Facile synthesis of enantiopure 1,1'-binaphthyl-2,2'-dicarboxylic acid via lipase-catalyzed kinetic resolution

Article abstract of DOI:10.1016/S0957-4166(99)00555-8

Enantiopure 1,1'-binaphthyl-2,2'-dicarboxylic acids (R)-1 and (S)-1 have been synthesized through the lipase-catalyzed kinetic resolution of the racemic 2,2-bis(hydroxymethyl)-1,1'-binaphthyl (±)-2 and subsequent oxidation of the hydroxymethyl groups. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0957-4166(99)00555-8

TETRAHEDRON:
ASYMMETRY
Pergamon
Tetrahedron: Asymmetry 10 (1999) 4763–4768
0
0
Facile synthesis of enantiopure 1,1 -binaphthyl-2,2 -dicarboxylic
acid via lipase-catalyzed kinetic resolution
∗
Toshiyuki Furutani, Masanori Hatsuda, Ritsuo Imashiro and Masahiko Seki
Product & Technology Development Laboratory, Tanabe Seiyaku Co., Ltd, 3-16-89, Kashima, Yodogawa-ku, Osaka 532-8505,
Japan
Received 1 November 1999; accepted 1 December 1999
Abstract
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0
Enantiopure 1,1 -binaphthyl-2,2 -dicarboxylic acids (R)-1 and (S)-1 have been synthesized through the lipase-
0
catalyzed kinetic resolution of the racemic 2,2-bis(hydroxymethyl)-1,1 -binaphthyl (±)-2 and subsequent oxidation
of the hydroxymethyl groups. © 2000 Elsevier Science Ltd. All rights reserved.
1. Introduction
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0
Enantiopure 1,1 -binaphthyl-2,2 -dicarboxylic acids 1 have received considerable attention as chiral
1
building blocks for such valuable compounds as chiral catalysts for asymmetric epoxidation. The con-
ventional method to prepare 1, however, requires toxic brucine or quinine for the resolution. To remove
2
3
these drawbacks resolutions of (±)-1 via 1-phenylethylamide and diastereoselective Ullmann reactions
with 2,2 -dihydroxy-1,1 -binaphthyl or an oxazoline as the chiral auxiliary have been reported.4b
Although excellent yields and strereoselectivities were accomplished, they are not completely satisfac-
tory for a practical use because they require a stoichiometric amount of the covalently-bonded chiral
auxiliary. Another synthesis of enantiopure 1 through palladium-catalyzed methoxycarbonylation of a
0
0
4a
0
0
5
ditriflate of 2,2 -dihydroxy-1,1 -binaphthyl was reported. However, it requires an expensive starting
material and reagents such as enantiopure 2,2 -dihydroxy-1,1 -binaphthyl and trifluromethanesulfonic
anhydride. A conceptually attractive catalytic asymmetric synthesis of enantiopure 2,2 -dimethyl-1,1 -
binaphthyl, a possible precursor of 1, has been reported. While it should provide the best approach
0
0
0
0
6
to 1, further investigation on an economical synthesis of the chiral ferrocenyl phosphine ligand or
development of an inexpensive alternative is needed for a practical large-scale preparation. We report
herein a novel and facile synthesis of 1 by means of the lipase-catalyzed kinetic resolution of the racemic
0
0
2
,2 -bis(hydroxymethyl)-1,1 -binaphthyl (±)-2.
∗
Corresponding author. Tel: +81 6 6300 2456; fax: +81 6 6300 2816; e-mail: m-seki@tanabe.co.jp
0
957-4166/99/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S0957-4166(99)00555-8
tetasy 3190

