A new approach to 1-deoxy-azasugars: Asymmetric synthesis of 1-deoxymannojirimycin and 1-deoxyaltronojirimycin

Article abstract of DOI:10.1039/a605128f

A concise and flexible method, based upon the kinetic resolution of racemic α-furfuryl amine derivatives, for the asymmetric synthesis of 1-deoxy-azasugars is described. (-)-1-Deoxymannojirimycin 1a has been synthesized in nine steps (5.8% overall yield) from the α-furfurylamine derivative 3 and its enantiomer (+)-1-deoxymannojirimycin 1b has been similarly synthesized in nine steps (3.7% overall yield) from (S)-3. (-)- and (+)-1-Deoxyaltronojirimycin, 16a and 16b, have also been synthesized in five steps (overall yields 21.5% and 25.4%, respectively) from the intermediates 9a and 9b, respectively.

Full text of DOI:10.1039/a605128f

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A new approach to 1-deoxy-azasugars: asymmetric synthesis of
1-deoxymannojirimycin and 1-deoxyaltronojirimycin
Yi-Ming Xu and Wei-Shan Zhou*
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu,
Shanghai 200032, China
A concise and flexible method, based upon the kinetic resolution of racemic á-furfuryl amine derivatives,
for the asymmetric synthesis of 1-deoxy-azasugars is described. (Ϫ)-1-D eoxymannojirimycin 1a has been
synthesized in nine steps (5.8% overall yield) from the á-furfurylamine derivative 3 and its enantiomer
(+)-1-deoxymannojirimycin 1b has been similarly synthesized in nine steps (3.7% overall yield) from (S)-3.
(Ϫ)- and (+)-1-D eoxyaltronojirimycin, 16a and 16b, have also been synthesized in five steps (overall yields
21.5% and 25.4%, respectively) from the intermediates 9a and 9b, respectively.
Naturally occurring polyhydroxylated piperidine alkaloids such
as (Ϫ)-1-deoxymannojirimycin 1a and (+)-1-deoxynojirimycin
2, which can be regarded as 1-deoxy-azasugars, have received
much attention in recent years. Deoxymannojirimycin 1a, iso-
lated from Lonchocarpus sp.,1 is a moderate inhibitor of several
α-mannosidases2 and a good inhibitor of mammalian α-
fucosidase.3 Deoxynojirimycin 2, first prepared by hydrogen-
derivative 3 by the reported procedure9 would yield (2R,6R)-4a
and (S)-3 which could be converted into the enantiomer of 4a
by treatment with m-CPBA (Scheme 1). Both 4a and its enan-
O
a
3
+
6
1
N
OMe
OMe
OMe
O
O
HO
Ts NH
Ts NH
(S)-3
b
Ts
OH
OH
4
3
(2R,6R)-4a
HO
OH
6
HO
OH
3
4
5
N
2
1
3
5
6
2
1
OH
OH
N
O
H
H
OMe
HO
N
1a
2
Ts
The numbering system shown in formula 1a has been used only for
compounds 1a, 1b and 16a, 16b; the numbering system used in the
systematic names for all other compounds is shown in formula 2
(2S,6S)-4b
Scheme 1 Reagents and conditions: a, Ti(OPri)4, -(+)-DIPT, TBHP,
silica gel, CaH2, CH2Cl2, 25 ЊC, 3 days; b, m-CPBA, CH2Cl2, RT
ation of a streptomyces product nojirimycin isolated from
mulberries,4 is an inhibitor of a number of glucosidases,5 and
it has potential for use in the therapy of diabetes mellitus,
hyperlipoproteinemia, cancer and arthritis.6 Because of the
biological activity of these compounds as well as their struc-
ture, the latter characterized by four contiguous chiral centres
and high density of functionality, much effort has been dir-
ected toward their stereoselective synthesis.7 Although the
majority of these syntheses seem to lack both flexibility and
general applicability, two published recently and employing
the dihydropyridone system as a building block for the
preparation of 1-deoxymannojirimycin 6b and 1-deoxyallo-
nojirimycin,8 are notable for their flexible, albeit multi-stage,
nature. In view of these problems development of concise and
flexible methods for the construction of such 1-deoxy-
azasugars continues to be of importance in probing structure–
activity correlations.
Our group has previously developed an efficient method for
kinetic resolution of racemic α-furfurylamine derivatives by
using a modified Sharpless asymmetric epoxidation reagent.9
This reaction afforded two versatile chiral building blocks, both
of which are very suitable for elaboration to a variety of alkal-
oid skeletons.10 Here we report the application of this method
to the synthesis of (Ϫ)- and (+)-1-deoxymannojirimycin, 1a 11
and 1b, as well as (Ϫ)- and (+)-1-deoxyaltronojirimycin, 16a
and 16b, which are analogues of 1a and 1b.
tiomer 4b are potential building blocks for the synthesis of 1-
deoxy-azasugars since the double bond and the carbonyl group
may be further functionalized. In view of this our strategy has a
potential to generate all isomers of 1-deoxy-azasugars.
Initially, we report on the use of 4a as a building block for the
synthesis of (Ϫ)-1-deoxymannojirimycin 1a.
As depicted in Scheme 2, treatment of 4a with triethyl ortho-
formate generated 5a, reduction of which with NaBH4 and
CeCl3ؒ7H2O afforded solely the alcohol 6a. In this, the configur-
ation of the hydroxy group was assigned by 2D-NOESY
spectroscopic analysis and found to be the reverse of that
desired for the target molecule. Inversion of this configuration
was successfully achieved by employing a Mitsunobu reaction.
Removal of the ethoxy group of 7a by NaBH4 in formic acid,
followed by Sharpless asymmetric dihydroxylation 12 led
exclusively to the diol 9a which was protected to give diacetate
10a. Although attempts to remove the methyl group in 10a
selectively with Me3SiI failed, demethylation proceeded
smoothly with BBr3. Since 2D-NOESY analysis of 11a (see Fig.
1) showed that there is no NOE correlation between H3 and H4,
nor between H2 and H3, the Mitsunobu reaction is clearly suc-
cessful with stereospecific introduction of β-dihydroxy groups
at C5 and C4.
