Ready access to 3-amino-2,3-dideoxysugars via regio- and stereo-selective tandem hydroamination-glycosylation of glycals

Article abstract of DOI:10.1039/c1ob05068k

A highly stereoselective BF₃·OEt₂-promoted tandem hydroamination-glycosylation on a glycal scaffold has been developed to form 3-amino-2,3-dideoxysugars in a one-pot procedure. This efficient multicomponent reaction protocol offers s

Full text of DOI:10.1039/c1ob05068k

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PAPER
Ready access to 3-amino-2,3-dideoxysugars via regio- and stereo-selective
tandem hydroamination–glycosylation of glycals†
Feiqing Ding, Ronny William, Siming Wang, Bala Kishan Gorityala and Xue-Wei Liu*
Received 13th January 2011, Accepted 2nd March 2011
DOI: 10.1039/c1ob05068k
A highly stereoselective BF3·OEt2-promoted tandem hydroamination–glycosylation on a glycal scaffold
has been developed to form 3-amino-2,3-dideoxysugars in a one-pot procedure. This efficient
multicomponent reaction protocol offers simplicity and general applicability to a broad range of
variations on each component.
Structurally-defined aminosugars such as 3-amino-2,3-dideoxy
sugars are of great importance and have stimulated tremen-
dous research interest, due to their prevalence in pharmaceu-
ticals such as anthracycline antibiotics,1 and natural products
such as L-ristosamine,2 L-daunosamine,3 nocardicyclins4 and L-
vancosamine.5 For example, L-ristosamine is the essential carbo-
hydrate motif in the structure of ristomycin, which is a member
of the antibiotic vancomycin family and plays a pivotal role in
platelet aggregation and diagnosis of von Willebrand’s disease.2
Appendage of L-vancosamine to the antibiotic vancomycin trans-
forms it into a potent drug for the treatment of methicillin-resistant
Staphylococcus aureus.6 The medicinal and glycobiological studies
of the intriguing activities of this class of aminosugars and
derivatives hinge on the synthetic ease of preparation of 3-amino-
2,3-dideoxyhexapyranoses.
Unfortunately, current syntheses are complicated due to the
inherent challenges associated with carbohydrate chemistry.7 It
is extremely cumbersome to achieve exclusive stereoselectivity in
the synthesis of 3-amino-2,3-dideoxyglycosides due to the non-
availability of a neighbouring participating group at the C-2
position that usually directs the glycosylation stereochemistry.
Such reactions normally provide a mixture of anomers. Moreover,
the synthesis of 3-amino-2,3-dideoxy sugars requires lengthy
synthetic routes resulting in diminished overall yields. Therefore,
many groups have been making great efforts on various synthetic
strategies to achieve more efficient syntheses of 3-amino-2,3-
dideoxysugars.8–11 For example, Smiatacz and co-workers syn-
thesized methyl and ethyl 3-amino-2,3-dideoxy- hexapyranoses
through 1,4-addition of hydrazoic acid to pseudoglycals and subse-
quent hydrogenation of the azide.8 Lowary and co-workers devel-
oped an alternative method which comprise photo-induced acylni-
trene aziridination reaction and hydrogenolytic aziridine opening
which finally furnished methyl 3-amino-2,3-dideoxyglycosides.9e
Colinas’s group reported an elegant b-stereoselective sulfonami-
doglycosylation of D-glycal, in which the replacement of HBr·PPh3
with BF3·OEt2 led to 3-amino derivatives.10 In another multistep
method, pseudoglycal was initially oxidized with stoichiometric
PhI(OH)OTs to the corresponding a,b-unsaturated ketone. Con-
jugate addition of a nucleophile to the resultant a,b-unsaturated
ketone and subsequent reductive amination completed the syn-
thesis of 3-amino-2,3-dideoxyglycosides.11 Although results from
most of the reports are encouraging, poor stereoselectivities, low
yields and multiple synthetic steps are the major impediments of
the reported strategies to widespread use.
In continuation of our strong interest in the synthesis of
biologically active aminosugars and glycosaminoglycans,12 herein,
we report a concise and robust synthetic approach that provides
3-amino-2,3-dideoxysugars with not only exclusive anomeric
stereoselectivity but also with a plethora of structural derivatives.
