Synthesis of 6-amino-1,6-anhydro-6-deoxysugar derivatives

Article abstract of DOI:10.1016/S0008-6215(98)00089-5

Staudinger reaction of triphenylphosphine with 2,3,4-tri-O-acetyl-6-O-p-tolylsulfonyl-β-d-glycopyranosyl azides led to an anomeric iminophosphorane which rearranged in situ by elimination of the sulfonate at C-6. The 1,6-anhydro-6-deoxy-6-triphenylphospho

Full text of DOI:10.1016/S0008-6215(98)00089-5

Carbohydrate Research 310 (1998) 9±16
Synthesis of 6-amino-1,6-anhydro-6-deoxysugar
derivatives
Dominique Lafont *, Andreas Wollny 1, Paul Boullanger
Â
Laboratoire de Chimie Organique II, Unite Mixte de Recherche CNRS 5622, Universite de Lyon 1,
Chimie Physique Electronique de Lyon, 43 Bd du 11 Novembre 1918, F-69622 Villeurbanne, France
Â
Received 2 February 1998; accepted 27 March 1998
Abstract
Staudinger reaction of triphenylphosphine with 2,3,4-tri-O-acetyl-6-O-p-tolylsulfonyl-ꢀ-d-gly-
copyranosyl azides led to an anomeric iminophosphorane which rearranged in situ by elimination
of the sulfonate at C-6. The 1,6-anhydro-6-deoxy-6-triphenylphosphonioamino-ꢀ-d-glycopyr-
anose salts thus obtained were transformed into the corresponding 2,3,4-tri-O-acetyl-6-amino-1,6-
anhydro-6-deoxy-ꢀ-d-glycopyranoses which were further N-acylated or N-alkoxycarbonylated. 1H
and 13C NMR of these products show the occurrence of two rotamers in solution, due to restricted
rotations around the amide bond. # 1998 Elsevier Science Ltd. All rights reserved
Keywords: 6-O-p-tolylsulfonyl-ꢀ-d-glycosyl azide ; Staudinger reaction ; 6-Amino-1,6-anhydro-6-deoxy-ꢀ-d-
glycopyranose derivatives
1. Introduction
d-gluco and d-galacto series since, in this case, a
conformational inversion would be necessary to
obtain the anhydro derivative [4]. Recently, Pradera
et al. showed that a 6-amino-1,6-anhydro-6-deoxy-
2,3,4-tri-O-mesyl-ꢀ-d-glucopyranose derivative could
be prepared by treatment of N-diethoxycarbonyl-
vinyl-2,3,4,6-tetra-O-mesyl-ꢀ-d-glucopyranosyl-
amine under basic conditions [5]. The attack of the
nitrogen atom was regiospeci®c at the 6-position.
With 2,3,6-tri-O-acyl-N-diethoxycarbonylvinyl-4-
O-mesyl-glycopyranosylamines, syntheses of O-pro-
tected 4-deoxy-4-diethoxycarbonylvinylaminoaldoses
were also possible, through nucleophilic substitu-
tion of the mesyloxy group at C-4 with inversion of
con®guration [6].
Only a few examples of 6-amino-1,6-anhydro-6-
deoxy sugars have been described in the literature.
Thus, treatment of 6-amino-6-deoxy-1,2-O-iso-
propylidene-ꢀ-l-idofuranose in acidic conditions
led to an acyclic derivative, which was transformed
under basic conditions into 6-amino-6-deoxy-l-
idopyranose. The latter underwent a spontaneous
and practically quantitative dehydratation into 6-
amino-1,6-anhydro-6-deoxy-ꢀ-l-idopyranose [1±4].
The anhydro ring closure was evidently favored by
the stereochemistry of the hydroxyl groups in
equatorial position. Under the same conditions, a
similar transformation was not observed in the
In our previous papers on ꢀ-glycosylation in the
2-amino-2-deoxy-d-glucose and lactosamine series,
starting from 1,2-trans-2-deoxy-2-iodo-ꢁ-d-glyco-
* Corresponding author.
1
On leave from the University of Stuttgart.
0008-6215/98/$Ðsee front matter # 1998 Elsevier Science Ltd. All rights reserved
PII S0008-6215(98)00089-5

10
D. Lafont et al./Carbohydrate Research 310 (1998) 9±16
pyranosyl azides [7,8], ꢀ-glycosides were obtained
by the Staudinger reaction of the azido function
with triphenylphosphine [9]. Nucleophilic attack of
the nitrogen at C-2 led to an unstable aziridine
intermediate, which was opened by the alcohol at
the anomeric position. A further application of the
Staudinger reaction towards the synthesis of 6-
amino-1,6-anhydro-6-deoxysugar derivatives (d-
gluco, d-galacto and d-manno series) is reported in
the present paper.
phosphonioamino salts was also supported by the
31P chemical shifts (ꢂ 43.26±45.69) and by the cou-
pling constants JC,P for Cipso, Cortho, Cmeta and
Cpara of the triphenyl-phosphonio moiety [8,24,25].
The salts 7±9 were transformed into the crude
3,4,6-tri-O-acetyl-6-amino-1,6-anhydro-6-deoxy-ꢀ-
d-glycopyranoses 10±12 by anionic exchange of the
anion [Dowex 2X8 (OH ) column in dichlor-
omethane] via the phosphonioamino hydroxide
derivative, which rearranged immediately, a€ord-
ing triphenylphosphine oxide as by-product. These
derivatives were not isolable by column chromato-
graphy and were used directly for N-protection
reactions. Futhermore, 1H NMR of 12 displayed a
second N-acetylated product 13, resulting from the
O >N migration of the O-2 acetyl group. This
was con®rmed by peracetylation of the mixture,
2. Results and discussion
Reaction of azido sugars or glycosyl azides and
their corresponding imino-phosphoranes has
already been reported in the literature [8,10±15].
Due to their ylide structure, in which the nitrogen
atom is negatively charged, sugar iminopho-
sphoranes are strong nucleophiles which could
intramolecularly substitute a 6-O-p-tolylsulfonyl
group in the same way as an anomeric hydroxyl
group [16] or mercapto group [17], leading to 1,6-
anhydro derivatives.
1
which a€orded 16 only. H and 13C NMR signals
of derivatives 10 and 11 were fully assigned at
500 MHz in hexadeuteroacetone, using NOESY
and 1H±13C 2D experiments. ROESY [26] was also
necessary for 10 in which most of the vicinal and
long-range coupling constants were of the same
order of magnitude [22,23].
