Enantioselective ring-opening reaction of epoxides with MeOH catalyzed by homochiral metal-organic framework

Article abstract of DOI:10.1246/bcsj.20110392

Two new copper metal-organic frameworks containing 2,2′-dihydroxy-1, 1′-binaphthalene-5,5′-dicarboxylic acid (5,5′-H ₂BDA) and 2,2′-dihydroxy-1,1′-binaphthalene-4,4′- dicarboxylic acid (4,4′-H₂BDA) have been prepared. X-ray structure determination of [Cu₂(5,5′-BDA)₂(H ₂O)₂]·MeOH·2H₂O (MOF-1) and [Cu₂(4,4′-BDA)₂(H₂O)₂] ·4H₂O (MOF-2) revealed similar 2D sheet structures, containing square-grid coordination networks, but differences in the stacking motif. The desolvated MOF-1 and -2 were used as Lewis acid catalysts in the asymmetric ring-opening reaction of epoxides with MeOH.

Full text of DOI:10.1246/bcsj.20110392

© 2012 The Chemical Society of Japan
Bull. Chem. Soc. Jpn. Vol. 85, No. 6, 709-714 (2012)
709
Enantioselective Ring-Opening Reaction of Epoxides with MeOH
Catalyzed by Homochiral Metal-Organic Framework
Koichi Tanaka,*1 Ken-ichi Otani,1 Takanori Murase,1
Shyota Nishihote,1 and Zofia Urbanczyk-Lipkowska*2
1Department of Chemistry and Materials Engineering, Faculty of Chemistry,
Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680
2Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, Poland
Received December 15, 2011; E-mail: ktanaka@kansai-u.ac.jp
Two new copper metal-organic frameworks containing 2,2¤-dihydroxy-1,1¤-binaphthalene-5,5¤-dicarboxylic acid
(5,5¤-H2BDA) and 2,2¤-dihydroxy-1,1¤-binaphthalene-4,4¤-dicarboxylic acid (4,4¤-H2BDA) have been prepared. X-ray
structure determination of [Cu2(5,5¤-BDA)2(H2O)2]¢MeOH¢2H2O (MOF-1) and [Cu2(4,4¤-BDA)2(H2O)2]¢4H2O (MOF-
2) revealed similar 2D sheet structures, containing square-grid coordination networks, but differences in the stacking
motif. The desolvated MOF-1 and -2 were used as Lewis acid catalysts in the asymmetric ring-opening reaction of
epoxides with MeOH.
In recent years, design and synthesis of metal-organic
frameworks (MOFs)1 aiming at developing functional zeolite
analogs have been a subject of research interest owing to their
potential applications in gas storage,2 separation,3 lumines-
cence,4 and heterogeneous catalysis.5 In particular, the design
of MOFs with homochirality has attracted considerable atten-
tion because of their applications in enantioselective separa-
tion and catalysis.6 Recently, we have synthesized a novel
chiral MOF (R)-MOF-1 (Scheme 1) and examined its use as
an effective catalyst for the asymmetric ring-opening of epox-
ides with amines7a and alcohols7b under heterogeneous condi-
tions. Herein, we report the synthesis and X-ray structure
determination of the isomeric chiral MOF (R)-MOF-2 from
2,2¤-dihydroxy-1,1¤-binaphthalene-4,4¤-dicarboxylic acid (4,4¤-
H2BDA, (R)-2) and the catalytic behavior of both (R)-MOF-1
and (R)-MOF-2 in the asymmetric ring-opening reactions of
several epoxides with MeOH (Scheme 2).
