Lipase-catalyzed esterification of a (±)-2,3-di(arylmethyl)-1,4- butanediol and its application to the synthesis of (S,S)-(+)-hinokinin

Article abstract of DOI:10.1081/SCC-200051037

Racemic trans-2,3-di[(3,4-methylenedioxy)benzyl]-1,4-butanediol (dihydrocubebin) 6 was enantioselectively esterified using lipases as catalysts with vinyl acetate. Optically active (S,S)-1,4-butanediol 6 obtained was selectively oxygenated with a Fetizon reagent, affording (S,S)-(+)-hinokinin 9 in a high yield.

Full text of DOI:10.1081/SCC-200051037

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Lipase‐Catalyzed Esterification of a
(±)‐2,3‐Di(Arylmethyl)‐1,4‐butanediol
and Its Application to the Synthesis of
(S,S)‐(+)‐Hinokinin
Toshiaki Morimoto a , Hazuki Nagai a & Kazuo Achiwa a
a School of Pharmaceutical Sciences , University of Shizuoka , Shizuoka,
Japan
Published online: 20 Aug 2006.
To cite this article: Toshiaki Morimoto , Hazuki Nagai & Kazuo Achiwa (2005) Lipase‐Catalyzed Esterification
of a (±)‐2,3‐Di(Arylmethyl)‐1,4‐butanediol and Its Application to the Synthesis of (S,S)‐(+)‐Hinokinin, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 35:6,
857-865, DOI: 10.1081/SCC-200051037
To link to this article: http://dx.doi.org/10.1081/SCC-200051037
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Synthetic Communicationsw, 35: 857–865, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1081/SCC-200051037
Lipase-Catalyzed Esterification of a
(+)-2,3-Di(Arylmethyl)-1,4-butanediol
and Its Application to the Synthesis of
(S,S)-(1)-Hinokinin
Toshiaki Morimoto, Hazuki Nagai, and Kazuo Achiwa
School of Pharmaceutical Sciences, University of Shizuoka,
Shizuoka, Japan
Abstract: Racemic trans-2,3-di[(3,4-methylenedioxy)benzyl]-1,4-butanediol (dihy-
drocubebin) 6 was enantioselectively esterified using lipases as catalysts with vinyl
acetate. Optically active (S,S)-1,4-butanediol 6 obtained was selectively oxygenated
with a Fetizon reagent, affording (S,S)-(þ)-hinokinin 9 in a high yield.
Keywords: Lipase, esterification, enantioselectivity, lignan, dihydrocubebin,
hinokinin
Among various types of strategies for enantioselective transformations based
on chemical and biological procedures, an enzymatic transformation is one
of the most efficient and practical ones for preparing optically active
compounds.[1] In a previous communication,[2] we reported a facile
synthesis of optically active 1,4-diol derivatives (2,5-hexanediol, its monoace-
tate, and diacetate) by lipase-catalyzed esterification of a mixture of racemic
and meso 1,4-diols with vinyl acetate. The chiral 2,5-hexanediol is a useful
key compound for preparing several optically active 2,5-substituted five-
membered heterocyclic compounds such as pyrrolidines[3] and phospho-
lanes.[4] On the other hand, lipase-catalyzed esterification of 1,4-butanediols
Received in Japan October 20, 2004
Address correspondence to Toshiaki Morimoto, School of Pharmaceutical
Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan. E-mail:
morimtt@u-shizuoka-ken.ac.jp