Therefore, 2,3,4-tri-O-acetyl-6-O-p-tolylsulfonyl-
ꢀ-d-gluco- and galactopyranosyl azides 3 and 4
were prepared in two steps from 1,2,3,4-tetra-O-
acetyl-6-O-p-tolyl-sulfonyl-d-gluco- and d-galacto-
pyranose 1 [18] and 2 [19], by treatment with 33%
hydrogen bromide in acetic acid and transforma-
tion of the glycosyl bromides into glycosyl azides
by phase transfer catalysis in the presence of
sodium azide according to Roy et al. [20]. 2,3,4-
Tri-O-acetyl-6-O-p-tolylsulfonyl-ꢀ-d-mannopyrano-
syl azide 6 was synthesized in three steps from
2,3,4,6-tetra-O-benzoyl-ꢀ-d-mannopyranosyl azide
5 [21], (i.e. debenzoylation according to Zemplen,
regioselective tosylation of the 6-OH and acetyla-
tion) in a 56% overall yield. Treatment of the
azides 3, 4 or 6 with a slight excess of triphenyl-
phosphine (1.05 equiv) in dichloromethane a€orded
quantitatively the expected 2,3,4-tri-O-acetyl-1,6-
anhydro-6-deoxy-6-triphenylphosphonioamino-ꢀ-d-
glycopyranose p-tolylsulfonates 7, 8 and 9. The
N-Acylation of the crude derivatives 10,11 and
the mixture 12,13 (pyridine/acetic anhydride) gave
the pure 6-acetamido-2,3,4-tri-O-acetyl-1,6-anhy-
dro-6-deoxy-ꢀ-d-glycopyranoses 14±16 in high
1
yields. H NMR spectra of 14,15 and 16 in deuter-
ochloroform revealed the presence of two con-
formers, the proportions of which were dependent
of their structures (14: 52/48, 15: 55/45, 16: 43/57).
This could be due to restricted rotations around
the amide bond [1,27±30]. On increasing the tem-
perature, in hexadeuterodimethyl-sulfoxide, the
signals coalescence was observed above 115 ꢀC
for compound 14. The presence of two rotamers
was also con®rmed by the 13C NMR spectra of
derivatives 14±16.
1
structure of these salts was evidenced from H-,
13C- and 31P NMR spectra; thus, 1H NMR
1
couplings values were characteristic of a C4 (D)
conformation as in 1,6-anhydrosugar derivatives
[22,23], and the presence of the C-6±N±C-1 bridge
1
was ascertained by H NMR couplings JH,P (J1,P
8.3±8.7 Hz, J6b,P 10±13 Hz) and 13C chemical shift
for C-6 (ꢂ 48.34±49.67 ppm). The formation of

D. Lafont et al./Carbohydrate Research 310 (1998) 9±16
11
tively, 0.019 mM for the cmc, 30.5 mN m 1 for ꢃ at
the interface and 39 A2 for ao. The cmc value was
very close to that found for octyl ꢀ-d-glucopyr-
anoside [33], but ao was smaller (49 A2 for octyl
ꢀ-d-glucopyranoside [34]), which could indicate a
lower hydratation of the carbohydrate head.
In conclusion, application of the Staudinger
reaction to 6-O-p-tolylsulfonyl-2,3,4-tri-O-acetyl-ꢀ-
d-glycopyranosyl azides allowed the formation of
6-amino-1,6-anhydro-6-deoxy-ꢀ-d-glycopyranose
derivatives, which could be N-alkoxycarbonylated
or N-acylated. This methodology is short and e-
cient, and well suited for the preparation of new
surfactants.
.
2. Experimental
General methods.ÐPyridine was dried by boiling
with CaH2 prior to distillation. Dichloromethane
was washed twice with water, dried with CaCl2 and
distilled from CaH2. Methanol was re¯uxed with
NaOMe before distillation. Pyridine and CH2Cl2
were stored over 4 A molecular sieves and MeOH
over 3 A molecular sieves. Melting points were
determined on a Buchi apparatus and were uncor-
rected. Thin layer chromatography was performed
on aluminium sheets coated with Silica Gel 60 F254
(E. Merck). Compounds were visualized by spray-
ing the TLC plates with dilute 15% aq H2SO4,
followed by charring at 150 ꢀC for a few min. Col-
umn chromatography was performed on Silica-gel
Geduran Si 60 (E. Merck). Optical rotations were
recorded on a Perkin±Elmer 241 polarimeter in a
1 dm cell at 21 C. H and 13C NMR spectra were
recorded with Bruker AC-200, AM-300 or DRX-
500 spectrometers working at 200, 300 or 500 MHz
and 50, 75.5 or 125 MHz, respectively, with Me4Si
as internal standard. Elemental analyses were per-
formed by the ``Laboratoire Central d'Analyses du
CNRS'' (Vernaison, France).
Since 6-N-acyl-6-amino-1,6-anhydro-6-deoxy-ꢀ-
d-glycopyranoses could ®nd applications in the
®eld of detergents, liquid crystals or surface-active
complexing agents, crude compound 10 was
alkoxycarbonylated or acylated. Thus, reaction of
10 in pyridine with an excess of alkyl chlor-
oformate (methyl or allyl chloroformate) or acyl
chloride (octanoyl or tetradecanoyl chloride)
a€orded the expected carbamates 17,18 and amides
19 and 20 in good to high yields. As for acetamide
1
derivatives, H and 13C NMR spectra of the car-
bamates also dispalyed the presence of two
rotamers at room temperature. Product 19 and 20
were deacetylated by the Zemplen procedure, and
solubility in water of the deprotected sugars 21 and
22 was determined. 1,6-Anhydro-6-deoxy-6-tetra-
decanoyl-amino-ꢀ-d-glucopyranose (21) was insol-
uble in water, contrary to 1,6-anhydro-6-deoxy-
6-octanoylamino-ꢀ-d-glucopyranose (22). Kra€t
ꢀ
1
ꢀ
temperature of 22 was shown to be below 20 C
2,3,4-Tri-O-acetyl-6-O-p-tolylsulfonyl-b-d-gluco-
pyranosyl azide (3).Ð1,2,3,4-Tetra-O-acetyl-6-O-p-
tolylsulfonyl-ꢁ,ꢀ-d-glucopyranose (1) [18] (4.50 g,
8.95 mmol) in CH2Cl2 (5 mL) was treated with
33% HBr in AcOH (12 mL). After 1.5 h, the mix-
ture was concentrated, the residue was dissolved in
CHCl3 (100 mL), the organic phase was washed
with cooled aq NaHCO3, then with water, dried
and concentrated again. To a soln of this glucosyl
and the surface tension (ꢃ) measurements were
carried out by the ring method of Lecomte du
Nouy [31] and corrected according to Harkins and
Jordan [32]. Measureꢀments were performed at
room temperature (20 C) and the cmc was deter-
mined at the break of the slope in the ꢃ versus
log[C] plots, as usual. The interfacial area per
molecule (ao) was calculated for concentrations
just below the cmc according to the Gibbs law. The
experimental values thus determined were, respec-
bromide
8.95 mmol, 1 equiv.) and NaN3 (2.33 g, 4 equiv) in
(8.95 mmol),
Bu4NHSO4
(3.04 g,

12
D. Lafont et al./Carbohydrate Research 310 (1998) 9±16
CH2Cl2 (50 mL), was added satd aq NaHCO3
(50 mL); the two phase mixture was vigorously
stirred for 2 h; addition of EtOAc (450 mL), wash-
ing of the organic phase with aq NaHCO3
(2Â100 mL), then with brine (100 mL), drying and
concentration a€orded the crude product 2 which
was recrystallized twice from absolute EtOH:
3.13ꢀg, yield 72%; mp 129±130 ꢀC (lit [35]. mp 128±
130 C); [ꢁ]d +19.0ꢀ (c 1.0, CHCl3); Rf 0.70 (1:1
EtOAc±petroleum ether).
