An economic, practical access to enantiopure 1,1′-bi-2-naphthols: enantioselective complexation of threo-(1S,2S)-N-benzyl-N,N-dimethyl[1,3-dihydroxy-1-(4′-nitrophenyl)]-2-propylammonium chloride

Article abstract of DOI:10.1016/j.tetasy.2006.02.015

An economic, convenient access to enantiopure (R)- and (S)-1,1′-bi-2-naphthol (BINOL) has been discovered. Racemic 1,1′-bi-2-naphthol was reacted with threo-(1S,2S)-N-benzyl-N,N-dimethyl-[1,3-dihydroxyl-1-(4′-nitrophenyl)]-2-propylammonium chloride (BDDNPAC) in water-containing acetonitrile under reflux until the solid dissolved completely, and then cooled to ambient temperature to isolate a yellow-greenish crystal consisting of BDDNPAC, (S)-BINOL, and water, which was analyzed by single crystal X-ray structural analysis. Enantiopure (S)- and (R)-1,1′-bi-2-naphthols were obtained in high yield after decomposition of the colored crystalline complex and evaporation of the acetonitrile solution removed from the complex crystals and successive crystallization. The chiral quaternary ammonium salt BDDNPAC can be recovered and reused without any decrease in efficiency.

Full text of DOI:10.1016/j.tetasy.2006.02.015

Tetrahedron: Asymmetry 17 (2006) 854–859
An economic, practical access to enantiopure
1,10-bi-2-naphthols: enantioselective complexation
of threo-(1S,2S)-N-benzyl-N,N-dimethyl[1,3-dihydroxy-
1-(40-nitrophenyl)]-2-propylammonium chloride
Wuzu Ha and Zixing Shan*
Department of Chemistry, Wuhan University, Wuhan 430072, China
Received 6 February 2006; accepted 17 February 2006
Available online 24 March 2006
Abstract—An economic, convenient access to enantiopure (R)- and (S)-1,10-bi-2-naphthol (BINOL) has been discovered. Racemic 1,10-
bi-2-naphthol was reacted with threo-(1S,2S)-N-benzyl-N,N-dimethyl-[1,3-dihydroxyl-1-(40-nitrophenyl)]-2-propylammonium chloride
(BDDNPAC) in water-containing acetonitrile under reflux until the solid dissolved completely, and then cooled to ambient temperature
to isolate a yellow-greenish crystal consisting of BDDNPAC, (S)-BINOL, and water, which was analyzed by single crystal X-ray struc-
tural analysis. Enantiopure (S)- and (R)-1,10-bi-2-naphthols were obtained in high yield after decomposition of the colored crystalline
complex and evaporation of the acetonitrile solution removed from the complex crystals and successive crystallization. The chiral qua-
ternary ammonium salt BDDNPAC can be recovered and reused without any decrease in efficiency.
ꢀ 2006 Elsevier Ltd. All rights reserved.
1. Introduction
However, most of these chiral compounds were prepared
from an expensive alkaloid, chiral amine, chiral epichloro-
hydrin or chiral sulfoxide, as a basic chiral starting mate-
rial. Therefore, the cost for the preparation is higher, and
from a practical point of view, most of them are not
economic.
Enantiomerically pure 1,10-bi-2-naphthols (BINOLs) pos-
sessing a C2-symmetric axis and their derivatives are very
important chiral ligands and auxiliaries, and have been
extensively used in catalytic and stoichiometric asymmetric
synthesis.1,2 To meet this progressive need, a large number
of preparative methods for enantiopure (S)- and (R)-BI-
NOL have been reported, including fractional crystalliza-
tion of diastereoisomers,3,4 resolution with enzymes or
microorganisms,5 asymmetric oxidation coupling,6 and
enantioselective complexation.7–13 As far as the complexa-
tion method is concerned, N-benzylcinchonidinium chlo-
ride,7 N-benzylcinchonidinium chloride,8 (S)-5-oxopyrro-
lidine-2-carboxanilide,9 (S,S)-1,2-diaminocyclohexane,10
chiral sulfoxide11 N-(3-chloro-2-hydroxy-propyl)-N,N,N-
trimethylammonium chloride,12 and ethers of tartaric acid
derivatives13 have been used as chiral complexing agents.