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T. Furutani et al. / Tetrahedron: Asymmetry 10 (1999) 4763–4768
2. Results and discussion
The enzymatic resolution of biaryls carrying axial chirality has so far been rarely described except
0
7
for an enantioselective reduction of racemic 2-formyl-1,1 -binaphthyls by baker’s yeast, and lipase-
0
0
8
catalyzed asymmetric acylation or hydrolysis of racemic 2,2 -dihydroxy-1,1 -binaphthyl derivatives.
0
0
We first attempted the enzymatic resolution of racemic 1,1 -binaphthyl-2,2 -dicarboxylic acid (±)-1.
However, all attempts failed even in the non-selective enzymatic esterification of (±)-1. The results are
in good accordance with the reported observation in that an aromatic carboxylic acid cannot be a substrate
9
for the enzymatic acyl-transfer reactions.
0
0
10
The kinetic resolution of 1,1 -bis(hydroxymethyl)-2,2 -binaphthyl (±)-2, a possible precursor of 1,
was thus investigated (Scheme 1
Scheme 1. a: Lipase SM, vinyl hexanoate, tert-BME, 30°C, 45 h; b: Lipase CE, vinyl hexanoate, tert-BME, 30°C, 24 h
)
as an alternative. The compound (±)-2 was prepared in four steps from 1-bromo-2-
10b
methylnaphthalene according to the reported procedure.
Several enzymes were tested for the
asymmetric acylation of (±)-2 with vinyl acetate used as an acyl donor in tert-butyl methyl ether
1
1
(
tert-BME). Among them, lipase SM (Serratia marcescens, lyophilized powder, Tanabe Seiyaku Co.,
Ltd) was found to catalyze selectively the acylation of (S)-2 to leave virtually enantiopure diol (R)-2
0 0
>99% e.e.) in 29% yield. In contrast to the lipase-catalyzed monoacylation of 2,2 -dihydroxy-1,1 -
(
8
b
binaphthyl, mono- and diacylation took place in the reaction to give the monoacylated (S)-2 in 60%
yield with poor selectivity (43% e.e.) along with diacylated compound in 10% yield (29% e.e.). The
yield of (R)-2 was improved when vinyl hexanoate was employed as the acyl donor to give (R)-2 (>99%
e.e.) in 41% yield.
The oxidation of the hydroxymethyl groups of (R)-2 to the dicarboxylic acid (R)-1 was then investigat-
ed. The reported method to prepare an aldehyde 3 requires three steps involving the treatment with toxic

T. Furutani et al. / Tetrahedron: Asymmetry 10 (1999) 4763–4768
4765
12
silver nitrate; direct oxidation of 2 to 3 using dinitrogen tetroxide failed. We found that treatment of the
enantiomerically pure diol (R)-2 with manganese(IV) oxide in toluene at ambient temperature provided
an aldehyde (R)-3 in 99% yield. The aldehyde (R)-3 was treated with sodium chlorite in the presence of
hydrogen peroxide to give the desired dicarboxylic acid (R)-1 (>99% e.e.) in 68% yield (Scheme 2).
2 2 2 2 2 4 2 3
Scheme 2. c: MnO , toluene; d: NaClO , H O , NaH PO , H O, CH CN
Further screening of the enzyme was required in order to obtain the antipode (S)-1 because the acylated
S)-2 of high enantiomeric purity was not obtained in the lipase SM-catalyzed asymmetric acylation of
±)-2. As a result of the screening, lipase CE (Humicola sp., Amano Pharmaceutical Co., Ltd) was found
(
(
to selectively acylate (R)-2, leaving (S)-2 in >99% e.e. and 45% yield. The enantiomerically pure diol
(S)-2 was subjected to the two-step oxidation to provide the corresponding dicarboxylic acid (S)-1 (>99%
e.e.) in 70% yield.
0
0
In conclusion, a facile synthesis of enantiopure 1,1 -binaphthyl-2,2 -dicarboxylic acids (R)-1 and (S)-1
was accomplished. Either enantiomer of 1 can be prepared by proper choice of the enzyme, i.e. lipase
SM for the R-isomer and lipase CE for the S-isomer. The present synthesis is advantageous in terms of
simple operations and high yields of the enzymatic resolutions without the use of any toxic resolving
agents.
3. Experimental
Melting points were measured using a Yamato melting point apparatus and are uncorrected. Infrared
spectra were taken by the use of a Perkin–Elmer 1600 infrared spectrometer and are reported as
−1
1
λmax(cm ). H NMR were recorded on a Bruker AC-200 (200 MHz) spectrometer and are reported
in δ values. Mass spectra were taken by using a HITACHI M-2000A mass spectrometer at an ionizing
potential of 70 eV. Microanalyses were performed by a Perkin–Elmer 2400 Series II CHNS/O analyser.
−1
Optical rotations were measured on a Perkin–Elmer 243 polarimeter, and [α] -values are given in 10
D
2
−1
deg cm g .
Thin-layer chromatography was performed on E. Merck 0.25 mm precoated glass backed plates
60 F254). Development was accomplished using either 20% phosphomolybdic acid in ethanol–heat
(
or visualized by UV light where feasible. Flash chromatography was accomplished using Kieselgel
0 (230–400 mesh, E. Merck). Lipase CE was a generous gift from Amano Pharmaceutical Co., Ltd.
Manganese(IV) oxide was purchased from Tosoh Corporation and used without further purification.
6