General procedure for the preparation of the
cyclic 1,6-anhydro-6-deoxy-6-triphenylphosphonio-
amino p-tolylsulfonates (7±9).ÐA soln of PPh3
(0.57±1.14 g, 2.17±4.34 mmol) in CH2Cl2 (2±4 mL)
was added dropwise under an argon atmosphere,
to a soln of the peracetylated 6-O-p-tolylsulfonyl
glycosylazides 3, 4 or 6 (1.00±2.00 g, 2.06±
4.12 mmol) in dry CH2Cl2 (6±12 mL). Evolution of
nitrogen started after a few minutes and the soln
1
was stirred overnight. After concentration, the H
2,3,4-Tri-O-acetyl-6-O-tosyl-b-d-galactopyranosyl
azide (4).ÐPrepared in 75% yield, as described
previously from 1,2,3,4-tetra-O-acetyl-6-O-tosyl-
NMR spectrum of the residue showed the presence
of the expected product besides some traces of
PPh3 and PPh3O, which could be removed by three
successive washings with CH2Cl2 (1 mL) and pet-
roleum ether (10 mL).
ꢀ
ꢁ,ꢀ-d-galactopyranose (2) [19]; mp 94 C (EtOH)
[lit [35] mp 92±94 ꢀC (diethyl ether)]; [ꢁ]d 16.3ꢀ (c
1.0, CHCl3); Rf 0.70 (1:1 EtOAc±petroleum ether).
2,3,4-Tri-O-acetyl-6-O-p-tolysulfonyl-b-d-manno-
pyranosyl azide (6).Ð2,3,4,6-Tetra-O-benzoyl-ꢀ-d-
mannopyranosyl azide (5) [21] (4.10 g, 6.60 mmol)
was treated overnight in MeOH (50 mL) contain-
ing a catalytic amount of sodium; after concentra-
tion, the residue was washed with petroleum ether
(3Â30 mL), dissolved in C5H5N (12 mL) and cooled
2,3,4-Tri-O-acetyl-1,6-anhydro-6-deoxy-6-triphenyl-
phosphonioamino-b-d-gluco-pyranose p-tolylsulfon-
ate (7).ÐObtained quantitatively as described
above from 2,3,4-tri-O-acetyl-6-O-p-tolylsulfonyl-
ꢀ-d-glucopyranosyl azide (3) (2.00 g, 4.12 mmol).
Amorphous hygroscopic solid; [ꢁ]d 12.9ꢀ (c 1.0,
1
CHCl3); H NMR (CD3COCD3): ꢂ 8.08±7.85 (m,
15 H, 3 Ph), 7.64 and 7.02 (2d, 4 H, J 8.2 Hz, CH3-
Ph), 5.67 (ddd, 1 H, J1,2, J1,3 1.4 Hz, J1,P 8.3 Hz, H-
1), 5.04 (dddd, 1 H, J3,5, J4,5 1.4 Hz, J5,6a 1.7 Hz,
J5,6b 6.8 Hz, H-5), 4.88 (dddd, 1 H, J3,4, J2,3 1.4 Hz,
H-3), 4.83 (dd, 1 H, H-4), 4.50 (dd, 1 H, H-2), 3.92
(dd, 1 H, J6a,6b 9.7 Hz, H-6a), 3.84 (ddd, 1 H, J6b,P
10.5 Hz, H-6b), 2.27 (s, 3 H, CH3Ph), 2.20, 2.10,
1.97 (3s, 9 H, CH3COO); 31P NMR (CDCl3): ꢂ
43.69; 13C NMR (CDCl3): ꢂ 169.11, 169.09, 168.46
(3 C, CH3COO), 144.55 (CSO2), 137.92 (CCH3),
136.06 (d, 3 C, JC,P 2.7 Hz, Cpara), 133.47 (d, 6 C,
JC,P 11.1 Hz, Cortho), 130.70 (d, 6 C, JC,P 14.3 Hz,
Cmeta), 127.92 and 125.92 (4 C, PhSO2), 117.88 (d,
3 C, JC,P 101.9 Hz, Cipso), 86.45 (d, JC1,P 3.2 Hz, C-
1), 76.19 (d, JC5,P 6.1 Hz, C-5), 68.71 (C-4), 68.57
(d, JC2,P 6.5 Hz, C-2), 68.25 (C-3), 49.05 (C-6),
21.01 (PhCH3), 20.68, 20.61, 20.37 (3 C,
CH3COO). Anal. Calcd for C37H38NO10PS, 2H2O
(755.76): C, 58.80; H, 5.60; N, 1.85. Found: C,
58.87; H, 5.44, N, 1.92.
ꢀ
to 12 C; a soln of TsCl (1.67 g, 8.76 mmol, 1.32
equiv) in C5H5N (6 mL) was added dropwise for
1 h and the mixture was allowed to reach room
temperature. Stirring was maintained overnight,
then the soln was concentrated and the residue was
puri®ed by column chromatography (EtOAc)
a€ording the 6-O-monosulfonate as a syrup
(1.66 g, 70% yield). The latter was immediatly
acetylated in a 2:1 mixture of C5H5N and Ac2O
(15 mL). After 16 h, concentration of the soln and
column chromatography of the residue (1:1
EtOAc±petroleum ether) a€orded the pure product
6 (1.79 g, 56% overall yield) as a cristalline solid:
mp 128±129 ꢀC; [ꢁ]d +43.0ꢀ (c 1.0, CHCl3); Rf 0.67
(1:1 EtOAc±petroleum ether); 1H NMR (CDCl3): ꢂ
7.80 and 7.34 (2d, 4 H, J 8.2 Hz, CH3-Ph), 5.41
(dd, 1 H, J1,2 1.2 Hz, J2,3 3.1 Hz, H-2), 5.15 (dd, 1
H, J3,4 10.1 Hz, J4,5 9.7 Hz, H-4), 5.01 (dd, 1 H, H-
3), 4.64 (d, 1 H, H-1), 4.15 (d, 2 H, J5,6a 4.5 Hz,
J5,6b 4.5 Hz, H-6a,6b), 3.80 (dt, 1 H, H-5), 2.45 (s, 3
H, CH3Ph), 2.17, 2.05, 1.98 (3s, 9 H, CH3COO);
13C NMR (CDCl3): ꢂ 169.87, 169.83, 169.63 (3 C,
CH3COO), 145.22 (CSO2), 132.42 (CCH3),
129.96 and 128.06 (4 C, PhSO2), 84.85 (C-1), 74.46,
70.72, 69.21, 65.44 (C-2,3,4,5), 67.91 (C-6), 21.66
(CH3Ph), 20.67, 20.59, 20.48 (3 C, CH3COO).
Anal. Calcd for C19H23N3O10S (485.46): C,
47.00; H, 4.78; N, 8.66. Found: C, 46.97; H, 4.91,
N, 8.78.
2,3,4-Tri-O-acetyl-1,6-anhydro-6-deoxy-6-triphenyl-
phosphonioamino-b-d-galactopyranose p-tolylsulf-
onate (8).ÐObtained quantitatively as described
above from 2,3,4-tri-O-acetyl-6-O-p-tolylsulfonyl-
ꢀ-d-galactopyranosyl azide (4) (2.00 g, 4.12 mmol).
