X. Hu et al. / Tetrahedron: Asymmetry 23 (2012) 1327–1331
1331
MeCN
OH
OH
OH
OH
.
2
+
COOH
COOH
reflux
N
H
N
H
molecular complex
MeCN
reflux
OH
OH
+
COOH
No reaction
N
H
Scheme 2. Interaction of (S)- and (R)-BINOL with (S)-proline in MeCN.
Crystal data for the 1:2 complex of (S)-proline and (S)-BINOL:
empirical formula, C45 ; formula weight, 687.76; calculated
density, 1.348 g/cm ; volume (V), 3388.75(6) Å ; crystal system,
Z.; Zhao, D. J. Tetrahedron: Asymmetry 1998, 9, 3985; (h) Wang, M.; Hu, B. F. J.
Org. Chem. 1995, 60, 7364.
H37NO
6
4
.
.
(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.
(a) Ha, W. Z.; Shan, Z. X. Tetrahedron: Asymmetry 2006, 17, 854–859; (b) Wang,
Y.; Sun, J.; Ding, K. L. Tetrahedron 2000, 56, 4447; (c) Toda, F.; Yoshizawa, K.;
Hyoda, S.; Toyota, S.; Chatziefthimiou, S.; Mavridis, I. M. Org. Biomol. Chem.
3
3
Orthorhombic; space group, P2(1)2(1)2(1); Z = 4; unit cell dimen-
o
sions, a = 27.272(2), b = 9.0398(8), c = 13.7458(12),
b = 90 ,
a
= 90 ,
o
o
ꢂ1
c = 90 ; absorption coefficient (l), 0.089 mm ; index
5
ranges ꢂ33 6 h 6 32, ꢂ10 6 k 6 11, ꢂ16 6 l 6 16; F(000), 1448;
GOF, 1.050.
2004, 2, 449; (d) Toda, F.; Atanaka, K. J. Org. Chem. 1994, 59, 5748; (e) Cai, D.;
Hughes, L. D.; Verhoeven, T. R.; Reider, P. J. Tetrahedron Lett. 1995, 36, 7991; (f)
Tanaka, K.; Okada, T.; Toda, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 1147; (g)
Toda, F.; Tanaka, K.; Stein, Z.; Goldberg, I. J. Org. Chem. 1994, 59, 5748.
Periasamy, M.; Bhanu Prasad, A. S.; Bhaskar Kanth, J. V.; Kishan Reddy, Ch.
Tetrahedron: Asymmetry 1995, 6, 341.
Acknowledgments
6
.
The project was supported by the Special Fund for Basic Scien-
tific Research of Central Colleges, South-Central University for
Nationalities and the National Nature Science Foundation of China
7. Periasamy, M.; Venkatraman, l.; Justin Thomas, K. R. J. Org. Chem. 1997, 62,
302.
4
8
.
Zixing, Shan; Ying, Xiong; Shiwen, Huang; Huarong, Yun; Dejie, Zhao Wuhan
Univ. J. Nat. Sci. 2000, 5, 469.
(
No. 21107143 and 20872115).
9.
We attempted to prepare a chelated chiral spiroborate (see Ref. 3d,e,g and
Periasamy, M. Pure & Appl. Chem. 1996, 68, 663–666) ester via rac-BINOL,
butyl borate and (S)-proline in refluxing acetonitrile. A white precipitate
isolated after refluxing for several hours. The white precipitate was
References
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recrystallized in CH
revealed that the product was a molecular complex consisting of BINOL and
S)-proline, instead of the desired spiroborate. This unsuccessful experiment
may mean that inclusion complexation between (S)-proline and BINOL
readily occurs. As result, we decided to examine the complexation
behaviour between racemic BINOL and (S)-proline in acetonitrile. We
found that complexation between (S)-proline and rac-BINOL could take
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crystals, and racemic BINOL was isolated as white, lightweight needles. This
crystalline property has been successfully applied to the separation of the
enantiomers and the racemate in non-racemic BINOL according to ‘kinetic’
crystallization.
3 2
CH OH. Spectroscopic analysis of the crystals obtained
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