Finally, deprotection of 11a by sodium naphthalenide fol-
We envisioned that kinetic resolution of the α-furfurylamine
lowed by chromatography on a column of Dowex-50 (H+) gave
J. Chem. Soc., Perkin Trans. 1, 1997
741

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O
OH
a
b
O
N
OR
SO2
4a
OMe
OMe
O
OBz
OMe
RO
OBz
EtO
N
EtO
N
a
b
9a
Ts
Ts
6a
OMe
N
5a
Ts
Ts
13a R = H
c
12a
c
14a
R = Ac
OBz
OBz
d
d
OMe
OMe
N
EtO
N
OH
OAc
Ts
8a
Ts
7a
HO
OH
AcO
OBz
OH
e
e
OH
N
H
N
Ts
OR
OAc
RO
OBz
OMe
AcO
OBz
16a
15a
g
h
1a
Scheme 3 Reagents and conditions: a, (i) SOCl2, NEt3, CCl4; (ii)
NaIO4, RuCl3ؒ3H2O (72.9%); b, 50% H2SO4(aq.), THF (76.5%); c,
Ac2O, pyridine, DMAP, RT (100%); d, BBr3, CH2Cl2, Ϫ78 ЊC (79.2%);
e, Na–naphthalene, DME, Ϫ60 ЊC (48.7%)
OH
N
N
Ts
Ts
R = H
10a R = Ac
11a
9a
f
OH
H4
Scheme 2 Reagents and conditions: a, HC(OEt)3, BF3ؒOEt2, 4 Å
molecular sieves THF, 0 ЊC (76.5%); b, NaBH4, CeCl3ؒ7H2O, MeOH
Ϫ30 ЊC (72.3%); c, DEAD–TPP, PhCO2H, THF, RT (91.7%); d,
NaBH4, HCO2H, 0 ЊC (86.7%); e, (DHQ)2-PHAL, OsO4, K3Fe(CN)6,
K2CO3, ButOH–H2O, RT, 2 days (84.8%); f, Ac2O, pyridine, DMAP,
RT (100%); g, BBr3, CH2Cl2, Ϫ78 ЊC (71.6%); h, Na–naphthalene,
DME, Ϫ60 ЊC (50.7%)
H3
AcO
AcO
H2
N
OBz
H5
Ts
Fig. 2 NOE correlations in 15a
evidence ring-opening of the cyclic sulfate12a occurs at C4 rather
than at C5 as expected.
Deprotection of 15a by sodium naphthalenide at Ϫ60 ЊC fol-
lowed by chromatography on a column of Dowex-50(H+) gave
(Ϫ)-1-deoxyaltronojirimycin 16a (overall yield of 21.5% in five
steps), mp 175 ЊC, [α]2D0 Ϫ30.7 (c 0.13 in MeOH).
In a similar way, (+)-1-deoxyaltronojirimycin 16b was syn-
thesized in five steps from 9b in an overall yield of 25.4%.
In summary, (Ϫ)-, (+)-1-deoxymannojirimycin, 1a and 1b,
and (Ϫ)-, (+)-1-deoxyaltronojirimycin, 16a and 16b, have been
synthesized; the method is based upon kinetic resolution of the
α-furfurylamine derivative 3. Work on (+)-1-deoxynojirimycin
2 and other analogues is in progress.
AcO
H3
OAc
H5
OBz
N
OH
H4
Ts
H2
Fig. 1 NOE correlations in 11a
(Ϫ)-1-deoxymannojirimycin 1a in 5.8% overall yield from 3, mp
185 ЊC, [α]2D0 Ϫ27† (c 0.1 in MeOH) [lit.,13 mp 185–187 ЊC,
[α]2D0 Ϫ26.7 (c 0.12 in MeOH)]. The H NMR and the mass
1
spectra of 1a were identical with those of an authentic sample.14
According to our strategy, we treated (S)-3, the slow reaction
product of kinetic resolution, with m-CPBA to obtain 4b. In
parallel with the reactions shown in Scheme 2 (+)-1-deoxy-
mannojirimycin 1b, the enantiomer of 1a, was synthesized
via 5b, 6b, 7b, 8b, 9b, 10b and 11b in 3.9% overall yield; it
had mp 175 ЊC, [α]2D0 +28.3 (c 0.17 MeOH); 5b, 6b, 7b, 8b, 9b,
10b and 11b represent the enantiomers of 5a, 6a, 7a, 8a, 9a, 10a
and 11a.
For the synthesis of (Ϫ)-1-deoxyaltronojirimycin 16a the
above-mentioned synthetic intermediate 9a was used (Scheme
3). Thus, 9a was first converted into the cyclic sulfate 12a by a
reported procedure.15 However 12a failed to undergo ring-
opening when treated with ammonium benzoate. We found,
however, that treatment of 12a with 20% H2SO4 gave two prod-
ucts 9a and 13a (1:1); with 50% H2SO4 the reaction produced
only 13a. Compound 13a was protected to give diacetate 14a
which when demethylated with BBr3 afforded 15a. The con-
figuration of 15a was deduced from its 2D NOESY spectrum
(see Fig. 2); this indicated that there was an NOE correlation
between H3 and H4, but no NOE correlation between H4 and
H5; on the other hand, H5 had an NOE correlation with the
benzoate protons, in contrast to H3 and H4 which did not.
The configuration of 13a was, therefore, confirmed. From this
Experimental
All non-aqueous reactions were carried out under nitrogen.
Tetrahydrofuran (THF), diethyl ether and dimethyl ether
(DME) were distilled from Na–benzophenone. Dichloro-
methane was distilled from CaH2. Titanium() isopropoxide
was purified by reduced pressure distillation and stored under an
inert atmosphere. Diisopropyl tartrate (DIPT) was obtained
from Tokyo Chemical Industry Co., Ltd. tert-Butyl hydroper-
oxide (TBHP) was obtained from Merck-Schuchardt Co. and
purified before use according to a standard procedure.16 Cal-
cium hydride was obtained from Fluka Co. Mps were measured
on a Büchi 535 melting-point apparatus and are uncorrected.
1H and 13C NMR spectra were measured on a Bruker AM-300
(300 MHz) with CDCl3 as solvent unless otherwise noted, and
values are reported in ppm using TMS as internal standard. IR
spectra were measured on a Schimadzu IR 400 spectrometer.
MS spectra were conducted on an HP5890 spectrometer or a
Finnigan MAT-8430 spectrometer. The optical rotations, [α]2D0,
were measured on a Perkin-Elmer 241 MC automatic polar-
imeter in a 1-dm cell and are recorded in units of 10Ϫ1 deg cm2
g
Ϫ1. Elemental analyses were performed by the Analytical
department of this Institute.
1-(2-Furyl)-2-methoxy-N-tosylethylamine 317
A 500-cm3 round three-necked flask was charged with SnCl2
† [α]D Values given in units of 10Ϫ1 deg cm2 gϪ1
.
