Regio- and stereoselective cyclizations of dianhydro sugar alcohols catalyzed by a chiral (salen)CoIII complex

Article abstract of DOI:10.1016/j.carres.2005.09.003

The (salen)Co^IIIOAc ((R,R)-1 and (S,S)-1) catalyzed cyclizations of the chiral dianhydro sugars, 1,2:5,6-dianhydro-3,4-di-O-methyl-d-glucitol (2), 1,2:5,6-dianhydro-3,4-di-O-methyl-d-mannitol (3), 1,2:5,6-dianhydro-3,4-di- O-methyl-l-iditol (4)

Full text of DOI:10.1016/j.carres.2005.09.003

Carbohydrate
RESEARCH
Carbohydrate Research 340 (2005) 2677–2681
Note
Regio- and stereoselective cyclizations of dianhydro sugar
alcohols catalyzed by a chiral (salen)CoIII complex
Toshifumi Satoh,a,b Tomoko Imai,a Satoshi Umeda,c Katsuyuki Tsuda,c
Hisaho Hashimotod and Toyoji Kakuchia,*
aDivision of Biotechnology and Macromolecular Chemistry, Graduate School of Engineering, Hokkaido University,
Sapporo 060-8628, Japan
bDivision of Innovative Research, Creative Research Initiative ‘Sousei’ (CRIS), Hokkaido University, Sapporo 001-0021, Japan
cDepartment of Materials Chemistry, Asahikawa National College of Technology, Asahikawa 071-8142, Japan
dDepartment of Science and Engineering for Materials, Tomakomai National College of Technology, Tomakomai 059-1275, Japan
Received 25 July 2005; received in revised form 6 September 2005; accepted 6 September 2005
Available online 22 September 2005
Abstract—The (salen)CoIIIOAc ((R,R)-1 and (S,S)-1) catalyzed cyclizations of the chiral dianhydro sugars, 1,2:5,6-dianhydro-3,4-
di-O-methyl-D-glucitol (2), 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol (3), 1,2:5,6-dianhydro-3,4-di-O-methyl-L-iditol (4), and
1,2:4,5-dianhydro-3-O-methyl-L-arabinitol (5), is a facile method for the synthesis of anhydroalditol alcohols. Cyclization of 2 using
(R,R)-1 and (S,S)-1 proceeded diastereoselectively to form 2,5-anhydro-3,4-di-O-methyl-D-mannitol (6) and 2,5-anhydro-3,4-di-O-
methyl-L-iditol (7), respectively. The cyclization of 3 and 5 is a novel method for obtaining 1,6-anhydro-3,4-di-O-methyl-D-mannitol
(11) and a stereoselective route to 1,5-anhydro-3-O-methyl-L-arabinitol (13). It is proposed that the reaction occurs via endo-selec-
tive cyclization of an epoxy alcohol produced by the endo-selective ring-opening of one of the two epoxide moieties in the starting
material.
ꢀ 2005 Elsevier Ltd. All rights reserved.
Keywords: Diastereoselective cyclization; Dianhydro sugars; endo-Selective cyclization; endo-Selective ring-opening; 1,2:5,6-Dianhydrohexitol;
1,2:4,5-Dianhydropentitol
Various anhydroalditol alcohols have been prepared due
not only to interest in their chemical and biochemical
properties, but also due to their use as chiral building
blocks for the synthesis of optically pure organic
compounds.1–8 In particular, regio- and stereoselective
cyclizations of dianhydro sugars, such as 1,2:5,6-dianhy-
drohexitols and 1,2:4,5-dianhydropentitols, are an inter-
esting approach for the stereocontrolled synthesis of
carbohydrate derivatives.9–16 For example, Kuszmann
reported that the regio- and stereoselective cyclizations
of 3,4-di-O-alkyl-1,2:5,6-dianhydro-D-mannitol and
3,4-di-O-alkyl-1,2:5,6-dianhydro-L-iditol with hydrogen
bromide produced the corresponding 2,5-anhydro-6-
bromo-6-deoxy-D-glucitol and 2,5-anhydro-1-bromo-1-
deoxy-D-glucitol, respectively.9 In addition, we reported
that the asymmetric cyclization of meso-1,2:5,6-dianhy-
drohexitols and meso-1,2:4,5-dianhydropentitols using
chiral (salen)CoIIIAc ((R,R)-1 and (S,S)-1) led to chiral
anhydroalditol alcohols in extremely high enantiomeric
excesses.14 These reactions arise from the enantioselec-
tive hydrolysis of one of the epoxides, followed by cycli-
zation of the resulting diol onto the other epoxide. We
were interested in further studying the cyclization of
asymmetric dianhydro sugars using (R,R)-1 and (S,S)-
1. We report here, the diastereoselective cyclizations of
1,2:5,6-dianhydro-3,4-di-O-methyl-D-glucitol (2) and
the regio- and stereoselective cyclization of 1,2:5,6-dian-
hydro-3,4-di-O-methyl-D-mannitol (3), 1,2:5,6-dianhy-
dro-3,4-di-O-methyl-L-iditol (4), and 1,2:4,5-dianhydro-
3-O-methyl-L-arabinitol (5), using (R,R)-1 and (S,S)-1
(Fig. 1).