threo-(1S,2S)-2-Amino-1-(40-nitrophenyl)-1,3-propanediol
[threo-(1S,2S)-ANP], a ‘chiral waste’ in the production of
chloromycetin, is one of the least expensive artificial chiral
materials available. Investigation into reaction and applica-
tion of threo-(1S,2S)-ANP is of significance for the devel-
opment of new varieties of chiral materials. Recently, we
conveniently prepared a number of ionic or non-ionic chi-
ral compounds14 using threo-(1S,2S)-ANP as a chiral start-
ing material, two of which have been successfully applied
to the resolution of racemic ibuprofen15 and the prepara-
tion of enatiomerically pure BINOLs.4h Herein, we
report the enantioselective complexation of a quaternary
ammonium salt derived from threo-(1S,2S)-ANP, threo-
(1S,2S)-N-benzyl-N,N-dimethyl-[1,3-dihydroxyl-1-(40-nitro-
phenyl)]-2-propylammonium
Scheme 1) to racemic BINOL and an economic, practical
preparation of enantiopure (S)- and (R)-BINOL.
chloride
(BDDNPAC,
*
Corresponding author. Tel.: +86 027 68764768; fax: +86 027
68754067; e-mail addresses: kenshan@public.wh.hb.cn; zxshan@whu.
edu.cn
0957-4166/$ - see front matter ꢀ 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2006.02.015

W. Ha, Z. Shan / Tetrahedron: Asymmetry 17 (2006) 854–859
855
OH
OH
OH
OH
Cl
NMe2
OH
OH
O2N
OH
OH
(
S
)-BINOL
(R)-BINOL
rac-BINOL
BDDNPC
Scheme 1. Chiral including agent BDDNPAC and 1,10-bi-naphthalene-2,20-diol (BINOL).
2. Results and discussion
bonding network including a water molecule (see later sec-
tion). This molecular complex was difficult to dissolve in
water and most of the familiar organic solvents; however,
it could be cleaved in certain cases. When the complex
was heated and refluxed in a mixture of a polar organic sol-
vent (e.g., ethyl acetate) and water, a two-phase solution
was formed. The organic phase was separated, evaporated,
and the residue recrystallized in toluene to give transpar-
ent, heavy crystals of enantiopure (S)-BINOL in 95% yield
based on the complex, the overall yield, 85%. The water
layer was evaporated to dryness under a reduced pressure
and the residue was recrystallized in ethanol. The BDDN-
PAC was recovered almost quantitatively, and could be re-
used in the formation of the molecular complex to furnish
the desired product in nearly the same yield as above. The
acetonitrile mother liquor removed from the molecular
complex was evaporated to provide an enriched (R)-BI-
NOL, which was extracted with Et2O (it has been proven
that the insoluble solid was a mixture of BDDNPAC and
the molecular complex), evaporated and recrystallized in
toluene to offer transparent, heavy crystals of enantiopure
(R)-BINOL in over 70% yield and a small amount of white,
needle racemic BINOL.17 It appears that the cheap chiral
quaternary ammonium salt can discriminate with high
enantioselectivity both the enantiomers of racemic BINOL
and form a molecular complex crystal with (S)-BINOL.
The process of chiral separation of BINOL via enantio-
selective complexation of the chiral host to racemic guest
was summarized in Scheme 3.
2.1. Separation of both the enantiomers of BINOL
via the formation of a molecular complex
The chiral quaternary ammonium salt threo-(1S,2S)-
N-benzyl-N,N-dimethyl-[1,3-dihydroxyl-1-(40-nitrophenyl)]-
2-propylammonium chloride, BDDNPAC has never been
reported, although its analogous N-alkyl bromide and
iodide has been prepared.16 We found that it could be con-
veniently synthesized in high yield from threo-(1S,2S)-ANP
via methylation with formic acid and formaldehyde and
sequential quaternization with benzyl chloride (Scheme
2). The basic chiral starting material threo-(1S,2S)-ANP,
from a pharmaceutical factory can be efficiently purified
via recrystallization in a mixed solvent of MeOH and
H2O. BDDNPAC as prepared above was allowed to reflux
with consistently stirring with racemic BINOL in water-
containing acetonitrile, until the solid completely dissolved,
and then cooled to room temperature. A large amount of
yellow-greenish crystals was isolated from the system.