Amorphous solid; [ꢁ]d +14.0ꢀ (c 1.0, CHCl3); H
1
NMR (CD3COCD3): ꢂ 8.08±7.85 (m, 15 H, 3 Ph),
7.64 and 7.02 (2d, 4 H, J 8.2 Hz, CH3-Ph), 5.62
(ddd, 1 H, J1,2, J1,3 1.4 Hz, J1,P 8.4 Hz, H-1), 5.34
(dddd, 1 H, J2,3, J3,5 1.4 Hz, J3,4 5.1 Hz, H-3), 5.24

D. Lafont et al./Carbohydrate Research 310 (1998) 9±16
13
(dd, 1 H, J4,5 4.4 Hz H-4), 5.02 (m, 1 H, H-5), 4.72
(dd, 1 H, H-2), 3.87 (dd, 1 H, J5,6a 1.5 Hz, J6a,6b
7.8 Hz, H-6a), 3.82 (ddd, 1 H, J5,6b 5.8 Hz, J6b,P
9.0 Hz, H-6b), 2.27 (s, 3 H, CH3Ph), 2.18, 1.99,
1.95 (3s, 9 H, CH3COO); 31P NMR (CDCl3): ꢂ
43.26; 13C NMR (CDCl3): ꢂ 169.08, 169.01, 168.96
(3 C, CH3COO), 144.72 (CSO2), 137.95 (CCH3),
136.13 (d, 3 C, JC,P 2.9 Hz, Cpara), 133.58 (d, 6 C,
JC,P 11.1 Hz, Cortho), 130.38 (d, 6 C, JC,P 13.2 Hz,
Cmeta), 127.93 and 125.98 (4 C, PhSO2), 117.92 (d,
3 C, JC,P 102.0 Hz, Cipso), 86.40 (d, JC1,P 3.3 Hz, C-
1), 74.55 (d, JC5,P 6.3 Hz, C-5), 71.00 (d, JC2,P
7.0 Hz, C-2), 67.03 (C-3), 63.94 (C-4), 48.34 (C-6),
21.05 (PhCH3), 20.54, 20.35, 20.33 (3 C,
CH3COO). Anal. Calcd for C37H38NO10PS, 2H2O
(755.76): C, 58.80; H, 5.60; N, 1.85. Found: C,
58.53; H, 5.38, N, 1.66.
a€orded a mixture of the expected product 10 or 11
(from 7 or 8) or 12/13 (from 9) with PPh3O. These
compounds were too instable to be puri®ed by
column chromatography on silica-gel.
NMR spectroscopy of crude 2,3,4-tri-O-acetyl-6-
amino-1,6-anhydro-6-deoxy-b-d-glucopyranose (10).
1H (CD3-COCD3): ꢂ 4.98 (ddd, 1 H, J1,2, J1,3
1.4 Hz, J1,5 0.6 Hz, H-1), 4.78 (dddd, 1 H, J2,3, J3,4,
J3,5 1.4 Hz, H-3), 4.54 (dddd, 1 H, J2,4, J4,5 1.4 Hz,
J4,6b 0.6 Hz, H-4), 4.50 (dddd, 1 H, J5,6a 7.0 Hz,
J5,6b 1.5 Hz, H-5), 3.15 (dd, 1 H, J6a,6b 10.2 Hz, H-
6a), 3.09 (ddd, 1 H, H-6b), 2.08, 2.06, 2.06 (3s, 9 H,
CH3COO); 13C (CD3COCD3): ꢂ 169.19, 169.10,
168.88 (3 C, CH3COO), 88.05 (C-1), 74.03 (C-5),
72.95 (C-4), 72.90 (C-2), 71.07 (C-3), 46.07 (C-6),
20.68, 20.59, 20.19 (3 C, CH3COO).
NMR spectroscopy of crude 2,3,4-tri-O-acetyl-6-
amino-1,6-anhydro-6-deoxy-b-d-galactopyranose
2,3,4-Tri-O-acetyl-1,6-anhydro-6-deoxy-6-triphenyl-
phosphonioamino-b-d-mannopyranose p-tolylsulf-
onate (9).ÐObtained quantitatively as described
above from 2,3,4-tri-O-acetyl-6-O-p-tolylsulfonyl-
ꢀ-d-mannopyranosyl azide (6) (1.00 g, 2.06 mmol).
1
(11). H (CD3-COCD3): ꢂ 5.16 (ddd, 1 H, J1,3, J2,3
1.4 Hz, J3,4 5.5 Hz, H-3), 5.08 (ddd, 1 H, J4,5
4.3 Hz, J4,6b 0.9 Hz, H-4), 4.98 (dd, 1 H, J1,2 1.4 Hz,
H-1), 4.62 (dd, 1 H, H-2), 4.37 (ddd, 1 H, J5,6a
1.0 Hz, J5,6b 6.4 Hz, H-5), 3.39 (dd, 1 H, J6a,6b
9.8 Hz, H-6a), 3.03 (ddd, 1 H, H-6b), 2.15, 2.13,
2.03 (3s, 9 H, CH3COO); 13C (CD3COCD3): ꢂ
170.23, 169.94, 169.79 (3 C, CH3COO), 88.03 (C-1),
73.86 (C-2), 72.77 (C-5), 68.52 (C-3), 66.96 (C-4),
44.78 (C-6), 20.87, 20.78, 20.60 (3 C, CH3COO).
Acetylation of the crude coumpounds 10, 11 or
12/13 with a 2:1 pyridine±Ac2O mixture (15 h) fol-
lowed by concentration a€orded products 14, 15 or
16 which were puri®ed by column chromatography
(7:1 EtOAc±EtOH).
ꢀ
1
Amorphous solid; [ꢁ]d 28.2 (c 1.0, CHCl3); H
NMR (CD3COCD3): ꢂ 8.12±7.85 (m, 15 H, 3 Ph),
7.63 and 7.02 (2d, 4 H, J 8.0 Hz, CH3-Ph), 5.78
(ddd, 1 H, J1,2 2.7 Hz, J1,3 0.7 Hz, J1,P 8.7 Hz, H-1),
5.35 (dddd, 1 H, J2,3 5.2 Hz, J3,4, J3,5 1.4 Hz, H-3),
5.09 (dddd, 1 H, J4,5 1.4 Hz, J5,6a 2.7 Hz, J5,6b
7.2 Hz, H-5), 5.03 (dd, 1 H, H-2), 5.01 (m, 1 H, H-
4), 4.05 (ddd, 1 H, J4,6a 1.4 Hz, J6a,6b 9.9 Hz, H-6a),
3.84 (ddd, 1 H, J6b,P 13.2 Hz, H-6b), 2.37 (s, 3 H,
CH3Ph), 2.27, 2.13, 1.70 (3s, 9 H, CH3COO); 31P
NMR (CDCl3): ꢂ 45.69; 13C NMR (CDCl3): ꢂ
169.19, 169.10, 168.88 (3 C, CH3COO), 144.70
(CSO2), 137.83 (CCH3), 135.94 (d, 3 C, JC,P 2.7 Hz,
Cpara), 133.63 (d, 6 C, JC,P 8.9 Hz, Cortho), 130.51
(d, 6 C, JC,P 13.2 Hz, Cmeta), 127.86 and 125.86 (4
C, PhSO2), 118.22 (d, 3 C, JC,P 101.9 Hz, Cipso),
86.64 (C-1), 75.66 (d, JC5,P 5.4 Hz, C-5), 71.09 (C-
4), 66.45 (C-3), 66.14 (d, JC2,P 6.4 Hz, C-2), 49.67
(C-6), 21.92 (PhCH3), 20.68, 20.59, 20.19 (3 C,
CH3COO). Anal. Calcd for C37H38NO10PS, 2H2O
(755.76): C, 58.80; H, 5.60; N, 1.85. Found: C,
58.89; H, 5.36, N, 1.79.