*
Corresponding author. Tel./fax: +81 11 706 6602; e-mail: kakuchi@
poly-mc.eng.hokudai.ac.jp
0008-6215/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2005.09.003

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T. Satoh et al. / Carbohydrate Research 340 (2005) 2677–2681
HO
HO
O
CH3O
O
O
H
N
H
N
S
CH3O
+
R
H3CO
OH
OH
Co
(R,R)-1
R
R
OCH3
OCH3
OCH3
O
O
O
OAc
8
6
H2O
3.3% (d.e. 88.6%)
89.3% (d.e. 91.2%)
2
2
(R,R)-1
(S,S)-1
OH
O
O
O
CH3O
OH
O
O
R
R
S
CH3O
H2O
S
+
H3CO
H3CO
R
HO
HO
OCH3
R
OCH3
OCH3
OCH3
OCH3
R
S
R
S
O
O
9
O
7
2.7% (d.e. 92.9%)
3
81.4% (d.e. 91.3%)
5
4
Scheme 1.
Figure 1. Structures for 1–5.
The dianhydro sugar with the (2S,5R)-configuration,
2, possesses two epoxy groups whose reactivities are non-
equivalent. The cyclization of 2 in the presence of (salen)-
CoIIIAc 1 (0.5 mol %) was carried out with 1.1 equiv of
water at room temperature. The color of the reaction
mixture changed from dark brown to light brown as
the reaction progressed. The reaction using (R,R)-1 was
complete in about 3 h, while that using (S,S)-1 needed
about 51 h for completion, thus showing that the cycliza-
tion of 2 with (R,R)-1 is more efficient than that with
(S,S)-1. The reaction results are summarized in Table 1
and compared with those of the cyclizations using HCl,
KOH, and the reaction without a catalyst. The cycliza-
tions of 2 under acidic and basic conditions gave the
two five-membered ring compounds, 2,5-anhydro-3,4-
di-O-methyl-D-mannitol (6) and 2,5-anhydro-3,4-di-O-
methyl-L-iditol (7), and the two six-membered ring com-
pounds, 1,5-anhydro-3,4-di-O-methyl-D-glucitol (8) and
2,6-anhydro-3,4-di-O-methyl-D-glucitol (9), although
the diastereoselectivities of these transformations were
low. On the contrary, the cyclizations using 1 as a cata-
lyst proceeded diastereoselectively to produce 6 in
89.3% (de 91.2%) yield for (R,R)-1 and 7 in 81.4% (de
91.3%) yield for (S,S)-1. Two six-membered ring com-
pounds 8 and 9 were also produced in 3.3% (de 88.6%)
and 2.7% (de 92.9%) yields using (R,R)-1 and (S,S)-1,
respectively (Scheme 1). The diastereomeric excesses
for the formation of the five-membered rings were over
90%. The proposed mechanism for the cyclization of 2
is illustrated in Scheme 2. Using (R,R)-1, endo-selective
ring-opening of one of the epoxide rings is followed by
cyclization to form the five-membered cyclic compound
6 as the major product. In contrast, when (S,S)-1 is used,
slow ring-opening of the other epoxide moiety proceeds,
followed by exo-cyclization leading to the diastereomeric
five-membered ring product, 7.