The crystal structure of the chiral polymeric metal-organic
complex (R)-MOF-2 viewed down the (100) axis is shown in
Figure 1. The complex is a neutral molecule with a dinuclear
structure in which two identical Cu(II) centers related by two-
fold symmetry are bridged by four carboxylate groups from
two 4,4¤-BDA ligands. Each Cu(II) atom is five-coordinated by
the combination of four O atoms from the carboxylate groups
and one O atom from a water molecule. The Cu atoms are
separated by a distance of 2.692(1) ¡. The Cu£O distances
in (R)-MOF-2 range from 1.917(5) to 2.104(5) ¡ and are very
close to the corresponding distances in (R)-MOF-1 (1.926(7)-
2.138(8) ¡).7a
In both MOF’s the longest Cu£O distances are those
involving O atoms from water molecules in apical positions
that are likely to be replaced by coordinated epoxide during
catalytic course. The neighboring layers are “glued” by a
system of hydrogen bonds involving four water molecules and
the hydroxy groups of BDA molecules. The long channels
are filled with four water molecules per asymmetric unit. The
crystals of (R)-MOF-1 have larger pores containing six waters
and one methanol molecule that is hydrogen bonded with O2 of
the carboxy group from Cu£Cu motif (Figure 2). In (R)-MOF-
2 available space is more restricted than in (R)-MOF-1 due to
smaller pore volume (Figure 3). The crystallographic data for
MOF-1 and MOF-2 are shown in Table 1.
Results and Discussion
(R)-MOF-1 was prepared according to our previously re-
ported method7a and dried under vacuum at 80 °C for 3 h prior to
use. (R)-MOF-2 was prepared by a similar reaction using (R)-28
instead of 2,2¤-dihydroxy-1,1¤-binaphthalene-5,5¤-dicarboxylic
acid ((R)-1). Treatment of enantiopure 4,4¤-H2BDA ((R)-2) with
Cu(NO3)2 in an aqueous MeOH solution with slow diffusion
of N,N-dimethylaniline at room temperature for several days
afforded [Cu2(4,4¤-BDA)2(H2O)2]¢4H2O ((R)-MOF-2) as dark
green prisms in 83% yield. The product was characterized by
infrared (IR) spectroscopy, thermogravimetric analysis (TGA),
and X-ray analysis. The IR spectrum of (R)-MOF-2 exhibited
Ring-Opening Reactions of Epoxides.
The catalytic
activity of (R)-MOF-1 and (R)-MOF-2 toward asymmetric
ring-opening reactions of epoxides with MeOH was examined
(Table 2). In a typical experiment, a solution of styrene oxide
(rac-3a, 0.5 mmol) in MeOH (0.5 mL) in the presence of (R)-
MOF-1 (20 mg, 0.046 mmol based on the formula unit) was
stirred at 25 °C for 24 h, and 2-methoxy-2-phenylethanol ((S)-
4a, 80% ee) and unreacted (S)-3a (7% ee) were obtained in
5% and 89% yields, respectively (Entry 1). In the absence of
¹
peaks for ¯OH and ¯CO2 at 3289 and 1609 cm¹1, respectively.
TGA showed that (R)-MOF-2 loses 17% of its total weight
within the temperature range 25-120 °C, corresponding to the
loss of six water molecules per formula unit.
Published on the web May 30, 2012; doi:10.1246/bcsj.20110392

710
Bull. Chem. Soc. Jpn. Vol. 85, No. 6 (2012)
Enantioselective Ring-Opening Reaction
O
O
O
O
O Cu
O
O
O
O Cu
O
O
O
L
Cu
O
Cu
O
O
O
L(COOH)2
N,N-dimethylaniline
MeOH-H2O
L
L
+
Cu(NO3)2 3H2O
O
O
O
O
O Cu
O
O
O
O Cu
O
O
O
L
Cu
O
Cu
O
O
O
MOF-1 or 2
CO2H
CO2H
OH
OH
OH
OH
L(COOH)2
:
or
CO2H
CO2H
5,5'-H2BDA(1)
4,4'-H2BDA(2)
Scheme 1. Synthesis of homochiral MOF.
