Total syntheses of (+)- and (-)-1-deoxynojirimycin (1,5-dideoxy-1,5-imino-D- and L-glucitol) and of (+)- and (-)-1-deoxyidonojirimycin (1,5-dideoxy-1,5-imino-D- and L-iditol) via furoisoxazoline-3-aldehydes

Article abstract of DOI:10.1016/S0008-6215(98)00287-0

The isoxazoline obtained by 1,3-dipolar cycloaddition of 2,2-diethoxyacetonitrile N-oxide to furan was converted into enantiomerically pure (-)-(3aS,5S,6S,6aR)- and (+)-(3aR,5R,6R,6aS)-3a,5,6,6a-tetrahydro-5,6-isopropylidenedioxyfuro[2,3-d]isoxazole-3-carbaldehyde, (-)-5 and (+)-5, respectively, through resolution with (1S,2S)-1,2-diphenylethylenediamine. The aldehydes 5 are required as latent 1,5-iminohexitol moieties in cross-aldolizations towards imino-C-disaccharides. In order to establish absolute configurations of 5, and to probe the projected uses, (+)-5 was converted into (+)-1-deoxynojirimycin [(+)-1, 3 steps, 58%] and into (-)-1,5-dideoxy-1,5-imino-l-iditol [(-)-2, 4 steps, 40%] adopting stereoselective routes. Similarly, (-)-1,5-dideoxy-1,5-imino-l-glucitol ((-)-1) and (+)-1,5-dideoxy-1,5-imino-D-iditol ((+)-2) were obtained with the same ease. Copyright (C) 1998 Elsevier Science Ltd.

Full text of DOI:10.1016/S0008-6215(98)00287-0

Carbohydrate Research 314 (1998) 25–35
Total syntheses of (+)- and (−)-1-deoxynojirimycin
(1,5-dideoxy-1,5-imino-D- and L-glucitol) and of (+)-
and (−)-1-deoxyidonojirimycin (1,5-dideoxy-1,5-imino-D-
and L-iditol) via furoisoxazoline-3-aldehydes
Christophe Schaller a, Pierre Vogel a,*, Volker Ja¨ger b
a Section de Chimie de l’Uni6ersite´ de Lausanne, BCH, CH-1015 Lausanne-Dorigny, Switzerland
b Institut fu¨r Organische Chemie der Uni6ersita¨t Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
Received 23 April 1998; revised 16 October 1998; accepted 19 October 1998
Abstract
The isoxazoline obtained by 1,3-dipolar cycloaddition of 2,2-diethoxyacetonitrile N-oxide to furan was converted
into enantiomerically pure (−)-(3aS,5S,6S,6aR)- and (+)-(3aR,5R,6R,6aS)-3a,5,6,6a-tetrahydro-5,6-isopropyli-
denedioxyfuro[2,3-d]isoxazole-3-carbaldehyde, (−)-5 and (+)-5, respectively, through resolution with (1S,2S)-1,2-
diphenylethylenediamine. The aldehydes 5 are required as latent 1,5-iminohexitol moieties in cross-aldolizations
towards imino-C-disaccharides. In order to establish absolute configurations of 5, and to probe the projected uses,
(+)-5 was converted into (+)-1-deoxynojirimycin [(+)-1, 3 steps, 58%] and into (−)-1,5-dideoxy-1,5-imino-L-iditol
[(−)-2, 4 steps, 40%] adopting stereoselective routes. Similarly, (−)-1,5-dideoxy-1,5-imino-L-glucitol ((−)-1) and
(+)-1,5-dideoxy-1,5-imino-D-iditol ((+)-2) were obtained with the same ease. © 1998 Elsevier Science Ltd. All rights
reserved.
Keywords: Sugars with nitrogen replacing ring oxygen; 1,5-Dideoxy-1,5-iminohexitols; 1,3-Dipolar cycloaddition; Asymmetric
synthesis; 1-Deoxynojirimycin; 1-Deoxy-ido-nojirimycin
increase selectivity and, perhaps, potency is
1. Introduction
to combine the iminoglycitol monomer with
the glycosyl part of the natural di- or
oligosaccharide substrate. Such structures
that have recently been referred to as imino-
C-disaccharides could be iminopolyols linked
to other sugar by a methylene or hydroxy-
methylene moiety [3].
As reported [4], we have used an aldol key
step to join the iminopolyol-aldehyde to the
three-position of respective hexoses for which
oxa-bicycloheptenones (naked sugars) served
as masked precursors. In an alternative way,
latent iminopolyol aldehydes might be em-
ployed for the cross-aldolization and be trans-
Pyranose and furanose analogues, where
nitrogen replaces oxygen in the ring (imi-
nosugars), have attracted considerable atten-
tion due to their ability to inhibit
glycohydrolases [1], making these compounds
potential therapeutic agents [2].
In many cases, however, several enzymes
even of different classes are inhibited or in-
sufficient activity is found. One approach to
* Corresponding author. Tel.: +41-21-6923971; fax: +41-
21-6923975.
E-mail address: pierre.vogel@ico.unil.ch (P. Vogel)
0008-6215/98/$ - see front matter © 1998 Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(98)00287-0

26
C. Schaller et al. / Carbohydrate Research 314 (1998) 25–35
A large number of syntheses of (+)-1 use
carbohydrates as starting materials [12,13].
Others start from myo-inositol [14], diethyl
L-tartrate [15], or pyroglutamic acid [16]. Two
asymmetric syntheses where diastereoselectiv-
ity is based on the use of a chiral auxiliary
have been reported [17]. Still other syntheses
rely on chemo-enzymatic processes [18,19].
Few de novo syntheses of iminosugars have
been proposed thus far [6,8,12,17a,20–22].
From 1982, Ja¨ger and Mu¨ller used cycloaddi-
tions of nitrile oxides to furan to engender
isoxazolines such as (9)-3, that was then
transformed into diol (9)-4 and finally into
several racemic 5-amino-5-deoxyfuranosides
and aminopolyols [6]. In independent, related
studies Vasella and Voeffray in 1982 suc-
ceeded in the synthesis of optically active no-
Scheme 1. Strategy to obtain imino-C-disaccharides from
tetrahydroisoxazoline-3-carbaldehydes.
formed to the imino-glycitol at the disaccha-
ride stage of B“A (Scheme 1). We describe
here the preparation of such aldehyde building
blocks, namely tetrahydrofuro-isoxazoline-3-
carbaldehydes C in optically active forms.
These aldehydes were obtained by nitrile oxide
cycloaddition to furan, subsequent bis(hy-
droxylation) of the adduct D, and auxiliary-
mediated separation of the racemic mixture.
The disaccharide precursor B would have to
be reduced and cyclized then, completing and
extending related routes to amino-sugars,
amino- and iminopolyols as proposed by
Ja¨ger et al. [5–8].