Table 1. Cyclization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-glucitol
(2) using chiral (salen)CoIIIOAc (1) and other conditions
Catalyst
Time (h) Temperature
Yieldb (%)
(ꢁC)
6
7
8
9
The C2 symmetric dianhydro sugars with the (2R,5R)-
and (2S,5S)-configurations (3 and 4, respectively) have
two epoxy groups of the same reactivity. Table 2 sum-
marizes the cyclization results of 3 and 4 using (R,R)-1
and (S,S)-1. The cyclization of 3 with (R,R)-1 proceeded
rapidly at room temperature and produced 2,5-anhydro-
3,4-di-O-methyl-D-glucitol (10), 1,6-anhydro-3,4-di-O-
methyl-D-mannitol (11), and 1,6:2,5-dianhydro-3,4-di-
(R,R)-1a
(S,S)-1a
HCla
3
51
24
24
7
rt
rt
rt
60
100
89.3
3.7 81.4
37.0 35.2 10.3 9.8
47.3 35.9 8.5 6.6
46.5 17.9 21.5 8.3
4.1
3.3 0.2
0.1 2.7
KOHa
None (H2O)
a [2]/[catalyst] = 200.
b Estimated by 13C NMR using the inverse gated spin decoupling
technique.
Co
α
OH
HO
O
α
6
8
S
(R,R)-1
CH3O
OCH3
CH3O
O
R
O
(S,S)-1
H2O
(R,R)-1
fast
β
OCH3
O
O
CH3O
S
R
Co
O
α
β
(S,S)-1
HO
OCH3
α
OH
7
9
R
CH3O
OCH3
CH3O
2
slow
S
O
O
H2O
OCH3
Scheme 2.

T. Satoh et al. / Carbohydrate Research 340 (2005) 2677–2681
2679
Table 2. Cyclization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol
(3) and 1,2:5,6-dianhydro-3,4-di-O-methyl-L-iditol (4) using chiral
(salen)CoIIIOAc (1)a
the molar fraction of (R,R)-1 in the reaction system led
to increasing yields of 11. This is the first synthesis of a
3,4-O-disubstituted 1,6-anhydro-D-mannitol derivative.
The cyclization of 4 with 1 exhibited a different reac-
tivity compared to that of 3. When (R,R)-1 was used, no
reaction was observed, while the cyclization using (S,S)-
1 afforded only the five-membered ring compound 10 in
49% yield. The formation of six- and seven-membered
ring analogs, or bicyclic compounds was not observed.
These results for the cyclizations of dianhydro sugars
2–4 indicate that (R,R)-1 and (S,S)-1 selectively coordi-
nate to the R- and S-epoxy groups in the dianhydro
sugar alcohol, respectively, leading to a stereoselective
ring-opening reaction. An almost complete reaction
was obtained for the cyclization of 3 with (R,R)-1 in
3 h, while the reaction of 4 with (S,S)-1 yielded the cyclic
compounds at nearly half conversion in 48 h. Similar re-
sults were also observed for the cyclization of 2. These
phenomena can be explained by the difference in the
coordinating power between the catalyst 1 and the
epoxy group,19–21 which arises from the configuration
of the epoxy group and the neighboring methoxy group
in the dianhydro sugars, that is, the S-epoxy group is in
a syn-configuration with the neighboring methoxy group
while the R-epoxy group is anti. The coordinating power
between the R-epoxy group and (R,R)-1, therefore, is
stronger than that between the S-epoxy group and
(S,S)-1 for the dianhydro sugar alcohols 2–4.
Dianhydro sugar 5 has two S-epoxy groups, but their
surroundings are nonequivalent; in one the methoxy
group is syn while in the other this group is anti. As
was seen for the cyclization of 2–4, the reaction of 5 with
(S,S)-1 proceeded smoothly to afford 1,5-anhydro-3-O-
methyl-L-arabinitol (13) in 85.0% yield, while no reaction
was observed with (R,R)-1 (Scheme 5). Compound 13
was formed through an extremely high regio- and stereo-
selective process, that is, the endo-selective ring-opening
of an epoxy group in 5 followed by 6-endo-cyclization,
as in the formation of 11 from 3.