742
J. Chem. Soc., Perkin Trans. 1, 1997

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(7.6 g) and THF (10 cm3) under N2 to which a solution of LiBr
(3.5 g) in THF (15 cm3) and chloromethoxymethane (3.1 cm3)
was added at room temperature (RT). After 10 min, the reac-
tion mixture was cooled to Ϫ78 ЊC and BuLi (1.6 mol dmϪ3; 100
cm3) was added to it dropwise. After the mixture had been
stirred at Ϫ78 ЊC for 1 h, a solution of N-furfuryltoluene-p-
sulfonamide (10 g) in THF (40 cm3) was added to it. After 30
min, the reaction mixture was warmed to Ϫ30 ЊC and then
treated with saturated aqueous NH4Cl and extracted with ethyl
acetate. The combined extracts were washed with brine, dried
(Na2SO4), concentrated under reduced pressure and the
residue flash column chromatographed on silica gel (light
petroleum–ethyl acetate, 7:1) to give 3 (4.8 g, 40.5%) as a solid,
mp 97.8 ЊC; νmax(KBr)/cmϪ1 3300, 3050, 2900, 1603 and 1460; δH
7.59 (2 H, d, J 8.3, Ph), 7.19 (2 H, d, J 8.3, Ph), 7.13 (1 H, m,
5-H), 6.12 (1 H, dd, J 1.8, 3.2, 4-H), 6.03 (1 H, d, J 3.2, 3-H),
5.14 (1 H, d, J 7.4, NH), 4.53 (1 H, m, α-H), 3.60 (1 H, dd, J 5.3,
9.7, CH2aOCH3), 3.44 (1 H, dd, J 4.9, 9.7, CH2bOCH3), 3.20
(3 H, s, OCH3) and 2.33 (3 H, s, Ts-CH3); m/z 295 (M+), 250
(M+ Ϫ CH2OCH3) and 155 (Ts+) (Found: C, 56.88; H, 5.71; N,
4.58. Calc. for C14H17NO4S: C, 56.93; H, 5.80; N, 4.74%).
Flash chromatography on silica gel (light petroleum–ethyl acet-
ate, 6:1) afforded 5a (917 mg, 76.5%) as a solid, mp 71.8 ЊC;
[α]2D0 Ϫ1.71 (c 2.75 EtOH). νmax(KBr)/cmϪ1 2900, 1700, 1600
and 1450; δH 7.58 (2 H, d, J 8.2, Ph), 7.25 (2 H, d, J 8.2, Ph),
6.77 (1 H, dd, J 4.4, 10.4, 5-H), 5.82 (1 H, d, J 10.4, 4-H), 5.64
(1 H, d, J 4.4, 6-H), 4.55 (1 H, t, J 7.1, 2-H), 4.05 (1 H, dd, J 7.1,
9.4, CHaHbOMe), 3.84 (1 H, dd, J 7.7, 10.0, CHaHbOMe), 3.69
(2 H, m, OCH2Me), 3.39 (3 H, s, OCH3), 2.41 (3 H, s, Ts-Me)
and 1.26 (3 H, t, J 7.0, OCH2Me); m/z 294 (M+ Ϫ EtO), 249
(M+ Ϫ EtO Ϫ CH2OMe) and 155 (Ts+) (Found: C, 56.40; H,
6.03; N, 4.02. Calc. for C16H21NO5S: C, 56.62; H, 6.24; N,
4.13%).
(2R,3R,6R)-1-Tosyl-6-ethoxy-2-methoxymethyl-1,2,3,6-tetra-
hydropyridin-3-ol 6a
CeCl3ؒ7H2O (307 mg, 0.82 mmol) was added at RT to a solu-
tion of compound 5a (559 mg, 1.65 mmol) in MeOH (10 cm3).
NaBH4 (219 mg, 5.8 mmol) was added in portions at Ϫ30 ЊC
to the mixture which was then stirred at the same temperature
for 1 h. Saturated aqueous NH4Cl was added at Ϫ10 ЊC to the
mixture which was then extracted with ethyl acetate (3 × 10
cm3). The combined extracts were washed with brine and dried
(Na2SO4). Flash chromatography on silica gel (light petroleum–
ethyl acetate, 7: 3) then gave 6a (407 mg, 72.3%) as a solid, mp
107.4 ЊC; [α]2D0 Ϫ1.8 (c 2.5 EtOH); νmax(KBr)/cmϪ1 3450, 2900,
1600 and 1440; δH 7.69 (2 H, d, J 8.3, Ph), 7.28 (2 H, d, J 8.0,
Ph), 5.72 (2 H, m, 4-H, 5-H), 5.39 (1 H, d, J 1.8, 6-H), 4.17 (1 H,
m, 3-H), 4.09 (1 H, t, J 9.4, 2-H), 3.87–3.79 (2 H, m, OCH2Me),
3.63 (1 H, dd, J 7.1, 9.3, CHaHbMe), 3.53 (1 H, dd, J 3.7, 9.3,
CHaHbOMe), 3.32 (3 H, s, OMe), 2.41 (3 H, s, Ts-Me) and 1.22
(3 H, t, J 7.0, OCH2Me); m/z 296 (M+ Ϫ EtO), 250 (M+ Ϫ
MeC6H4) and 155 (Ts+) (Found: C, 56.37; H, 6.94; N, 4.11.
Calc. for C16H23NO5S: C, 56.29; H, 6.79; N, 4.10%).
(S)-1-(2-Furyl)-2-methoxy-N-tosylethylamine (S)-3 and
(2R,6R)-N-tosyl-6-hydroxy-2-methoxymethyl-1,2,3,6-
tetrahydropyridin-3-one 4a 9
To a solution of Ti(OPri)4 (0.99 cm3, 3.4 mmol) in CH2Cl2 (6
cm3) was added CaH2 (14 mg), silica gel (31 mg) and -(+)-
DIPT (0.85 cm3, 4.1 mmol) successively under N2 at Ϫ20 ЊC.
After 10 min, a solution of (±)-3 (1.0 g, 3.4 mmol) in CH2Cl2 (6
cm3) was added to the reaction mixture which was then stirred
for a further 10 min before anhydrous TBHP (7.01 mol dmϪ3
;
1.45 cm3, 10.2 mmol) was injected into it. After the reaction
mixture had been stirred for 3 days at RT, 10% aqueous tartaric
acid (10 cm3) was added to it at Ϫ20 ЊC. Vigorous stirring was
continued for 4 h at RT until the aqueous layer became clear.