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T. Furutani et al. / Tetrahedron: Asymmetry 10 (1999) 4763–4768
0
0
3
.1. (R)-2,2 -Bis(hydroxymethyl)-1,1 -binaphthyl (R)-2 (acyl donor: vinyl acetate)
11
Into a mixture of (±)-2 (1.0 g, 3.2 mmol) in tert-BME (100 mL) were added lipase SM (lyophilized
powder, 1.0 g), vinyl hexanoate (9.3 g, 0.11 mol) and water (50 µl), and the mixture was stirred at 30°C
for 24 h. The mixture was filtered and the filtrate was evaporated in vacuo. The residue was purified
by silica gel column chromatography (n-hexane:AcOEt, 4:1) to give (R)-2 (290 mg, 29%) (>99% e.e.),
monoacetyl (S)-2 (679 mg, 60%) and diacetyl (S)-2 (127 mg, 10%). (R)-2: colorless crystals; mp 170°C
1
0a
−1
1
(
4
7
lit. 168–170°C); IR (KBr) νmax 3247, 3040, 2930, 2875 cm ; H NMR (CDCl ) δ 3.87 (brs, 2H),
3
.09 (d, J=12 Hz, 2H), 4.36 (d, J=12 Hz, 2H), 7.00–7.04 (m, 2H), 7.18–7.26 (m, 2H), 7.40–7.49 (m, 2H),
.74–7.78 (m, 2H), 7.90–8.01 (m, 4H). MS m/z: 314 (M ); [α]D +68.5 (c 1.0, CHCl ) (lit. [α]D
67.9 (c 1.06, acetone)). Anal. calcd for C H O : C, 84.05; H, 5.77. Found: C, 83.80; H, 5.66; >99%
+
25
10a
23
3
+
2
2
18
2
e.e. (HPLC: Chiralcel OD (Daicel), n-hexane:ethanol, 60:1, 1 mL/min, 30°C, 224 nm); monoacetyl (S)-
0
0
2
1
7
((S)-2-acetoxymethyl-2 -hydroxymethyl-1,1 -binaphthyl): colorless oil; IR (Nujol) ν
3420, 3058,
max
−1 1
738 cm ; H NMR (CDCl ) δ 1.91 (s, 3H), 4.30 (s, 2H), 4.70–4.96 (m, 2H), 7.00–7.10 (m, 2H),
.20–7.30 (m, 2H), 7.40–7.51 (m, 2H), 7.64–7.69 (m, 1H), 7.81–8.01 (m, 5H); MS m/z: 356 (M ); 43%
3
+
e.e. (HPLC: Chiralcel OD (Daicel), n-hexane:ethanol, 60:1, 1 mL/min, 30°C, 224 nm); diacetyl (S)-
0
0
−1
1737 cm ; H NMR
max
1
2
(
2
((S)-2,2 -bis(acetoxymethyl)-1,1 -binaphthyl): colorless oil; IR (Nujol) ν
CDCl ) δ 1.85 (s, 6H), 4.74–4.89 (m, 4H), 7.04–7.08 (m, 2H), 7.21–7.29 (m, 2H), 7.43–7.51 (m,
H), 7.65–7.70 (m, 2H), 7.91–8.03 (m, 4H); MS m/z: 398 (M ); 29% e.e. (The e.e. was determined
by conversion to 2,2 -bis(hydroxymethyl)-1,1 -binaphthyl by the treatment with NaOMe in methanol
3
+
0
0
followed by HPLC analysis (HPLC: Chiralcel OD (Daicel), n-hexane:ethanol, 60:1, 1 mL/min, 30°C,
224 nm).)
0
0
3
.2. (R)-2,2 -Bis(hydroxymethyl)-1,1 -binaphthyl (R)-2 (acyl donor: vinyl hexanoate)
7
Into a mixture of (±)-2 (200 mg, 0.64 mmol) in tert-BME (17 mL) were added lipase SM (lyophilized
powder, 40 mg), vinyl hexanoate (2.8 g, 16.4 mmol) and water (20 µl), and the mixture was stirred at
0°C for 45 h. The mixture was filtered and the filtrate was evaporated in vacuo. The residue was purified
3
by silica gel column chromatography (n-hexane:AcOEt, 4:1) to give (R)-2 (82 mg, 41%) (>99% e.e.) in
1
colorless crystals. Mp, IR, H NMR and MS spectra were identical with those of (R)-2 obtained above;
optical purity: >99% e.e. (HPLC: Chiralcel OD (Daicel), n-hexane:ethanol, 60:1, 1 mL/min, 30°C, 224
nm).
0
0
3
.3. (S)-2,2 -Bis(hydroxymethyl)-1,1 -binaphthyl (S)-2
Using the same procedure as for the synthesis of (R)-2 (experiment 3.2.) except using lipase CE and
1
the reaction period of 24 h, the compound (S)-2 was obtained in 45% yield. Mp 169°C; IR, H NMR
and MS spectra of (S)-2 were identical with those of (R)-2; [α]D25 −70.7 (c 1.05, CHCl ). Anal. calcd
3
for C H O : C, 84.05; H, 5.77. Found: C, 83.69; H, 5.69; >99% e.e. (HPLC: Chiralcel OD (Daicel),
2
2
18
2
n-hexane:ethanol, 60:1, 1 mL/min, 30°C, 224 nm).
0
0
3
.4. (R)-2,2 -Diformyl-1,1 -binaphthyl (R)-3
A mixture of (R)-2 (500 mg, 1.6 mmol) in toluene (10 mL) was added MnO (5 g) and the mixture
2
was stirred at 25°C for 17 h. The mixture was filtered through Celite and the filtrate was evaporated in
−1 1
vacuo to give (R)-3 (486 mg, 99%) in colorless oil. IR (Nujol) νmax 1692, 1608, 1594 cm ; H NMR