Specifically, we envisioned a straightforward synthesis of 3-amino-
2,3-dideoxyglycosides by a three-component reaction of 3,4,6-
tri-O-acetyl-D-glycal with two (N-, and O-, or S-containing)
nucleophiles in a one-pot manner. This methodology involves
regio- and stereoselective glycosylation and C-3 amination on the
protected glycal scaffold (Fig. 1).
Fig. 1 Our plan for quick access to 3-amino-2,3-dideoxysugars via regio-
and stereoselective tandem hydroamination/glycosylation of glycals.
Results and discussion
We first determined whether our proposed one-pot three-
component reaction was a viable strategy to form the de-
sired products. In fact, when 3,4,6-tri-O-acetyl-D-glucal (1a), p-
toluenesulfonamide (2a) and benzyl alcohol (3a) were subjected
to a one-pot reaction in the presence of 1.1 equiv of triflic acid
Division of Chemistry and Biological Chemistry, School of Physical
and Mathematical Sciences, Nanyang Technological University, Singapore
637371. E-mail: xuewei@ntu.edu.sg; Fax: +65 6791 1961
† Electronic supplementary information (ESI) available: NMR spectra for
compounds 4a–4z. See DOI: 10.1039/c1ob05068k
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Table 1 Optimization of the one-pot three-component tandem hydroam-
conditions for the one-pot synthesis were found to be 2.2 equiv
of BF3·OEt2, at room temperature with DCE as solvent under
nitrogen for 30 min (Table 1, entry 16).
ination/glycosylation reactiona
With the optimized reaction conditions in hand, we investigated
the substrate scope by carrying out the reaction with various
nucleophiles. As shown in Table 2, a wide range of aromatic and
aliphatic alcohols and thiols gave the desired aminoglycosides with
exclusive a-stereoselectivities in high yields. A series of 3-amino-
2,3-dideoxyglucosides 4b–4p were prepared in good to excellent
yields (66–95%) (Table 2, entries 1–12). It was observed that
long chain alcohols, alcohols bearing an electron withdrawing
group, aromatic and hindered aliphatic thiols gave products in
slightly lower yields (Table 2, entries 1, 7, 11 and 12, 4d, 4k,
4o and 4p). With this expedited protocol, we synthesized L-
menthol glucoside 4q in 77% yield (Table 2, entry 13), which is
a commonly seen 3-amino-2,3-dideoxysugar motif appended to
biologically important natural products.13 To our delight, all of
the glycosylation products were obtained as pure diastereomers.
In our protocol, aromatic and aliphatic sulfonamides achieve
the best results (Table 2, entries 14 and 15). For instance, TsNH2,
NsNH2 and MsNH2 proved to be excellent nucleophiles, providing
the corresponding products in high yields and anomeric selectivi-
ties. Likewise, the reaction with benzyl carbamate (CbzNH2) gave
the corresponding 3-amino-2,3-dideoxyglucoside 4t in moderate
yield (Table 2, entry 16). The benzyloxycarbonyl (Cbz) group
in the resulting product could be easily transformed into free
amino group. Interestingly, when 3,4-6-tri-O-acetyl-D-glucal 1a
was treated with tert-butyl carbamate (BocNH2) under the same
reaction conditions, the deprotected product 4u was isolated
after purification (Table 2, entry 17). In contrast, reaction of
trimethylsilyl azide (TMSN3) with tri-O-acetyl-D-glucal 1a proved
to be unsuccessful. Finally, the analogous reaction of tri-O-acetyl-
D-galactal 1b with TsNH2 and aromatic or aliphatic alcohols also
afforded the corresponding 3-amino-2,3-dideoxygalactosides 4v–
4z in good to excellent yields with exclusive a anomeric selectivity
(Table 2, entries 18–21).
We felt that the investigation of the mechanisms would be
worthwhile due to the diastereoselectivity of the reaction, even
in the absence of a neighbouring directing group at C-2. To gain
insight into the mechanism by which BF3·OEt2 promotes this
reaction, we performed simple 19F NMR spectroscopic studies.