After separation of the organic layer, the aqueous layer was
washed with CH2Cl2 (×3). The organic layer was filtered off
through a pad of silica gel and the filtrate was concentrated
under reduced pressure. The residue was dissolved in ether (10
cm3) and treated with saturated aqueous FeSO4 (10 cm3) for 10
min at 0 ЊC. The organic layer was washed with brine, dried
(Na2SO4) and concentrated under reduced pressure to afford an
oil which was purified by flash column chromatography on sil-
ica gel (light petroleum–ethyl acetate, 9:1) to afford a mixture
of (S)-3 and -(+)-DIPT. This mixture was dissolved in a mix-
ture of THF–H2O (3:1; 8 cm3) and treated with LiOHؒH2O
(0.16 g) for 2 h at 0 ЊC. The organic layer was separated, washed
with brine, dried (Na2SO4) and concentrated under reduced
pressure to give (S)-3 (0.44 g, 44%), [α]2D0 Ϫ5.4 (c 1.0 EtOH). The
spectral data (IR, 1H NMR) were identical with those of (±)-3.
The above silica gel column was then washed with light
petroleum–ethyl acetate (5:1) to produce 4a (0.45 g, 42.7%), mp
101.3 ЊC; [α] +3.24 (c 2.9 EtOH); νmax(film)/cmϪ1 3370, 2920,
1700, 1600 and 1450 cmϪ1; δH 7.77 (2 H, d, J 8.2, Ph), 7.30 (2 H,
d, J 8.2, Ph), 6.94 (1 H, dd, J 5.0, 10.3, 5-H), 6.08 (1 H, d, J 10.3,
4-H), 5.95 (1 H, dd, J 5.0, 11.4, 6-H), 4.77 (1 H, d, J 11.6, OH),
4.54 (1 H, m, 2-H), 3.69 (1 H, dd, 2.1, 9.6, CHaHbOMe), 3.44 (1
H, dd, J 2.5, 9.6, CHaHbOMe), 3.23 (3 H, s, OMe) and 2.42 (3
H, s, Ts-Me); m/z 311 (M+), 294 (M+ Ϫ H2O) and 155 (Ts+)
(Found: C, 54.12; H, 5.31; N, 4.30. Calc. for C14H17NO5S: C,
54.01; H, 5.50; N, 4.50%).
(2R,3S,6R)-1-Tosyl-6-ethoxy-2-methoxymethyl-1,2,3,6-tetra-
hydro-3-pyridyl benzoate 7a
To a solution of 6a (284 mg, 0.83 mmol) in dried THF (8 cm3)
were added triphenylphosphine (436 mg, 1.66 mmol), benzoic
acid (203 mg, 1.66 mmol) and diethyl azodicarboxylate
(DEAD) (0.26 cm3, 1.66 mmol) at RT. After the reaction mix-
ture had been stirred for 3 h, it was evaporated and the residue
diluted with CH2Cl2 (30 cm3). The resulting solution was
washed with saturated aqueous NaHCO3 and water and dried
(MgSO4). Flash chromatography on silica gel (light petroleum–
ethyl acetate, 15:1) then gave 7a (340 mg, 91.7%) as an oil;
[α]2D0 +3.75 (c 1.2 EtOH); νmax(film)/cmϪ1 2900, 1730, 1600 and
1460; δH 7.75–7.64 (4 H, m, Ph), 7.52 (1 H, m, Ph), 7.35 (2 H, m,
Ph), 7.10 (2 H, d, J 8.2, Ph), 6.17 (1 H, dd, J 4.2, 10.1, 4-H), 6.04
(1 H, dd, J 5.0, 10.1, 5-H), 5.58 (1 H, d, J 4.1, 3-H), 5.37 (1 H, d,
J 5.2, 6-H), 4.36 (1 H, dd, J 5.0, 10.0, 2-H), 3.89 (1 H, dd, J 7.1,
9.4, OCHaHbMe), 3.72–3.62 (2 H, m, OCHaHbMe, CHaHb-
OMe), 3.53 (1 H, dd, J 5.0, 10.0, CHaHbMe), 3.37 (3 H, s,
OMe), 2.21 (3 H, s, Ts-Me) and 1.22 (3 H, t, J 7.0, OCH2Me);
m/z 400 (M+ Ϫ EtO), 354 (M+ Ϫ CH3C6H4), 155 (Ts+) and 105
(C6H5CO+) (Found: C, 61.49; H, 5.96; N, 2.84. Calc. for
C23H27NO6S: C, 62.00; H, 6.11; N, 3.14%).
(2R,3S)-1-Tosyl-2-methoxymethyl-1,2,3,6-tetrahydro-3-pyridyl
benzoate 8a
NaBH4 (87 mg, 2.3 mmol) was added in portions to a solu-
tion of 7a (340 mg, 0.76 mmol) in 88% formic acid (8 cm3) at
0 ЊC. After being stirred for 1 h the mixture was evaporated
under reduced pressure and water (5 cm3) was added to the
residue. The resulting mixture was extracted with ethyl acetate
(3 × 10 cm3) and the combined extracts were washed with sat-
urated aqueous NaHCO3 and brine, dried (Na2SO4) and evap-
orated under reduced pressure. Flash chromatography on silica
gel (light petroleum–ethyl acetate, 10:1) then gave 8a (256 mg,
86.7%) as a solid, mp 92.5 ЊC; [α]2D0 +14.8 (c 1.0 EtOH);
νmax(KBr)/cmϪ1 2900, 1720, 1600 and 1460 cmϪ1; δH 7.89 (2 H,
(2R,6R)-1-Tosyl-6-ethoxy-2-methoxymethyl-1,2,3,6-
tetrahydropyridin-3-one 5a
To a solution of 4a (1.1 g, 3.54 mmol) in THF (10 cm3) were
added 4 Å molecular sieves (165 mg), triethyl orthoformate
(1.47 cm3, 8.84 mmol) and BF3ؒEt2O (45 mm3) at 0 ЊC.
After the reaction mixture had been stirred for 3 h at 0 ЊC it was
diluted with water (10 cm3) and extracted with ether. The com-
bined extracts were washed with brine and dried (Na2SO4).