O
O
O
O
O
O
Cu
O
O
OCu
O
O
O
O
Cu
Cu
O
O
O
HO OH
OMe
O
HO
HO
HO
HO
OH
R
R
MeOH
a: R = Ph
b: R = CH2Ph
c: R = CH2OPh
d: R = CH2OCH2Ph
O
O
O
O
O
O
Cu
Cu
O
O
O
O
O
O
O
Cu
O
Cu
O
O
OH
HO
(R)-MOF-1
Scheme 2. Enantioselective ring-opening reaction of epoxide.
catalyst, unreacted rac-3a was recovered. When the reactions
were performed at higher temperatures (40 and 60 °C), the
enantiomeric excess (ee) of unreacted 3a increased, while that
of product 4a decreased (Entries 2 and 3). The highest ee of
recovered 3a (98%) was obtained in the reaction performed
at 60 °C (Entry 3). It has been reported that desolvation can
generate coordinatively unsaturated sites, that is, Lewis acid
sites, in MOFs with similar paddle-wheel Cu2 clusters.9 Thus,
we compared the catalytic results using the samples desolvated
and un-desolvated and make clear the effect of desolvation.
However, almost the same reactivity and enantioselectivity
were obtained using the un-solvated (R)-MOF-1 (Entry 4),
assuming that one water molecule located on Cu atom of (R)-
MOF-1 is easily exchanged for epoxide substrate during
catalytic cycles. The effect of the particle sizes of MOF on the
catalytic activities was not recognized by using the grinding
powder of (R)-MOF-1 (Entry 5). Next, we performed reactions
using (R)- and (S)-3a as substrates to evaluate the relative
rate at each temperature. When the reaction was carried out at
25 °C, (S)-4a (>99% ee) and (R)-4a (>99% ee) were obtained

K. Tanaka et al.
Bull. Chem. Soc. Jpn. Vol. 85, No. 6 (2012)
711
Figure 3. Stereochemistry of the coordination sphere in
(R)-MOF-2.
Table 1. Crystallographic Data for MOF-1 and MOF-2
Figure 1. Crystal structure of (R)-MOF-2 viewed down the
(100) axis; four water molecules of crystallization omitted
for clarity.
MOF-17a
MOF-2
Crystal system
Space group
a/¡
b/¡
c/¡
monoclinic
P21
15.620(5)
11.377(4)
15.620(5)
monoclinic
C2
13.445(1)
20.102(1)
9.1833(7)
¡/°
¢/°
94.88(5)
90.374(6)
£/°
V/¡3
Z
2766(2)
2
2481.4(3)
4
F(000)
1032
1.210
0.833
19335/8263
0.0745
904
1.191
1.565
12458/3548
0.0856
¹3
dcalcd/Mg m
¹1
® (Mo/Cu K¡)/mm
refl/total indep./2·(I)
R1
N
Figure 2. Stereochemistry of the coordination sphere in
(R)-MOF-17a with close proximity of methanol molecule:
O15£O2 distance 2.873(6) ¡ and apical water molecules
O13 and O14.
formed using Cu(OAc)2 or Cu(NO3)2 as catalyst, rac-4a was
obtained in 16% and 23% yield, respectively (Entries 14 and
16). This suggests that the reaction is catalyzed by Lewis
acidic Cu sites in the chiral MOF. With a combination of
(R)-BINOL and Cu(OAc)4 as catalyst, the reaction proceeded
more efficiently than in the presence of only (R)-BINOL
(Entry 15).
The reaction could be extended to several epoxides, such
as 1,2-epoxy-3-phenylpropane (3b), 1,2-epoxy-3-phenoxy-
propane (3c), and 1-benzyloxy-2,3-epoxypropane (3d). In
these reactions, however, the regioselectivity changed, and
1-methoxy-3-phenylpropan-2-ol (5b), 1-methoxy-3-phenoxy-
propan-2-ol (5c), and 1-benzyloxy-3-methoxypropan-2-ol (5d)
were formed in relatively low yields and lower enantioselec-
tivities (Entries 17-22).