6-Acetamido-2,3,4-tri-O-acetyl-1,6-anhydro-6-
deoxy-b-d-glucopyranose
described above from 7 (0.695 mmol); 0.192 g
(14).ÐObtained
as
ꢀ
(84%): mp 124 C; [ꢁ]d 45.8ꢀ (c 1.0, CHCl3); Rf
1
0.31 (EtOAc); major rotamer (52%): H NMR
(CDCl3): ꢂ 5.74 (bs, 1 H, H-1), 4.93 (bs, 1 H, H-3),
4.88 (bs, 1 H, H-2), 4.72 (m, 1 H, H-5), 4.63 (bs, 1
H, H-4), 3.65 (m, 2 H, H-6a,6b), 2.20, 2.19, 2.17,
2.08 (4s, 12 H, CH3CO); 13C NMR (CDCl3): ꢂ
169.70, 169.15, 168.31, 167.82 (4 C, CH3CO), 84.00
(C-1), 75.65 (C-5), 69.66 (C-4), 68.87 (C-3), 66.36
(C-2), 44.76 (C-6), 22.19, 20.78, 20.68, 20.56 (4 C,
CH3CO); minor rotamer (48%): 1H NMR
(CDCl3): ꢂ 5.51 (bs, 1 H, H-1), 4.91 (bs, 1 H, H-3),
4.69 (m, 1 H, H-5), 4.67 (bs, 1 H, H-4), 4.61 (bs, 1
H, H-2), 3.72 (dd, 1 H, J5,6a 6.6 Hz, J6a,6b 9.2 Hz,
H-6a), 3.59 (d, 1 H, H-6b), 2.17, 2.16, 2.10, 2.08
(4s, 12 H, CH3CO); 13C NMR (CDCl3): ꢂ 169.94,
169.63, 168.76, 166.90 (4 C, CH3CO), 83.88 (C-1),
General procedure for the preparation of the
6-acetamido-2,3,4-tri-O-acetyl-1,6-anhydro-6-deoxy-
b-d-hexopyranoses (14±16).ÐA soln of the crude
salts 7, 8 or 9, prepared from 3, 4 or 6 (0.337 g,
0.695 mmol) and PPh3 (0.191 g, 1.05 equiv in
CH2Cl2 (1 mL), was applied at the top of a column
of Dowex 2X8 (OH ) in CH2Cl2 and eluted with
the same solvent. Concentration of the eluate

14
D. Lafont et al./Carbohydrate Research 310 (1998) 9±16
74.88 (C-5), 69.26 (C-4), 68.78 (C-3), 68.31 (C-2),
46.32 (C-6), 22.09, 20.78, 20.68, 20.50 (4 C,
CH3CO). Anal. Calcd for C14H19NO8 (329.30): C,
51.06; H, 5.82; N, 4.25. Found: C, 51.04; H, 5.94;
N, 4.18.
(CDCl3): ꢂ 170.05, 169.25, 169.20, 167.05 (4 C,
CH3CO), 82.55 (C-1), 76.00 (C-5), 72.31 (C-4),
67.98 (C-3), 67.39 (C-2), 46.98 (C-6), 22.68, 21.30,
21.03, 20.95 (4 C, CH3CO). Anal. Calcd for
C14H19NO8, H2O (347.316): C, 48.41; H, 6.09; N,
4.03. Found: C, 48.12; H, 5.74, N, 3.91.
General procedure for the preparation of N-
alkoxycarbonyl and N-acyl derivatives of the 2,3,4-
tri-O-acetyl-6-amino-1,6-anhydro-6-deoxy-b-d-gluco-
pyranose (17±20).ÐAlkyl chloroformate or acyl
chloride (1.3 equiv.) was added at 0 ꢀC to a soln of
crude compound 10 [obtained from the salts 7
(0.695 mmol) as previously described] in C5H5N
(5 mL). Stirring was maintained overnight; the soln
was then concentrated and the residue was puri®ed
by column chromatography.
6-Acetamido-2,3,4-tri-O-acetyl-1,6-anhydro-6-
deoxy-b-d-galactopyranose (15).ÐObtained as
described abovꢀe from 8 (0.695 mmol); 0.187 g
(82%): mp 124 C; [ꢁ]d +22.1ꢀ (c 1.0, CHCl3); Rf
1
0.30 (EtOAc); major rotamer (55%): H NMR
(CDCl3): ꢂ 5.66 (dd, 1 H, J1,2, J1,3 1.5 Hz, H-1),
5.33±5.30 (m, 1 H, H-3), 5.27 (dd, 1 H, J3,4 5.4 Hz,
J4,5 4.3 Hz, H-4), 5.04 (dd, 1 H, J2,3 1.9 Hz, H-2),
4.58±4.54 (m, 1 H, H-5), 3.77 (d, 1 H, J6a,6b 8.8 Hz,
H-6a), 3.61 (dd, 1 H, J5,6b 5.9 Hz, H-6b), 2.18, 2.14,
2.09, 2.03 (4s, 12 H, CH3CO); 13C NMR (CDCl3):
ꢂ 169.83, 169.64, 169.46, 169.21 (4 C, CH3CO),
84.09 (C-1), 73.72 (C-5), 70.94 (C-2), 67.34 (C-3),
64.70 (C-4), 44.31 (C-6), 22.57, 21.00, 20.76, 20.76
2,3,4-Tri-O-acetyl-1,6-anhydro-6-deoxy-6-methoxy-
carbonylamino-b-d-glucopyranose (17).ÐObtained
as described above from 10 and methyl chlor-
oformate; the crude product was puri®ed by col-
umn chromatography (2:1 EtOAc±petroleum
ether); 0.212 g (88%): oily material; [ꢁ]d 36.0ꢀ (c
1.0, CHCl3); Rf 0.50 (2:1 EtOAc±petroleum ether);
1
(4 C, CH3CO); minor rotamer (45%): H NMR
(CDCl3): ꢂ 5.46 (dd, 1 H, J1,2, J1,3 1.7 Hz, H-1),
5.33±5.30 (m, 1 H, H-3), 5.27 (dd, 1 H, J3,4 5.4 Hz,
J4,5 4.3 Hz, H-4), 4.77 (dd, 1 H, J2,3 1.7 Hz, H-2),
4.54±4.52 (m, 1 H, H-5), 3.76 (d, 1 H, J6a,6b
10.9 Hz, H-6a), 3.52 (dd, 1 H, J5,6b 6.1 Hz, H-6b),
2.16, 2.11, 2.08, 2.04 (4s, 12 H, CH3CO); 13C NMR
(CDCl3): ꢂ 170.05, 169.21, 168.49, 167.15 (4 C,
CH3CO), 84.24 (C-1), 74.46 (C-5), 69.00 (C-2),
67.42 (C-3), 64.82 (C-4), 45.58 (C-6), 22.59, 20.99,
20.77, 20.77 (4 C, CH3CO). Anal. Calcd for
C14H19NO8 (329.30): C, 51.06; H, 5.82; N, 4.25.
