Highly enantioselective preparation of C2-symmetrical diols: Microbial hydrolysis of cyclic carbonates

Article abstract of DOI:10.1016/S0957-4166(00)00144-0

A new type of microbial enantioselective hydrolysis of C₂-symmetrical cyclic carbonates is disclosed. During the screening test of the five-membered substrate (4,5-dimethyl-1,3-dioxolan-2-one 5), Pseudomonas diminuta was selected as the best strain to perform the stereoselective hydrolysis. The reaction of dl-5 with this microorganism in aqueous media containing THF as the co-solvent afforded (S,S)-5 and (R,R)-butanediol 1 in excellent yields. It was found that the ring size did not affect the reactivity and enantioselectivity although the enzyme had a high substrate specificity for the side chain. A six-membered cyclic carbonate, dl-4,6-dimethyl-1,3-dioxan-2-one 6, was smoothly hydrolyzed with higher enantioselectivity to afford the optically active (S,S)-6 and (R,R)-2,4-pentanediol 2. Copyright (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0957-4166(00)00144-0

Tetrahedron: Asymmetry 11 (2000) 1965±1973
Highly enantioselective preparation of C2-symmetrical diols:
microbial hydrolysis of cyclic carbonates
Kazutsugu Matsumoto,* Youichi Sato, Megumi Shimojo and Minoru Hatanaka
Department of Applied Chemistry and Biotechnology, Faculty of Engineering, Fukui University, Bunkyo 3-9-1,
Fukui 910-8507, Japan
Received 15 March 2000; accepted 11 April 2000
Abstract
A new type of microbial enantioselective hydrolysis of C2-symmetrical cyclic carbonates is disclosed.
During the screening test of the ®ve-membered substrate (4,5-dimethyl-1,3-dioxolan-2-one 5), Pseudomonas
diminuta was selected as the best strain to perform the stereoselective hydrolysis. The reaction of dl-5 with this
microorganism in aqueous media containing THF as the co-solvent a€orded (S,S)-5 and (R,R)-butanediol
1 in excellent yields. It was found that the ring size did not a€ect the reactivity and enantioselectivity
although the enzyme had a high substrate speci®city for the side chain. A six-membered cyclic carbonate,
dl-4,6-dimethyl-1,3-dioxan-2-one 6, was smoothly hydrolyzed with higher enantioselectivity to a€ord the
optically active (S,S)-6 and (R,R)-2,4-pentanediol 2. # 2000 Elsevier Science Ltd. All rights reserved.
1. Introduction
Optically active diols with C2-symmetry, such as 2,3-butanediol 1 and 2,4-pentanediol 2, are
very useful as chiral auxiliaries (Fig. 1).1 The compounds and their derivatives have also been
used as C2-symmetrical chiral catalysts in asymmetric reactions.2 Much e€ort has already been
devoted to the preparation of such compounds in an optically active form.3,4 Kinetic resolution
of the diol derivatives with hydrolytic enzymes is one of the more attractive methods.5 These
methods, however, are not always satisfactory in terms of their yield, stereoselectivity, and simplicity
of operation.
Figure 1.
* Corresponding author. Fax: +81-776-27-8747; e-mail: mkazu@acbio.acbio.fukui-u.ac.jp
0957-4166/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0957-4166(00)00144-0

1966
K. Matsumoto et al. / Tetrahedron: Asymmetry 11 (2000) 1965±1973
Recently, the enzymatic enantioselective hydrolysis of cyclic carbonates has been disclosed as a
useful procedure for the preparation of optically active diols (Scheme 1).6 We also reported that
Porcine Pancreas Lipase (PPL, EC 3.1.1.3, Type II from Sigma) eciently catalyzed the hydrolysis
of various kinds of mono-substituted cyclic carbonates, resulting in the formation of a variety of
optically active 1,2- and 1,3-diols.7 This type of reaction proceeds irreversibly because the acyl
moiety of the substrate leaves the reaction system as carbon dioxide. We now present the ®rst
example of the preparation of optically active C2-symmetrical diols via the microbial hydrolysis
of the corresponding racemic cyclic carbonates (R1=R2=alkyl).
Scheme 1.
2. Results and discussion
2.1. Enzymatic hydrolysis of 4,5-dimethyl-1,3-dioxolan-2-one 5 containing dl- and meso-isomers
Cyclic carbonates 5±8 were readily synthesized by the treatment of the corresponding diols 1±4
with pyridine and bis(trichloromethyl)carbonate (triphosgene) as shown in Scheme 2.
Scheme 2.
We selected the mixture of stereoisomers of 4,5-dimethyl-1,3-dioxolan-2-one 5 (dl-form:meso-
form=42:58) (Scheme 3) as the screening substrate and the selection of the enzyme system
focused on not only the enantioselectivity but also the diastereoselectivity of the enzymatic
hydrolysis. In the beginning, the enzymatic hydrolysis of 5 was carried out with PPL using the
same procedure as that previously reported.7 Unfortunately, PPL did not catalyze the hydrolysis
of 5 at all in regardless of the reaction conditions used. Thus, we started screening microorganisms
in terms of their hydrolytic ability of 5.
First, the screening test was carried out by GLC analysis with tetralone as the internal standard.
In the screening test of 109 strains of stock cultures, 25 strains were selected for further screening
because they smoothly produced 1 with the remaining 5 in a relatively high diastereomeric ratio.

