An improved method for the resolution of 1,1′-binaphthalene-2,2′-diol via a phosphite using (-)-menthol as a resolving agent

Article abstract of DOI:10.1080/10426500210215

(-)-Menthol reacts with phosphorus trichloride to afford menthyl phosphorodichloridite 2, which further reacts with racemic 1,1′-binaphthalene-2,2′-diol to give phosphite (±)-3 in the presence of triethylamine. (±)-3 can be easily separated by fractional crystallization to form the crystal (+)-(S)-3 and the mother liquor (-)-(R)-3. Then both the crystal and the mother liquor are treated with the AcOH-H₂O to obtain enantiomeric pure (-)-(S)-1 and (+)-(R)-1 respectively, with enantiomeric excess up to 99.7%.

Full text of DOI:10.1080/10426500210215

This article was downloaded by: [Pennsylvania State University]
On: 10 August 2014, At: 13:05
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the Related
Elements
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/gpss20
An Improved Method for the Resolution of 1,1′-
Binaphthalene-2,2′-Diol via a Phosphite Using (-)-
Menthol as a Resolving Agent
Jue Xiao Cai a , Zheng Hong Zhou a , Kang Ying Li a , Chi Hung Yeung b & Chu Chi Tang a
a State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic
Chemistry , Nankai University , Tianjin, P. R. China , 300071
b Open Laboratory of Chirotechnology and Department of Applied Biology and Chemical
Technology , The Hong Kong Polytechnic University , Hong Kong, P. R. China
Published online: 27 Oct 2010.
To cite this article: Jue Xiao Cai , Zheng Hong Zhou , Kang Ying Li , Chi Hung Yeung & Chu Chi Tang (2002) An Improved
Method for the Resolution of 1,1′-Binaphthalene-2,2′-Diol via a Phosphite Using (-)-Menthol as a Resolving Agent, Phosphorus,
Sulfur, and Silicon and the Related Elements, 177:1, 189-193, DOI: 10.1080/10426500210215
To link to this article: http://dx.doi.org/10.1080/10426500210215
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur and Silicon, 2002, 177:189–193
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
AN IMPROVED METHOD FOR THE RESOLUTION
OF 1,10-BINAPHTHALENE-2,20-DIOL VIA
A PHOSPHITE USING ( )-MENTHOL AS A
RESOLVING AGENT
Jue Xiao Cai,a Zheng Hong Zhou, Kang Ying Li,a
Chi Hung Yeung,b and Chu Chi Tanga
State Key Laboratory of Elemento-Organic Chemistry, Institute
of Elemento-Organic Chemistry, Nankai University, Tianjin,
P. R. China, 300071a and Open Laboratory of Chirotechnology
and Department of Applied Biology and Chemical Technology,
The Hong Kong Polytechnic University, Hong Kong, P. R. Chinab
(Received May 16 2001.)
( )-Menthol reacts with phosphorus trichloride to afford menthyl
phosphorodichloridite 2, which further reacts with racemic 1,10-
binaphthalene-2,20-diol to give phosphite ( )-3 in the presence of tri-
ethylamine. ( )-3 can be easily separated by fractional crystallization
to form the crystal (+)-(S)-3 and the mother liquor ( )-(R)-3. Then both
the crystal and the mother liquor are treated with the AcOH-H2 O to
obtain enantiomeric pure ( )-(S)-1 and (+)-(R)-1 respectively, with
enantiomeric excess up to 99.7%.
Keywords: Fractional crystallization; optically activity; phosphite;
resolution
INTRODUCTION
Optically active 1,10-binaphthalene-2,20-diol has become quite an
important chiral source in different fields of chirotechnology, espe-
13
cially in asymmetric synthesis.1
Its synthesis and resolution have
been extensively studied and various resolution methods have been
reported.14 Among the reported resolution methods, the formation
22
25
of phosphoric acid derivatives,15
boric acid derivatives,23
and
34
inclusion complexes26
are the most important.
Address correspondence to Chu Chi Tang, State Key Laboratory of Elemento-Organic
Chemistry, Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, P. R.
China, 300071.
189

190
J. X. Cai et al.
The resolution based on cyclic phosphoric acid and its derivatives is
the earliest and most widely used method so far because many types of
resolving agents can be utilized and yield both enantiomers with high
enantiomeric purity. However, the main shortcoming of this method is
that cyclic phosphoric acid derivatives have to be cleaved by LiAlH4 to
obtain optically active 1, leading to added expense, strict experiment
conditions, and difficulty to for large scale preparations.
Recently a new convenient method via cyclic borate ester has been
reported. Compared with the phosphoric acid method, LiAlH4 is not
required. But the utility of borane as the starting material restricts its
application in large-scale preparation.
Compound 1 can also react with many chiral amines, such as
alkaloids, to form an inclusion complex containing two diasteromers.
Both enantiomers of 1 can be obtained easily by separation of the
diasteromeric inclusion complexes. This method has proved to be
convenient and can be applied to large scale preparation due to mild
reaction conditions. However, the alkaloid resolving agents are too
expensive.
Herein we report a novel convenient method via phosphite that
proved to be very simple and effective for resolution of racemic 1,10-
binaphthalene-2,20-diol.