In this study, the regioselective cyclization of dian-
hydro-alditol derivatives was achieved using chiral
(salen)CoIII catalysts. These reactions involve the stereo-
selective coordination of the catalyst with the substrate
leading to the ring-opening of one epoxy group by the
Substrate
Catalyst
Time (h)
Yieldc (%)
10
11
12
3
(R,R)-1
(R,R)-1b
(S,S)-1
3
3
6
57.2
30.4
0
27.9
35.0
0
5.9
6.8
0
4
(R,R)-1
(S,S)-1
6
48
0
49.1
0
0
0
0
a [Substrate]/[catalyst] = 200, temperature—rt.
b [3]/[catalyst] = 0.5.
c Estimated by 13C NMR using the inverse gated spin decoupling
technique.
O-methyl-D-glucitol (12) in 57.2%, 27.9%, and 5.9%
yields, respectively, as shown in Table 2 and Scheme 3.
On the contrary, when (S,S)-1 was used, no product
was obtained and unreacted 3 was recovered. The pro-
posed mechanism for the formation of the products is
shown in Scheme 4. First, the dianhydro sugar alcohol
3 is coordinated with (R,R)-1 to allow the endo-cleavage
of the first epoxy group by water. During the next intra-
molecular cyclization, 5-exo-cyclization of the second-
ary hydroxyl group as predicted by BaldwinÕs rules17
afforded 10. When the second epoxy group is also coor-
dinated with (R,R)-1, intramolecular cyclization leads to
7-endo-cyclization, as was also observed using Jacob-
senÕs catalyst,18 to produce the seven-membered com-
pound 11. It is noteworthy that the seven-membered
ring product 11 was formed by the 7-endo cyclization
of the initially formed epoxy alcohol, meaning that its
formation ignored the inherent stereoelectronic prefer-
ence for the intramolecular exo-attack during the cycli-
zation of 3.17 The mechanism for the formation of 11
was supported by the following results: the increase in
O
O
CH3O
HO
O
OH
OH
O
CH3O
CH3O
(R,R)-1
3
+
+
H2O
HO
OCH3
OCH3
OCH3
11
10
12
Scheme 3.
OH
5-Exo
HO
(R,R)-1
O
(R,R)-1
10
11
CH3O
R
R
Co
O
OCH3
O
CH3O
R
R
OCH3
7-Endo
OH
H2O
O
Co
3
R
CH3O
OCH3
(R,R)-1
R
Co O
Scheme 4.

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T. Satoh et al. / Carbohydrate Research 340 (2005) 2677–2681
O
technique. The residue was purified by column
chromatography.
HO
(S,S)-1
H2O
(R,R)-1
H2O
No reaction
5
CH3O
OH
85.0%
1.3. 1,2:4,5-Dianhydro-3-O-methyl-L-arabinitol (5)
13
Compound 5 was prepared from D-arabinitol as previ-
ously described (see Supplementary data).13 Bp 73 ꢁC
Scheme 5.
23
(22 mmHg); ½aꢁD ꢀ10.7 (c 1.0, CHCl3); 1H NMR
addition of water followed by regioselective cyclization
via ring-opening of the remaining epoxy group. The
difference in the coordinating power between the cata-
lyst and the epoxy group arises from the configuration
of the epoxy group and the neighboring methoxy group.
The coordinating power with the catalyst was shown to
be stronger when the epoxy group is anti to this sub-
stituent as opposed to syn. As a result, these cyclizations
formed specific anhydroalditol alcohols in a highly
stereoselective manner.
(CDCl3): d 2.66 (dd, 1H, J = 4.9, 2.9 Hz, CH2), 2.76
(dd, 1H, J = 5.0, 2.7 Hz, CH2), 2.79–2.87 (m, 3H), 3.05
(ddd, 1H, J = 5.6, 2.9, 2.7 Hz, CH), 3.12 (ddd, 1H, J =
6.6, 2.9, 2.7 Hz, CH), 3.50 (s, 3H, –OCH3); 13C NMR
(CDCl3): d 42.92 (CH2), 45.26 (CH2), 50.69 (CH),
52.35 (CH2), 58.29 (–OCH3), 81.82 (CH). Anal. Calcd
for C6H10O3: C, 55.37; H, 7.74. Found: C, 54.70; H, 7.59.