K. Matsumoto et al. / Tetrahedron: Asymmetry 11 (2000) 1965±1973
1967
Scheme 3.
In the second screening, the enantioselectivity of the products were measured by GLC analysis
using a capillary column coated with CP-Cyclodextrin-B-236-M19 (Chromopack). Finally,
Pseudomonas diminuta (FU0090), which was a bacteria isolated from the soil and classi®ed by
NCIMB Japan Co., Ltd., gave the best result (Table 1). After the reaction of 5 (100 ml, ca. 17
mM) with P. diminuta in 50 mL of medium for 6 h at 30ꢀC, 5 was completely consumed and
highly optically active (S,S)-5 (92% ee) was recovered in 22% yield. Changing the reaction time
to 24 h promoted the kinetic resolution to give enantiomerically pure (S,S)-5 in 15% yield. The
absolute con®guration of the resulting (S,S)-5, ‰aŠ2D0=^27.7 (c 1.01, CHCl3), was determined by
comparing its speci®c rotation sign with that of the authentic sample (R,R)-5, ‰aŠ2D4=+27.6 (c 1.09,
CHCl3), derived from commercially available (R,R)-1. These results indicate that the enzymatic
hydrolysis proceeds with very high enantio- and diastereoselectivities to get (S,S)-5 from the
mixture of dl- and meso-isomers. On the other hand, the yield of the resulting diol 1 was lower
than the theoretical one and the ratio of the dl- to meso-isomers and the ee of (R,R)-1 was
inconsistent with the rule of kinetic resolution. The further analysis of the reaction products
detected considerable amounts of acetoin 9 which was produced by the enzymatic oxidation of
the resulting 1 in the cells (Scheme 4).8 Thus, the decrease in the yield, de, and ee of 1 could be
explained by the enzymatic oxidation±reduction process occurring between 1 and 9. The formation
of acetoin 9 was also observed in the case of dl-5 as the substrate.
Table 1
Stereoselective hydrolysis of 5 (mixture of dl- and meso-form) with Pseudomonas diminuta
Scheme 4.

1968
K. Matsumoto et al. / Tetrahedron: Asymmetry 11 (2000) 1965±1973
2.2. Enantioselective hydrolysis of dl-4,5-dimethyl-1,3-dioxolan-2-one 5a
In order to prepare (R,R)-1 with a high ee, we examined the suppression of the oxidation±
reduction process mentioned above by the addition of organic solvents as an inhibitor against
oxidoreductase because the method was the simplest way to control the enzymatic reaction
system. The dl-5 substrate was separated from the mixture of diastereoisomers by column chroma-
tography on silica gel (Scheme 5). The addition of a water-miscible organic solvent, such as
acetone, DMF, DMSO, and dioxane, to the reaction broth of P. diminuta did not improve the
yield of the diol 1, and did not suppress the production of 9. However, the addition of THF was
found to give the best results, and i-Pr2O and AcOEt also reduced the side reaction. These results
are shown in Table 2. Under the conditions of 30ꢀC for 12 h in aqueous media containing 8%
THF, the reaction proceeded with high stereoselectivity to a€ord both enantiomers, (S,S)-5 (35%
ee) in 81% and (R,R)-1 (95% ee), ‰aŠ2D6=^13.2 (c 0.80, CHCl3), in 18% yields (conv.9=0.27, E
value9=55). Although the hydrolysis was apparently slower than that under the conditions
without THF, changing the reaction time from 12 to 48 h improved the ee of (S,S)-5 (95% ee,
conv.9=0.51, E value9=70). In all cases, acetoin 9 was not detected by capillary GLC analysis.
Scheme 5.
Table 2
Enantioselective hydrolysis of dl-5 with Pseudomonas diminutaa
2.3. Microbial hydrolysis of other substrates
We examined this microbial reaction of other C2-symmetrical cyclic carbonates (Scheme 6).
First, we tried the reaction using the cyclohexanediol derivative dl-7. The procedure was the same
when using dl-5 as the substrate. After the reaction for 72 h, the remaining substrate 7 and the
hydrolyzed product 3 were isolated in 58% and 43% isolated yields, respectively, but both
compounds were racemates. On the other hand, the substrate having diethyl groups, dl-4,5-diethyl-