858
T. Morimoto, H. Nagai, and K. Achiwa
bearing 2,3-di(arylmethyl) groups has not been utilized for the synthesis of
optically active, useful compounds, and only a few applications of lipase-
catalyzed reactions to the synthesis of optically active lignans have
appeared.[5] We report herein enantioselective esterification (optical
resolution) of a racemic 1,4-butanediol, (+)-2,3-bis[3,4-(methylenedioxy)
benzyl]-1,4-butanediol (dihydrocubebin) 6 using lipases, and its application
to the enantioselective synthesis of a chiral lignan, (S,S)-2,3-bis[(3,4-methyl-
enedioxy)benzyl]butyrolactone [(þ)-hinokinin] 9.
A substrate 1,4-diol, racemic 2,3-bis[3,4-(methylenedioxy)benzyl]-1,
4-butanediol [(+)-dihydrocubebin] 6 was prepared from piperonal 1 by a
route as shown in Scheme 1. Piperonal 1 was condensed with diethyl
succinate in the presence of sodium ethoxide (Stobbe condensation[6]),
yielding arylidenesuccinic acid monoester 2. After conversion of the car-
boxylic group to the potassium salt, selective reduction of the ester group
was carried out with calcium borohydride prepared in situ from calcium
chloride and sodium borohydride,[7] yielding the corresponding b-arylidene-
butyrolactone 3 (85%). Catalytic hydrogenation of 3 was carried out with
Pd on carbon, affording the corresponding b-arylmethylbutyrolactone 4
(78%). The lactone 4 was allowed to react with piperonal 1 in the presence
of LDA, and succeeding hydrogenolysis of an a-(a0-hydroxy)arylmethyl
derivative thus obtained was carried out using a catalyst of Pd(OH)2 on
carbon, which yielded racemic trans-2,3-bis[(3,4-methylenedioxy)benzyl]
butyrolactone ((+)-hinokinin) 5 in high overall yield (90%). The lactone 5
was reduced with lithium aluminum hydride, affording racemic 2,3-bis[3,4-
(methylenedioxy)benzyl]-1,4-butanediol ((+)-dihydrocubebin) 6 (97%).
Lipase-catalyzed esterification of 6 was carried out with excess vinyl
acetate (without solvent) at room temperature (rt) in the presence of various
lipases (lipases MY-30, AY, OF, CCL, AH, QL, and PL). The results are sum-
marized in Table 1. The products (diacetate 7, monoacetate 8, and diol 6) were
Scheme 1.

+-2,3-Di(Arylmethyl)-1,4-butanediol
859
Table 1. Lipase-catalyzed esterification of (+)-dihydrocubebin 6a
Diacetate 7,
C.Y. (%),b
ee (%)c
Monoacetate
8, C.Y. (%),b
ee (%)c
Time
(h)
Diol 6, C.Y.
(%),b ee (%)c
Entry
Lipase
1
2
3
4
5
6
7
lipase MY-30
lipase AY
lipase OF
lipase CCL
lipase AH
lipase QL
lipase PL
96
48
96
72
15
20
7
29, 64 (R,R)
47, 64 (R,R)
15, 11 (S,S)
27, 62 (R,R)
23, 54 (S,S)
57, 33 (S,S)
41, 36 (S,S)
53, 22 (S,S)
48, 49 (S,S)
65, 6 (R,R)
54, 12 (S,S)
65, 23 (R,R)
40, 48 (R,R)
52, 28 (R,R)
13, 98 (S, S)
3, 96 (S, S)
18, 12 (S, S)
15, 94 (S, S)
7, .99 (S, S)
—
—
aAll reactions were carried out by stirring a mixture of substrate 6 (1 mmol) and
lipase (300 mg) in vinyl acetate (5 mL).
bIsolated yield by preparative TLC.
cDetermined by HPLC analysis (CHIRALCEL OD-H) of diol 6 (after hydrolysis
of 7 and 8).
easily separated by silica-gel chromatography. The ee value and the absolute
configuration of each product were determined by HPLC (CHIRALCEL OD-
H) of the diol (after hydrolysis in case of the acetates) and by comparing the
sign of the specific rotation of the diol with reported data,[8] respectively.
Although all the lipases did not show high efficiency in enantioselectivity of
the esterification of 6 in contrast to our previous results with 2,5-hexanediol,[2]
lipases MY-30, AY, CCL, and AH (entries 1, 2, 4, and 5) gave relatively better
results than others. Relative acetylation rates and the absolute configuration of
the major enantiomers of diacetate 7, monoacetate 8, and diol 6 are depicted in
Figure 1. Optically active diol (S, S)-6 with high ee was isolated although the
yield was not high [entry 1: 98% ee, 13% (26% theoretical) yield; entry 4: 94%
ee, 15% (30% theoretical) yield].
Selective mono-oxygenation of diol (S,S)-6 was easily carried out with
Fetizon reagent[9] (silver carbonate-Celite), yielding (S,S)-(þ)-hinokinin 9
in high yield (Scheme 2). The absolute configuration was determined by
comparing the sign of the specific rotation with reported data [(R,R)-(2)-
hinokinin].[10]