1.4. 2,5-Anhydro-3,4-di-O-methyl-D-mannitol (6) and
1,5-anhydro-3,4-di-O-methyl-D-glucitol (8)
1. Experimental
Compounds 6 and 8 were obtained by the reaction of 2
with water and (R,R)-1 for 3 h at rt. After removing the
catalyst, the residue was purified by column chromato-
graphy using EtOAc/CH3OH (5/1) as the eluant. Evap-
oration of the fractions having Rf values of 0.34 and 0.45
gave 6 (colorless liquid, 89.3% yield (de 91.2%)), and 8
(colorless liquid, 3.3% yield (de 88.6%)), respectively.
1.1. General methods
The H (400 MHz) and 13C NMR (100 MHz) spectra
1
were recorded using a JEOL JNM-A400 II spectro-
meter. All signals were expressed as ppm downfield from
tetramethylsilane used as the internal standard (d value
in CDCl3). Diastereomeric excess (de) values were esti-
mated by 13C NMR using the inverse gated spin decou-
pling technique with a 7.0 s delay and 6000 scans at
25 ꢁC (45ꢁ pulse angle). Optical rotations were measured
using a JASCO DIP 1000 digital polarimeter with a so-
dium lamp. D-Arabinitol was prepared by the reduction
of D-arabinose.22 The catalysts (R,R)-1 and (S,S)-1 were
prepared by reported procedures.23 For the preparation
of 2, 3, and 4, the Kuszmann method was used.24 These
dianhydro sugars were distilled over CaH2 under vac-
uum before the reactions. Column chromatography
was performed using silica gel 60 (particle size 0.063–
0.200 mm, Merck). Thin-layer chromatography was per-
formed using silica gel 60 F254 (0.25 mm thick, Merck).
1
Compound 6: H NMR (CDCl3): d 4.15–4.01 (m, 2H),
3.80–3.62 (m, 6H), 3.40 (s, 6H, –OCH3), 2.95–2.73 (br
s, 2H, –OH); 13C NMR (CDCl3): d 85.80 (CH), 83.21
(CH), 62.70 (–CH2OH), 57.59 (–OCH3). Compound 8:
1H NMR (CDCl3): d 3.94 (dd, 1H J = 11.2, 5.6 Hz),
3.74–3.63 (m, 5H), 3.50 (s, 3H, –OCH3), 3.46 (s, 3H,
–OCH3), 3.24–3.12 (m, 1H), 3.04–3.01 (m, 1H), 2.85
(br s, 2H, –OH); 13C NMR (CDCl3): d 88.22 (CH),
79.89 (CH), 79.50 (CH), 69.65 (CH), 69.27 (–CH2OH),
61.68 (–CH2OH), 60.68 (–OCH3), 60.16 (–OCH3).
1.5. 2,5-Anhydro-3,4-di-O-methyl-L-iditol (7) and
2,6-anhydro-3,4-di-O-methyl-D-glucitol (9)
Compounds 7 and 9 were obtained by the reaction of 2
with water and (S,S)-1 for 51 h at rt. The products were
purified by column chromatography using EtOAc/
CH3OH (5/1) as the eluant. Evaporation of fractions
having Rf values of 0.35 and 0.45 gave 7 (colorless
liquid, 81.4% yield (de 91.3%)) and 9 (colorless liquid,
1.2. General procedure for the cyclization of dianhydro
sugar alcohols
All reactions were carried out under ambient atmos-
phere. A typical procedure is as follows: Water (57 lL,
3.17 mmol) was added to 2 (0.50 g, 2.87 mmol) and
(R,R)-1 (9.2 mg, 1.39 · 10ꢀ2 mmol), and the mixture
was stirred for 3 h while occasionally checking the pro-
gress of the reaction by thin-layer chromatography.