in 13% and 1% yields, respectively (Entries 6 and 7). Similar
reactions at 40 and 60 °C afforded (S)-4a and (R)-4a in 48%
and 5% yields (at 40 °C) (Entries 8 and 9), and in 95% and
25% yields (at 60 °C) (Entries 10 and 11), respectively. This
implies that the (R)-3a enantiomer of styrene oxide reacts with
MeOH approximately 13 times (at 25 °C), 10 times (at 40 °C)
and 4 times (at 60 °C) faster than its (S)-3a counterpart in
the presence of (R)-MOF-1. However, the same reaction using
(R)-MOF-2 as the catalyst showed poor results in terms of
reactivity and enantioselectivity. For example, when a solution
of rac-3a (0.5 mmol) in MeOH (0.5 mL) in the presence of
(R)-MOF-2 (20 mg) was stirred at 40 °C for 24 h, (R)-4a (7%
ee) and unreacted rac-3a were obtained in 4% and 90% yields,
respectively (Entry 12). The poor results may be due to the
low accessibility of the substrate to Lewis acidic Cu sites of
(R)-MOF-2. In (R)-MOF-2 available space is more restricted
than in (R)-MOF-1 due to smaller pore volume (Figures 3
and 4). Another factor that might influence reaction yield and
stereospecifity in the case of (R)-MOF-2, is lack of precisely
localized MeOH molecules that can be directly utilized during
the methanolysis reaction. Moreover, when the reaction was
performed using (R)-1,1¤-bi-2-naphthol (BINOL) as the cata-
lyst, almost no reactivity or enantioselectivity was observed
(Entry 13). On the other hand, when the reaction was per-
Reaction Heterogeneity.
To confirm the heterogeneity
of the reaction, methanolysis of styrene oxide was performed
at 40 °C under the conditions described in Table 2, and the
solid (R)-MOF-1 catalyst was filtered from the reaction mix-
ture when the formation of 2-methoxy-2-phenylethanol (4a)
reached 20% conversion. After removal of the solid catalyst,
the solution was further stirred at 40 °C in the absence of the
catalyst. After 72 h, no additional product formation was
observed in the absence of the solid catalyst (Figure 4).
Recycling Test. The reusability of the (R)-MOF-1 catalyst
was also investigated for the methanolysis of styrene oxide

712
Bull. Chem. Soc. Jpn. Vol. 85, No. 6 (2012)
Enantioselective Ring-Opening Reaction
Table 2. Ring-Opening Reactions of Various Epoxides with MeOH
cat. (20 mg)
OMe
OH
O
+
+
MeOH
OH
OMe
R
R
R
24 h
0.5 mL
3 (0.5 mmol)
4
5
a: R = Ph
c: R = CH2OPh
b: R = CH2Ph d: R = CH2OCH2Ph
Unreacted 3
Yield/%, Ee/%
Product 4 or 5
Yield/%, Ee/%
Entry
Catalyst
Epoxide
Temp/°C
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
(R)-MOF-1
(R)-MOF-1
(R)-MOF-1
(R)-MOF-1a)
(R)-MOF-1b)
(R)-MOF-1
(R)-MOF-1
(R)-MOF-1
(R)-MOF-1
(R)-MOF-1
(R)-MOF-1
(R)-MOF-2
(R)-BINOLc)
Cu(OAc)2
rac-3a
rac-3a
rac-3a
rac-3a
rac-3a
(R)-3a
(S)-3a
(R)-3a
(S)-3a
(R)-3a
(S)-3a
rac-3a
rac-3a
rac-3a
rac-3a
rac-3a
rac-3b
rac-3b
rac-3c
rac-3c
rac-3d
rac-3d
25
40
60
40
40
25
25
40
40
60
60
40
40
40
40
40
60
60
60
60
60
60
89, 7(S)
76, 23(S)
29, 98(S)
76, 23(S)
72, 22(S)
80, >99(R)
96, >99(S)
50, >99(R)
92, >99(S)
0
72, >99(S)
90, 0
96, 2(R)
81, 0
56, 3(R)
65, 0
83, 23(S)
0, 0
4a, 5, 80(S)
4a, 21, 70(S)
4a, 66, 37(S)
4a, 21, 72(S)
4a, 21, 72(S)
4a, 13, >99(S)
4a, 1, >99(R)
4a, 48, >99(S)
4a, 5, >99(R)
4a, 95, >99(S)
4a, 25, >99(R)
4a, 4, 7(R)
4a, 3, 6(S)
4a, 16, 0
4a, 39, 11(S)
4a, 23, 0
5b, 11, 24(R)
5b, 80, 0
(R)-BINOLc) + Cu(OAc)2
Cu(NO3)2
(R)-MOF-1
Cu(NO3)2
(R)-MOF-1
Cu(NO3)2
(R)-MOF-1
Cu(NO3)2
66, 8(S)
0, 0
77, 2(S)
0, 0
5c, 25, 27(R)
5c, 92, 0
5d, 15, 9(R)
5d, 82, 0
a) Un-desolvated. b) Powdered. c) 1,1¤-Bi-2-naphthol.