860
T. Morimoto, H. Nagai, and K. Achiwa
Figure 1. Relative acetylation rates and the absolute configuration of major
enantiomers.
In summary, we have carried out lipase-catalyzed esterification of a 1,4-
diol, racemic 2,3-bis[3,4-(methylenedioxy)benzyl]-1,4-butanediol [(+)-dihy-
drocubebin] with vinyl acetate, and found that this diol is a relatively difficult
substrate for enantioselective esterification. However, a highly enantiomeri-
cally rich diol, (S,S)-dihydrocubebin, was able to be isolated. Oxygenation
with Fetizon reagent gave (S,S)-(þ)-hinokinin in high yield.
EXPERIMENTAL
Melting points (mp) were determined on a micro hot-stage apparatus and are
1
uncorrected. H- and 13C-NMR spectra were recorded on a JEOL JNM-EX
Scheme 2.

+-2,3-Di(Arylmethyl)-1,4-butanediol
861
270 spectrometer in CDCl3 solution at 270 and 67.8 MHz, respectively.
Chemical-shift values are expressed in ppm based on tetramethylsilane. IR
spectra were measured on a JASCO IR-810 spectrometer. Optical rotations
were measured on a JASCO DIP-140 digital polarimeter. Mass spectra were
measured on JEOL-JMS-AX 505 W (GC-MS) and JEOL-JMS-SX 102
(FAB-MS) instruments. High-performance liquid chromatography (HPLC)
was carried out with a Waters 600E equipped with a column CHIRALCEL
OD-H (2-propanol/hexane). Column chromatographic isolation was
conducted using silica gel (Kieselgel 60, 70–230 mesh, Merck). Kieselgel
60 F254 plates (Merck) were employed for preparative TLC. In general, all
organic reagents were used as purchased. Lipases were supplied by Amano
Pharmaceutical Co., Ltd. and Meito Sangyo Co., Ltd.; lipases (supported on
Celite): MY-30 (Candida rugosa), AY (Candida rugosa), OF (Candida
rugosa), CCL (Candida rugosa), AH (Pseudomonas sp.), QL (Alcaligenes
sp.), and PL (Alcaligenes sp.). THF was distilled over sodium metal/benzo-
phenone ketyl and used as peroxide-free.
(+)-3-[3,4-(Methyleledioxy)benzyl]butyrolactone 4
To a stirred and ice-cooled solution of (E)-4-[3,4-(methylenedioxy)phenyl]-3-
ethoxycarbonyl-3-butenoic acid 2 (2.0 g, 7.2 mmol) in ethanol (15 mL) was
added a solution of 2 M KOH (4 mL), and the mixture was stirred for
15 min and concentrated in vacuo. The residue was dissolved in ethanol
(100 mL), stirred, and cooled in an ice bath. To the stirred solution were
added calcium chloride (2.3 g, 21 mmol), sodium borohydride (1.06 g,
28 mmol), and a solution of KOH (170 mg, 3 mmol) in ethanol (15 mL), and
the mixture was stirred at rt for 3 h. After ice-cooling, the reaction mixture
was acidified to pH 1 with 6M HCl and stirred at rt for 0.5 h. After concen-
tration, the residue was extracted with ether (200 mL) and the extract was
washed successively with water and brine, dried over MgSO4, and concen-
trated in vacuo. The residue was purified by silica gel column chromatography
(hexane/AcOEt ¼ 9/1), affording (E)-3-[3,4-(methylenedioxy)benzylidene]-
butyrolactone 3 (1.34 g, 85%) as crystals, mp 137–1408C. IR (nujol) cm21
:
1
1740 (C55O). H-NMR (CDCl3) d: 3.40 (s, 2H), 4.99 (s, 2H), 5.98 (s, 2H),
6.36 (s, 1H), 6.73 (d, J ¼ 8.9 Hz, 1H), 6.74 (s, 1H), 6.82 (d, J ¼ 8.9 Hz,
1H). 13C-NMR (CDCl3) d: 33.1, 73.3, 101.3, 107.9, 108.6, 122.5, 123.8,
127.9, 129.8, 147.2, 148.0, 175.2. To a solution of 3 (218 mg, 1.0 mmol)
was added 5% Pd on carbon (20 mg). The mixture was stirred at rt
overnight under an atmosphere of hydrogen (1 atm). After filtration and con-
centration, the residue was subjected to bulb-to-bulb distillation under reduced
pressure, affording 4 (171 mg, 78%) as a liquid [bp 270–3008C (bath temp.)/
1
15 mmHg]. IR (neat) cm21: 1770 (C55O). H-NMR (CDCl3) d: 2.24 (dd,
J ¼ 6.9, 17.5 Hz, 1H), 2.56 (dd, J ¼ 7.9, 17.5 Hz, 1H), 2.68 (m, 2H), 2.80