Careful scrutiny of the NMR data suggests that BF3·OEt2 is
coordinated to the oxygen atom of the glycal. In our control NMR
experiments, BnOH and TsNH2 were combined with BF3·OEt2,
and as predicted, BF3·OEt2 did not show any observable shift
from the original 19F NMR signal, suggesting negligible or no
interaction between these nucleophiles and BF3·OEt2.14 However,
upon the addition of glycal to the remaining nucleophiles, shifts of
the 19F signal were observed, which indicates the formation of the
boron–sugar complex (Fig. 2). This result implies that BF3·OEt2
is coordinated to the glycal. Though a detailed mechanism of
the present protocol awaits further studies, a simple plausible
pathway is postulated (Scheme 1). Our proposed mechanism
involves formation of intermediary allyloxocarbenium ion 6 as
a result of expulsion of the acetoxy group. Initial diastereofacial
selective attack of the N-nucleophile at C3 of the more stable
twisted boat conformation is followed by a rapid proton transfer
to generate oxocarbenium ion 7. Finally, preferential axial attack
of the alcohol nucleophile at the anomeric position, as a result of
Entry
Promoter
Solvent
Time (min)
Yield (%)b
1
2
3
4
5
6
7
8
TfOH (1.1)
Amberlyst-15 (1.1)
TFA (1.1)
H3PO4 (1.1)
CSA (1.1)
p-TsOH (1.1)
Cu(OTf)2 (1.1)
ZnCl2 (1.1)
(C6F5)3B (1.1)
BF3·OEt2 (1.1)
BF3·OEt2 (2.2)
BF3·OEt2 (2.2)
BF3·OEt2 (2.2)
BF3·OEt2 (2.2)
BF3·OEt2 (2.2)
BF3·OEt2 (2.2)
TMSOTf (2.2)
SnCl4 (2.2)
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DCM
toluene
toluene
toluene
DMF
THF
MeCN
DCM
DCE
DCE
30
31
—
trace
—
—
—
—
—
—
45
90
—
—
trace
91
93
90
92
180
120
180
180
180
180
180
180
120
30
30
30
30
30
9
10
11
12
13
14
15
16
17
18
30
30
30
DCE
a Reactions were carried out with 3,4,6-tri-O-acetyl-D-glucal 1a (50 mg,
0.18 mmol), TsNH2 2a (1.1 equiv), BnOH 3a (1.1 equiv) in 2 mL of solvent.
b Isolated yields. DCE = 1, 2-dichloroethane.
(TfOH) in toluene at room temperature for 30 min, the desired
aminoglycoside 4a was obtained with exclusive a-stereoselectivity
but in a low yield of 31% (Table 1, entry 1). The structural and
stereochemical characterization of 4a was determined by extensive
NMR experiments (1H, 13C, COSY, HMQC, HMBC, NOESY, see
supporting information†).
To further optimize this process, we conducted a series of ex-
periments to evaluate various promoters and solvents. The results
of the preliminary screening are listed in Table 1. For different
Brønsted acids tested, such as Amberlyst-15, TFA, H3PO4, p-
TsOH and CSA, the desired product was not detected even after
prolonged reaction times (Table 1, entries 2–6). We started to
try Lewis acids such as Cu(OTf)2, ZnCl2, and (C6F5)3B, but also
failed to transform starting materials into the desired 3-amino-
2,3-dideoxysugars (Table 1, entries 7–9). However, it is worthy of
note that the reaction was found to proceed with the strong Lewis
acid BF3·OEt2 (1.1 equiv), albeit with extended reaction time and
with a moderate yield of 45% (Table 1, entry 10). However, an
increase in the promoter loading (2.2 equiv) was found to improve
the yield to 90% (Table 1, entry 11). Amongst different solvents
screened, 1,2-dichloroethane (DCE) was found to be superior to
other solvents in terms of reaction time, percentage yield and
activity profile (entry 16). When the reaction was carried out
with other strong Lewis acids TMSOTf (2.2 equiv) and SnCl4
(2.2 equiv), the product could also be obtained in comparable
yields (Table 1, entries 17 and 18). It is noteworthy that this
tandem hydroamination–glycosylation reaction is operationally
simple, easy to carry out and more importantly, devoid of by-
products. When we tested the crude reaction mixture by NMR,
there was no indication of a double bond, suggesting that there is
no formation of a Ferrier product. Thus, the optimized reaction
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Table 2 Substrate scope studies for BF3·OEt2-promoted one-pot three-component a-selective tandem hydroamination–glycosylation reactiona
Entry
1
1
R–NH2
NuH
Productb
Yield (%)c
TsNH2 2a
88 (4b)
84 (4c)
66 (4d)
2
3
4
1a
1a
1a
2a
2a
2a
95
82
85
5
6
1a
1a
2a
2a
90
85 (4i)
88 (4j)
7
8
9
1a
1a
1a
2a
2a
2a
76
76
91
10
11
1a
1a
2a
2a
83
71
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Table 2 (Contd.)