K. Matsumoto et al. / Tetrahedron: Asymmetry 11 (2000) 1965±1973
1969
1,3-dioxolan-2-one 8, was not hydrolyzed under the same conditions. Thus, the enzyme has a
high substrate speci®city for the side chain.
Scheme 6.
Next, we tried the hydrolysis of a six-membered cyclic carbonate, dl-4,6-dimethyl-1,3-dioxan-2-
one 6, having dimethyl groups similar to those of 5 (Scheme 7). In the case of 6, THF was not
used as the co-solvent because the oxidation of the resulting 2,4-pentanediol 2 did not occur even
without THF. The substrate dl-6 was smoothly hydrolyzed with higher enantioselectivity
(conv.=0.51 and E value=75 for 24 (h) to a€ord the optically active (S,S)-6 (94% ee;
‰aŠ2D8=^74.5 (c 1.10, CHCl3)) and (R,R)-2 (91% ee; ‰aŠ2D8=^31.2 (c 1.55, CHCl3), lit.10 [a]d=^41.3
(CHCl3)) in 36 and 26% isolated yields, respectively. The reaction could be continued to over
50% conversion leading to the enantiomerically pure (S,S)-6. As a result, the ring size does not
a€ect the reactivity and enantioselectivity
Scheme 7.
3. Conclusion
We have demonstrated a new procedure for the preparation of optically active C2-symmetrical
diols, ®ve-membered 5 and six-membered 6 substrates, via the microbial enantioselective hydrolysis
of the corresponding cyclic carbonates. In both cases, the hydrolytic enzyme catalyzed the
hydrolysis of the (R,R)-isomers of the cyclic carbonates faster than the (S,S)-isomers. Further
investigations into this reaction are now in progress.
4. Experimental
4.1. General
1H (400 or 500 MHz) and 13C (100 or 125 MHz) NMR spectra were measured on a JEOL
JNM FX-400 or Lambda 500 with tetramethylsilane (TMS) as the internal standard. IR spectra