862
T. Morimoto, H. Nagai, and K. Achiwa
(m, 1H), 3.98 (dd, J ¼ 5.9, 9.2 Hz, 1H), 4.30 (dd, J ¼ 6.9, 9.2 Hz, 1H), 5.91
(s, 2H), 6.59 (d, J ¼ 7.9 Hz, 1H), 6.64 (s, 1H), 6.73 (d, J ¼ 7.9 Hz, 1H).
13C-NMR (CDCl3) d: 34.0, 37.2, 38.5, 72.5, 101.0, 108.4, 108.9, 121.6,
132.0, 146.3, 147.9, 176.9. Anal. Calcd for C12H12O4: C, 65.44; H, 5.49.
Found: C, 65.11; H, 5.49. Spectral data were well consistent with those
reported previously.[5,11]
(+)-2,3-Bis[(3,4-methylenedioxy)benzyl]butyrolactone
((+)-Hinokinin) 5
To a stirred and cooled (2308C) solution of lithium diisopropylamide (LDA),
which was prepared from diisopropylamine (121 mg, 1.2 mmol) and n-butyl-
lithium (1.7 M in hexane, 0.70 mL, 1.2 mmol) in THF (3 mL) under Ar, was
added a solution of 4 (220 mg, 1.0 mmol) in THF (1 mL) and the mixture
was stirred for 0.5 h. Then a solution of piperonal 1 (150 mg, 1.0 mmol) in
THF (1 mL) was added at the same temperature, and the stirring was
continued for 0.5 h. Saturated NH4Cl solution (2 mL) was added and the
mixture was stirred at rt for 0.5 h. The organic layer was extracted with
ether (30 mL). The extract was washed with brine, dried over MgSO4, and
concentrated in vacuo. The residue was purified by preparative TLC
(hexane/AcOEt ¼ 1/1), affording a crude diastereomeric mixture of trans-
2-fa-hydroxy-3,4-(methylenedioxy)benzyl-3-[3,4-(methylenedioxy)benzyl]-
butyrolactone (358mg, 97%) as an oil. Crude trans-2fa-hydroxy-3,4-(methy-
lenedioxy)benzyl-3-[3,4-(methylenedioxy)benzyl]g-butyrolactone (370 mg,
1.0 mmol) was dissolved in a mixed solvent of acetic acid (15 mL) and THF
(15 mL), and 20% Pd(OH)2 on carbon (100 mg) was added. The mixture
was stirred at rt overnight under an atmosphere of hydrogen (1 atm). After fil-
tration and concentration, the residue was purified by preparative TLC
(hexane/AcOEt ¼ 1/1), affording 5 (320 mg, 90%) as a solid. Recrystalliza-
tion from EtOH gave analytically pure 5 as prisms; mp 104–1058C. IR (nujol)
1
cm21: 1760 (C55O). H-NMR (CDCl3) d: 2.50 (m, 4H), 2.83 (dd, J ¼ 6.9,
14.2 Hz, 1H), 3.00 (dd, J ¼ 4.8, 14.2 Hz, 1H), 3.85 (dd, J ¼ 7.0, 9.2 Hz,
1H), 4.12 (dd, J ¼ 6.6, 9.2 Hz, 1H), 5.94 (s, 4H), 6.45–6.75 (m, 6H). 13C-
NMR (CDCl3) d: 34.8, 38.3, 41.3, 46.5, 71.1, 101.0, 108.2, 108.3, 108.8,
109.5, 121.5, 122.2, 131.4, 131.7, 146.3, 146.5, 147.9, 178.4. GC-MS (EI)
m/z: 354 (Mþ). Spectral data were consistent with those reported
previously.[12]
(+)-2,3-Bis[3,4-(methylenedioxy)benzyl]-1,4-butanediol
((+)-Dihydro-cubebin) 6
To a stirred and ice-cooled solution of lithium aluminun hydride (520 mg,
13.6 mmol) in THF was added a solution of (+)-hinokinin 5 (2.4 g,

