkylcinchonidinium halides (6) are very effective for the
resolution of I , the 6,6'-dibromo derivative 2, and the
biphenanthryldiol 3 by the formation of inclusion complexes. For example, when a solution of N-benzylcinchonidinium
chloride (6a)IS1(0.74 g, 1.76 mmol) and rac-1 (1 g, 3.5 mmol)
in MeOH (20 mL) was kept at room temperature for 6 h, a
1 : 1 inclusion complex of 6 a and (+)-1 was obtained, which
precipitated as colorless prisms (0.89 g, 72% yield, m.p.
240-244 "C). The 1 : 1 complex was decomposed with dilute
HCl. Subsequent extraction with AcOEt, followed by evaporation of the solvent gave (+)-1 (95% ee; 0.35 g, 70% yield,
[a],, = + 31.5 (c = 1.O, THF)). Recrystallization of the crude
product from MeOH gave (+)-1 (100% ee; 0.3g, 60%
yield, [a], = + 33.2 (c = 1.O, THF)). The filtrate left after
separation of the complex of 6 a and (+)-1 was treated with
dilute HC1 to give (-)-1 (42% ee; 0.62 g, 124% yield,
[a],, = - 13.9 (c = 1.O, THF)). This method is also effective
for the separation of the enantiomers of 2. In this case when
a solution of 6 a (0.95 g, 2.26 mmol) and rac-2f91(2 g,
4.5 mmol) in MeOH (2 mL)/AcOEt (10 mL) was kept at
room temperature for 6 h, a 1 :1 inclusion complex of 6 a and
(-)-2 was obtained, which precipitated in the form of colorless prisms (1.7 g, 89% yield, m.p. 229-232 "C). Decomposition of the complex with dilute HC1 gave (-)-2 (99% ee;
0.82 g, 82% yield, [a],,
= - 51.0 (c = 0.9, THF)). From the
filtrate left after the separation of the inclusion complex,
(+)-2 (79% ee; 1.1 g, 110% yield, [a],= +40.7 (c =1.0,
THF)) was isolated by treatment with dilute HCI. The enantiomeric purities of 1 and 2 were determined by HPLC by
using a column containing an optically active solid phase,
Chiralpak AS,"'] and hexane/EtOH (95 : 5 ) as an eluent.
Interestingly, however, 6 a was not suitable for the separation of the e-nantiomers of 3, because 6 a does not fork an
inclusion complex with 3. In contrast this separation was
achieved by the use of N-butylcinchonidinium bromide
(6b).["] For example, when a solution of 6b (0.14 g,
0.33 mmol) and rac-3 (0.25 g, 0.65 mmol) in MeCN (10 mL)
was kept at room temperature for 24 h, a 1 :1 inclusion complex of 6 b and (+)-3 was obtained, which precipitated as
colorless prisms (0.22 g, 83% yield, m.p. 168-169 "C). Decomposition of the complex with dilute HCl gave ( + ) - 3
(100% ee; 0.1 g, 80% yield, [a],,
= +58 (c =1.0, CHCI,)).
From the filtrate left after the separation of the inclusion
complex, (-)-3 (58% ee; 0.15 g, 80% yield, [a],, = - 35
( c = 1.5, CHC1,)) was isolated by treatment with dilute HCI.
The enantiomeric purity of 3 was determined by HPLC by
using a column containing an optically active solid phase,
Chiralcel OC,f'ol and hexane/iPrOH (90: 10) as an eluent.
The cinchonidinium salt 6 b, however, does not form inclusion complexes with 1 or 2. It is interesting that the inclusion
behavior of the cinchonidinium derivatives 6 varies dramatically depending on the alkyl substituent at the bridgehead N
atom of these compounds. This might be due to a kind of
molecular recognition in the inclusion crystal.