To assign the absolute configuration of the
respective building blocks C and the derived
hydroxypiperidines, C was converted to a se-
ries of 1,5-dideoxy-1,5-iminohexitols—de-
oxynojirimycin and the like—by the routes
similar to those used for higher 1,5-iminopoly-
ols [7,8]. This resulted in new and efficient
syntheses of enantiomers of 1-deoxynojir-
imycin (1) (gluco series) and of the 5-epimers
(2) (ido series) presented in this paper.
jirimycin,
advancing
the
1,3-dipolar
cycloaddition of nitrones with an a-mannosyl
auxiliary to furan. In both of these furan
approaches, the enol ether double bond of the
respective dihydrofuran cycloadducts was
dioxygenated, with peracid/methanol [6] or
with osmium tetroxide/N-methylmorpholine
N-oxide [17a].
Dondoni et al. [22] have synthesized (−)-
nojirimycin from -serine. 1-Deoxy-L-idonojiri-
L
mycin ((−)-2) has been prepared, first by
Paulsen et al. [9] and then by Fowler et al. [23]
and Sasinkova´ et al. [13l]. Several syntheses of
5-amino-5-deoxy-L-idose derivatives have been
published, all starting from D-glucose [24].
As we required protected forms of latent
iminopolyols-aldehydes C as building blocks
for convergent syntheses of imino-C-disacchar-
ides, we looked for a method to synthesize
and to separate the racemic mixture of C to
obtain both enantiomerically pure aldehydes.
As detailed below, this proved possible by
applying the resolution technique of Alexakis
and Mangeney [25]. In a complementary ap-
proach, optically active nitrileoxides have
been used and the resulting mixture of
diastereomers were separated later in the syn-
thesis [7,8,26].
In 1967, Paulsen et al. [9] prepared the first
iminosugars: (+)-1-deoxynojirimycin ((+)-1:
1,5-dideoxy-1,5-imino-D-glucitol) and (−)-1-
deoxyidonojirimycin ((−)-2: 1,5-dideoxy-1,5-
imino-L-iditol). Isolation of (+)-1 from a
Morus species was reported in 1976 [10]; it was
later observed together with other iminosugars
in various plants and in microorganisms
[11,12].
2. Results and discussion
The isoxazoline (9)-3 was obtained from
the reaction between 2-nitroethanal diethyl ac-

C. Schaller et al. / Carbohydrate Research 314 (1998) 25–35
27
tion starting with (−)-5 furnished (−)-1. The
highly stereoselective course of these CꢀN hy-
drogenations extends results obtained with
higher homologues (3-substituted side-chains)
[8].
etal and furan (75%) [6,27]. Bis(hydroxylation)
with N-methylmorpholine N-oxide and a cat-
alytic amount of osmium tetroxide [7,8,17a]
gave the 6-exo isomers (9)-4 (88%) as a 3:1
mixture of anomers. Diol protection and
transacetalation of (9)-4 (with concentrated
H2SO4 and acetone) provided the racemic
aldehyde (9)-5 (92%). Its reaction with (−)-
(1S,2S)-diphenylethanediamine [25] in ether
gave a mixture of diastereomeric imidazoli-
dines (−)-6 (40%) and (+)-7 (45%) which
were readily separated, first by crystallization
to yield (+)-7, and then by chromatographic
purification of the residue to give (−)-6. The
diastereomeric purity of both (−)-6 and (+)-
7 was determined by HPLC to exceed 98%.
The aldehydes (−)-5 (L-xylo) and (+)-5 (D-
xylo) were liberated by selective acidic hydrol-
ysis (1 N H2SO4, Et2O, 25 °C) with 95% yield
and recovery of (−)-(1S,2S)-diphenylethane-
diamine (97%). Enantiomeric ratios of (−)-5
and (+)-5 are considered to be greater than
99:1, as determined by HPLC (Chiralcel OD–
H, 1:1 i-PrOH/hexane). The absolute configu-
ration of (−)-5 (L-xylo) and (+)-5 (D-xylo)
was established by chemical correlation, i.e.
by conversion of (+)-5 into 1-deoxynojir-
imycin [(+)-1] and of (−)-5 into (−)-1. (For
other examples of optically pure isoxazolines,
see [7,8,28]).
Reduction of (+)-5 with lithium alu-
minium hydride [6] in ether gave the
aminodiol (−)-10 (66%). Its relative configu-
1
ration was derived from H NMR data (JH,H
,
NOEs) of the pentacyclic compound (−)-11
obtained by reaction of (−)-10 with one
equivalent of glutaraldehyde (MeOH, 25 °C).
The relative configuration of (−)-11 was
1
given by 2D NOESY H NMR (NOEs be-
tween signals assigned to protons 1-H, 3-H
and 8-H) and by coupling constants between
vicinal proton pairs. Here, the hydride deliv-
ery to the CꢀN bond of the isoxazoline moiety
occurred from the least-hindered face of the
tricyclic system as anticipated [5,6]. The oppo-
site diastereoselectivity observed for the cata-
lytic hydrogenation (+)-9“(+)-1 suggests
that the O–N bond is hydrogenolyzed first
and that the 3-hydroxy group of the interme-
diate imine plays a lateral control on its
hydrogenation.
Protection of aminodiol (−)-10 by a mod-
ification of Oku’s procedure [29], gave the
carbamate (−)-12 (81%). Deprotection (8:1
CF3COOH–H2O, 4 °C) then led to the fura-
nose (+)-13 (81%), the hydrogenation of
which (Pd/C, MeOH, 25 °C) provided the
Reduction of the isoxazoline-3-carbalde-
hyde (+)-5 with sodium borohydride in
methanol afforded the alcohol (+)-8 (90%).
Deprotection (8:1 CF3COOH–H2O, 4 °C)
then gave a 3.4:1 mixture of anomers (+)-9
(100%). Hydrogenation (Pd/C, MeOH, 25 °C)
provided (+)-1 in 65% yield. The same opera-
imino-
operations carried out with (−)-5 led to its
enantiomer (+)-2 ( -ido).
L
-iditol (−)-2 in 95% yield. The same
D

28
C. Schaller et al. / Carbohydrate Research 314 (1998) 25–35
A more straightforward route to (+)-2 was
achieved from (+)-10 via the formation of
the 1,6-anhydro- -ido-piperidinose (−)-14
overall yield of 60% (including an enzymatic
oxidation step). However, the present work
realizes the shortest synthesis of (+)-1 start-
ing from achiral, inexpensive starting materi-
als; it also give the (so far) shortest approach
D
(9:1 CF3COOH–H2O, 25 °C; then Dowex 1
(OH− form, 93%)) [30], the hydrogenation of
which (Pd/C, H2O, 25 °C) provided (+)-2 in
77% yield. Treatment of the aminodiol (9)-
10 with trifluoroacetic acid (90%), followed
by triethylsilane in trifluoroacetic acid pro-
vided racemic 2-amino-2-deoxy-iditol (9)-15
[31] characterized as the hexa-acetyl derivative
(9)-16 (75%, 2 steps).
to the synthesis of -deoxynojirimycin (−)-1.