J. Chem. Soc., Perkin Trans. 1, 1997
743

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m, Ph), 7.75 (2 H, d, J 8.3, Ph), 7.55 (1 H, m, Ph), 7.34 (2 H, m,
Ph), 7.16 (2 H, d, J 8.1, Ph), 6.04 (2 H, m, 4-H, 5-H), 5.45 (1 H,
d, J 4.2, 3-H), 4.56 (1 H, t, J 7.0, 2-H), 4.11 (1 H, dd, J 4.2, 18.4,
CHaHbOMe), 3.73 (1 H, dd, J 1.7, 18.4, CHaHbOMe), 3.48 (2
H, m, CH2OMe), 3.33 (3 H, s, OMe) and 2.34 (3 H, s, Ts-Me);
m/z 356 (M+ Ϫ CH2OMe), 234 (M+ + 1 Ϫ MeC6H4Ph), 155
(Ts+) and 105 (PhCO+) (Found: C, 62.96; H, 5.90; N, 5.54. Calc.
for C21H23NO5S: C, 62.82; H, 5.77; N, 3.49%).
silica gel (light petroleum–ethyl acetate, 3:2) gave 11a (226 mg,
71.6%) as a solid, mp 45.5 ЊC, [α]2D0 Ϫ2.0 (c 2.75 EtOH);
νmax(film)/cmϪ1 3350, 1740, 1720, 1600 and 1450; δH 7.76 (2
H, d, J 7.3, Ph), 7.66 (2 H, d, J 8.2, Ph), 7.59 (1 H, t, J 7.4,
Ph), 7.40 (2 H, t, J 7.7, Ph), 7.00 (2 H, d, J 8.1, Ph), 5.33 (1
H, t, J 3.1, 5-H), 5.21 (1 H, d, J 2.7, 4-H), 5.11 (1 H, m, 3-
H), 4.25 (1 H, t, J 7.0, 2-H), 4.13–3.98 (2 H, m, CH2OMe),
3.88 (1 H, dd, J 6.1, 11.4, 6-Ha), 3.41 (1 H, dd, J 11.3, 13.6,
6-Hb), 2.18 (3 H, s, Ts-Me), 2.14 (3 H, s, CH3CO) and 2.04
(3 H, s, MeCO); m/z 474 (M+ Ϫ CH2OH), 414 (M+ Ϫ C6H4),
250 (M+ Ϫ C6H4 Ϫ PhCO Ϫ AcO), 155 (Ts+) and 105 (PhCO+)
(Found: C, 56.92; H, 5.36; N, 2.43. Calc. for C24H27NO9S: C,
57.02; H, 5.38; N, 2.77%).
(2R,3S,4R,5R)-1-Tosyl-4,5-dihydroxy-2-methoxymethyl-3-
piperidyl benzoate 9a
A 25-cm3 round bottom flask was charged with tert-butyl alco-
hol (6 cm3), water (6 cm3), K3Fe(CN)6 (862 mg, 2.6 mmol),
K2CO3 (361 mg, 2.6 mmol), (DHQ)2-PHAL (2 mg) and a solu-
tion of OsO4 in toluene (25 mg cmϪ3; 0.9 cm3). Compound 8a
(350 mg, 0.87 mmol) was then added to the resulting hetero-
geneous slurry which was then vigorously stirred at RT for 2
days. The reaction was quenched by addition of Na2SO3 (989
mg) to the mixture and this was followed by ethyl acetate (5
cm3), added after 20 min. The resulting mixture was extracted
with ethyl acetate (3 × 5 cm3) and the combined extracts were
dried (Na2SO4) and evaporated. Subsequent purification by
flash chromatography on silica gel (light petroleum–ethyl acet-
ate, 1:1) gave 9a (322 mg, 84.8%) as a solid, mp 131.5 ЊC; [α]2D0
Ϫ6.13 (c 1.5 EtOH); νmax(film)/cmϪ1 3400, 2900, 1720, 1600 and
1450; δH 7.85 (2 H, m, Ph), 7.66–7.56 (3 H, m, Ph), 7.42 (2 H, t,
J 7.6, Ph), 7.07 (2 H, d, J 8.3, Ph), 5.28 (1 H, dd, J 1.1, 3.2, 3-H),
4.33 (1 H, m, 2-H), 3.93–3.80 (5 H, m, CH2OMe, 4-H, 5-H, 6-
Ha), 3.41 (3 H, s, OMe), 3.22 (1 H, m, 6-Hb) and 2.27 (3 H, s, Ts-
Me); m/z 390 (M+ Ϫ CH2OMe), 372 (M+ Ϫ H2O Ϫ CH2OMe),
105 (PhCO+) and 91 (MeC6H4+) (Found: C, 57.73; H, 5.97; N,
2.97. Calc. for C21H25NO7S: C, 57.92; H, 5.79; N, 3.22%).
(Ϫ)-1-Deoxymannojirimycin 1a
A solution of sodium naphthalenide in DME was prepared by
addition of DME (1.5 cm3) to a mixture of sodium (39 mg, 9.7
mmol) and naphthalene (222 mg, 9.7 mmol). The resulting mix-
ture was stirred at RT for 1 h. To a solution of 11a (55 mg, 0.11
mmol) in DME (2 cm3) was added sodium naphthalenide (0.6
cm3) under N2 at Ϫ60 ЊC. The reaction mixture was stirred for
1 h at Ϫ60 ЊC and then quenched by the addition of saturated
aqueous NH4Cl (2 cm3) at Ϫ30 ЊC. The resulting mixture was
separated and the organic layer was extracted with water (3 × 5
cm3). The combined aqueous solutions were washed with ether
and concentrated under reduced pressure. The residue was
chromatographed on Dowex-50(H+) (first elution with MeOH,
then concentrated aqueous NH3) to afford 1a (9 mg, 50.7%) as a
solid, mp 185 ЊC; [α]2D0 Ϫ27 (c 0.1 MeOH) [lit.,13 mp 185–
187 ЊC, [α]2D0 Ϫ26.7 (0.12 in MeOH)]; δH (D2O) 4.07 (1 H, m,
5-H), 3.85 (2 H, d, J 3.7 CH2OH), 3.72–3.62 (2 H, m, 3-H, 4-
H), 3.08 (1 H, dd, J 1.9, 14.3, 6-Ha), 2.83 (1 H, d, br, J 14.3, 6-
Hb) and 2.55 (1 H, m, 2-H) [Found (HRMS): m/z, 163.0866.
Calc. for C6H13NO4: 163.0844].