+-2,3-Di(Arylmethyl)-1,4-butanediol
863
6.8 mmol) in THF (15 mL), and the stirring was continued at 08C for 0.5 h and
then at rt for 1 h. To the reaction mixture were added AcOEt (3 mL), dichloro-
methane (70 mL), and a solution of 5% NaOH (7 mL). After stirring for 1 h at
rt, the mixture was filtered through Celite, and the filtrate was concentrated in
vacuo. The residue was purified by silica-gel column chromatography
(hexane/AcOEt ¼ 4/1ꢀ1/2), affording 6 (2.34 g, 97%) as crystals; mp 103–
1
1058C. IR (nujol) cm21: 3250 (OH). H-NMR (CDCl3) d: 1.83 (br, 2H), 2.59
(dd, J ¼ 5.9, 13.5 Hz, 2H), 2.72 (dd, J ¼ 8.6, 13.5 Hz, 2H), 3.65 (m, 2H), 3.75
(br, 2H), 3.93 (s, 2H), 5.90 (s, 4H), 6.59 (d, J ¼ 7.7 Hz, 2H), 6.63 (s, 2H),
6.75 (d, J ¼ 7.7 Hz, 2H). 13C-NMR (CDCl3) d: 35.8, 44.2, 59.9, 100.7, 108.0,
109.3, 121.8, 134.3, 145.6, 147.5. FAB-MS (NBA) m/z: 359 (M þ H)þ. Anal.
Calcd for C20H22O6: C, 67.03; H, 6.19. Found: C, 67.02; H, 6.27.
Lipase-Catalyzed Esterification of (+)-2,3-Bis[3,4-(methylenedioxy)-
benzyl]-1,4-butanediol 6
Typical Procedure
A mixture of 6 (358 mg, 1 mmol), lipase CCL (300 mg), and vinyl acetate
(5 mL) was stirred at rt for 72 h. The lipase was removed by filtration
though Celite, and the filtrate was concentrated in vacuo. The residue was
subjected to preparative TLC separation (hexane/AcOEt ¼ 2/1), affording
the corresponding diacetate 7 (120 mg, 26.9%; 62% ee), monoacetate 8
(216 mg, 53.7%; 12% ee), and diol 6 (52 mg, 14.5%; 93.7% ee). The ee
value of the product 6 was determined by HPLC (CHIRALCEL OD-H),
and the ee values of the esters 7 and 8 were also measured after hydrolysis
to the corresponding diol. The absolute configuration of each product was
determined by comparing the sign of the specific rotation of the diol with
the reported one.[8]
(R,R)-(þ)-2,3-Bis[3,4-(methylenedioxy)benzyl]-1,4-butanediol
diacetate 7
A viscous liquid, 62% ee, [a]D25 þ1.95 (c ¼ 0.2, CHCl3). 1H-NMR (CDCl3) d:
2.06 (s, 6H), 2.15 (m, 2H), 2.54 (dd, J ¼ 7.9, 13.9Hz, 2H), 2.67 (dd, J ¼ 6.7,
13.9Hz, 2H), 4.00 (dd, J ¼ 5.3, 11.2Hz, 2H), 5.92 (s, 4H), 6.52
(d, J ¼ 8.2 Hz, 1H), 6.54 (s, 1H), 6.70 (s, J ¼ 8.2 Hz, 1H). 13C-NMR (CDCl3)
d: 20.9, 34.9, 40.0, 64.2, 100.9, 108.1, 109.1, 121.8, 133.4, 145.7, 147.7, 170.9.
(S,S)-(2)-2,3-Bis[3,4-(methylenedioxy)benzyl]-1,4-butanediol
monoacetate 8
A viscous liquid, 12% ee, [a]2D5 20.09 (c ¼ 0.56, CHCl3). 1H-NMR (CDCl3)
d: 1.92 (m, 1H), 2.00 (br, 1H), 2.04 (s, 3H), 2.16 (m, 1H), 2.49-2.74 (m, 4H),