The crystals were then separated from the mother liquor
to be treated later. The IR spectra of the crystal showed
the characteristic absorption of BINOL and BDDNPAC,
and the absorption of the OH groups of BINOL shifted
to a lower frequency field. Its 1H NMR spectra clearly indi-
cated that it included equimolar BINOL and BDDNPAC.
It can be seen by comparison of the 1H NMR spectra with
those of BDDNPAC and BINOL that the hydroxylic pro-
tons of BINOL shifts considerably downfield (to 9.23 ppm)
as well as that of the hydroxylic protons in the salt shift
slightly upfield, meaning that the crystal can be a molecular
complex, and where all the hydroxylic protons are in
hydrogen-bonding environment. Its single crystal X-ray
diffraction analysis result showed that BDDNPAC and BI-
NOL were connected together via a complicated hydrogen-
2.2. Molecular and crystal structure of the complex
A hot water-containing acetonitrile solution of the mole-
cular complex was slowly cooled to room temperature to
furnish a yellow-greenish single crystal suitable for
X-ray crystal structure analysis with dimensions of
NH2
OH
O2N
OH
)-ANP
threo-(1S,2S
NH2
NMe2
OH
+NMe2
OH
Cl-
PhCH2Cl
Me2CO
HCHO + HCOOH
O2N
OH
O2N
O2N
OH
)-ANP
OH
threo-(1S,2S)-DMANP
reflux, 24 h
82%
70%
OH
BDDNPAC
threo-(1S,2S
Scheme 2. Preparation of threo-(1S,2S)-N-benzyl-N,N-dimethyl-[1,3-dihydroxyl-1-(40-nitrophenyl)]-2-propylammonium chloride, BDDNPAC.

856
W. Ha, Z. Shan / Tetrahedron: Asymmetry 17 (2006) 854–859
As shown in Figure 2, there is a complicated hydrogen-
rac-BINOL
BDDNPAC
MeCN-H2O
+
bonding system in the molecular complex, where all the
hydroxylic H atoms are in a hydrogen-bonding environ-
ment, and H2O and Clꢀ are used as bridges between the
chiral quaternary ammonium salt molecules or between a
quaternary ammonium salt molecule and a BINOL mole-
cule. For a BINOL, it is connected directly or indirectly
with three quaternary ammonium salt molecules via three
hydrogen bonds. More accurately, one of the hydroxyl
groups of BINOL is used as proton donor in a H bonding
[O(6)–H(6F)–Cl(1)], while the other plays a different role in
the formation of hydrogen bond, that is, it is used as a pro-
ton donor in one instance [O(7)–H(5F)–O(5)] and as a pro-
ton acceptor in another instance [O(5)–H(4F)–O(4)]. For a
quaternary ammonium salt BDDNPAC molecule, it can
simultaneously connect directly or indirectly with two BI-
NOL molecules and three BDDNPAC molecules via
hydrogen bonds, of which three connections include hydro-
gen bonds generated from two hydrogen atoms of a water
molecule, respectively. It appears that the existence of a
water molecule is a key factor in the formation of the
molecular complex. It not only makes bonding occur effi-
ciently between the salt molecules via hydrogen bond inter-
action and the salt molecules arrange in head-to-head
mode along the c-axis to form layer structure, but also pro-
vides appropriate connectors for the embedding of BINOL
and the formation of the hydrogen-bonding network.
complex crystal
90%
solution
evaporation
extraction
MeCOOEt-H2O
residue
74% ee
crystallization
R)-BINOL
organic phase
evaporation,
crystallization
)-BINOL
S
water phase
evaporation,
crystallization
(
100% ee
over 70%
(
BDDNPAC
over 95%
100% ee
85%
Scheme 3. Separation of both the enantiomers of racemic BINOL via
enantioselective inclusion complexation of BDDNPAC.