L
4. Experimental
General methods.—See Ref. [33].
(9)-(3aRS,6RS,6aSR)-3-(Diethoxymethyl)-
3a,5,6,6a - tetrahydrofuro[2,3 - d]isoxazole - 5,6-
diol [(9)-4].—N-methylmorpholine N-oxide
(6.35 g, 47 mmol) and a 0.1 M solution of
OsO4 (1 mL) were added successively to a
stirred solution of (9)-3-(diethoxymethyl)-
3a,6a-dihydrofuro[2,3-d]isoxazole ((9)-3 [6a],
5.0 g 23.44 mmol) in 4:1 acetone–water (75
mL). After stirring at 60 °C for 3 h, the sol-
vent was evaporated under reduced pressure
and the residue extracted with EtOAc (80 mL,
three times). The combined extracts were
washed with 1 N HCl saturated with NaCl (60
mL, twice), then with a saturated solution of
NaHCO3/NaCl (60 mL). After drying
(MgSO4), the solvent was evaporated under
reduced pressure and the residue recrystallized
from 1:1 ether–light petroleum to give 5.10 g
(88%) of (9)-4 as a 3:1 mixture of anomers,
colorless crystals, mp 68–69 °C. UV (MeCN):
u 210 nm (m=3900); IR (KBr): w 3390, 2975,
2900, 1620, 1480, 1450, 1340, 1215, 1180,
3. Conclusion
Enantiomerically pure tetrahydrofurano-
isoxazoline-3-carbaldehydes (+)- and (−)-5
are now readily available for use as building
blocks with latent 1,5-iminohexitol moieties in
cross-aldolizations towards imino-C-disaccha-
rides. The absolute configuration of 5, and the
stereochemical course of the reductive cycliza-
tion have been established by correlation of
the resulting 1,5-dideoxy-1,5-iminohexitols 1
and 2, respectively, with natural (+)-de-
oxynojirimycin and the known iminoiditols.
This also represents a new, stereodivergent
approach to the syntheses of 1-deoxynojir-
1
1065, 950, 860, 795 cm−1. H NMR (CD3OD,
3
400 MHz) of the major anomer: l 5.65 (d, J
7.5 Hz, 3a-H), 5.40 (s, CH(OEt)2), 5.36 (s,
5-H), 4.88 (s, 2 OH), 4.84 (d, 3J 7.5 Hz, 6a-H),
4.27 (s, H-6), 3.86–3.60 (m, 4 H, 2 OCH2Me),
1.30–1.24 (m, 6 H, 2 Me); 13C NMR
(CD3OD, 100.61 MHz) of the major anomer:
imycin [(+)-1] and 1-deoxy- -idonojirimycin
L
((−)-2), and of their enantiomers, (−)-1 and
(+)-2. Including the resolution step, (+)-1
[and (−)-1] was prepared in 8 steps and 15%
overall yield starting from furan and 2-ni-
troethanal diethylacetal taking advantage of
an efficient separation of the racemic mixture
of furoisoxazoline adducts after bis(hydroxyl-
ation). Iminosugar (−)-2 [and (+)-2] was
obtained in eight steps and 11% overall yield.
As expected, this synthesis of (+)-1 cannot
compete with the most efficient one reported
by Kinast and Schedel [32] which converts
1
l 158.4 (s, C-3), 105.1 (d, J(C,H) 172 Hz,
1
C-5), 97.9 (d, J(C,H) 163 Hz, CH(OEt)2),
90.2 (d, 1J(C,H) 163 Hz, C-6a), 88.3 (d,
1
1J(C,H) 168 Hz, C-3a), 81.0 (d, J(C,H) 154
1
Hz, C-6), 64.0 and 63.2 (2 t, J(C,H) 143 Hz,
1
2 OCH2Me), 15.3 (q, J(C,H) 126 Hz, 2 Me).
CIMS (NH3): m/z 265 ([M+NH4]+, 3), 248
([M+H]+, 7), 202 (100), 173 (61), 156 (4),
126 (24), 97 (18), 75 (5). Anal. Calcd for
C10H17NO6 (247.24): C, 48.58; H, 6.93; N,
5.67. Found: C, 48.73; H, 6.82; N, 5.59.
D-glucose into (+)-1 in four steps with an

C. Schaller et al. / Carbohydrate Research 314 (1998) 25–35
29
(−)-6 (1.35 g, 40%) and additional (+)-7
(9) - (3aRS,5RS,6RS,6aSR) - 3a,5,6,6a-
Tetrahydro-5,6-isopropylidenedioxyfuro[2,3-d]-
isoxazole-3-carbaldehyde [(9)-5].—A mix-
ture of (9)-4 (5.15 g, 20.83 mmol), concen-
trated H2SO4 (5.9 mL), and Sikkon (55 g,
Fluka) in anhyd acetone (180 mL) was
stirred at 25 °C for 3 h. After neutralization
through portionwise addition of Na2CO3 (50
g), the solution was filtered and the solvent
evaporated under reduced pressure. Purifica-
tion by column chromatography on silica gel
(400 g, 5:1 light petroleum–EtOAc) and then
distillation under reduced pressure (0.1 kPa,
140 °C) afforded 4.08 g (92%) of (9)-5 as a
colorless oil. UV (MeCN): u 243 nm (m=
7800); IR (film): w 2990, 2940, 2860, 1695,
1575, 1375, 1215, 1160, 1080, 1030, 760
(0.50 g, total 45%).