(2R,3S,4R,5R)-1-Tosyl-4,5-diacetoxy-2-methoxymethyl-3-
piperidyl benzoate 10a
To a solution of 9a (312 mg, 0.9 mmol) in pyridine (1 cm3) was
added acetic anhydride (0.5 cm3) and N,N-dimethylamino-
pyridine (DMAP; 1 mg). The reaction mixture was stirred for
24 h at RT after which it was evaporated under reduced pressure
and the residue treated with water (3 cm3). The resulting mix-
ture was extracted with ethyl acetate (3 × 5 cm3) and the com-
bined extracts were washed successively with saturated aqueous
CuSO4 and brine, dried (Na2SO4) and evaporated. Purification
of the residue by flash chromatography on silica gel (light
petroleum–ethyl acetate, 4:1) gave 10a (372 mg, 100%) as a
solid, mp 133.8 ЊC; [α]2D0 Ϫ3.46 (c 1.5 CHCl3); νmax(film)/cmϪ1
2900, 1750, 1730, 1600 and 1450; δH 7.83 (2 H, d, J 7.2, Ph),
7.68 (2 H, d, J 8.3, Ph), 7.57 (1 H, t, J 6.3, Ph), 7.41 (2 H, t, J
7.7, Ph), 7.05 (2 H, d, J 8.2, Ph), 5.36 (2 H, s, 4-H, 5-H), 5.12 (1
H, m, 3-H), 4.51 (1 H, t, J 8.1, 2-H), 3.94 (1 H, dd, J 5.3, 13.6,
6-Ha), 3.82 (1 H, t, J 8.9, CHaHbOMe), 3.70 (1 H, dd, J 7.5,
10.1, CHaHbOMe), 3.42 (3 H, s, OMe), 3.33 (1 H, dd, J 11.4,
13.6, 6-Hb), 2.24 (3 H, s, Ts-Me), 2.14 (3 H, s, MeCO) and
2.03 (3 H, s, MeCO); m/z 474 (M+ Ϫ CH2OMe), 414 (M+ + 1 Ϫ
AcO Ϫ CH2OH), 155 (Ts+) and 105 (PhCO+) (Found: C, 58.01;
H, 5.83; N, 2.66. Calc. for C25H29NO9S: C, 57.79; H, 5.63; N,
2.70%).
(2S,6S)-1-Tosyl-6-hydroxy-2-methoxymethyl-1,2,3,6-tetra-
hydropyridin-3-one 4b
A solution of m-CPBA (692 mg, 3.2 mmol) in CH2Cl2 (4 cm3)
was added to a solution of (S)-3 (860 mg, 2.9 mmol) in CH2Cl2
(5 cm3) at RT and the reaction mixture was stirred for 14 h. The
reaction was quenched by the addition of saturated aqueous
NaHCO3 (10 cm3) to the mixture at 0 ЊC. After separation of
the layers, the aqueous layer was extracted with ether (3 × 15
cm3) and the combined extracts were washed with brine, dried
(Na2SO4) and concentrated under reduced pressure. Sub-
sequent flash chromatography on silica gel (light petroleum–
ethyl acetate, 5:1) gave 4b (809 mg, 89.2%) as a solid, mp
101.3 ЊC; [α]D20 Ϫ2.0 (c 1.1 EtOH); the spectral data (IR, H
NMR) were identical with those of 4a.
1
(2S,6S)-1-Tosyl-6-ethoxy-2-methoxymethyl-1,2,3,6-tetrahydro-
pyridin-3-one 5b
As described for the preparation of its enantiomer 5a from 4a,
compound 5b was prepared from 4b (780 mg, 2.5 mmol); the
product (583 mg, 68.6%) had mp 72.0 ЊC; [α]2D0 +2.84 (c 2.5
EtOH). The spectral data were identical with those of 5a.
(2S,3S,6S)-1-Tosyl-6-ethoxy-2-methoxymethyl-1,2,3,6-tetra-
hydropyridin-3-ol 6b
As described for the preparation of its enantiomer 6a from 5a,
compound 6b was prepared from 5b (365 mg, 1.2 mmol); the
product (289 mg, 72.2%) had mp 107.1 ЊC; [α]2D0 +2.04 (c 2.4
EtOH). The spectral data were identical with those of 6a.
(2R,3S,4R,5R)-1-Tosyl-4,5-diacetoxy-2-hydroxymethyl-3-
piperidyl benzoate 11a
A dried 25-cm3 round bottom flask was charged with 10a (324
mg, 0.62 mmol) and CH2Cl2 (5 cm3) under N2 at RT; a solution
of BBr3 in CH2Cl2 (1 mol dmϪ3; 6.2 cm3) was then added at
Ϫ78 ЊC to the flask. After 1 h the reaction mixture was warmed
to Ϫ20 ЊC at which temperature stirring was continued for
5 h. The reaction was quenched by the addition of saturated
aqueous NaHCO3 (3 cm3) to the mixture which was then
extracted with ethyl acetate (3 × 5 cm3). The combined extracts
were washed with brine, dried (Na2SO4) and concentrated
under reduced pressure. Subsequent flash chromatography on
(2S,3R,6S)-1-Tosyl-6-ethoxy-2-methoxymethyl-1,2,3,6-tetra-
hydro-3-pyridyl benzoate 7b
As described for the preparation of its enantiomer 7a from 6a,
compound 7b was prepared from 6b (115 mg, 0.34 mmol); the
product (130 mg, 86.6%) was an oil; [α]2D0 Ϫ3.96 (c 2.4 EtOH).
The spectral data were identical with those of 7a.
744
J. Chem. Soc., Perkin Trans. 1, 1997

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(2S,3R)-1-Tosyl-2-methoxymethyl-1,2,3,6-tetrahydro-3-pyridyl
benzoate 8b
As described for the preparation of its enantiomer 8a from 7a,
compound 8b was prepared from 7b (120 mg, 0.27 mmol). The
product (90 mg, 83.3%) had mp 92.5 ЊC; [α]2D0 Ϫ11.0 (c 1.0,
EtOH). The spectral data were identical with those of 8a.
afford 13a (85 mg, 76.5%) as an oil; [α]2D0 Ϫ3.8 (c 0.5, EtOH);
νmax(film)/cmϪ1 3450, 2900, 1720, 1600 and 1450 cmϪ1; δH 7.93 (2
H, d, J 7.6, Ph), 7.67 (2 H, d, J 8.2, Ph), 7.60 (1 H, m, Ph), 7.44
(2 H, t, J 7.7, Ph), 7.11 (2 H, d, J 8.2, Ph), 5.48 (1 H, s, 3-H),
4.52 (1 H, m, 2-H), 3.99 (3 H, m, 4-H, 5-H, 6-Ha), 3.66 (2 H, d,
J 5.5, CH2OMe), 3.35 (3 H, s, OMe), 3.14 (1 H, m, 6-Hb) and
2.30 (3 H, s, Ts-Me); m/z 436 (M+ Ϫ 1), 390 (M+ Ϫ CH2OMe),
372 (M+ Ϫ H2O Ϫ CH2OMe), 250 (M+ Ϫ 1 Ϫ Ts Ϫ OMe), 155
(Ts+), 105 (PhCO+) and 91 (MeC6H4+) (Found: C, 57.97; H,
5.99; N, 3.95. Calc. for C21H25NO7S: C, 57.92; H, 5.79; N,
3.22%).