1970
K. Matsumoto et al. / Tetrahedron: Asymmetry 11 (2000) 1965±1973
were recorded with a Hitachi 270-30 spectrometer. Mass spectra were obtained with a JEOL
JMS-700T by the EI method. Optical rotations were measured with a Jasco DIP-181 and DIP-1030
polarimeter. GLC data were taken on a Hitachi 163, and capillary GLC on a Hitachi C-3000.
HPLC data were obtained on a Jasco TRI ROTAR-VI and UVIDEC-100-VI. Merck Kieselgel
60 F254 Art.5715 was used for analytical TLC. Preparative TLC was performed on Merck Kieselgel
60 F254 Art.5744. Column chromatography was performed with Merck Kieselgel 60 Art.7734.
Kugelrohr distillation was performed with a Shibata GTO-250RS. Melting points were obtained
on a Yanako melting point apparatus and were not corrected. Porcine Pancreas Lipase (PPL, EC
3.1.1.3, Type II) was purchased from Sigma Chemical Co. All other chemicals were also obtained
from commercial sources.
4.2. Preparation of cyclic carbonates 5±8
4.2.1. 4,5-Dimethyl-1,3-dioxolan-2-one 5
Under an argon atmosphere, pyridine (13.2 g, 168 mmol) was added to a solution of commer-
cially available 2,3-butanediol (1, mixture of dl- and meso-isomers; 3.00 g, 33.6 mmol) in CH2Cl2
(70 mL) at 0ꢀC, followed by addition of a solution of triphosgene (8.08 g, 27.1 mmol) in CH2Cl2
at ^78ꢀC. The mixture was then slowly warmed to 0ꢀC and stirred for 1 h. The reaction was
stopped with a sat. NH4Cl aqueous solution and the products were extracted with CH2Cl2 (Â3).
The organic layer was washed with 1 M HCl (Â2), brine, sat. NaHCO3 aqueous solution, and
brine, and dried over Na2SO4. After evaporation, the residue was puri®ed by column chroma-
tography on silica gel, followed by Kugelrohr distillation (bath temperature, 190ꢀC (33 mmHg))
to give the mixture of diastereoisomers of 5 (dl-form:meso-form=42:58) as a colorless oil (3.58 g,
92%). The isomers could be separated by column chromatography on silica gel (hexane:AcOEt=
7:1).
1
Compound dl-5: H NMR (500 MHz, CDCl3) d 1.44±1.48 (m, 6H), 4.31±4.38 (m, 2H); 13C
NMR (125 MHz, CDCl3) d 18.3, 79.8, 154.5; IR (neat) 2990, 1800, 1370, 1200, 1080, 780 cm^1;
MS m/z (rel. intensities) 116 (M+, 76), 101 (68), 86 (29), 71 (22), 57 (100); HRMS m/z 116.0467
(116.0473 calcd for C5H8O3, M+).
1
meso-5: H NMR (500 MHz, CDCl3) d 1.35±1.39 (m, 6H), 4.81±4.87 (m, 2H); 13C NMR (125
MHz, CDCl3) ꢀ 14.1, 75.9, 154.4; IR (neat) 2990, 1800, 1370, 1200, 1080, 780 cm^1; MS m/z (rel.
intensities) 116 (M+, 8), 101 (68), 86 (0.8), 71 (2), 43 (100); HRMS m/z 116.0510 (116.0473 calcd
for C5H8O3, M+).
4.2.2. dl-4,6-Dimethyl-1,3-dioxan-2-one 6
According to the procedure for the preparation of 5 described above, dl-2,4-pentanediol 2 (406
1
mg, 3.89 mmol) was converted to dl-6 (336 mg, 66%) as a colorless oil: H NMR (500 MHz,
CDCl3) d 1.44 (d, J=6.5 Hz, 6H), 1.94 (dd, J1=J2=5.5 Hz, 2H), 4.73 (qt, J1=5.5 Hz, J2=6.5
Hz, 2H); 13C NMR (125 MHz, CDCl3) d 20.8, 72.5, 149.4; IR (neat) 2990, 1740, 1400, 1200, 1120,
770 cm^1; MS m/z (rel. intensities) 130 (M+, 12), 89 (3), 71 (7), 42 (100); HRMS m/z 130.0636
(130.0630 calcd for C6H10O3, M+).
4.2.3. dl-3a,4,5,6,7,7a-Hexahydro-1,3-benzodioxol-2-one 7
According to the procedure for the preparation of 5 described above, dl-1,2-cyclohexanediol 3
(500 mg, 4.30 mmol) was converted to dl-7 (423 mg, 69%) as a colorless oil: 1H NMR (400 MHz,
CDCl3) d 1.33±1.52 (m, 2H), 1.52±1.79 (m, 2H), 1.79±2.02 (m, 2H), 2.19±2.36 (m, 2H), 4.02 (td,