25
Data for (−)-6.—Colorless oil, [h]
589
25
25
25
435
−106°, [h]
−221°, [h]
−112°, [h]
−127°, [h]
577
25
405
546
−269° (c 1.0, CHCl3); UV
(MeCN): u 205 nm (m=20000); IR (film): w
3355, 3030, 2990, 2935, 1495, 1455, 1420,
1385, 1375, 1225, 1165, 1085 cm−1; H NMR
1
(CDCl3, 400 MHz): l 7.32–7.22 (m, 10 H Ar),
3
3
5.95 (d, J 6.5 Hz, H-3a), 5.91 (d, J 3.6 Hz,
3
H-5), 5.41 (s, H-2%), 5.08 (d, J 6.5 Hz, H-6a),
3
4.87 (d, J 3.6 Hz, H-6), 4.23 (s, H-4%, H-5%),
2.90–2.60 (br. s, 2 NH), 1.56 and 1.40 (2 s,
Me2C); 13C NMR (CDCl3, 100.61 MHz): l
159.4 (s, C-3), 140.0, 139.8, 128.6, 128.4,
127.7, 127.5, 127.2, 127.0 (12 C Ar), 113.8 (s,
1
CMe2), 106.3 (d, J(C,H) 184 Hz, C-5), 87.3
1
1
(d, J(C,H) 163 Hz, C-6), 86.7 (d, J(C,H) 164
1
cm−1; H NMR (CDCl3, 400 MHz): l 9.95
1
Hz, C-3a), 84.8 (d, J(C,H) 161 Hz, C-6a),
3
(s, CHO), 5.85 (d, J 3.5 Hz, H-5), 5.80 (d,
70.4 (d, 1J(C,H) 149 Hz, C-4% or C-5%), 69.0 (d,
3
3J 6.4 Hz, H-3a), 5.17 (d, J 6.4 Hz, H-6a),
1J(C,H) 153 Hz, C-2%), 68.5 (d, J(C,H) 141
1
3
4.90 (d, J 3.5 Hz, H-6), 1.52 and 1.38 (2 s,
1
Hz, C-5% or C-4%), 27.8 and 26.9 (2 q, J(C,H)
Me2C); 13C NMR (CDCl3, 100.61 MHz): l
128 Hz, Me2C). CIMS (NH3): m/z 408 ([M+
H]+, 1), 377 (1), 302 (9), 283 (2), 244 (31), 215
(4), 165 (7), 106 (51), 83 (100). Anal. Calcd for
C23H25N3O4 (407.47): C, 67.80; H, 6.18; N,
10.31. Found: C, 67.74; H, 6.25; N, 10.35.
Data for (+)-7.—Colorless solid, mp 141–
1
183.9 (d, J(C,H) 190 Hz, CHO), 158.6 (s,
1
C-3), 114.2 (s, CMe2), 106.2 (d, J(C,H) 185
1
Hz, C-5), 90.6 (d, J(C,H) 165 Hz, C-6), 83.8
1
1
(d, J(C,H) 162 Hz, C-6a), 82.5 (d, J(C,H)
1
166 Hz, C-3a), 27.7 and 26.9 (2 q, J(C,H)
127 Hz, Me2C); CIMS (NH3): m/z 231
([M+NH4]+, 100), 198 (87), 100 (4), 85
(20). Anal. Calcd for C9H11NO5 (213.19): C,
50.71; H, 5.20; N, 6.57. Found: C, 50.71; H,
5.11; N, 6.43.
25
25
25
142 °C. [h] +48°, [h] +49°, [h] +56°,
589
577
546
25
25
[h] +92°, [h] +108° (c 1.0, CHCl3); UV
435
405
(MeCN): u 206 nm (m=21000); IR (KBr): w
3345, 3030, 2990, 2940, 1495, 1455, 1385,
1375, 1225, 1160, 1080, 995 cm−1; H NMR
1
Mixture of (−)-(3aS,4%S,5S,5%S,6S,6aR)-3-
(4%,5% - diphenylimidazolid - 2% - yl) - 3a,5,6,6a-
tetrahydro-5,6-isopropylidenedioxyfuro[2,3-d]-
isoxazole [(−) - 6] and (+) - (3aR,4%S,5R,5%S,
6R,6aS) - 3 - (4%,5% - diphenylimidazolid - 2% - yl)-
3a,5,6,6a-tetrahydro-5,6-isopropylidenedioxy-
furo[2,3-d]isoxazole [(+)-7].—A mixture of
aldehyde (9)-5 (1.78 g, 8.35 mmol) and
1S,2S-(−)-diphenylethanediamine (1.78 g,
8.38 mmol) in Et2O (30 mL) was stirred at
(CDCl3, 400 MHz): l 7.31–7.25 (m, 10 H Ar),
3
3
5.93 (d, J 3.5 Hz, H-5), 5.90 (d, J 6.5 Hz,
3
H-3a), 5.42 (s, H-2%), 5.06 (d, J 6.5, H-6a),
3
4.86 (d, J 3.5, H-6), 4.23 (s, H-4%, H-5%),
2.90–2.60 (br. s, 2 NH), 1.56 and 1.41 (2 s,
Me2C); 13C NMR (CDCl3, 100.61 MHz): l
159.2 (s, C-3), 140.1, 139.4, 128.5, 128.4,
127.6, 127.0, 126.9 (12 C Ar), 113.8 (s, CMe2),
1
106.3 (d, J(C,H) 184 Hz, C-5), 87.2 and 87.1
1
(2 d, J(C,H) 163 Hz, C-3a, C-6a), 84.8 (d,
˚
1J(C,H) 161 Hz, C-6), 70.6 and 69.1 (2 d,
25 °C for 10 h under Ar in the presence of 4 A
1
1J(C,H) 149 Hz, C-4%, C-5%), 69.6 (d, J(C,H)
molecular sieves (2 g). The solution was
filtered through Celite, evaporated to dryness,
and the residue crystallized in Et2O (200 mL).
Filtration gave (+)-7 (1.01 g, 30%). The
mother liquor was concentrated and purified
by column chromatography on silica gel (1:3
AcOEt–light petroleum, 1% NEt3) to yield
1
153 Hz, C-2%), 27.8 and 26.9 (2 q, J(C,H) 127
Hz, Me2C); CIMS (NH3): m/z 408 ([M+H]+,
2), 407 (M+ , 2), 302 (8), 259 (11), 219 (20),
’
153 (8), 106 (45), 83 (100). Anal. Calcd for
C23H25N3O4 (407.47): C, 67.80; H, 6.18; N,
10.31. Found: C, 67.89; H, 6.14; N, 10.38.

30
C. Schaller et al. / Carbohydrate Research 314 (1998) 25–35
(−) - (3aS,5S,6S,6aR) - 3a,5,6,6a - Tetra-
1.39 (2 s, Me2C); 13C NMR (CDCl3, 100.61
MHz): l 157.9 (s, C-3), 114.0 (s, CMe2), 106.1
hydro - 5,6 - isopropylidenedioxyfuro[2,3 - d]-
isoxazole-3-carbaldehyde [(−)-5].—A mix-
ture of (−)-6 (1.0 g, 2.45 mmol), Et2O (60
mL) and 1 N H2SO4 (25 mL) was stirred
vigorously at 25 °C for 30 min. The aqueous
phase was extracted with Et2O (20 mL, twice).