T. Furutani et al. / Tetrahedron: Asymmetry 10 (1999) 4763–4768
4767
(
CDCl ) δ 7.24 (dd, J=0.5, 8.4 Hz, 2H), 7.37 (ddd, J=1.3, 7.0, 8.3 Hz, 2H), 7.64 (ddd, J=1.3, 6.8, 7.8
3
Hz, 2H), 8.00 (d, J=8.2 Hz, 2H), 8.13 (d, J=8.7 Hz, 2H), 8.22 (d, J=8.2 Hz, 2H), 9.62 (d, J=0.8 Hz, 2H).
MS m/z: 310 (M ); [α]D +3.2 (c 1.04, CHCl3).
+
25
0
0
3
.5. (S)-2,2 -Diformyl-1,1 -binaphthyl (S)-3
Using the same procedure for the synthesis of (R)-3, the compound (S)-3 was obtained in quantitative
1
yield as a colorless oil which showed the same IR, H NMR and MS spectra as the compound (R)-3
2
5
except specific rotation: [α]D −3.1 (c 1.01, CHCl3).
0
0
3
.6. (R)-1,1 -Binaphthyl-2,2 -dicarboxylic acid (R)-1
Into a mixture of (R)-3 (1 g, 3.2 mmol), NaH PO ·H O (260 mg, 1.9 mmol) and H O (0.8 mL)
2
4
2
2
2
in CH CN (10 mL) was added dropwise NaClO (1 g, 11 mmol) in H O (10 mL) at 25°C for 15 min
3
2
2
and the mixture was stirred at 40°C for 20 min. After adding Na SO (60 mg, 0.5 mmol), the mixture
2
3
was evaporated in vacuo. The mixture was acidified by adding 2N HCl and extracted with AcOEt. The
extracts were washed with water, dried over anhydrous MgSO and evaporated in vacuo. The crystals
4
formed were collected by adding n-hexane to afford (R)-1 (755 mg, 68%) in colorless crystals. Mp 200°C
2
b
−1
1
(
7
1
dec.) (lit. 197–199°C (dec.)); IR (KBr) νmax 1696 cm ; H NMR (DMSO-d ) δ 7.04–7.26 (m, 4H),
6
+
25
.44–7.53 (m, 4H), 7.89–8.00 (m, 4H), 8.11–8.15 (m, 2H); MS m/z: 342 (M ); [α]
+127.0 (c 1.0,
546
N NaOH) (lit.2 [α]546 +127.0 (c 1.0, 1N NaOH)). Anal. calcd for C H O : C, 77.18; H, 4.12.
b
25
22
14
4
Found: C, 77.15; H, 3.99; >99% e.e. (HPLC: Chiralcel OD (Daicel), n-hexane:ethanol:trifluoroacetic
acid, 90:10:0.1, 1 mL/min, 35°C, 254 nm).
0
0
3
.7. (S)-1,1 -Binaphthyl-2,2 -dicarboxylic acid (S)-1
Using the same procedure for the synthesis of (R)-1, the compound (S)-1 was obtained in 70% yield
1
from (S)-3 as colorless crystals which showed the same mp, IR, H NMR and MS spectra as the
compound (R)-1 except specific rotation: [α]54625 −127.0 (c 1.0, 1N NaOH) (lit. [α]546 −127.0
2b
25
(
c 1.0, 1N NaOH)).
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quaternary ammonium salt with l-ephedrin:1 (a) Bringmann, G.; Hinrichs, J. Tetrahedron: Asymmetry 1997, 8, 4121–4126.
10a
0b
(b) Maigrot, N.; Mazaleyrat, J.-P. Synthesis 1985, 317–320.
1
1
1. Matsumae, H.; Shibatani, T. J. Ferment. Bioorg. 1994, 77, 152–158.
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