864
T. Morimoto, H. Nagai, and K. Achiwa
3.59 (d, J ¼ 5.6 Hz, 2H), 4.03 (dd, J ¼ 5.8, 10.5 Hz, 1H), 4.12 (dd, J ¼ 7.0
10.5 Hz, 1H), 5.89 (s, 4H), 6.52–6.71 (m, 6H). 13C-NMR (CDCl3) d: 20.8,
34.5, 34.8, 39.8, 43.0, 61.9, 64.5, 100.7, 107.9, 109.1, 121.6, 122.0, 133.7,
134.0, 145.6, 145.7, 147.5, 171.0.
(S,S)-(þ)-2,3-Bis[3,4-(methylenedioxy)benzyl]-1,4-butanediol 6
93.7% ee, [a]2D4 þ30.2 (c ¼ 0.5, CHCl3). [lit.,8 (R,R)-(2)-dihydrocubebin,
(R,R)-6: [a]1D7 –32.4 (c ¼ 3.3, CHCl3)].
(1)-Hinokinin (S,S)-9
To a solution of (S,S)-6 (94% ee; 179 mg, 0.5 mmol) in toluene (6 mL) was
added Fetizon reagent (0.9 g), which was prepared from AgNO3, Na2CO3,
and Celite according to a reported procedure. The mixture was stirred and
heated under reflux for 3 h. After cooling to rt, the reaction mixture was
filtered through Celite, and the filtrate was concentrated in vacuo. The
residue was purified by preparative TLC (hexane/AcOEt ¼ 1/1), affording
(S,S)-9 (170 mg, 96%); mp 104–1058C (EtOH); [a]2D4 þ32.8 (c ¼ 1.88,
CHCl3) [lit.,10 (R,R)-(2)-hinokinin: [a]D17-34.0 (c ¼ 0.98, CHCl3)]. IR
1
(nujol) cm21: 1760 (C55O). H-NMR (CDCl3) d: 2.50 (m, 4H), 2.82 (dd,
J ¼ 6.9, 14.2 Hz, 1H), 2.98 (dd, J ¼ 5.0, 14.0 Hz, 1H), 3.84 (dd, J ¼ 7.1,
9.1 Hz, 1H), 4.10 (dd, J ¼ 6.7, 9.4 Hz, 1H), 5.94 (s, 4H), 6.45–6.75
(m, 6H). 13C-NMR (CDCl3) d: 34.7, 38.2, 41.2, 46.3, 70.9, 100.8, 108.2,
108.3, 108.8, 109.5, 121.5, 122.2, 131.2, 131.5, 146.1, 146.3, 147.7, 178.3.
GC-MS (EI) m/z: 354 (Mþ). Spectral data were identical to those reported
previously.[12]
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