The combined organic phases were dried
(MgSO4) and the solvent was evaporated un-
der reduced pressure. The residue was distilled
(0.1 kPa, bp 140 °C) giving 496 mg (95%) of
(−)-5 as a colorless oil that solidified at −
20 °C. The aqueous phase was made basic
with 1 N NaOH and extracted with CH2Cl2
(20 mL, five times). The combined organic
extracts were dried (MgSO4) and the solvent
was evaporated under reduced pressure giving
505 mg (97%) of (−)-(1S,2S)-1,2-diphenyl-
1
(d, J(C,H) 184 Hz, C-5), 86.9 and 86.5 (2 d,
1
1J(C,H) 163 Hz, C-3a, C-6a), 84.8 (d, J(C,H)
1
168 Hz, C-6), 56.7 (t, J(C,H) 146 Hz, CH2-
1
C(3)), 27.8 and 26.9 (2 q, J(C,H) 127 Hz,
Me2C); CIMS (NH3): m/z 216 ([M+H]+,
31), 200 (83), 170 (9), 158 (66), 128 (14), 112
(35), 100 (100), 85 (93). Anal. Calcd for
C9H13NO5 (215.2): C, 50.23; H, 6.09; N, 6.51.
Found: C, 50.25; H, 6.00; N, 6.56.
(−) - (3aS,5S,6S,6aR) - 3a,5,6,6a - Tetrahy-
dro - 5,6 - isopropylidenedioxyfuro[2,3 - d]isox-
azole-3-methanol [(−)-8].—Same procedure
as for the preparation of (+)-8, starting from
25
25
25
(−)-5. [h]
−104°, [h]
−109°, [h]
589
25
577
546
25
405
−124°, [h]
−209°, [h]
−251° (c 1.0,
435
CHCl3). Anal. Calcd. for C9H13NO5 (215.2):
C, 50.23; H, 6.09; N, 6.51. Found: C, 50.30;
H, 6.07; N, 6.59.
25
25
ethanediamine. (−)-5: [h]
−208°, [h]
−440°, [h]
589
25
577
25
25
−217°, [h]
−269°, [h]
546
435
405
(+)-(3aR,5R&5S,6R,6aS)-3a,5,6,6a-Tetra-
hydro - 5,6 - dihydroxyfuro[2,3 - d]isoxazole - 3-
methanol [(+)-9].—A solution of (+)-8 (175
mg, 0.813 mmol) in 8:1 CF3COOH–H2O (10
mL) was stirred at 4 °C for 15 h. The solvent
was evaporated under reduced pressure and
the residue purified by column chromatogra-
phy on silica gel (15 g, EtOAc) to give 142 mg
(100%) of (+)-9 as a 3.4:1 mixture of
−480° (c 1.0, CHCl3).
(+) - (3aR,5R,6R,6aS) - 3a,5,6,6a - Tetrahy-
dro - 5,6 - isopropylidenedioxyfuro[2,3 - d]isoxaz-
ole-3-carbaldehyde [(+)-5].—Same procedure
as for the preparation of (−)-5, starting with
25
25
25
(+)-7. [h]
+205°, [h]
+214°, [h]
589
25
577
546
25
405
+246°, [h]
+435°, [h]
+477° (c 1.0,
435
CHCl3). Other spectral data were identical to
those of (9)-5.
25
25
anomers, colorless oil. [h]
+43°, [h]
589
577
(+) - (3aR,5R,6R,6aS) - 3a,5,6,6a - Tetra-
hydro-5,6-isopropylidenedioxyfuro[2,3-d]isox-
azole-3-methanol [(+)-8].—NaBH4 (38 mg, 1
mmol) was added portionwise to a stirred
solution of (+)-5 (102 mg, 0.48 mmol) in
MeOH (1.5 mL) cooled to 5 °C. After the
addition of H2O (1.0 mL), the mixture was
extracted with CH2Cl2 (3×3 mL). The com-
bined organic extracts were dried (MgSO4)
and the solvent was evaporated under reduced
pressure. The residue was recrystallized from
1:3 EtOAc–light petroleum, giving 93 mg
(90%) of (+)-8 as white crystals, mp 94–
25
25
25
+46°, [h] +51°, [h] +80°, [h] +91°
546
435
405
(c 1.0, MeOH); UV (MeCN): u 212 nm (m=
1800); IR (film): w 3350, 2930, 1420, 1035, 945
1
cm−1; H NMR (CD3OD, 400 MHz) of the
3
major anomer: l 5.70 (d, J 7.7 Hz, H-3a),
5.32 (s, H-5), 4.79 (d, 3J 7.7 Hz, H-6a), 4.44 (s,
2 H, CH2OH), 4.21 (s, H-6). 13C NMR
(CD3OD, 100.61 MHz): l 160.5 (s, C-3), 105.1
1
1
(d, J(C,H) 173 Hz, C-5), 89.5 (d, J(C,H) 163
1
Hz, C-6a), 88.4 (d, J(C,H) 163 Hz, C-3a),
81.4 (d, 1J(C,H) 154 Hz, C-6), 56.4 (t, 1J(C,H)
145 Hz, CH2–O); CIMS (NH3): m/z 178
([M+3]+, 100), 165 (23), 152 (10), 129 (5), 95
(23). Anal. Calcd for C6H9NO5 (175.14): C,
41.15; H, 5.18; N, 8.00. Found: C, 41.14; H,
5.24; N, 7.96.
25
25
25
96 °C. [h]
+104°, [h]
+109°, [h]
589
25
577
25
546
+123°, [h]
+208°, [h]
+250° (c 1.0,
435
405
CHCl3); UV (MeCN): u 209 nm (m=3200); IR
(KBr): w 3465, 2990, 1460, 1385, 1230, 1165,
(−)-(3aS,5S&5R,6S,6aR)-3a,5,6,6a-Tetra-
hydro - 5,6 - dihydroxyfuro[2,3 - d]isoxazole - 3-
methanol [(−)-9].—Same procedure as for
the preparation of (+)-9, starting from (−)-
1115, 1080, 1040, 985 cm−1
;
1H NMR
(CDCl3, 400 MHz) l 5.85 (d, 3J 3.5 Hz, H-4a),
3
3
5.68 (d, J 6.5 Hz, H-3a), 5.00 (d, J 6.5 Hz,
3
25
25
25
25
435
H-6a), 4.81 (d, J 3.5 Hz, H-6), 4.55 (m, 2 H,
8. [h] −45°, [h] −46°, [h] −51°, [h]
589
577
546
3
25
CH2OH), 2.04 (t, J 6.1 Hz, OH), 1.53 and
−79°, [h] −90° (c 0.5, MeOH).