0.20 mm · 0.18 mm · 0.17 mm. Final atomic coordinates
of the crystal, along with lists of anisotropic thermal
parameters, hydrogen coordinates, bond lengths, and bond
angles, have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication no.
CCDC-287999. Data can be obtained, on request, from
the Director, Cambridge Crystallographic Data Centre,
12 Union Road, Cambridge, CB2 1EZ, UK (fax: (+44)
1223-336-033; e-mail: deposit@ccdc.cam.cn; web: http//
www.ccdc.cam.ac.uk). Figure 1 shows the numbering
scheme of the molecular complex. The intermolecular orga-
nization and association in the complex are depicted in Fig-
ure 2. The structural parameters exhibited for the various
moieties in the complex are in good agreement with the
standard values.
The chiral quaternary ammonium salt molecule layers
assembled via a hydrogen bond have a specific configura-
tion, and have a very strong chirality recognition ability
with regards to racemic BINOL. As a result, only (S)-BI-
NOL molecules are permitted to inset between the layers
(i.e., the absolute configuration of the BINOL is limited
as levorotatory) and connected with chiral quaternary
Figure 1. Perspective view of the molecular complex of BDDNPAC, (S)-BINOL and water showing the numbering scheme.

W. Ha, Z. Shan / Tetrahedron: Asymmetry 17 (2006) 854–859
857
˚
Figure 2. Hydrogen bonding in the molecular complex consisting of BDDNPAC, (S)-BINOL and H2O shown as dotted lines (bond lengths: A). O(5)–
H(5F)–O(7): O(5)–H(5F), 0.93 (6); O(7)–H(5F), 1.72 (6); O(5)–O(7), 2.648 (4). O(6)–H(6F)–Cl(1): O(6)–H(6F), 0.87 (4); Cl(1)–H(6F), 2.17 (4); O(6)–Cl(1),
3.034 (3). O(3)–H(3F)–Cl(1): O(3)–H(3F), 0.81; Cl(1)–H(3F), 2.28(5); O(3)–Cl(1), 3.077 (3). O(7)–H(7F)–Cl(1): O(7)–H(7F), 0.87 (4); Cl(1)–H(7F), 2.21
(4); O(7)–Cl(1), 3.074 (4). O(7)–H(7E)–O(1): O(7)–H(7E), 0.74 (5); O(1)–H(7E), 2.25 (5); O(7)–O(1), 2.925 (5). O(4)–H(4F)–O(5): O(4)–H(4F), 0.90 (6);
O(5)–H(4F), 1.94 (6); O(4)–O(5), 2.811 (4). Bond angles for hydrogen bonds (ꢁ): O(6)–H(6F)–Cl(1), 173 (4); O(5)–H(5F)–O(7), 173 (5); O(7)–H(7F)–Cl(1),
169 (4); O(7)–H(7E)–O(1), 153 (6); O(3)–H(3F)–Cl(1), 167 (5); O(4)–H(4F)–O(5), 161 (5); H(7F)–O(7)–H(7E), 118(5).
Figure 3. The packing diagram of the molecular complex of the chiral quaternary ammonium salt BDDNPAC, (S)-BINOL and water. Hydrogen bonds
are shown as dotted lines.
ammonium salt molecules together via specific hydrogen
bonds to form a supramolecular network. The ordered
connection of BDDNPAC and (S)-BINOL molecules
engenders a stable three-dimensional architecture, where
the chloride ion, the oxygen atom of water molecule and
the hydroxylic O(5) atom of (S)-BINOL are located at
the node of the hydrogen-bonding network. The packing
diagram of the molecular complex of the chiral quaternary
ammonium salt BDDNPAC, (S)-BINOL and water is
shown in Figure 3.