Previously we have shown that 1 forms crystalline inclusion complexes with the alkali metal hydroxides LiOH,
NaOH, KOH, and CsOH, and that these hydroxides can be
isolated from aqueous solution by using the complex formation with l.['" The presence of strong hydrogen bonds between the OH groups of 1 and the HO-ions of the alkali
Q VCH VerlugsgeseIlschu/rmhH, 0-69451 Wernheim. 1993
0570-0833/93/0808-1147$10.00+ ,2510
metal hydroxide in these complexes has been observed by the
measurement of the IR spectra. Hydrogen bonds are also
formed between the OH groups of 1, 2, and 3 and the halogen counterions of 6. This was clarified by X-ray structure
analyses of the corresponding inclusion
X-ray crystal structures of these complexes will be reported
in detail in the future.
Noteworthy is the very efficient chiral recognition in the
formation of inclusion compkxes of 6 with C, symmetrical
chiral biaryldiol derivatives such as 1, 2, o r 3. They are particularly useful for the separation of the enantiomers of
biaryldiols. It is also interesting that the behavior of the
cinchonidine derivatives 6 is completely different from that
of cinchonidine itself; the latter does not form inclusion
complexes with 1, 2, o r 3.[l4lThese findings may be applicable to other combinations of salts of alkaloids or simple
chiral alkylamines with biaryldiol derivatives.
breakthrough: he provided valuable experimental evidence
in support of the wide-reaching validity of the (4n + 2) rule
for aromatic n-electron systems."] Moreover, in agreement
with H M O calculation^,^^^ it has been determined that also
[22]annulene 1 b shows aromaticity at low temperatures,
whereas resonance stabilization in [26]annulene 1c is no
longerI4' sufficient to stabilize the molecule in a planar conformation with aromatic properties.
Received: March 12, 1993 [Z 5913 IE]
German version: Angew. Chrm. 1993. 105. 1266
[I] R. Noyori, I. Tomino, Y. Tanimoto, M. Nishizawa, 1 Am. Chem Soc.
1984,106,6709; D. Seebach, A. K. Beck, S. Roggo, A. Wonnacott, Chem.
Ber. 1985,118,3673; B. M. Trost, D. J. Murphy, Orgunometallirs 1985,4,
1143; J.-T. Wang. X. Fan, X. Feng, Y.-M. Qian, S-vnrhesis 1989. 291.
[2] F. Toda, K. Mori, 2. Stein, I. Goldberg, Tetrahedron Lett. 1989. 30. 1841;
K. Mori, F. Toda, Bull. Chem. Soc. Jpn. 1990,63,2127; F. Toda, K. Mori.
J. Chem. Sur. Chem. Cummun. 1986. 1059; F. Toda. K. Mori, ihid. 1986.
1357; F. Toda, K. Mori. Z. Stein, I. Goldberg, J Urg. Chem. 1988,53,308.
[3] F. Toda, K. Mori, J. Okada. Chem. Leu. 1988. 131.
[4] F. Toda. K . Tanaka, Tetruhedron Leu. 1988.29. 1807; F. Toda. K. Tanaka.
J Urg. Chem. 1991, 56. 7332; G:H. Lee, Y Wing, K.Tdnaka. F. Toda,
Chem. Lett. 1988, 781.
[5] J. Brussee. J. L. G. Groenedijk, J. M. te Koppele, A. C. A. Jansen. Terruhedron 1985. 41, 3313; S . Miyano, K. Kawahara. Y. Inoue. H. Hashimoto,
Chem. Letl. 1987. 355; M. Kawashimd, A. Hirdyama, ihid. 1990, 2299.
[6] F. Toda, K.Tanaka. J. U r g . Chem. 1988, 53. 3607: F. Toda. K. Tdndka,
L. R. Nassimbeni. M. Niven. Chem. Letl. 1988, 1371.
171 D. Seebach, H:O. Kalinowskyi, B. Bastani. G. Crass. H. Daum, H. Dorr.
N. P. DuPreez. V. Ehrig. W. Langer. C. Nussler, H.-A. Oei. M. Schmidt.
Hell,. Chim. Actu 1977. 60, 301.