Table 3. Recycling Tests on (R)-MOF-1 in the Methanolysis
of Styrene Oxide at 40 °C
(a)
3a
Recycle run
Yield/%
Ee/%
1st
2nd
3rd
20
18
22
62
72
69
(b)
proceeds as follows: Initially, only (R)-3a from the racemic
mixture coordinates to a Lewis acidic Cu site on (R)-MOF-1 to
form an adduct predominantly owing to steric reasons. Next,
methanol attacks the ¡-carbon atom (benzyl position) of the
coordinated (R)-3a from the backside to give (S)-4a with
inversion of stereochemistry, while the other enantiomer from
the starting racemate, (S)-3a, remains unchanged. On the other
hand, methanol would likely attack the less hindered side of
(R)-3d to afford (S)-5d with no inversion of the stereogenic
center (Scheme 3).
Time/h
Figure 4. Heterogeneity test of styrene oxide methanolysis
at 40 °C a) in the presence of (R)-MOF-1 or b) after
filtration of the catalyst at 20% conversion.
at 40 °C under the conditions described in Table 2. As shown
in Table 3, (R)-MOF-1 maintained a high level of performance
for up to at least two recycles.
Reaction Mechanism. The mechanism of kinetic reso-
lution of styrene oxide (rac-3a) catalyzed by (R)-MOF-1 could
be inferred from the methanolysis of styrene oxide, because
the methoxy group was incorporated at the ¡-carbon of 3a to
afford product 4a exclusively. The suggested mechanism
Conclusion
In summary, we have synthesized two isomeric homochiral
MOFs (MOF-1 and MOF-2) having chiral BINOL units.
Homochiral MOF-1 was found to be highly active in catalyzing

K. Tanaka et al.
Bull. Chem. Soc. Jpn. Vol. 85, No. 6 (2012)
713
O
O
"inversion"
OMe
O
O
O Cu
O
O
OH
(S)-
(S)-
rac-
+
Cu O
O
O
O
3a
4a
3a
(R)-
O
O
Me
O
H
"retention"
OH
O Cu
O
O
Cu O
rac-
O
(R)-
O
O
OMe
3d
O
O
O
5d
+
O
(R)-
(S)-
O
O
O
Me
H
3d
Scheme 3. Possible reaction mechanism.
the asymmetric ring-opening reaction of epoxides with meth-
anol and was shown to function as a heterogeneous, recyclable,
and reusable catalyst. Further investigation of the scope and
limitations of this catalytic system are currently underway.
CCDC-730355, contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
at “http://www.ccdc.cam.ac.uk/conts/retrieving.html” (or from
the Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge, CB2 1EZ, U.K.; E-mail: deposit@ccdc.
cam.sc.uk).
Experimental
1H NMR spectra were recorded on a JEOL JNM-GSX 400
spectrometer with tetramethylsilane as the internal standard.
IR spectra were recorded on a JASCO FT-IR 4100 spectrom-
eter. TGA was performed on a Rigaku TG-8120 instrument.
Enantiomeric excesses were determined either by high-perfor-
mance liquid chromatography (HPLC) on a Chiralpak OD, OD-
H, or AS (Daisel), or by a Shimadzu GC-2014 system equipped
with a flame ionization detector and a Chiraldex £-TA column.