3. Conclusion
A novel, inexpensive chiral quaternary ammonium salt
BDDNPAC for the preparation of enantiopure (R)- and
(S)-BINOL has been discovered, which was synthesized
from
threo-(1S,2S)-2-amino-1-(40-nitrophenyl)-1,3-pro-
panediol as a chiral starting material. A mixture of BDDN-
PAC and racemic BINOL was refluxed in water-containing
acetonitrile and dissolved to furnish a homogeneous yellow
solution, which was cooled to room temperature to isolate

858
W. Ha, Z. Shan / Tetrahedron: Asymmetry 17 (2006) 854–859
a yellow-greenish crystal consisting of BDDNPAC, (S)-BI-
NOL, and water in a 1:1:1 molar ratio, in which there was a
complicated, but ordered H-bonding network. The com-
plex crystal gave enantiopure (S)-BINOL in very high yield
after simple treatment. The mother liquor removed from
the complex crystal offered enantiopure (R)-BINOL after
evaporation, extraction, and crystallization. On the other
hand, the chiral quaternary ammonium salt can be conve-
niently recovered and reused. The procedure separating
both the enantiomers of BINOL via enantioselective com-
plexation is simple, efficient, and economic. This is perhaps
one of the most practical preparative methods for enantio-
pure (R)- and (S)-BINOL for the time being.
J = 9 Hz, 1H), 3.47 (s, 2H, mixed together with water in
the solvent, disappeared after adding D2O), 3.26–3.31 (m,
1H), 3.26 (s, 3H), 3.21 (s, 3H). 13C NMR (DMSO-d6): d
153.7, 150.4, 147.9, 134.8, 134.3, 130.9, 130.0, 129.4,
129.2, 129.1, 128.8, 128.5, 126.5, 125.1, 124.4, 122.9,
119.3, 116.1, 74.4, 70.5, 69.0, 57.8, 51.0, 50.3. IR (KBr,
cmꢀ1): 3418, 1603, 1520, 1479, 1437, 1348, 1294, 1257,
1098, 1009, 950, 760. The mother liquor was evaporated
to dryness, and the residue treated, with stirring, with
diethyl ether, filtered, and the indissoluble solid (0.65 g)
combined with the above colored crystals and added to a
3:2 (v/v) mixture of ethyl acetate and water. The mixture
was heated and refluxed until the solid dissolved com-
pletely (for about 1 h), and then cooled to room tempera-
ture, the organic layer was separated, and the water
phase extracted with diethyl ether (20 mL · 3). The organic
phases were combined and dried over anhydrous Na2SO4,
evaporated to remove the solvents, to give 1.32 g of solid.
The solid was recrystallized in toluene to afford 1.22 g of
4. Experimental
4.1. General
IR spectra were recorded on a Testscan Shimadzu FTIR
8000 in KBr.1H and 13C NMR spectra were performed
on a Varian Mercury VS 300, d values (ppm) relative to
Me4Si. MS was recorded on a VG ZAB-HF-3F spectro-
meter. Optical rotations were measured on a PE-341 Mc
polarimeter. Melting points were determined on a VEB
Wagetechnik Rapio PHMK05 instrument, and are uncor-
rected. Ee values were obtained by comparison with the
maximum of specific rotation.
transparent, heavy crystal of (S)-1,10-bi-2-naphthol, overall
20
yield, 85%; Mp 206–208 ꢁC; ½aꢁD ¼ ꢀ35:4 (c 1.78, THF),
21
100% ee {lit.7a: ½aꢁD ¼ ꢀ34 (c 1, THF)}. The water layer
was evaporated to dryness, and the residue was recrystal-
lized in ethanol–water to give 2.1 g BDDNPAC, 95%
recovery efficiency. The recovered salt could be reused for
resolution of racemic BINOL and almost same result was
obtained.