405

C. Schaller et al. / Carbohydrate Research 314 (1998) 25–35
31
1
Hz, C-4), 77.5 (d, J(C,H) 157 Hz, C-3), 66.5
(+)-1-Deoxynojirimycin [1,5-dideoxy-1,5-
imino- -glucitol; (+)-1].—A mixture of (+)-
1
1
(t, J(C,H) 142 Hz, C-6), 52.5 (d, J(C,H) 134
D
1
Hz, C-5), 26.7 and 26.0 (2 q, J(C,H) 126 Hz,
9 (150 mg, 0.86 mmol), MeOH (5 mL) and
10% Pd/C (10 mg) was degassed, pressurized
with H2 (0.1 MPa), and shaken at 25 °C for 15
h. After filtration (Celite) the solvent was
evaporated under reduced pressure. The
residue was purified by column chromatogra-
phy on Dowex 1 (10 g, OH− form, eluent
Me2C); CIMS (NH4): m/z 220 ([M+H]+,
20), 202 (7), 188 (50), 162 (7), 129 (33), 113
(36), 100 (100), 85 (87). Anal. Calcd for
C9H17NO5 (219.2): C, 49.31; H, 7.82; N, 6.39.
Found: C, 49.38; H, 7.80; N, 6.47. (Lit. [29]
mp 183–185 °C, [h]
25
589
−3.3° (c 1, MeOH)).
(+) - 5 - Amino - 5 - deoxy - 1,2 - O - isopropyl-
idene i- -idofuranose [(+)-10].—Prepared as
(−)-10, starting from (−)-5. [h] +4°, [h]
H2O) yielding 91 mg (65%) of (+)-1 as a
25
D
colorless solid, mp 194–195 °C. [h]
+44°,
589
25
589
25
25
577
25
25
25
25
[h]
+50°, [h]
+55°, [h]
+90°, [h]
577
546
435
405
25
546
25
435
+5°, [h] +6°, [h] +12°, [h] +15° (c
405
+107° (c 0.2, H2O). Anal. Calcd for
0.9, MeOH). Anal. Calcd. for C9H17NO5
(219.2): C, 49.31; H, 7.82; N, 6.39. Found: C,
49.29; H, 7.68; N, 6.33.
C6H13NO4 (163.17): C, 44.17; H, 8.03; N, 8,58.
Found: C, 44.40; H, 7.99. (Lit. [10b] mp
25
196 °C, [h] +47°; H2O).
589
(−)-(1S,3S,4R,5R,7R,8S,11S)-4,5-Isopro-
pylidenedioxy - 2,6,10 - trioxa - 15 - azatetracy-
clo[9.3.1.03,7.08,15]pentadecane [(−)-11].—A
mixture of (−)-10 (30 mg, 0.137 mmol),
MeOH (0.3 mL) and glutaraldehyde (24 mL,
0.137 mmol) was stirred at 25 °C for 12 h. The
solvent was evaporated under reduced pres-
sure and the residue purified by column chro-
matography on silica gel (4 g, 2:1
CH2Cl2–EtOAc) giving 26.4 mg (68%) of (−)-
(−) - 1,5 - Dideoxy - 1,5 - imino -
L
- glucitol
[(−)-1].—This compound was prepared from
(−)-9 following the procedure used for the
preparation of (+)-1. Yield: 65% mp 193–
25
25
25
195 °C. [h] −46°, [h] −44°, [h] −40°,
589
577
546
25
25
[h]
−81°, [h]
−96° (c 0.3, H2O). Anal.
435
405
Calcd for C6H NO4 (163.17): C, 44.17; H,
13
8.03; N, 8.58. Found: C, 44.26; H, 8.04; N,
8.52.
(−)-5-Amino-5-deoxy-1,2-O-isopropylidene
25
25
11 as a colorless oil. [h]
−0.8°, [h] 0°,
589
577
i- -idofuranose [(−)-10].—LiAlH4 (150 mg,
L
25
546
25
435
25
[h]
+0.2°, [h]
−1.3°, [h]
−1.7° (c
405
3.9 mmol) was added portionwise to a stirred
solution of (+)-5 (277 mg, 1.3 mmol) in
anhydrous Et2O (5 mL). After stirring at
25 °C for 4 days, H2O (0.15 mL), 20% aq
NaOH (0.10 mL) and then H2O (0.3 mL) were
added. After stirring at 25 °C for 2 h, MgSO4
(1.5 g) was added and the mixture was stirred
at 25 °C for another 2 h. Filtration (Celite)
and solvent evaporation under reduced pres-
0.25, CHCl3). IR (film): w 2935, 1460, 1375,
1295, 1265, 1200, 1165, 1075, 1015, 965 cm−1
;
1H NMR (CDCl3, 400 MHz): l 5.93 (d, J 3.8
3
3
Hz, H-5), 4.72 (dd, J 3.3, 2.0 Hz, H-11), 4.57
3
3
(d, J 3.8 Hz, H-4), 4.54 (dd, J 10.3, 2.7 Hz,
2
3
H-8), 4.26 (dd, J 8.0, J 2.7 Hz, H-9), 4.17 (d,
3J 2.0 Hz, H-3), 4.09 (dd, J 8.0, J 8.0 Hz,
H%-9), 3.98 (dd, 3J 4.0, 2.0 Hz, H-1), 3.81–3.77
(m, H-8), 2.00–1.97 (m, 1 H), 1.82–1.68 (m, 3
H), 1.64–1.54 (m, 1 H), 1.30–1.21 (m, 1 H,
H-12, H-13, H-14), 1.48 and 1.32 (2 s, Me2C)
(assignments confirmed by a NOESY spec-
trum). 13C NMR (CDCl3, 100.61 MHz): l
2
3
sure yielded 188 mg (66%) of (−)-10 as a
25
colorless solid, mp 178–179 °C. [h]
−4°,
589
25
25
25
25
[h]
−5°, [h]
−6°, [h]
−12°, [h]
577
546
435
405
−15° (c 1.1, MeOH); UV (MeCN): u 200 nm
(m=500); IR (KBr): w 3360, 2985, 2935, 1375,
1
111.5 (s, Me2C), 104.1 (d, J(C,H) 183 Hz,
1215, 1165, 1070, 1015 cm−1
;
1H NMR
1
C-5), 86.0, 84.0 and 83.9 (3d, J(C,H) 160 Hz,
3
1
(CDCl3, 400 MHz): l 5.97 (d, J 3.6 Hz, H-1),
C-1, C-7, C-11), 79.8 (d, J(C,H) 152 Hz,
3
3
1
4.49 (dd, J 3.6, 0.5 Hz, H-2), 4.32 (dd, J 2.9,
C-4), 72.2 (d, J(C,H) 148 Hz, C-8), 65.5 (t,
3
1J(C,H) 150 Hz, C-9), 54.1 (d, J(C,H) 141
1
0.5 Hz, H-3), 4.18 (dd, J 2.9, 1.7 Hz, H-4),
2
3
2
1
3.74 (dd, J 11.0, J 5.3 Hz, H-6), 3.66 (dd, J
Hz, C-8), 29.8 (t, J(C,H) 131 Hz, C-12 or
3
3
1
11.0, J 5.3 Hz, H%-6), 3.28 (ddd, J 5.3, 5.3,
1.7 Hz, H-5), 1.49 and 1.32 (2 s, Me2C); 13C
NMR (CDCl3, 100.61 MHz): l 111.5 (s,
CMe2), 105.1 (d, J(C,H) 183 Hz, C-1), 85.4
(d, J(C,H) 161 Hz, C-2), 78.2 (d, J(C,H) 154
C-14), 29.0 (t, J(C,H) 127 Hz, C-13), 26.4
1
and 26.0 (2 q, J(C,H) 127 Hz, Me2C), 18.5 (t,
1J(C,H) 130 Hz, C-14 or C-12). CIMS (NH3):
m/z 285 ([M+2]+, 46), 284 ([M+H]+, 100),
282 (11), 268 (9), 225 (6), 154 (2), 113 (8).