Synthesis of [Cu2(4,4¤-BDA)2(H2O)2]¢4H2O ((R)-MOF-2).
N,N-Dimethylaniline was slowly diffused into a mixture
solution of MeOH (5 mL) and water (1.5 mL) containing
Cu(NO3)2¢3H2O, (48 mg, 0.2 mmol) and (R)-(+)-28 (75 mg,
0.2 mmol) at room temperature. After several days, (R)-MOF-2,
[Cu2(4,4¤-BDA)2(H2O)2]¢4H2O (86 mg, 83% yield) were ob-
tained as dark green prisms. IR(cm¹1): 3289, 1609, 1513, 1340,
1267, 1234, 992, 903, 803, 767, 737.
Typical Procedure for the Methanolysis of Styrene Oxide
(3a). (R)-MOF-1 (20 mg) is desolvated at 80 °C for 3 h prior
to reaction. The resultant solid catalyst is suspended in a MeOH
(0.5 mL) solution of styrene oxide 3a (0.06 g, 0.5 mmol) and
stirred for 24 h. Then, the solid catalyst was collected by filtra-
tion, washed with MeOH. All MeOH portions are combined
and evaporated under reduced pressure, and the yield is deter-
1
mined by NMR. H NMR (400 MHz, CDCl3): ¤ 7.39-7.25 (m,
Ph, 5H), 4.31 (dd, J = 3.8, 8.5 Hz, 1H), 3.72-3.56 (m, CH2OH,
2H), 3.30 (s, OMe, 3H), 2.74 (bs, OH, 1H). The optical purity
of 2-methoxy-2-phenylethanol (4a) was determined by HPLC
using Chiralpak IA (Daicel) column (hexane/2-PrOH: 97/3,
flow rate 0.3 mL min¹1, t = 37 min (S), t = 45 min (R)). The
optical purity of styrene oxide 3a was determined by HPLC
using Chiralpak AS (Daicel) column. (hexane/2-PrOH: 99/1,
flow rate 0.3 mL min¹1, t = 26 min (R), t = 29 min (S)).
Typical Procedure for the Methanolysis of 1,2-Epoxy-3-
X-ray Crystallography. X-ray data of the (R)-MOF-2 were
collected on a Bruker ApexII system using Cu K¡ radiation
at 293 K. Unit cell parameters: a = 13.445(1), b = 20.102(1),
phenylpropane (3b).
(R)-MOF-1 (20 mg) desolvated as
above is suspended in a MeOH (0.5 mL) solution of 1,2-epoxy-
3-phenylpropane (3b) (0.067 g, 0.5 mmol) and stirred at 60 °C
for 24 h. Then, the solid catalyst was collected by filtration,
washed with MeOH. All MeOH portions are combined and
evaporated under reduced pressure, and the yield is determined
c = 9.1833(7) ¡, ¢ = 90.374(6)°, V = 2481.4(3) ¡3, dcalcd
=
¹3
¹1
1.191 Mg m
,
®(Cu K¡) = 1.565 mm
,
F(000) = 1044;
monoclinic, space group C2, Z = 4. 12458 reflections were
collected. The structure was solved by direct methods and
refined by full-matrix least squares using SHELXS97 and
SHELXL97 programs.10 Final R1 = 0.0856 and wR2 = 0.2155
for 3548 unique reflections with I > 2·(I). Several hydrogen
atoms from water molecules could not be found from difference
Fourier maps.
1
by NMR. H NMR (400 MHz, CDCl3): ¤ 7.33-7.21 (m, 5H),
4.04 (m, 1H), 3.42-3.39 (m, 2H), 3.37 (s, 3H), 2.80-2.78 (m,
2H). The optical purity of 1-methoxy-3-phenylpropan-2-ol (5b)
was determined by HPLC using Chiralcel OD-H (Daicel)
column (hexane/2-PrOH: 18/1, flow rate 0.5 mL min¹1, t =

714
Bull. Chem. Soc. Jpn. Vol. 85, No. 6 (2012)
Enantioselective Ring-Opening Reaction
Chem. Soc. 2004, 126, 5666. c) R. Matsuda, R. Kitaura, S.