K. Matsumoto et al. / Tetrahedron: Asymmetry 11 (2000) 1965±1973
1971
J1=9.5 Hz, J2=5.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) d 22.8, 27.9, 83.3, 154.9; IR (neat)
2920, 1795, 1105, 1040, 785 cm^1; MS m/z (rel. intensities) 142 (M+, 21), 97 (58), 83 (90), 57 (100);
HRMS m/z 142.0622 (142.0630 calcd for C7H10O3, M+).
4.2.4. dl-4,5-Diethyl-1,3-dioxolan-2-one 8
To a solution of trans-3-hexene 10 (1.00 g, 11.9 mmol) in acetone (60 mL) and H2O (40 mL)
were added 4-methylmorpholine N-oxide (5.74 g, 59.4 mmol), tert-butanol (5 mL) and a catalytic
amount of OsO4, and the mixture was stirred at rt overnight. After addition of NaS2O3 and stirring
for 30 min, the mixture was ®ltrated through a Celite pad, and the products were extracted with
AcOEt (Â3) from the ®ltrate, washed with brine, and dried over Na2SO4. After evaporation, the
residue was puri®ed by column chromatography on silica gel to give dl-3,4-hexanediol 4 as a
colorless oil (869 mg, 62%): 1H NMR (400 MHz, CDCl3) d 0.99 (t, J=7.5 Hz, 6H), 1.36±1.53 (m,
2H), 1.53±1.72 (m, 2H), 2.30 (br.s, 1H), 2.35 (s, 1H), 3.26±3.44 (m, 2H); 13C NMR (125 MHz,
CDCl3) d 9.9, 26.2, 75.4; IR (neat) 3390, 2960, 1460, 1070, 970 cm^1; MS m/z (rel. intensities) 118
(M+, 15), 101 (100), 71 (100), 60 (100); HRMS m/z 118.0979 (118.0994 calcd for C6H14O2, M+).
According to the procedure for the preparation of 5 described above, dl-4 (498 mg, 4.22 mmol)
1
was converted to dl-8 (561 mg, 92%) as a colorless oil: H NMR (400 MHz, CDCl3) d 1.04 (t,
J=7.5 Hz, 6H), 1.62±1.82 (m, 4H), 4.09±4.12 (m, 2H); 13C NMR (125 MHz, CDCl3) d 8.5, 26.7,
82.5; IR (neat) 2970, 1795, 1185, 1040, 775 cm^1; MS m/z (rel. intensities) 144 (M+, 5), 115 (18), 71
(22), 43 (100); HRMS m/z 144.0779 (144.0786 calcd for C7H12O3, M+).
4.3. Screening of microorganisms for hydrolysis of 5
The basal medium for screening of microorganisms consists of glucose (10 g), polypeptone (7
g), and yeast extract (5 g) in 1 L of 100 mM phosphate bu€er (pH 6.5).
In the ®rst screening, a loopful of each microorganism from a nutrient slant was transferred to
a test tube containing 5 mL of the sterilized basal medium. After cultivation for 48 h at 30ꢀC, 10
mL of 5 (the mixture of diastereoisomers) was added to the suspension of grown cells and
incubation was continued for an additional 24 h. The products were extracted with ether and
analyzed by GLC. The conditions of GLC analysis were as follows: column, butanediol succinate±
uniport B (GL Science Inc.); injection, 140ꢀC; oven, 120ꢀC; carrier gas, N2; head pressure, 0.2 kg/
cm2; dl-1: 0.87 min, meso-1: 0.97 min; dl-5: 3.7 min, meso-5: 5.6 min; tetralone 11.0 min (internal
standard).
In the second screening, the enantiomeric excesses of the products were analyzed by capillary
GLC. The conditions of capillary GLC analysis were as follows: column, CP-Cyclodextrin-B-236-
M19 (Chromopack), 0.25 mmÂ50 m, Inc.; injection, 100ꢀC; detection, 100ꢀC; oven, 80ꢀC; carrier
gas, He; head pressure, 2.4 kg/cm2; (S,S)-1 15.7 min, (R,R)-1 16.0 min, (R,R)-5 53.3 min, (S,S)-5
54.2 min.
4.4. Typical procedure for hydrolysis of cyclic carbonates with Pseudomonas diminuta
A 500 mL Erlenmeyer ¯ask each containing 100 mL of sterilized basal medium was inoculated
with a loopful of P. diminuta, and incubated for 48 h at 30ꢀC. To the broth was added 100 mL
(113 mg) of 5 (the mixture of diastereoisomers) and the cultivation was continued. After 50 mL of
acetone was added to the mixture following by saturation with NaCl and ®ltration through a
Celite pad, the products were extracted with AcOEt, and the organic layer was dried over