(2S,3R,4S,5S)-1-Tosyl-4,5-dihydroxy-2-methoxymethyl-3-
piperidyl benzoate 9b
As described for the preparation of its enantiomer 9a from 8a,
compound 9b was prepared from 8b (90 mg, 0.22 mmol). The
product (79 mg, 80.9%) had mp 132.0 ЊC; [α]2D0 Ϫ1.32 (c 2.5
EtOH). The spectral data were identical with those of 9a.
(2R,3S,4S,5R)-1-Tosyl-4,5-diacetoxy-2-methoxymethyl-3-
piperidyl benzoate 14a
(2S,3R,4S,5S)-1-Tosyl-4,5-diacetoxy-2-methoxymethyl-3-
piperidyl benzoate 10b
As described for the preparation of its enantiomer 10a from 9a,
compound 10b was prepared from 9b (55 mg, 0.13 mmol). The
product (66 mg, 100%) had mp 134.0 ЊC; [α]2D0 +3.56 (c 2.5
CHCl3). The spectral data were identical with those of 10a.
To a solution of 13a (80 mg, 0.18 mmol) in pyridine (1 cm3) was
added acetic anhydride (0.5 cm3) and N,N-dimethylamino-
pyridine (DMAP; 1 mg). The reaction mixture was stirred for
24 h at RT, after which it was evaporated under reduced pres-
sure, diluted with water, and extracted with ethyl acetate (3 × 5
cm3). The combined extracts were washed with saturated aque-
ous CuSO4 and brine, dried (Na2SO4) and evaporated to give a
residue. This was purified by flash chromatography on silica gel
(light petroleum–ethyl acetate, 4:1) to yield 14a (95 mg, 100%)
as an oil; [α]2D0 Ϫ2.3 (c 2.0 CHCl3); νmax(film)/cmϪ1 2900, 1740,
1600 and 1450; δH 7.84 (2 H, d, J 7.3, Ph), 7.70 (2 H, d, J 8.2,
Ph), 7.61 (1 H, t, J 7.4, Ph), 7.43 (2 H, m, Ph), 7.08 (2 H, d, J
8.2, Ph), 5.56 (1 H, m, 3-H), 5.50 (1 H, dd, J 3.3, 10.3, 4-H), 5.18
(1 H, m, 5-H), 4.42 (1 H, s, 2-H), 4.25 (1 H, dd, J 5.5, 13.2, 6-
Ha), 3.78 (2 H, d, J 3.4, CH2OMe), 3.42 (3 H, s, OMe), 3.34 (1
H, dd, J 10.8, 13.3, 6-Hb), 2.27 (3 H, s, Ts-Me), 2.07 (3 H, s,
MeCO) and 1.95 (3 H, s, MeCO); m/z 520 (M+ + 1), 488
(M+ + 1 Ϫ OMe), 474 (M+ Ϫ CH2OMe), 414 (M+ Ϫ PhCO),
155 (Ts+) and 105 (PhCO+) (Found: C, 57.84; H, 5.34; N, 2.49.
Calc. for C25H29NO9S: C, 57.79; H, 5.63; N, 2.70%).
(2S,3R,4S,5S)-1-Tosyl-4,5-diacetoxy-2-hydroxymethyl-3-
piperidyl benzoate 11b
As described for the preparation of its enantiomer 11a from
10a, compound 11b was prepared from 10b (73 mg, 0.14 mmol).
The product (50 mg, 70.4%) had mp 45.0 ЊC; [α]2D0 +2.7 (c 1.8
EtOH). The spectral data were identical with those of 11a.
(+)-1-Deoxymannojirimycin 1b
As described for the preparation of its enantiomer 1a from 11a,
compound 1b was prepared from 11b (44 mg, 0.09 mmol). The
product (5 mg, 35.2%) had mp 185 ЊC; [α]2D0 +25.7 (c 0.17
MeOH). The spectral data were identical with those of 1a.
(2R,3S,4S,5R)-1-Tosyl-3-benzoyloxy-2-methoxymethyl-
piperidine 4,5-cyclic sulfate 12a
(2R,3S,4S,5R)-1-Tosyl-2,3-diacetoxy-5-hydroxymethyl-3-
piperidyl benzoate 15a
To a solution of 9a (165 mg, 0.38 mmol) in dried CH2Cl2 (1.5
cm3) was added Et3N (210 mm3, 1.52 mmol) and a solution of
SOCl2 (42 mm3, 0.57 mmol) in CH2Cl2 (0.5 cm3) under N2 at
0 ЊC. After being stirred for 30 min the reaction mixture was
diluted with cold ether (5 cm3), washed with cold water, dried
(Na2SO4) and concentrated under reduced pressure to give an
intermediate sulfide as an oil. This crude product, dissolved in a
mixture of aceonitrile (1 cm3), CCl4 (1 cm3) and water (1 cm3),
was treated with RuCl3ؒ3H2O (1 mg) and NaIO4 (242 mg, 1.14
mmol) at 0 ЊC. After 2 h the reaction mixture was diluted with
ether (5 cm3) and extracted with ether (3 × 5 cm3). The
combined extracts were washed with brine, dried (Na2SO4) and
concentrated under reduced pressure. Subsequent flash chro-
matography on silica gel (light petroleum–ethyl acetate, 9:1)
gave 12a (137 mg, 72.9%) as a solid, mp 111.8 ЊC; [α]2D0 +3.2 (c
1.7, CHCl3); νmax(KBr)/cmϪ1 2940, 1750, 1600 and 1450; δH 8.00
(2 H, m, Ph), 7.77 (2 H, d, J 8.2, Ph), 7.63 (1 H, m, Ph), 7.48 (2
H, m, Ph), 7.29 (2 H, m, Ph), 5.77 (1 H, t, J 3.6, 3-H), 5.26 (1 H,
m, 5-H), 5.11 (1 H, t, J 4.9, 4-H), 4.51 (1 H, m, 2-H), 4.03 (1 H,
m, 6-Ha), 3.62 (3 H, m, CH2OMe-H2, 6-Hb), 3.34 (3 H, s, OMe)
A dried 25-cm3 round bottom flask was charged with 14a (87
mg, 0.17 mmol) in CH2Cl2 (1.5 cm3) under N2 at RT; a solu-
tion of BBr3 in CH2Cl2 (1 mol dmϪ3; 1.7 cm3) was then added to
it at Ϫ78 ЊC. After 1 h the reaction mixture was warmed to
Ϫ20 ЊC, at which temperature it was stirred for 5 h. The reac-
tion was quenched by the addition of saturated aqueous
NaHCO3 (3 cm3) to the mixture which was then extracted with
ethyl acetate (3 × 5 cm3). The combined extracts were washed
with brine, dried (Na2SO4) and concentrated under reduced
pressure. Subsequent flash chromatography on silica gel (light
petroleum–ethyl acetate, 3:2) gave 15a (67 mg, 79.2%) as an oil.