[8] S. Colonna, A. Re, H. Wynberg, J. Chem. Sor. Perktn Truns. 1 1981, 547.
[9] M. Vondenhof, J. Mattay. Tetruhedron Lett. 1990, 31. 985.
[lo] Chiralpdk AS and Chiralcel OC are available from Ddicel Chemical Industries, Ltd.. Himeji (Japan).
[11] S. Julia. A. Ginebreda. J. Guixer, J. Masana, A. Tomds, S. Colonna, L
Chem. Sop. Perkin Truns. 11981, 574.
1121 F. Toda, K. Tanaka. M. C. Wong. T. C. W. Mak. Chem. Lerr. 1987. 2069.
[I31 F. Toda, K. Tanaka, I. Goldberg, unpublished results.
[14] However, quinine itself forms an inclusion complex with the 7,7'-bis(benzyloxy) derivative of 1: P. P. Castro. T. M. Georgiadis, F. Diederich, J.
Org. Chem. 1989.54, 5835.
Porphyrins with Aromatic 26~-Electron
By Thomas Wessel, Burchard Franck,* Manfred Moiler,*
Ute Rodewald, and Mechthild Lage
With the synthesis of the aromatic [18]annulene 1 a, the
hexavinylogous benzene, Sondheimerl'] achieved a major
Organisch-chemisches lnstitut der Universitit
Orleansring 23, D-48149 Munster (FRG)
Telefax: Int. code + (251)839-772
Dr. M. Moller, Dip].-Ing. U. Rodewald, M. Llge
Anorganisch-chemisches Institut der Universitiit Munster (FRG)
[**I Novel porphyrinoids, Part 12. This work was supported by the Deutsche
Forschungsgemeinschaft, the Fonds der Chemischen Industrie, and BASF
AG (LudwigshaFen). Part 11 : [5].
VerlujisjieseN~rliuftmhH, 0-69451 Weinheim, 1993
= Z(26n)
We report here on the synthesis of [26]porphyrin 2c, its
crystal structure, its diatropicity, and initial investigations
o n electrophilic substitution. Thus it has been demonstrated
that this cyclic, conjugated system with 26 a electrons is aromatic. Furthermore, the phenyl- and alkyl-substituted
[26]porphyrins 8 a and 8b, respectively, and a [26]azaporphyrin 9 were synthesized.
We recently described the synthesis of stable, aromatic
[22]porphyrins, for example, 2b with 22 a-electron perimeters;I5% like the parent porphyrin 2 a, 2 b is a bisazaannulene. The pyrrole units situated at the corners stabilize the
planar conformation without impairing the annulenoid conjugation, by the formation of individual n-electron sextets.
Octaethyl[l8]porphyrin 2a prepared by Hans Fischer
et al.['1 developed into the most frequently used porphyrin.
In a similar way the bis- and tetravinylogues 2 a and 212,
respectively, may find manifold applications.
Our synthesis of [26]porphyrin 3" had helped to clarify
whether the ( 4 n + 2) rule no longer applies to [26]annulene 1 c in general or only to annulene-type conjugated cyclic
systems. Like compound 4,'12' described almost at the same
time by LeGoff et al., significant diamagnetic ring current
effects in the 'H N M R spectrum demonstrated that this system is aromatic. Furthermore, diatropic 26 n-electron systems have been described in which the annulene perimeter is
planar, stabilized by six pyrrole units,1'3*141
or by allene and
ethyne groups (dehydroannulenes)." In one case, a crystal
structure analysis was carried out for a corrinoid
hexapyrrole.[' 41
In memory of Franz Sondheimer
[*] Prof. Dr. B. Franck. Dr. T. Wessel
2a: n = O(18n)
2b: n = 1(2%)
1 b: n = 1 (2%)
lc: ff = 2(26n)
2 [email protected]
B 10.00+ .ZSjO
Angew. Chem. Int. Ed. Engl. 1993, 32, No. X
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enantiomers, alkylcinchonidinium, separating, complexation, halide, binaphthyl, dihydroxy, biphenanthryl
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