1
1
1

32
C. Schaller et al. / Carbohydrate Research 314 (1998) 25–35
25 25
25
[h] +28°, [h] +47°, [h] +56° (c 0.36,
Product decomposes at room temperature and
no elemental analysis could be made.
546
435
405
MeOH); Anal. Calcd for C17H23NO7 (353.37):
C, 57.78; H, 6.56; N, 3.96. Found: C, 57.79;
H, 6.66; N, 3.88.
(−) - 5 - Benzyloxycarbonylamino - 5 - deoxy-
1,2-O-isopropylidene-i-
L
-idofuranose
[(−)-
(+) - 5 - Benzyloxycarbonylamino - 5 - deoxy-
12].—To a solution of aminodiol (−)-10 (60
mg, 0.274 mmol) in aq. EtOH 50% (4.5 mL)
was added NaHCO3 (41 mg, 0.49 mmol, 1.8
equiv) and CbzCl (45 mL, 0.328 mmol, 1.2
equiv) and the reaction mixture was stirred at
25 °C for 1 h 30 min. After addition of AcOEt
(10 mL) the reaction mixture was extracted
twice with NaHCO3 (4 mL). The organic
phase was dried over MgSO4, and the product
purified by column chromatography on silica
gel (2:1 AcOEt–light petroleum), yielding 78.4
mg (81%) of colorless crystals (mp 138–
L-idofuranose [(+)-13].—A solution of carba-
mate (−)-12 (68 mg, 0.192 mmol) in 8:1
CF3COOH–H2O (6 mL) was stirred at 4 °C
for 15 h. The solvents were removed by evap-
oration and the product was purified by
column chromatography on silica gel
(AcOEt), yielding 49 mg (81%) of (+)-13 as
25
25
577
25
546
colorless oil. [h]
+37°, [h]
+41°, [h]
589
25
25
405
+46°, [h]
+76°, [h]
+90° (c 0.12,
435
MeOH); UV (MeCN): u 267 nm (m=360), 261
(425), 257 (470), 251 (430), 208 (6500); IR
(film): w 3390, 3030, 2970, 1710, 1455, 1410,
25
25
25
139 °C). [h]
−29°, [h]
−24°, [h]
−50°, [h]
−25°, [h]
589
577
546
1310, 1275, 1110, 1070, 700 cm−1; H NMR
25
25
1
−59° (c 0.45,
435
405
MeOH); UV (MeCN): u 257 nm (m=585), 251
(545), 207 (7900); IR (film): w 3355, 3065,
2990, 1700, 1530, 1455, 1375, 1215, 1165,
(CD3OD, 400 MHz): l 7.38–7.33 (m, 5 H Ar),
3
5.42 (d, J 1.7 Hz, H-1), 5.18 (s, 2 H, –
3
OCH2Ph), 4.37 (dd, J 4.4, 4.4 Hz, H-5), 4.03
1
3
1075, 1015, 860, 740 cm−1; H NMR (CDCl3,
(d, J 8.0 Hz, H-6a), 3.66–3.62 (m, H-4, H-
3
3
400 MHz): l 7.39–7.30 (m, 5 H Ar), 5.93 (d,
3J 3.7 Hz, H-1), 5.44 (d, 3J 7.5 Hz, H–N), 5.12
(AB, JAB 12.2 Hz, 1 H, −OCH2−), 5.07
(AB, JAB 12.2 Hz, 1 H, −OCH2−), 4.53 (d,
6b), 3.48 (dd, J 8.1, 8.0 Hz, H-3), 3.40 (dd, J
8.0, 1.75 Hz, H-2); 13C NMR (CD3OD, 100.61
MHz): l 155.1 (s, CO), 137.4 (s, C Ar), 129.6,
3
129.4 and 129.1 (3 d, J(C,H) 165, 160, 160
3
1
3J 3.7 Hz, H-2), 4.26 (d, J 2.5 Hz, H-3), 4.19
Hz, 5 C Ar), 88.3 (d, J(C,H) 168 Hz, C-1),
3
1
1
(dd, J 6.7, 2.5 Hz, H-4), 4.09–4.04 (m, H-5),
77.0 (d, J(C,H) 145, C-3), 76.7 (d, J(C,H)
2
3
2
1
3.86 (dd, J 11.1, J 3.9, H-6a), 3.68 (dd, J
144, C-2), 73.2 (d, J(C,H) 150 Hz, C-4), 68.9
3
1
11.1, J 5.9, H-6b), 2.97 (br. s, 2-OH), 1.49
(t, J 147 Hz, –OCH2Ph), 66.8 (t, J(C,H) 150
1
and 1.31 (2 s, Me2C); 13C NMR (CDCl3,
Hz, C-6), 58.4 (d, J(C,H) 152, C-5); CIMS
100.61 MHz): l 157.1 (s, CO), 136.0 (s, C Ar),
(NH4): m/z 313 (M+, 14), 296 (37), 252 (21),
162 (17), 91 (100). Anal. Calcd for C14H19NO7
(313.31). C, 53.67; H, 6.11; N, 4.47. Found: C,
53.73; H, 5.96; N, 4.45.
1
128.5, 128.2 and 128.0 (3 d, J(C,H) 160, 160,
158 Hz, 5 C Ar), 111.6 (s, CMe2), 104.4 (d,
1J(C,H) 184 Hz, C-1), 85.2 (d, J(C,H) 162
1
1
Hz, C-2), 80.1 (d, J(C,H) 147 Hz, C-4), 74.8
(−) - 5 - Benzyloxycarbonylamino - 5 - deoxy-
1
1
(d, J(C,H) 151 Hz, C-3), 67.2 (t, J(C,H) 147
D
-idofuranose [(−)-13].—Prepared from (+)-
Hz, –OCH2Ph), 62.6 (t, 1J(C,H) 147 Hz, C-6),
12 following the procedure used for the prepa-
1
25
589
25
577
52.1 (d, J(C,H) 141 Hz, C-5), 26.7 and 26.0
ration of (+)-13. [h]
−38°, [h]
−38°,
1
25
25
25
(2 q, J(C,H) 130, 126 Hz, Me2C); CIMS
[h] −45°, [h] −76°, [h] −88° (c 0.12,
546
435
405
(NH4): m/z 355 ([M+2]+, 14), 354 ([M+
H]+, 56), 310 (16), 278 (7), 246 (3), 220 (12),
150 (5), 91 (100). Anal. Calcd for C17H23NO7
(353.37): C, 57.78; H, 6.56; N, 3.96. Found: C,
MeOH).