Resolution of 1,10-Binaphthalene-2,20-Diol
191
RESULTS AND DISCUSSION
Buono has reported a method via cyclic phosphite using ( )-menthol
as the resolving agent.22 In Buono’s procedure, ( )-menthol reacts
with PCl3 to afford menthyl phosphorodichloridite 2. Then crude 2
is treated with racemic 1 to give corresponding cyclic phosphites
3. Both diasteromerically pure phosphites (+)-(S)-3 and ( )-(R)-3
can be easily separated by fractional crystallization and are fur-
ther oxidized to the corresponding (+)-(S)-4 and ( )-(R)-4, which
are then treated with LiAlH4 to afford ( )-(S)-1 and (+)-(R)-1. This
resolution method employs readily available ( )-menthol as the resolv-
ing agent, providing both enantiomers high optical purity and overall
yield. However, the method suffers from a high price and inconvenience
of LiAlH4, especially for large scale preparations.
Recently we found that AcOH H2O hydrolysis of phosphites (+)-
(S)-3 and ( )-(R)-3 proceeds smoothly in satisfactory yield to give opti-
cally active ( )-(S)-1 and (+)-(R)-1. The experimental results show that
phosphites can be directly hydrolyzed to obtain the target compounds
without further oxidation nor LiAlH4 reduction. These improvements
make the method more practical and easier to perform for large-scale
preparations. The resolution process is shown in Scheme 1.
SCHEME 1
EXPERIMENTAL SECTION
Specific rotations were measured by a Perkin Elmer 241MC polarme-
ter. The e.e. values were determined by HPLC with a chiral column
(Kromasil KR100-100CHI-TBB, Hexane/i-PrOH = 95:5). 1H NMR
(200MHz) data were recorded with a Bruker AC-200 spectrometer using
TMS as an internal standard, 31P NMR (80.1MHz) data were recorded
using 85% H3PO4 as an external standard.
Preparation and Resolution of Phosphites 3
Phosphites 3 were prepared and resolved using Buono’s method.22 From
the crystal fraction, diasteromerically pure (+)-(S)-3 was obtained with

192
J. X. Cai et al.
83.2% yield: m.p. 176 180 C; [ ]2D0 = + 364.8 (c1, CH2Cl2);31 P NMR
151.9 ppm (CDCl3) (single signal); 1H NMR (CDCl3) 0.67 0.97
(m, 5H), 1.41 1.60(m, 5H), 1.65(d, 2H), 2.10(d, H), 2.24 2.44(m, H),
7.24 7.53(m, 8H), 7.67 7.98(m, 4H). The mother liquor containing
( )-(R)-3 was used for the next step.
Preparation of Optically Active 1
To the diasteromerically pure (+)-(S)-3 AcOH (15 mL) and H2O (5 mL)
were added under stirring and heated to reflux to give a clear solution.
After refluxing for an additional 30 min, the solvent was removed un-
der reduced pressure to yield a semisolid residue. After 24 h at room
temperature, large white crystals formed and were collected by filtra-
tion. The white solid separated was washed with toluene (10 mL 2)
and recrystallized from toluene (70 mL) to give 9.3 g of ( )-(S)-1: m.p.
208 210 C; [ ]2D0
(based on starting racemic 1).
=
37.3 (c1, THF); 99.7% e.e.; overall yield is 97.1%
The mother liquor containing ( )-(R)-3 was evaporated to dryness
under reduced pressure to give 25 g of viscous oil. To the residue,
AcOH (15 mL) and H2O (5 mL) were added and heated under re-
flux until a clear solution was obtained. After refluxing for addi-
tional 30 min, the reaction mixture was cooled to room tempera-
ture. After 2 h, powdery crystals were observed. Racemic 1 (3.8 g;
m.p. 216 219 C; [ ]2D0 = 0 , c1, THF) was collected by filtration.
The filtrate was distilled in vacuum to yield a viscous oil. White
crystals formed after 24 h at room temperature. The white crystals
(8.6 g; [ ]2D0 = +35.0 , c1, THF) were collected by filtration and washed
with toluene (7 mL 2), then recrystallized from toluene (50 mL) to give
7.0 g of white crystals (+)-(R)-1: m.p. 208 210 C; [ ]2D0 = +37.2 (c1,
THF); 99.9% e.e.; overall yield is 73.3% (based on starting racemic 1).
ACKNOWLEDGMENTS
Financial support by the National Natural Science Foundation of China
(No. 29872016) and the Hong Kong Polytechnic University ASD Fund
are gratefully acknowledged.
REFERENCES
[1] J. K. Whitesell, Chem. Rev., 89, 1581 (1989).
[2] C. Rosini, L. Franzini, A. Raffaelli, and P. Salvadori, Synthesis 503 (1992).
[3] G. Bringmann, R. Walter, and R. Weirich, Angew. Chem. Int. Ed. Engl. 29, 977
(1990).