The etheral solution removed from the indissoluble solid
was dried over anhydrous Na2SO4, evaporated, and the
residue was recrystallized in toluene to furnish 1.0 g trans-
parent crystal (R)-BINOL (70% yield). Mp 206–208 ꢁC;
threo-(1S,2S)-2-Amino-1-(40-nitrophenyl)-1,3-propanediol
[threo-(1S,2S)-ANP] was presented by Wuhan Pharma-
ceutical Factory as a gift, and purified via crystallization,
20
20
21
mp 161–163 ꢁC, ½aꢁD ¼ þ31:4 (c 1, 6 M HCl); threo-
½aꢁD ¼ þ34:8 (c 1.84, THF), 100% ee {lit.7a: ½aꢁD ¼ ꢀ34
(c 1, THF)} and 0.35 g white, lightweight needle, an almost
racemic BINOL (Mp 216–218 ꢁC).
(1S,2S)-N-Benzyl-N,N-dimethyl-[1,3-dihydroxyl-1-(40-nitro-
phenyl)]-2-propylammonium chloride (BDDNPAC) was
conveniently synthesized in high yield from threo-(1S,2S)-
ANP via methylation with formic acid and formaldehyde
4.3. X-ray crystal structure analysis of the complex
and sequential quaternization with benzyl chloride, 176–
20
178 ꢁC; ½aꢁD ¼ þ48:8 (c 1.184, EtOH); MS (FBA): 331
A single crystal suitable for X-ray structural analysis was
obtained by slowly cooling a hot, water-containing aceto-
nitrile solution of the complex to room temperature. A
yellow-brownish crystal of dimensions 0.20 mm ·
0.18 mm · 0.17 mm was mounted on a glass fiber. X-ray
diffraction intensity data collection and cell refinement
were performed on Bruker P4 four-circle diffractometer
equipped with a graphite monochromator. A total of
5516 unique reflections were collected using MoKa-
(MþC
, 100). Racemic 1,10-bi-2-naphthol was pur-
18H23N2O4
chased from Guangxi Xinjing Science and Technology
Co. Ltd., and without special treatment prior to use.
4.2. Resolution of racemic 1,10-bi-2-naphthol via
enantioselective complexation
1,10-Bi-2-naphthol (2.86 g,10 mmol) and chiral quaternary
ammonium salt BDDNPAC (2.20 g, 6 mmol) were added
to a water-containing acetonitrile (40 mL). The mixture
was refluxed until the solid dissolved completely to form
a homogeneous solution. The solution was cooled to room
temperature, yellow-greenish crystals isolated out of the
solution and filtered. The solid was collected and washed
˚
(k = 0.71073 A) radiation by the x–2h scan technique at
291(2) K, of which 4085 reflections had I > 2r(I) and were
used in the structure solution and refinements. The correc-
tions for Lp factors and empirical absorption were applied
to the intensity data. All calculations were performed on
Enraf-Nonius Molen/VAX Software using the program
SHELXL-97. The structure was solved by direct methods
and refined on F2 using a full-matrix least-squares tech-
nique. The non-hydrogen atoms were also refined by a
full-matrix least-squares technique, anisotropically, and
hydrogen atoms were included but not refined. Cell dimen-
sions were obtained by the least-squares refinement of well-
centered 289 reflections in the range of 2 < h < 25.1ꢁ. The
final cycle of full-matrix least-squares refinement was based
on 5422 observed reflections and 459 variable parameters.
with acetonitrile (about 10 mL), dried, and quantified,
20
3.03 g, 90% yield; Mp 178–210 ꢁC; ½aꢁD ¼ ꢀ25:9 (c 1.012,
1
DMF); H NMR (DMSO-d6): d 9.36 (s, 2H, disappeared
after adding D2O), 8.28 (d, J = 8.1 Hz, 2H), 7.86–7.86
(m, 6H), 7.67 (s, 2H), 7.54 (s, 3H), 7.39 (d, J = 9.0 Hz,
2H), 7.28 (s, 1H, disappeared after adding D2O), 7.24–
7.12 (m, 4H), 6.94 (d, J = 7.8 Hz, 2H), 5.90 (s, 1H, disap-
peared after adding D2O), 5.59–5.57 (m, 1H), 5.14–4.99
(AB system, 2H), 3.87 (d, J = 13.2 Hz, 1H), 3.75 (d,

W. Ha, Z. Shan / Tetrahedron: Asymmetry 17 (2006) 854–859
859
Z. X.; Xiong, Y.; Li, W. Z.; Zhao, D. J. Tetrahedron:
Asymmetry 1998, 9, 3985; (d) Shan, Z. X.; Xiong, Y.; Zhao,
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1373; (h) Liu, D. J.; Shan, Z. X.; Liu, F.; Xiao, C. G.; Lu, G.