(−)-1,6-Anhydro-
D
-ido-piperidinose [(−)-
14].—A solution of aminodiol ((+)-10 (54
mg, 0.246 mmol) in 9:1 CF3COOH–H2O was
stirred at 25 °C for 90 min. The solvents were
removed by evaporation to dryness, the
residue was dissolved in water (2 mL) and
passed through a column of Dowex 1 (OH−
form) and eluted with water. The resulting
57.84; H, 6.46; N, 3.98. (Lit. [29] mp 140–
141 °C, [h] −24.5 (c 0.5, CHCl3)).
25
589
(+)-5-Benzyloxycarbonylamino-5-deoxy-1,
2-O-isopropylidene-i- -idofuranose [(+)-12].
D
—This compound was prepared from (+)-
10 following the procedure used for the prepa-
solution was lyophilized to give (−)-14 (33
mg, 83%) as white solid (135 °C, dec). [h]
25
25
25
ration of (−)-12. [h]
+24°, [h]
+25°,
589
577
589

C. Schaller et al. / Carbohydrate Research 314 (1998) 25–35
25 25
33
25
poured into Ac2O (0.6 mL), pyridine (1 mL)
and DMAP (5 mg) and stirred for 15 h at
25 °C. The solvents were removed by evapora-
tion and the residue purified by column chro-
matography on silica gel (6:1 AcOEt–light
petroleum) to give 17.9 mg of polyacetate
(9)-16 (75%, two steps) as colorless oil. UV
(MeCN): u 194 (m=5000); IR (film): w 3360,
3060, 2960, 1745, 1675, 1540, 1435, 1370,
−109°, [h]
−112°, [h]
−128°, [h]
577
546
435
−220°, [h]24055 −264° (c 0.7, H2O). Anal. Calcd
for C6H11NO4 (161.2): C 44.72; H 6.88; N
8.69. Found: C, 44.60; H, 6.93; N, 8.63. (Lit.
25
589
[30] -isomer: mp 140 °C (dec), [h] +114.5
L
(c 1, H2O)).
(+)-1-Deoxy- -ido-nojirimycin [(+)-2].—
D
(a) From tetrol (−)-13: a mixture of tetrol
(−)-13 (40 mg, 0.128 mmol) in MeOH (5 mL)
and Pd/C 10% (10 mg) was degassed, pressur-
ized with H2 (0.1 MPa) and shaken at 25 °C
for 15 h. After filtration (Celite), the solvent
was evaporated under reduced pressure. The
residue was purified by column chromatogra-
phy on Dowex 1 (OH− form, eluent H2O)
yielding 20 mg (95%) of (+)-2. (b) From
(−)-anhydrosugar (−)-14: a mixture of an-
hydrosugar (−)-14 (28 mg, 0.174 mmol) in
H2O (4 mL) and Pd/C 10% (10 mg) was
degassed, pressurized with H2 (0.1 MPa) and
shaken at 25 °C for 15 h. After filtration
(Celite), the solvent was evaporated under re-
duced pressure. The residue was purified by
column chromatography on Dowex 1 (OH−
form, eluent H2O) yielding 22 mg (77%) of
(+)-2 as white crystals (MeOH–Et2O) mp
1220, 1050, 735 cm−1; H NMR (CDCl3, 400
1
3
MHz): l 5.76 (d, J 9.5 Hz, H–N), 5.42 (ddd,
3J 6.4, 4.7, 3.6 Hz, H-5), 5.28–5.22 (m, H3+
3
H4), 4.60 (dddd, J 9.5, 6.0, 5.7, 3.4 Hz, H-2),
4.23 (dd, 2J 11.9 Hz, 3J 4.7, H-6a), 4.09 (dd, 2J
3
2
11.5 Hz, J 5.7 Hz, H-1a), 4.05 (dd, J 11.9
3
2
3
Hz, J 6.4 Hz, H-6b), 3.99 (dd, J 11.5 Hz, J
6.0 Hz, H-1b), 2.13 (s, NHAc), 2.10, 2.07,
2.05, 2.04 (4 s, 5 OAc). 13C NMR (CDCl3,
100.61 MHz): l 170.6, 170.3, 170.0, 169.9,
1
169.8 (5 s, 5 Ac), 69.5 and 69.2 (2 d, J(C,H)
1
150, 149 Hz, C3+C4), 68.9 (d, J(C,H) 149
1
Hz, C-5), 62.7 (t, J(C,H) 150 Hz, C-1), 61.8
1
1
(t, J(C,H) 150 Hz, C-6), 47.7 (d, J(C,H) 140
1
Hz, C-2), 23.1, 20.7, 20.6, 20.5 (4 q, J(C,H)
130 Hz, 6-CH3); CIMS (NH3): 434 ([M+1]+,
0.5), 374 (8), 318 (6), 259 (12), 219 (12), 144
(13), 71 (100). Anal. Calcd for C18H27NO11
(433.40): C, 49.88; H, 6.28; N, 3.23. Found: C,
49.84; H, 6.25; N, 3.19.
25
25
577
25
546
137–139 °C. [h]
+28°, [h]
+31°, [h]
589
25
25
405
+33°, [h] +54°, [h] +65° (c 0.5, H2O).
435
Anal. Calcd for C6H13NO4 (163.2): C, 44.17;
H, 8.03; N, 8.58. Found: C, 44.01; H, 7.89; N,
8.50.
Acknowledgements
(−)-1-Deoxy- -ido-nojirimycin [(−)-2].—
L
Prepared from (+)-13 following the proce-
This work was supported by the Swiss Na-
tional Science Foundation (Bern) and the
Fonds Herbette (Lausanne).
25
dure used for the preparation of (+)-2. [h]
589
25
25
546
25
−27°, [h] −28°, [h] −32°, [h] −52°,
577
435
25
405
[h]
−62° (c 0.33, H2O); Anal. Calcd for
C6H13NO4 (163.2): C, 44.17; H, 8.03; N, 8.38.
Found: C, 44.18; H, 7.88; N, 8.41. (Lit. [9] mp
References
25
589
139–141 °C, [h] −31°, (c 1, H2O)).
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