Found: C, 51.20; H, 5.82; N, 3.98.
1
major rotamer (62%): H NMR (CDCl3): ꢂ 5.48
(bs, 1 H, H-1), 4.87±4.65 (m, 4 H, H-2,3,4,5), 3.77
(s, 3 H, COOCH3), 3.60 (m, 2 H, H-6a,6b), 2.17,
2.07, 2.07 (3s, 9 H, CH3COO); 13C NMR (CDCl3):
ꢂ 169.51, 169.20, 168.44 (3 C, CH3COO), 153.12
(NCOO), 83.59 (C-1), 74.67 (C-5), 69.45 (C-4),
68.67 (C-3), 67.06 (C-2), 52.74 (COOCH3), 45.25
(C-6), 20.67, 20.60, 20.37 (3 C, CH3COO); minor
rotamer (38%): 1H NMR (CDCl3): ꢂ 5.57 (bs, 1 H,
H-1), 4.87±4.65 (m, 4 H, H-2,3,4,5), 3.77 (s, 3 H,
COOMe), 3.60 (m, 2 H, H-6a,6b), 2.17, 2.07, 2.07
(3s, 9 H, CH3COO); 13C NMR (CDCl3): ꢂ 169.51,
169.20, 168.44 (3 C, CH3CO), 153.12 (NCOO),
84.12 (C-1), 75.36 (C-5), 69.45 (C-4), 68.67 (C-3),
66.77 (C-2), 52.74 (COOCH3), 45.25 (C-6), 20.67,
20.60, 20.37 (3 C, CH3COO). Anal. Calcd for
C14H19NO9 (345.30): C, 48.69; H, 5.55; N, 4.06.
Found: C, 48.36; H, 5.62, N, 3.94.
6-Acetamido-2,3,4-tri-O-acetyl-1,6-anhydro-6-
deoxy-b-d-mannopyranose (16).ÐObtained as
described above from 9 (0.695 mmol); 0.189 g
(82%): oily material; [ꢁ]d 94.1ꢀ (c 1.0, CHCl3); Rf
1
0.31 (EtOAc); major rotamer (57%): H NMR
(CDCl3): ꢂ 5.48 (dd, 1 H, J1,2 2.5 Hz, J1,3 1.4 Hz,
H-1), 5.32 (ddd, 1 H, J2,3 5.1 Hz, J3,4 1.9 Hz, H-3),
5.24 (dd, 1 H, H-2), 4.84 (dd, 1 H, J4,5 1.7 Hz, H-4),
4.68 (ddd, 1 H, J5,6a 1.7 Hz, J5,6b 6.8 Hz, H-5),
3.78±3.66 (m, 2 H, H-6a,6b), 2.18, 2.10, 2.08, 2.06
(4s, 12 H, CH3CO); 13C NMR (CDCl3): ꢂ 169.84,
169.64, 168.41, 167.82 (4 C, CH3CO), 84.62 (C-1),
75.45 (C-5), 72.06 (C-4), 67.85 (C-3), 67.75 (C-2),
45.64 (C-6), 22.78, 20.99, 20.69, 20.69 (4 C,
CH3CO); minor rotamer (43%): 1H NMR
(CDCl3): ꢂ 5.94 (dd, 1 H, J1,2, 2.7 Hz, J1,3 1.2 Hz,
H-1), 5.35 (dd, 1 H, J2,3 5.3 Hz, J3,4 1.8 Hz, H-3),
5.16 (dd, 1 H, H-2), 4.83 (dd, 1 H, J4,5 1.7 Hz, H-4),
4.71 (m, 1 H, H-5), 3.77±3.66 (m, 2 H, H-6a,6b),
2.18, 2.10, 2.08, 2.06 (4s, 12 H, CH3CO); 13C NMR
2,3,4-Tri-O-acetyl-6-allyloxycarbonylamino-1,6-
anhydro-6-deoxy-b-d-glucopyranose (18).ÐObtained
as described above from 10 and allyl chlor-
oformate; the crude product was puri®ed by
column chromatography (5:2 EtOAc±petroleum
ether); 0.237 g (92%): oily material; [ꢁ]d 38.6ꢀ (c
1.0, CHCl3); Rf 0.70 (2:1 EtOAc±petroleum ether);
1
major rotamer (63%): H NMR (CDCl3): ꢂ 5.93
(m, 1 H, allyl CH=), 5.52 (bs, 1 H, H-1), 5.35 and
5.25 (m, 2 H, allyl CH2=), 4.88±4.65 (m, 6 H,
H-2,3,4,5, allyl CH2), 3.60 (m, 2 H, H-6a,6b), 2.17,

D. Lafont et al./Carbohydrate Research 310 (1998) 9±16
15
2.07, 2.07 (3s, 9 H, CH3CO); 13C NMR (CDCl3): ꢂ
169.65, 169.34, 168.60 (3 C, CH3COO), 152.39
(NCOO), 132.20 (CH=), 117.94 (CH2=), 83.65
(C-1), 74.85 (C-5), 69.53 (C-4), 68.86 (C-3), 67.19
(C-2), 66.18 (CH2O), 45.36 (C-6), 20.83, 20.74,
2,3,4-Tri-O-acetyl-1,6-anhydro-6-deoxy-6-octano-
ylamino-b-d-glucopyranose (20).ÐObtained as
described above from 10 and octanoyl chloride; the
crude product was puri®ed by column chromato-
graphy (5:2 EtOAc±petroleum ether); 0.241 g
(84%): mp 78±80 ꢀC; [ꢁ]d 28.3ꢀ (c 1.0, CHCl3); Rf
0.62 (5:2 EtOAc±petroleum ether); major rotamer
1
20.53 (3 C, CH3COO); minor rotamer (37%): H
NMR (CDCl3): ꢂ 5.93 (m, 1 H, allyl CH=), 5.57
(bs, 1 H, H-1), 5.35 and 5.25 (m, 2 H, allyl CH2=),
4.88±4.65 (m, 6 H, H-2,3,4,5, allyl CH2), 3.60 (m,
2 H, H-6a,6b), 2.17, 2.07, 2.07 (3s, 9 H, CH3COO);
13C NMR (CDCl3): ꢂ 169.65, 169.34, 168.60 (3 C,
CH3COO), 152.39 (NCOO), 132.42 (CH=), 117.94
(CH2=), 84.31 (C-1), 75.54 (C-5), 69.71 (C-4),
68.86 (C-3), 66.90 (C-2), 66.18 (CH2O), 45.36
(C-6), 20.83, 20.74, 20.53 (3 C, CH3COO). Anal.
Calcd for C16H21NO9 (371.335): C, 51.75; H,
5.70; N, 3.77. Found: C, 51.69; H, 5.79, N,
3.67.