Kitagawa, Y. Kubota, R. V. Belosludov, T. C. Kobayashi, H.
Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita, Nature 2005,
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2009, 38, 1294. e) A. Phan, C. J. Doonan, F. J. Uribe-Romo, C. B.
Knobler, M. O’Keeffe, O. M. Yaghi, Acc. Chem. Res. 2010, 43, 58.
21.9 min (S), t = 26.8 min (R)). The optical purity of 1,2-
epoxy-3-phenylpropane (3b) was determined by HPLC using
Chiralcel OD-H (Daicel) column. (hexane/2-PrOH: 18/1, flow
rate 0.5 mL min¹1, t = 14.4 min (R), t = 17.4 min (S)).
Typical Procedure for the Methanolysis of 1,2-Epoxy-3-
phenoxypropane (3c).
(R)-MOF-1 (20 mg) desolvated as
3
a) K. Uemura, S. Kitagawa, M. Kondo, K. Fukui, R.
above is suspended in a MeOH (0.5 mL) solution of 1,2-epoxy-
3-phenoxypropane (3c) (0.075 g, 0.5 mmol) and stirred at 60 °C
for 24 h. Then, the solid catalyst was collected by filtration,
washed with MeOH. All MeOH portions are combined and
evaporated under reduced pressure, and the yield of 1,2-epoxy-
3-phenoxypropane (3c) and 1-methoxy-3-phenoxypropan-2-ol
(5c) was determined by GC (Chiraldex £-TA, 140 °C, N2 gas,
linear velocity of 29.8 cm min¹1, t = 6.84 min (3c), t = 14.8
min (5c)). The optical purity of 1-methoxy-3-phenoxypropan-2-
Kitaura, H.-C. Chang, T. Mizutani, Chem.®Eur. J. 2002, 8, 3586.
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ol (5c) was determined by HPLC using Chiralpak OD (Daicel)
¹1
column (hexane/2-PrOH: 90/10, flow rate 1.0 mL min
,
t = 10.4 min (S), t = 19.8 min (R)). The optical purity of 1,2-
epoxy-3-phenoxypropane (3c) was determined by HPLC using
Chiralpak OD (Daicel) column (hexane/2-PrOH: 90/10, flow
rate 1.0 mL min¹1, t = 7.94 min (S), t = 13.0 min (R)).
4
For reviews, see: a) M. D. Allendorf, C. A. Bauer, R. K.
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Typical Procedure for the Methanolysis of 1-Benzyloxy-
2,3-epoxypropane (3d). (R)-MOF-1 (20 mg) desolvated as
above is suspended in a MeOH (0.5 mL) solution of 1-benzyl-
oxy-2,3-epoxypropane (3d) (0.082 g, 0.5 mmol) and stirred
at 60 °C for 24 h. Then, the solid catalyst was collected by
filtration, washed with MeOH. All MeOH portions are com-
bined and evaporated under reduced pressure, and the yield
of 1-benzyloxy-2,3-epoxypropane (3d) and 1-benzyloxy-3-
methoxypropan-2-ol (5d) was determined by GC (Chiraldex
£-TA, 140 °C, N2 gas, linear velocity of 29.8 cm min¹1, t =
8.85 min (3d), t = 29.8 min (5d)). The optical purity of 1-
benzyloxy-3-methoxypropan-2-ol (5d) was determined by
HPLC using Chiralcel AS (Daicel) column (hexane/2-PrOH:
90/10, flow rate 0.5 mL min¹1, t = 19.2 min (R), t = 26.3 min
(S)). The optical purity of 1-benzyloxy-2,3-epoxypropane (3d)
was determined by HPLC using Chiralcel AS (Daicel) column
(hexane/2-PrOH: 90/10, flow rate 0.5 mL min¹1, t = 12.8 min
(R), t = 16.0 min (S)).
5
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