J.; Qin, J. G. Helv. Chim. Acta 2003, 86, 157.
Convergence with unweighted and weighted agree-
ment factors was achieved at R = 0.0529 and Rw =
2
0.0907 (w = 1/[ns2(Fo ) + (0.0481P)2 + 0.0000P] where P =
2
2
(Fo + 2Fc )/3, S = 0.0140(14), and Fc* = kFc[1 + 0.001 ·
Fc nl3/sin(2nq)]ꢀ1/4). The maximum and minimum peaks
2
on the final diꢀff3erence Fourier map correspond to 0.224
˚
and ꢀ0.150 eA
.
Crystal data for a 1:1:1 complex of BDDNPAC, (S)-BI-
NOL, and water: empirical formula, C38H39ClN2O7; for-
mula weight, 671.16; calculated density, 1.284 g/cm3;
5. (a) Kazlauskas, R. J. J. Am. Chem. Soc. 1989, 111, 4953; (b)
Kazlauskas, R. J. Org. Synth. 1991, 70, 60; (c) Miyano, S.;
Kawahara, K.; Inone, Y.; Hashimoto, H. Chem. Lett. 1987,
355; (d) Fujjmoto, Y.; Iwadate, H.; Ikekawa, N. J. Chem.
Soc., Chem. Commun. 1985, 1333; (e) Wu, S. H.; Zhang, L.
Q.; Chen, C. S.; Girdaukas, G.; Sih, C. J. Tetrahedron Lett.
1985, 26, 4323.
6. (a) Miyano, S.; Tobita, M.; Nawa, M.; Sato, S.; Hashimoto,
J. J. Chem. Soc., Chem. Commun. 1980, 1223; (b) Miyano, S.;
Handa, S.; Shimizu, K.; Tagami, K.; Hashimoto, H. Bull.
Chem. Soc. Jpn. 1984, 57, 1943; (c) Brussee, J.; Groemendijk,
J. L. G.; te Kopple, J. M.; Janse, A. C. A. Tetrahedron 1985,
41, 3313; (d) Smricina, M.; Lorenc, M.; Hanus, V.; Sedomera,
P.; Kocovsky, P. J. Org. Chem. 1992, 57, 1917.
3
˚
volume (V), 1736.5(6) A ; crystal system, monoclinic; space
group, P2(1); Z = 2; unit cell dimensions, a = 12.547(3),
b = 10.265(2), c = 14.075(3), b = 106.98(3)ꢁ; absorption
coefficient (l), 0.162 mmꢀ1; index ranges 0 6 h 6 15,
ꢀ12 6 k 6 12, ꢀ17 6 l 6 16; F(000), 708; GOF, 1.031.
Acknowledgements
We thank the National Natural Science Foundation of
China 20372053 for financial support.
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17. Enantiopure (R)- and (S)-BINOL are different from racemic
BINOL in crystalline behavior in benzene or toluene. In the
two solvents, enantiopure isomers are separated out as a
colorless, transparent, heavy crystal, and that racemic BINOL
is isolated as a white, lightweight needle. This crystalline
property has been successfully applied to the separation of the
enantiomer and the racemate in a non-racemic BINOL. In our
experiment, the water-containing acetonitrile solution
removed from the molecular complex crystal was evaporated
to dryness to furnish a solid mixture of (R)-BINOL and a
small amount of the dissolved molecular complex, BDDN-
PAC and racemic BINOL (for BINOL, it is either the
unchanged starting material or the result of racemization of
(R)-BINOL during heating). The solid mixture was worked up
with Et2O, (R)- and racemic BINOL entered into the solution.
When the ethereal solution was evaporated and the residue
was crystallized in toluene, enantiopure BINOL was efficiently
separated from the racemate.