1
(54%): H NMR (CDCl3): ꢂ 5.76 (bs, 1 H, H-1),
4.93 (bs, 1 H, H-3), 4.88 (bs, 1 H, H-2), 4.72 (m, 1
H, H-5), 4.61 (bs, 1 H, H-4), 3.66 (m, 2 H, H-
6a,6b), 2.33 (m, 2 H, CH2CO), 2.19, 2.18, 2.06 (3s,
9 H, CH3COO), 1.67 (m, 2 H, CH2CH2CO), 1.26
(m, 8 H, 4 CH2), 0.88 (t, 3 H, J 6.4 Hz, CH3CH2);
13C NMR (CDCl3): ꢂ 170.55, 170.06, 169.87,
168.36 (4 C, 3 CH3CO, CH2CO), 84.30 (C-1), 75.79
(C-5), 70.07 (C-4), 69.13 (C-3), 66.74 (C-2), 45.84
(C-6), 34.75, 31.65, 29.37, 29.05, 24.36, 22.59 (6
CH2), 20.93, 20.83, 20.73 (3 C, CH3CO), 14.05
(CH3CH2); minor rotamer (46%): 1H NMR
(CDCl3): ꢂ 5.55 (bs, 1 H, H-1), 4.90 (bs, 1 H, H-3),
4.72 (m, 1 H, H-5), 4.68 (bs, 1 H, H-4), 4.61 (bs, 1
H, H-2), 3.70 (dd, 1 H, J5,6a 6.6 Hz, J6a,6b 9.2 Hz,
H-6a), 3.58 (d, 1 H, H-6b), 2.28 (m, 2 H, CH2CO),
2.20, 2.16, 2.07 (3s, 9 H, CH3CO), 1.67 (m, 2 H,
CH2CH2CO), 1.26 (m, 8 H, 4 CH2), 0.88 (t, 3 H, J
6.4 Hz, CH3CH2); 13C NMR (CDCl3): ꢂ 170.06,
169.76, 169.20, 168.82 (4 C, 3 CH3CO, CH2CO),
83.50 (C-1), 74.83 (C-5), 69.42 (C-4), 69.04 (C-3),
68.60 (C-2), 44.87 (C-6), 34.69, 31.65, 29.22, 29.02,
25.27, 22.59 (6 CH2), 20.93, 20.82, 20.64 (3 C,
CH3CO), 14.05 (CH3CH2). Anal. Calcd for
C20H31NO8 (413.455): C, 58.10; H, 7.56; N, 3.39.
Found: C, 58.05; H, 7.72; N, 3.33.
2,3,4-Tri-O-acetyl-1,6-anhydro-6-deoxy-6-tetra-
decanoylamino-b-d-glucopyranose (19).ÐObtained
as described above from 10 and tetradecanoyl
chloride; the crude product was puri®ed by column
chromatography (4:3 EtOAc±petroleum ether);
ꢀ
0.280 g (81%): mp 58±59 C; [ꢁ]d 26.0ꢀ (c 1.0,
CHCl3); Rf 0.44 (1:1 EtOAc±petroleum ether);
1
major rotamer (52%): H NMR (CDCl3): ꢂ 5.76
(bs, 1 H, H-1), 4.94 (bs, 1 H, H-3), 4.88 (bs, 1 H,
H-2), 4.73 (m, 1 H, H-5), 4.63 (bs, 1 H, H-4), 3.65
(m, 2 H, H-6a,6b), 2.34 (m, 2 H, CH2CO), 2.20,
2.18, 2.07 (3s, 9 H, CH3COO), 1.67 (m, 2 H,
CH2CH2CO), 1.26 (m, 20 H, 10 CH2), 0.88 (t, 3 H,
J 6.4 Hz, CH3CH2); 13C NMR (CDCl3): ꢂ 170.61,
170.15, 169.84, 168.28 (4 C, 3 CH3CO, CH2CO),
84.22 (C-1), 75.66 (C-5), 69.99 (C-4), 69.05 (C-3),
66.66 (C-2), 45.77 (C-6), 34.67, 31.81, 29.53±29.01,
25.19±24.29, 22.57 (12 CH2), 20.81, 20.70, 20.63 (3
C, CH3COO), 14.00 (CH3CH2); minor rotamer
1,6-Anhydro-6-deoxy-6-tetradecanoylamino-b-d-
glucopyranose (21).ÐThe product 19 (0.249 g,
0.50 mmol) was dissolved in dry MeOH (15 mL)
and treated with a catalytic amount of NaOMe.
After 16 h at room temperature, the mixture was
concentrated and the residue was puri®ed on a
short column of silica-gel (6:1 EtOAc±EtOH);
1
(48%): H NMR (CDCl3): ꢂ 5.55 (bs, 1 H, H-1),
4.92 (bs, 1 H, H-3), 4.69 (m, 1 H, H-5), 4.68 (bs, 1
H, H-4), 4.61 (bs, 1 H, H-2), 3.70 (dd, 1 H, J5,6a
6.6 Hz, J6a,6b 9.2 Hz, H-6a), 3.58 (d, 1 H, H-6b),
2.34 (m, 2 H, CH2CO), 2.21, 2.16, 2.07 (3s, 9 H,
CH3CO), 1.67 (m, 2 H, CH2CH2CO), 1.26 (m, 20
H, 10 CH2), 0.88 (t, 3 H, J 6.4 Hz, CH3CH2); 13C
NMR (CDCl3): ꢂ 169.99, 169.69, 169.14, 168.75 (4
C, 3 CH3CO, CH2CO), 83.39 (C-1), 74.72 (C-5),
69.30 (C-4), 68.91 (C-3), 68.47 (C-2), 44.79 (C-6),
34.61, 31.81, 29.53±29.01, 25.19±24.29, 22.57 (12
CH2), 20.81, 20.71, 20.52 (3 C, CH3CO), 14.00
(CH3CH2). Anal. Calcd for C26H43NO8 (497.61):
C, 62.75; H, 8.71; N, 2.81. Found: C, 62.94; H,
8.87; N, 2.63.
ꢀ
0.154 g (83%): mp 97±98 C; [ꢁ]d 3.0ꢀ (c 1.0, 1:1
CHCl3±EtOH); Rf 0.55 (6:1 EtOAc±EtOH); major
rotamer (75%): 1H NMR (C5D5N): ꢂ 6.27 (bs, 1 H,
H-1), 4.94 (bd, 1 H, J5,6b 6.5 Hz, H-5), 4.59 (m, 2
H, H-3,4), 4.18 (bs, 1 H, H-2), 4.05 (d, 1 H, J6a,6b
8.5 Hz, H-6a), 3.72 (dd, 1 H, H-6b), 2.35 (t, 2 H,
CH2CO), 1.77 (m, 2 H, CH2CH2CO), 1.19 (m, 20
H, 10 CH2), 0.84 (t, 3 H, J 6.4 Hz, CH3CH2);
1
minor rotamer (25%): H NMR (C5D5N): ꢂ 5.99
(bs, H-1), 4.92 (bd, 1 H, J5,6b 7.8 Hz, H-5), 4.59 (m,
2 H, H-3,4), 4.33 (bs, 1 H, H-2), 4.25 (d, 1 H, J6a,6b
10.4 Hz, H-6a), 3.90 (dd, 1 H, H-6b), 2.43 (t, 2 H,

16
D. Lafont et al./Carbohydrate Research 310 (1998) 9±16
CH2CO), 1.77 (m, 2 H, CH2CH2CO), 1.19 (m, 20
H, 10 CH2), 0.84 (t, 3 H, J 6.4 Hz, CH3CH2). Anal.
Calcd for C20H37NO5 (371.50): C, 64.66; H, 10.04;
N, 3.77. Found: C, 64.81; H, 10.02; N, 3.72.