Resolution of 1,10-Binaphthalene-2,20-Diol
193
[4] K. Maruoka, T. Itoh, T. Shirasaka, and H. Yamamoto, J. Am. Chem. Soc., 110, 310
(1988).
[5] M. Terada, K. Mikami, and T. Nakai, Tetrahedron Lett., 32, 935 (1991).
[6] K. Maruoka, and H. Yamamoto, J. Am. Chem. Soc., 111, 789 (1989).
[7] J. F. G. A. Jahan, and B. L. Feringa, J. Org. Chem., 55, 4168 (1990).
[8] K. Tomioka, M. Shindo, K. Koga, J. Am. Chem. Soc., 111, 8266 (1989).
[9] T. Mukaiyama, A. Inubushi, S. Suda, R. Hara, and S. Kobayshi,Chem. Lett., 1015
(1990).
[10] J.-M. Bao, W. D. Wulff, and A. L. Rheingold, J. Am. Chem. Soc., 115, 3814 (1993).
[11] M. Terada, Y. Motoyama, and K. Mikami, Tetrahedron Lett., 35, 6693 (1994).
[12] K. Mikami, and S. Matsukawa, Tetrahedron Lett., 35, 3133 (1994).
[13] K. Tanaka, M. Ahn, Y. Watanabe, and K. Fuji, Tetrahedron Asymm., 7, 1771 (1996).
[14] Z.-P. Zhong, C.-J. Cao, and N. Zhu, Youji Huaxue, 19, 448 (1999).
[15] P. Ge, Y.-J. Yi, and C.-N. Zhang, Chinese J. Pharm., 22, 80 (1991).
[16] T. Yasufumi, H.-C. Park, I. Kenji, O. Atsuko, and M. Sotaro, Synthesis, 222 (1990).
[17] J. Jacques, C. Fouquey, and R. Viterbo, Tetrahedron Lett., 4617 (1971).
[18] Z.-L. Xu, W.-H. Huang, L. Wu, and S.-K. Xie, Youji Huaxue, 6, 475 (1985).
[19] B. Q. Gong, W.-Y. Chen, and B.-F. Hu, J. Org. Chem., 56, 423 (1991).
[20] M. Wang, S.-Z. Liu, J. Liu, and B.F. Hu, J. Org. Chem., 60, 7364 (1995).
[21] D. Fabbri, G. Delogu, and O. De Lucchi, J. Org. Chem., 58, 1748 (1993).
[22] J.-M. Brunel, and G. Buono, J. Org. Chem., 58, 7313 (1993).
[23] Z.-X. Shan, G.-P. Wang, B. Duan, and D.-J. Zhao, Tetrahedron Asymm., 7, 2847
(1996).
[24] Z.-X. Shan, F.-Y. Chen, S.-W. Huang, D.-J. Zhao, and Z.-Z. Jing, Tetrahedron
Asymm., 8, 1175 (1997).
[25] Z.-X. Shan, Y. Xiong, and D.-J. Zhao, Tetrahedron, 55, 3893 (1999).
[26] M. Kawashima, and A. Hirayama, Chem. Lett., 2299 (1990).
[27] M. Kawashima, and R. Hirata, Bull. Chem. Soc. Jpn., 66, 2002 (1993).
[28] K. Tanaka, T. Okada, and F. Toda, Angew. Chem. Int. Ed. Engel., 32, 1147 (1993).
[29] F. Toda, K. Tanaka, Z. Stein, and Z. Goldberg, J. Org. Chem., 59, 5748 (1994).
[30] Q.-S. Hu, D. Vitharana, and L. Pu, Tetrahedron Asymm., 6, 2123 (1995).
[31] D.-W. Cai, D. L. Hughes, T. R. Verhoeven, and P. J. Reider, Tetrahedron Lett., 36,
7991 (1995).
[32] M. Periasamy, B. Prasad, and K. Reddy, Tetrahedron Asymm., 6, 341 (1995).
[33] L. Verkatraman, Tetrahedron Asymm., 7, 2471 (1996).
[34] M. Periasamy, L. Venkatraman, and K. R. Justin Thomas, J. Org. Chem., 62, 4302
(1997).