[α]2D0 Ϫ3.1 (c 1.2 EtOH); νmax(film)/cmϪ1 3510, 1760, 1740, 1600
and 1460; δH 7.79 (2 H, t, J 7.1, Ph), 7.69 (2 H, d, J 8.1, Ph), 7.59
(1 H, m, Ph), 7.41 (2 H, t, J 7.7, Ph), 7.06 (2 H, d, J 8.1, Ph),
5.56 (1 H, dd, J 2.4, 3.1, 3-H), 5.37 (1 H, dd, J 3.3, 10.3, 4-H),
5.19 (1 H, m, 5-H), 4.39 (1 H, m, 2-H), 4.27 (1 H, dd, J 5.5, 13.6,
6-Ha), 4.00 (2 H, d, J 5.8, CH2OH), 3.28 (1 H, dd, J 10.7, 13.6,
6-Hb), 2.23 (3 H, s, Ts-Me), 2.05 (3 H, s, CH3CO) and 1.93 (3 H,
s, CH3CO); m/z 474 (M+ Ϫ CH2OH), 414 (M+ Ϫ MeC6H4), 292
(M+ Ϫ 1 Ϫ PhCO Ϫ MeC6H4), 250 (M+ Ϫ PhCO Ϫ MeC6H4 Ϫ
AcO), 155 (Ts+), 105 (PhCO+) and 91 (MeC6H4+) (Found: C,
56.59; H, 5.30; N, 2.57. Calc. for C24H27NO9S: C, 57.02; H, 5.38;
N, 2.77%).
and 2.42 (3 H, s, Ts-Me); m/z 452 (M+ Ϫ CH2OMe), 354
+
(M+ Ϫ 2 Ϫ SO4Ph), 155 (Ts+), 105 (PhCO+) and 91 (MeC6H4
)
(Found: C, 51.02; H, 4.59; N, 2.53. Calc. for C21H23NO9S2: C,
50.70; H, 4.66; N, 2.82%).
(2R,3S,4S,5R)-1-Tosyl-4,5-dihydroxy-2-methoxymethyl-3-
piperidyl benzoate 13a
(Ϫ)-1-Deoxyaltrojirimycin 16a
Sodium naphthalenide (0.69 cm3) was added to a solution of
15a (70 mg, 0.14 mmol) in DME (2 cm3) under N2 at Ϫ60 ЊC.
The reaction mixture was stirred for 1 h at Ϫ60 ЊC and then
quenched by the addition of saturated aqueous NH4Cl (3 cm3)
at Ϫ30 ЊC. The resulting mixture was separated and the organic
layer was extracted with water (3 × 5 cm3). The combined
aqueous layers were washed with ether and concentrated under
reduced pressure. Subsequent chromatography of the residue
To a solution of 12a (127 mg, 0.26 mmol) in THF (2 cm3) was
added 50% H2SO4 (0.4 cm3) at RT. The reaction mixture was
held at 40 ЊC for 24 h after which it was diluted with water (5
cm3) at room temperature and extracted with ethyl acetate
(3 × 5 cm3). The combined extracts were dried (Na2SO4) and
evaporated to give a residue which was purified by flash chrom-
atography on silica gel (light petroleum–ethyl acetate, 1:1) to
J. Chem. Soc., Perkin Trans. 1, 1997
745

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on Dowex-50(H+) (first elution with MeOH, then concentrated
aqueous NH3) afforded 16a (11 mg, 48.7%) as a solid, mp
175 ЊC; [α]2D0 Ϫ30.7 (c 0.13 MeOH); δH (D2O) 4.06 (2 H, s,
CH2OMe), 3.97 (1 H, dd, J 5.0, 14.6, 3-H), 3.89 (2 H, m, 4-H,
5-H), 3.16 (1 H, dd, J 5.4, 13.7, 6-Ha), 3.06 (1 H, dd, J 4.5, 9.4,
2-H) and 2.98 (1 H, d, br, J 14.8, 6-Hb); δC(D2O) 73.04, 71.52,
68.53, 63.13, 58.53 and 47.23; m/z (FABMS) 164 (M+ + 1) and
133 (M+ + 1 Ϫ CH2OH).
and the State Key Laboratory of Bio-Organic & Natural
Products Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences for support of this work. We also
thank Dr. Zhi-Min Wang for valuable discussions.
References
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piperidyl benzoate 13b
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1994, 2621.
15 Y. Gao and K. B. Sharpless, J. Am. Chem. Soc., 1988, 110, 7538.
16 T. Shono, Y. Matsumura, K. Tsubata and K. Uchida, J. Org. Chem.,
1986, 51, 2590.
(2S,3R,4R,5S)-1-Tosyl-4,5-diacetoxy-2-methoxymethyl-3-
piperidyl benzoate 14b
As described for the preparation of its enantiomer 14a from
13a, compound 14b was prepared from 13b (86 mg, 0.20 mmol).
The product (97 mg, 94.5%) was an oil, [α]2D0 +2.6 (c 2.4
CHCl3). The spectral data were identical with those of 14a.
(2S,3R,4R,5S)-1-Tosyl-4,5-diacetoxy-2-hydroxymethyl-3-
piperidyl benzoate 15b
As described for the preparation of its enantiomer 15a from
14a, compound 15b was prepared from 14b (87 mg, 0.17 mmol).
The product (75 mg, 88.6%) was an oil, [α]2D0 +3.5 (c 3.7
EtOH). The spectral data were identical with those of 15a.
(+)-1-Deoxyaltrojirimycin 16b
As described for the preparation of its enantiomer 16a from
15a, compound 16b was prepared from 15b (75 mg, 0.15 mmol).
The product (12 mg, 49.5%) had mp 175 ЊC; [α]2D0 +28.3 (c 0.17
MeOH). The spectral data were identical with those of 16a.
17 E. J. Corey and T. M. Eckrich, Tetrahedron Lett., 1983, 24, 3163.
Paper 6/05128F
Received 23rd July 1996
Acknowledgements
We thank the National Natural Science Foundation of China
Accepted 14th October 1996
746
J. Chem. Soc., Perkin Trans. 1, 1997