1972
K. Matsumoto et al. / Tetrahedron: Asymmetry 11 (2000) 1965±1973
Na2SO4. Evaporation and puri®cation a€orded 1 and 5. The results are shown in Table 1. The
yields were determined by GLC analysis.
Enantioselective hydrolysis of the other substrates were carried out by means of the same
procedure. In the cases of dl-5, 6, and 7, the substrates were added to the broth with THF (4 mL)
as the co-solvent. The results are shown in the text. All the spectral data (1H and 13C NMR, IR,
and MS) of cyclic carbonates were in full agreement with those of the racemates. Properties of the
products and the determination methods of the ees are as follows.
26
1
Compound (R,R)-1: 95% ee, ‰aŠD =^13.2 (c 0.80, CHCl3); H NMR (500 MHz, CDCl3) ꢀ
1.16±1.20 (m, 6H), 2.47 (br.s, 2H), 3.48±3.56 (m, 2H); 13C NMR (125 MHz, CDCl3) ꢀ 19.3, 72.5;
IR (neat) 3365, 2970, 1375, 1060, 890 cm^1; MS m/z (rel. intensities) 90 (M+,14), 75 (18), 57 (47),
45 (100); HRMS m/z 90.0687 (90.0681 calcd for C4H12O2, M+). The absolute con®guration was
con®rmed by comparing its speci®c rotation sign with that of the commercially available (R,R)-1;
‰aŠ2D6=^14.1 (c 0.53, CHCl3), lit.11 ‰aŠD26=^12.8 (neat). The ee was determined by capillary GLC
analysis with CP-Cyclodextrin-B-236-M19 under the conditions mentioned above.
Compound (S,S)-5: >99% ee, ‰aŠ2D0=^27.7 (c 1.01, CHCl3). The absolute con®guration was
con®rmed by comparing its speci®c rotation sign with that of the authentic sample (R,R)-5,
‰aŠ2D4=+27.6 (c 1.09, CHCl3), derived from commercially available (R,R)-1 with triphosgene and
pyridine in CH2Cl2. The ee was determined by capillary GLC analysis with CP-Cyclodextrin-B-
236-M19 under the conditions mentioned above.
Compound (R,R)-2: 91% ee; ‰aŠ2D8=^31.2 (c 1.55, CHCl3); 1H NMR (500 MHz, CDCl3) ꢀ 1.16
(d, J=6.5 Hz, 6H), 1.51 (dd, J1=J2=5.5 Hz, 2H), 3.55 (br.s, 1H), 4.06 (qt, J1=5.5 Hz, J2=6.5
Hz, 2H); 13C NMR (125 MHz, CDCl3) ꢀ 23.2, 45.8, 65.0; IR (neat) 3365, 2970, 1660, 1380, 1125
cm^1; MS m/z (rel. intensities) 105 (55, M++H), 103 (17), 89 (100), 71 (100); HRMS m/z 105.0924
(105.0915 calcd for C5H13O2, M++H). The absolute con®guration was con®rmed by comparing
its speci®c rotation sign with the reported one; lit.10 [a]d=^41.3 (CHCl3). The ee was determined
1
by H NMR analysis of the corresponding bis-(+)-MTPA ester 12 which was transformed in a
conventional manner. Signals at ꢀ 4.97±5.07 (m, 1H, CH3CH, (R,R)) and 5.08±5.20 (m, 1H,
CH3CH, (S,S)) were observed in the case of the racemic sample.
Compound (S,S)-6: 94% ee, ‰aŠ2D8=^74.5 (c 1.10, CHCl3). The ee was determined by similar
analysis of the corresponding diol 2 derived from 6 with K2CO3 in MeOH.
ꢀ
1
Compound 3: a white solid, mp 98±100 C; H NMR (500 MHz, CDCl3) ꢀ 1.18±1.34 (m, 2H),
1.61±1.77 (m, 2H), 1.89±2.03 (m, 2H), 3.27±3.44 (m, 2H) 4.28 (br.s, 2H); 13C NMR (125 MHz,
CDCl3) ꢀ 24.3, 32.8, 75.6; IR (CHCl3 solution) 3405, 2940, 1715, 1060, 930 cm^1; MS m/z (rel.
intensities) 116 (27, M+), 98 (36), 83 (30), 70 (100); HRMS m/z 116.0861 (116.0837 calcd for
C6H12O2, M+). The ee was determined by capillary GLC analysis with CP-Cyclodextrin-B-236-
M19 (Chromopack) column; injection, 140ꢀC; detection, 140ꢀC; oven, 120ꢀC; carrier gas, He;
head pressure, 2.4 kg/cm2; retention times, 22.9 and 24.1 min (the absolute con®gurations were
not determined).
Compound 7: The ee was determined by similar analysis of the corresponding diol 3 derived
from 7 with K2CO3 in MeOH.
Acknowledgements
We thank Professor Kimio Isa (Fukui University) for helpful discussion on mass spectroscopic
analysis.

K. Matsumoto et al. / Tetrahedron: Asymmetry 11 (2000) 1965±1973
1973
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