After the reaction was complete, the mixture was diluted
with water, filtered through a membrane (nitrocellulose,
1.0 lm), and the filtrate concentrated. To estimate the
conversion, the residue was analyzed by 13C NMR
spectroscopy using the inverse gated spin decoupling
1
2.7% yield (de 92.9%)), respectively. Compound 7: H
NMR (CDCl3): d 4.30–4.20 (m, 2H), 3.96 (d, 2H),
3.90–3.75 (m, 4H), 3.45 (s, 6H, –OCH3), 2.48–2.30 (br
s, 2H, –OH); 13C NMR (CDCl3): d 84.91 (CH), 79.44
(CH), 61.62 (–CH2OH), 58.06 (–OCH3). Compound 9:
1H NMR (CDCl3): d 4.09–4.03 (m, 1H), 3.84–3.60 (m,
5H), 3.54 (s, 6H, –OCH3), 3.24–3.10 (m, 2H), 3.06 (br
s, 2H, –OH); 13C NMR (CDCl3): d 76.05 (CH), 75.91
(CH), 74.57 (CH), 66.45 (CH), 64.45 (–CH2OH), 61.92
(–CH2OH), 58.52 (–OCH3), 58.46 (–OCH3).

T. Satoh et al. / Carbohydrate Research 340 (2005) 2677–2681
2681
1.6. 2,5-Anhydro-3,4-di-O-methyl-D-glucitol (10), 1,6-
anhydro-3,4-di-O-methyl-D-mannitol (11) and 1,6:2,5-
dianhydro-3,4-di-O-methyl-D-glucitol (12)
References
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Compounds 10–12 were obtained by the hydration of 3
with (R,R)-1 after 3 h at rt. After removing the catalyst,
the products were purified by column chromatography
using EtOAc/acetone (1/1) as the eluant. Evaporation
of the fractions having Rf values of 0.37, 0.25, and
0.66 gave 10 (colorless liquid, 57.2% yield), 11 (colorless
liquid, 27.9% yield), and 12 (colorless liquid, 5.9% yield),
respectively. Compound 10: the 1H NMR and 13C
NMR chemical shifts of 10 were as reported previ-
1
ously.11 Compound 11: H NMR (CDCl3): d 4.20–4.05
8. Aghmiz, M.; Aghmiz, A.; Diaz, Y.; Masdeu-Bulto, A.;
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(m, 2H, H-2,5), 3.95–3.60 (m, 6H, H-1,3,4,6), 3.52 (s,
6H, –OCH3), 2.75–2.63 (br s, 2H, –OH); 13C NMR
(CDCl3): d 81.39 (C-3,4), 71.39 (C-1,6), 69.20 (C-2,5),
59.16 (–OCH3). Anal. Calcd for C8H16O5: C, 49.99; H,
8.39. Found: C, 49.69; H, 8.48. FD-MS m/z (relative
intensity), 192 (M+ꢀ100), 193 (MH+ꢀ28.8). Compound
9. Kuszmann, J. Carbohydr. Chem. 1979, 73, 93–101.
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1
12: H NMR and 13C NMR chemical shifts of 12 were
the same as reported previously.11
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mol. Rapid Commun. 1999, 20, 55–58.
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1.7. 1,5-Anhydro-3-O-methyl-L-arabinitol (13)
Compound 13 was obtained by the reaction of 5 with
water and (S,S)-1 for 48 h at rt. After removing the cat-
alyst, the products were purified by column chromato-
graphy using EtOAc as the eluant. Evaporation of the
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25
oil, 85.0%). ½aꢁD +77.8 (c 1.0, CHCl3), 1H NMR
(D2O): d 4.23 (m, 1H, H-4), 3.91 (m, 3H, H-1,2,5),
3.58 (dt, 1H, H-5), 3.46 (s, 3H, –OCH3), 3.32 (dq,
1H), 3.21 (t, 1H, H-1); 13C NMR (D2O): d 85.01 (C-
3), 72.73 (C-5), 72.09 (C-1), 68.38 (C-2), 67.26 (C-4),
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Supplementary data
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Supplementary data associated with this article can be
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2005.09.003.
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