[10] A. Messmer, I. Pinter, and F. Szego, Angew. Chem,
76 (1964) 227±228.
[11] I. Pinter, J. Kovacs, A. Messmer, A. Kalman, G.
Toth, and B.K. Lindberg, Carbohydr. Res., 72
(1979) 289±296.
[12] J. Kovacs, I. Pinter, F. Szego, G. Toth, and A.
Messmer, Acta Chim. Acad. Sci. Hung., 101 (1979)
7±16.
[13] V. Zsoldos-Mady, I. Pinter, P. Sandor, and A.
Messmer, Carbohydr. Res., 281 (1996) 321±326.
[14] Z. Gyorgydeak, L. Szilagyi, and H. Paulsen, J.
Carbohydr. Chem., 12 (1993) 139±163.
[15] V. Maunier, P. Boullanger, and D. Lafont, J. Car-
bohydr. Chem., 16 (1997) 231±235 and ref. therein.
[16] D. Lafont, P. Boullanger, O. Cadas, and G.
Descotes, Synthesis, (1989) 191±194 and refs.
therein.
[17] H. Driguez, J.C. McAuli€e, R.V. Stick, D.M.G.
Tilbrook, and S.J. Williams, Aust. J. Chem., 49
(1996) 343±348 and refs. therein.
[18] E. Hardegger and R.M. Montavon, Helv. Chim.
Acta, 29 (1946) 1199±1203.
[19] H. Ohle and H. Thiel, Chem. Ber., 66 (1933) 525±
532.
[20] F.D. Tropper, F.O. Anderson, S. Braun, and R.
Roy, Synthesis, (1992) 618±620.
[21] Z. Gyorgydeak and H. Paulsen, Liebigs Ann.
Chem., (1977) 1987±1991.
[22] R.G.S. Ritchie, N. Cyr, and A.S. Perlin, Can. J.
Chem., 54 (1976) 2301±2309.
[23] T.B. Grindley and R. Thangarasa, Carbohydr.
Res., 172 (1988) 311±318.
[24] J. Kovacs, I. Pinter, and A. Messmer, Carbohydr.
Res., 141 (1985) 57±65.
1,6-Anhydro-6-deoxy-6-octanoylamino-b-d-gluco-
pyranose (22).ÐPrepared as described above from
21 (0.206 g, 0.50 mmol). The crude product was
puri®ed on a short column of silica-gel (4:1
ꢀ
EtOAc±EtOH); 0.121 g (84%): mp 69±70 C; [ꢁ]d
5.8ꢀ (c 1.0, H2O); Rf 0.35 (4:1 EtOAc±EtOH);
1
major rotamer (75%): H NMR (C5D5N): ꢂ 6.31
(bs, 1 H, H-1), 4.99 (bd, 1 H, J5,6b 6.9 Hz, H-5),
4.62 (m, 2 H, H-3,4), 4.17 (bs, 1 H, H-2), 4.05 (d, 1
H, J6a,6b 8.4 Hz, H-6a), 3.71 (dd, 1 H, H-6b), 2.36
(t, 2 H, CH2CO), 1.77 (m, 2 H, CH2CH2CO), 1.16
(m, 8 H, 4 CH2), 0.79 (t, 3 H, J 6.4 Hz, CH3CH2);
13C NMR (C5D5N): ꢂ 170.74 (CH2CO), 88.09 (C-
1), 79.92 (C-5), 74.18, 72.71, 69.80 (3 C, C-2,3,4),
46.69 (C-6), 35.06, 32.08, 29.75, 29.59, 24.99, 23.00
(6 CH2), 14.38 (CH3CH2); minor rotamer (25%):
1H NMR (C5D5N): ꢂ 6.00 (bs, 1 H, H-1), 4.96 (bd,
1 H, J5,6b 8.4 Hz, H-5), 4.59 (m, 2 H, H-3,4), 4.35
(bs, 1 H, H-2), 4.25 (d, 1 H, J6a,6b 10.3 Hz, H-6a),
3.89 (dd, 1 H, H-6b), 2.45 (t, 2 H, CH2CO), 1.77
(m, 2 H, CH2CH2CO), 1.19 (m, 8 H, 4 CH2), 0.84
(t, 3 H, J 6.4 Hz, CH3CH2); 13C NMR (C5D5N): ꢂ
169.42 (CH2CO), 88.35 (C-1), 79.07 (C-5), 74.18,
72.87, 72.22 (3 C, C-2,3,4), 46.46 (C-6), 35.06, 32.08,
29.75, 29.59, 25.65, 23.00 (6 CH2), 14.38 (CH3CH2).
Anal. Calcd for C14H25NO5 (287.35): C, 58.51; H,
8.77; N, 4.87. Found: C, 58.74; H, 8.82; N, 4.83.
[25] J. Kovacs, I. Pinter, A. Messmer, G. Toth, and H.
Duddeck, Carbohydr. Res., 166 (1987) 101±111.
[26] AA. Bothner-By, R.L. Stephens, and J. Lee, J. Am.
Chem. Soc., 106 (1984) 811±813.
[27] D. Lafont and P. Boullanger, J. Carbohydr. Chem.,
11 (1992) 567±586.
References
[1] H. Paulsen and K. Todt, Angew. Chem., 77 (1965)
589.
[2] H. Paulsen and K. Todt, Chem. Ber., 99 (1966)
3450±3460; H. Paulsen and K. Todt, Chem. Ber.,
100 (1967) 512±520.
[28] W.A. Szarek, S. Wolfe, and J.K.N. Jones, Tetra-
hedron Lett., 38 (1964) 2743±2750.
[3] W. Meyer zu Reckendorf and N. Wassiliadou-
Micheli, Chem. Ber., 101 (1968) 2294±2301.
[4] H. Paulsen and K. Todt, Adv. Carbohydr. Chem.,
23 (1968) 115±232.
[29] M.L. Wolfrom, J.L. Minor, and W.A. Szarek,
Carbohydr. Res., 1 (1965) 156±165.
[30] H. Paulsen and K. Todt, Chem. Ber., 100 (1967)
3385±3396, 3397±3404.
[5] M.A. Pradera, D. Olano, and J. Fuentes, Tetra-
hedron Lett., 36 (1995) 8653±8656.
[31] P. Lecomte du Nouy, J. Gen. Physiol., 1 (1918)
521±524.
[6] J. Fuentes, D. Olano, and M.A. Pradera, Tetra-
hedron: Asymmetry, 8 (1997) 3443±3456.
[7] D. Lafont, P. Guilloux, and G. Descotes, Carbo-
hydr. Res., 193 (1989) 61±73.
[32] W.D. Harkins and H.F. Jordan, J. Am. Chem.
Soc., 52 (1930) 1751±1772.
[33] Th. Bocker and J. Thiem, Tenside Surf. Det., 26
(1989) 318±324.
[8] D. Lafont, P. Boullanger, F. Carvalho, and Ph.
Vottero, Carbohydr. Res., 297 (1997) 117±126.
[9] H. Staudinger and J. Meyer, Helv. Chim. Acta, 2
(1919) 635±646.
[34] A.R. van Buuren and H.J.C. Berendsen, Langmuir,
10 (1994) 1703±1713.
[35] Z. Gyorgydeak and L. Szilagyi, Liebig Ann. Chem.,
(1987) 235±242.