Entry
12
1
R–NH2
NuH
Productb
Yield (%)c
75
1a
2a
13
14
1a
1a
2a
77
3a
3a
85 (4rb)
91 (4rc)
85 (4rd)
88 (4re)
74 (4rf)
15
1a
92
16
17
18
1a
1a
CbzNH2 2h
BocNH2 2i
2a
3a
3a
3a
72
54
87
19
20
21
1b
1b
1b
2a
2a
2a
3h
83
78 (4x)
77 (4y)
3n
87
a Reaction conditions: 1 (0.18 mmol, 1.0 equiv), 2 (1.1 equiv), 3 (1.1 equiv), BF3·OEt2 (2.2 equiv), DCE (2 mL). b All new products were characterized by
IR, HRMS, 1H NMR and 13C NMR. c Isolated yields. DCE = 1, 2-dichloroethane.
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General procedure for synthesis of 3-amino-2,3-dideoxysugars
To a solution of 3,4,6-tri-O-acetyl-D-glucal 1a (50 mg, 0.18 mmol)
and nitrogen nucleophiles 2 (1.1 equiv) in DCE (2 mL) was
added oxygen or sulfur nucleophiles 3 (1.1 equiv) under N2
atmosphere. BF3·OEt2 (50 mL, 0.4 mmol, 2.2 equiv) was then
added to this mixture. The reaction mixture was stirred for 30 min
at room temperature, quenched with saturated NaHCO3 (3 mL)
and subsequently extracted with CH2Cl2 (5 mL). The extract was
dried and concentrated. The residue was subjected to column
chromatography (silica gel, hexane–EtOAc) to obtain pure 3-
amino-2,3-dideoxysugar 4.
Fig. 2 19F NMR spectra of (a) BF3·OEt2, (b) BF3·OEt2 and BnOH,
(c) BF3·OEt2 and TsNH2, and (d) BF3·OEt2, BnOH, TsNH2, and
tri-O-acetyl-D-glucal in CD2Cl2.
Benzyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-a-
D-glucopyranoside (4a). Compound 4a (82 mg, 93% yield) was
prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and benzyl alcohol 3a (21 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +41.9 (c 1.0
CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.68 (d, J = 8.0 Hz, 2H),
7.27–7.41 (m, 7H), 6.03 (d, J = 9.2 Hz, 1H), 4.88 (d, J = 2.8 Hz,
1H), 4.72 (d, J = 12 Hz, 1H), 4.64 (dd, J = 10.4, 4.0 Hz, 1H), 4.51
(d, J = 12 Hz, 1H), 4.28–4.33 (m, 1H), 4.13–4.28 (m, 2H), 3.92 (q,
J = 3.6 Hz, 1H), 2.41 (s, 3H), 2.08 (s, 3H), 2.05 (s, 3H), 1.81 (dt,
J = 9.6, 3.6 Hz, 1H), 1.47 (dd, J = 14.4, 2.0 Hz, 1H); 13C NMR
(CDCl3, 100 MHz): d 170.7, 170.4, 143.3, 138.0, 136.4, 129.8,
128.7, 128.3, 127.9, 126.9, 96.2, 69.7, 67.0, 64.6, 62.7, 48.0, 32.9,
21.5, 20.9, 20.8; IR (CHCl3): 3280, 1738, 1539, 1367, 1236, 1170,
1031, 743 cm-1; HRMS (ESI) m/z [M + H]+ calcd for C24H30NO8S
492.1692, found 492.1701.
Scheme 1 Proposed reaction mechanism.
possible hydrogen bonding between the incoming O-nucleophile
and sulfonamido group as shown in structure 8,15 provided solely
the thermodynamically favoured 1,3-cis a-isomer.
Conclusions
In summary, a highly stereoselective BF3·OEt2-promoted amino-
glycosylation of glucals has been developed in a one-pot manner.
This efficient multicomponent reaction protocol offers simplicity
and general applicability to a broad range of variations on
each component. Because of the aforementioned advantages,
the present methodology is believed to be able to find broad
applications in glycochemistry.
Butyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-a-D-
glucopyranoside (4b). Compound 4b (72 mg, 88% yield) was
prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and n-butanol 3b (18 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +54.8 (c
0.5 CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.70 (d, J = 8.0 Hz,
2H), 7.29 (d, J = 8.0 Hz, 2H), 6.08 (d, J = 9.2 Hz, 1H), 4.81 (d,
J = 3.6 Hz, 1H), 4.62 (dd, J = 10.4, 4.0 Hz, 1H), 4.31 (dd, J =
12.0, 4.8 Hz, 1H), 4.11–4.21 (m, 2H), 3.89 (q, J = 3.6 Hz, 1H),
3.71–3.73 (m, 1H), 3.38–3.40 (m, 1H), 2.43 (s, 3H), 2.07 (s, 3H),
2.06 (s, 3H), 1.78 (dt, J = 14.8, 3.6 Hz, 1H), 1.24–1.45 (m, 5H),
0.98 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz): d 170.7,
170.5, 143.3, 138.0, 129.8, 126.9, 97.1, 68.1, 67.0, 64.4, 62.8, 48.1,
32.8, 31.4, 21.5, 21.0, 20.8, 19.4, 13.8; IR (CHCl3): 3420, 1740,
1643, 1229, 1161, 1055, 754 cm-1; HRMS (ESI) m/z [M + Na]+
calcd for C21H31NO8SNa 480.1668, found 480.1676.
Experimental
General
All reactions were performed under an argon atmosphere. Unless
specified, all reagents and starting materials were purchased from
commercial sources and used as received. Solvents were purified
following standard literature procedures. Analytical thin layer
chromatography (TLC) was performed using pre-coated silica
gel plate. Visualization was achieved by UV light (254 nm)
and/or KMnO4 stain. Flash chromatography was performed
using silica gel and a gradient solvent system (EtOAc–hexane
as eluent). NMR spectra were recorded at room temperature
on Bruker ACF 300, Bruker DPX 400, Bruker AMX 500, and
JEOL ECA 400 NMR spectrometers. Chemical shifts (ppm) were
recorded with tetramethylsilane (TMS) as the internal reference
standard. Multiplicities are given as: s (singlet), bs (broad singlet),
d (doublet), t (triplet), dd (doublet of doublets) or m (multiplet).
The number of protons (n) for a given resonance is indicated by
nH and coupling constants are reported in Hz. Solid samples were
examined as a thin film between NaCl salt plates. High resolution
mass spectra (HRMS) were recorded on Waters Q-Tof premierTM
mass spectrometer.
Hexyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-a-D-
glucopyranoside (4c). Compound 4c (73 mg, 84% yield) was
prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and 1-hexanol 3c (25 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +54.7 (c
1.0 CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.61 (d, J = 8.0 Hz,
2H), 7.20 (d, J = 8.0 Hz, 2H), 6.00 (d, J = 8.8 Hz, 1H), 4.72
(d, J = 3.2 Hz, 1H), 4.53 (dd, J = 10.4, 4.0 Hz, 1H), 4.23 (dd,
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J = 12.0, 4.8 Hz, 1H), 4.03–4.09 (m, 2H), 3.81 (q, J = 3.6 Hz, 1H),
3.59–3.64 (m, 1H), 3.27–3.32 (m, 1H), 2.34 (s, 3H), 1.98 (s, 3H),
1.97 (s, 3H), 1.71 (dt, J = 14.8, 3.6 Hz, 1H), 1.25–1.54 (m, 9H),
0.84 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz): d 170.7,
170.4, 143.3, 138.0, 129.7, 126.8, 97.1, 68.4, 67.0, 64.4, 62.8, 48.1,
32.8, 31.4, 29.7, 25.9, 22.6, 21.5, 21.0, 20.8,14.0; IR (CHCl3): 3327,
2926, 1742, 1342, 1240, 1163, 1055, 735 cm-1; HRMS (ESI) m/z
[M + H]+ calcd for C23H36NO8S 486.2162, found 486.2161.
(s, 3H), 2.08 (s, 3H), 2.07 (s, 3H), 1.82 (dt, J = 14.8, 4.0 Hz, 1H),
1.47 (dd, J = 18.4, 2.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz): d
170.7, 170.4, 143.4, 138.0, 133.0, 129.8, 126.9, 118.2, 96.3, 68.6,
66.9, 64.5, 62.7, 48.0, 32.8, 21.5, 21.0, 20.8; IR (CHCl3): 3265,
2955, 1742, 1339, 1238, 1163, 1035, 656 cm-1; HRMS (ESI) m/z
[M + Na]+ calcd for C20H27NO8SNa 464.1355, found 464.1367.
Isopropyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4g). Compound 4g (68 mg, 85% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and 2-propanol 3g (15 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +53.9 (c 1.0
CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.71 (d, J = 8.4 Hz, 2H),
7.29 (d, J = 8.4 Hz, 2H), 6.16 (d, J = 8.8 Hz, 1H), 4.94 (d, J =
3.2 Hz, 1H), 4.61 (dd, J = 10.8, 4.0 Hz, 1H), 4.31 (dd, J = 12.0,
4.8 Hz, 1H), 4.16–4.22 (m, 2H), 3.87–3.92 (m, 2H), 2.42 (s, 3H),
2.07 (s, 3H), 2.06 (s, 3H), 1.78 (dt, J = 14.8, 3.6 Hz, 1H), 1.38
(dd, J = 10.8, 2.4 Hz, 1H), 1.30 (d, J = 6.0 Hz, 3H), 1.16 (d, J =
6.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz): d 170.7, 170.4, 143.3,
138.0, 129.7, 126.9, 95.3, 70.6, 67.2, 64.5, 62.8, 48.1, 33.2, 23.4,
21.5, 21.4, 21.0, 20.8; IR (CHCl3): 3323, 2970, 1741, 1369, 1230,
1163, 1091, 987, 665 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for
C20H29NO8SNa 466.1512, found 466.1501.
Octadecyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4d). Compound 4d (77 mg, 66% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and 1-octadecanol 3d (66 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +44.9 (c 1.0
CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.70 (d, J = 8.0 Hz, 2H),
7.28 (d, J = 8.0 Hz, 2H), 6.08 (d, J = 8.8 Hz, 1H), 4.81 (d, J =
2.8 Hz, 1H), 4.62 (dd, J = 10.4, 4.0 Hz, 1H), 4.29 (dd, J = 12.0,
4.8 Hz, 1H), 4.17–4.30 (m, 2H), 3.85 (q, J = 3.6 Hz, 1H), 3.69–3.71
(m, 1H), 3.36–3.38 (m, 1H), 2.42 (s, 3H), 2.07 (s, 3H), 2.06 (s, 3H),
1.77 (dt, J = 14.8, 3.6 Hz, 1H), 1.25–1.54 (m, 33H), 0.88 (t, J =
6.4 Hz, 3H); 13C NMR (CDCl3, 100 MHz): d 170.7, 170.4, 143.3,
138.1, 129.7, 126.8, 97.1, 68.4, 67.0, 64.4, 62.8, 48.1, 36.6, 32.8,
31.9, 29.7, 29.66, 29.65, 29.61, 29.5, 29.4, 29.3, 26.2, 24.7, 22.7,
21.5, 21.0, 20.8, 14.1; IR (CHCl3): 3421, 2924, 1741, 1342, 1240,
1163, 1055, 756, 498 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for
C35H59NO8SNa 676.3859, found 676.3857.
Isopentanyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-glucopyranoside (4h). Compound 4h (76 mg, 90% yield)
was prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and 3-pentanol 3h (22 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +47.2 (c 1.0
CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.70 (d, J = 8.0 Hz, 2H),
7.28 (d, J = 8.0 Hz, 2H), 6.18 (d, J = 8.8 Hz, 1H), 4.92 (d, J =
3.2 Hz, 1H), 4.60 (dd, J = 10.4, 3.6 Hz, 1H), 4.17–4.31 (m, 3H),
3.89 (q, J = 3.6 Hz, 1H), 3.50–3.53 (m, 1H), 2.42 (s, 3H), 2.07
(s, 3H), 2.06 (s, 3H), 1.76 (dt, J = 14.8, 4.0 Hz, 1H), 1.63–1.66
(m, 2H), 1.48–1.54 (m, 2H), 1.39 (dd, J = 14.4, 2.8 Hz, 1H), 0.98
(q, J = 7.2 Hz, 3H), 0.85 (q, J = 7.2 Hz, 3H); 13C NMR (CDCl3,
100 MHz): d 170.7, 170.5, 143.3, 138.0, 129.7, 126.9, 96.1, 81.4,
67.2, 64.7, 62.9, 48.1, 33.1, 26.7, 25.0, 21.5, 21.0, 20.8, 9.9, 9.0; IR
(CHCl3): 3304, 2935, 1742, 1342, 1229, 1163, 989 cm-1; HRMS
(ESI) m/z [M + Na]+ calcd for C22H33NO8SNa 494.1825, found
494.1811.
Propargyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4e). Compound 4e (75 mg, 95% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and propargyl alcohol 3e (12 mL, 0.2 mmol) and purified by
column chromatography (hexane–ethyl acetate = 5 : 1). [a]D20
=
1
+51.5 (c 1.0 CHCl3); H NMR (CDCl3, 400 MHz): d 7.72 (d,
J = 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 5.82 (d, J = 8.8 Hz, 1H),
5.05 (d, J = 3.2 Hz, 1H), 4.65 (dd, J = 10.4, 4.0 Hz, 1H), 4.32 (dd,
J = 12.0, 4.4 Hz, 1H), 4.09–4.27 (m, 3H), 3.91 (q, J = 3.6 Hz, 1H),
3.38–3.40 (m, 1H), 2.46 (s, 1H), 2.42 (s, 3H), 2.08 (s, 3H), 2.04 (s,
3H), 1.87 (dt, J = 14.8, 4.0 Hz, 1H), 1.50 (dd, J = 18.4, 2.4 Hz,
1H); 13C NMR (CDCl3, 100 MHz): d 170.7, 170.4, 143.4, 137.8,
129.8, 126.9, 95.7, 78.1, 75.5, 66.8, 64.7, 62.6, 54.8, 47.8, 32.7, 21.5,
21.0, 20.8; IR (CHCl3): 3306, 2922, 1738, 1339, 1242, 1161, 1042,
758 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for C20H25NO8SNa
462.1199, found 462.1201.
Cyclopentyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-glucopyranoside (4i). Compound 4i (72 mg, 85% yield)
was prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and cyclopentanol 3i (18 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +43.6 (c
0.5 CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.70 (d, J = 8.0 Hz,
2H), 7.29 (d, J = 8.0 Hz, 2H), 6.15 (d, J = 9.2 Hz, 1H), 4.89 (d,
J = 3.2 Hz, 1H), 4.62 (dd, J = 10.4, 3.6 Hz, 1H), 4.32 (dd, J =
12.4, 4.8 Hz, 1H), 4.16–4.21 (m, 3H), 3.86–3.91 (m, 1H), 2.42 (s,
3H), 2.08 (s, 3H), 2.06 (s, 3H), 1.61–1.86 (m, 9H), 1.36 (dd, J =
14.4, 2.8 Hz, 1H); 13C NMR (CDCl3, 100 MHz): d 170.7, 170.4,
143.3, 138.1, 129.7, 126.9, 95.9, 79.9, 67.1, 64.6, 62.8, 48.2, 33.5,
Allyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-a-D-
glucopyranoside (4f). Compound 4f (65 mg, 82% yield) was
prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and allyl alcohol 3f (14 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +115.5 (c
1.0 CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.72 (d, J = 8.0 Hz,
2H), 7.29 (d, J = 8.0 Hz, 2H), 6.02 (d, J = 9.2 Hz, 1H), 5.87–5.93
(m, 1H), 5.25–5.31 (m, 2H), 4.87 (d, J = 3.2 Hz, 1H), 4.64 (dd, J =
10.4, 4.0 Hz, 1H), 4.32 (dd, J = 12.0, 4.4 Hz, 1H), 4.14–4.23 (m,
3H), 3.98 (dd, J = 12.8, 6.0 Hz, 1H), 3.91 (q, J = 3.6 Hz, 1H), 2.42
3934 | Org. Biomol. Chem., 2011, 9, 3929–3939
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33.1, 31.8, 23.4, 23.0, 21.5, 21.0, 20.8; IR (CHCl3): 3422, 1740,
1340, 1228, 1161, 485 cm-1; HRMS (ESI) m/z [M + Na]+ calcd
for C22H31NO8SNa 492.1668, found 492.1669.
1240, 1163, 1057, 499 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for
C21H29NO9SNa 494.1461, found 494.1435.
Phenethyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4m). Compound 4m (81 mg, 91% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and 2-phenylethanol 3m (24 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +48.2 (c 1.0
Cyclohexyl
3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-glucopyranoside (4j). Compound 4j (76 mg, 88% yield)
was prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and cyclohexanol 3j (21 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +63.4 (c
0.25 CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.71 (d, J = 8.0 Hz,
2H), 7.29 (d, J = 8.0 Hz, 2H), 6.26 (d, J = 8.8 Hz, 1H), 4.89 (d, J =
3.2 Hz, 1H), 4.61 (dd, J = 10.8, 3.6 Hz, 1H), 4.30 (dd, J = 12.0,
4.8 Hz, 1H), 4.18–4.24 (m, 2H), 3.89 (q, J = 3.6 Hz, 1H), 3.60–3.65
(m, 1H), 2.42 (s, 3H), 2.07 (s, 3H), 2.06 (s, 3H), 1.90–1.92 (m,
1H), 1.70–1.80 (m, 4H), 1.41 –1.55 (m, 2H), 1.23–1.38 (m, 5H);
13C NMR (CDCl3, 100 MHz): d 170.7, 170.4, 143.3, 138.1, 129.7,
126.9, 95.3, 76.0, 67.2, 64.6, 62.8, 48.2, 33.3, 33.2, 31.3, 25.5, 23.9,
23.5, 21.5, 21.0, 20.8; IR (CHCl3): 3419, 1638, 1340, 1230, 1163,
517 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for C23H33NO8SNa
506.1825, found 506.1830.
1
CHCl3); H NMR (CDCl3, 400 MHz): d 7.63 (d, J = 8.0 Hz,
2H), 7.27–7.38 (m, 7H), 5.85 (d, J = 9.2 Hz, 1H), 4.76 (d, J =
3.2 Hz, 1H), 4.55 (dd, J = 10.8, 4.0 Hz, 1H), 4.18 (dd, J = 12.0,
4.4 Hz, 1H), 3.94–4.06 (m, 2H), 3.82–3.84 (m, 1H), 3.65–3.69 (m,
2H), 2.91–2.94 (m, 2H), 2.41 (s, 3H), 2.05 (s, 3H), 2.00 (s, 3H),
1.71 (dt, J = 9.6, 3.6 Hz, 1H), 1.39 (dd, J = 14.4, 2.4 Hz, 1H);
13C NMR (CDCl3, 100 MHz): d 170.7, 170.4, 143.3, 138.6, 138.1,
129.7, 128.8, 128.3, 126.9, 126.6, 97.0, 68.9, 68.5, 66.7, 62.6, 47.9,
36.1, 32.9, 21.5, 20.9, 20.8; IR (CHCl3): 3421, 1740, 1647, 1340,
1240, 1163, 752, 492 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for
C25H31NO8SNa 528.1668, found 528.1664.
Phenethyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4m). Compound 4m (81 mg, 91% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and 2-phenylethanol 3m (24 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +48.2 (c 1.0
2¢-Nitroethyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-glucopyranoside (4k). Compound 4k (65 mg, 76% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and 2-nitroethanol 3k (15 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +34.2 (c 0.5
CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.70 (d, J = 8.0 Hz, 2H),
7.30 (d, J = 8.0 Hz, 2H), 5.66 (d, J = 9.2 Hz, 1H), 4.88 (d, J =
3.2 Hz, 1H), 4.62–4.69 (m, 3H), 4.22–4.27 (m, 3H), 4.09–4.13 (m,
1H), 3.88–3.99 (m, 2H), 2.42 (s, 3H), 2.07 (s, 3H), 2.03 (s, 3H),
1.85 (dt, J = 14.8, 4.0 Hz, 1H), 1.38 (dd, J = 14.2, 2.8 Hz, 1H);
13C NMR (CDCl3, 100 MHz): d 170.7, 170.3, 143.4, 138.0, 129.8,
126.8, 97.7, 74.8, 66.7, 65.0, 63.9, 62.6, 47.7, 32.7, 21.5, 20.9, 20.8;
IR (CHCl3): 3421, 1734, 1638, 1558, 1340, 1230, 1161, 497 cm-1;
HRMS (ESI) m/z [M + Na]+ calcd for C19H26N2O10SNa 497.1206,
found 497.1193.
1
CHCl3); H NMR (CDCl3, 400 MHz): d 7.63 (d, J = 8.0 Hz,
2H), 7.27–7.38 (m, 7H), 5.85 (d, J = 9.2 Hz, 1H), 4.76 (d, J =
3.2 Hz, 1H), 4.55 (dd, J = 10.8, 4.0 Hz, 1H), 4.18 (dd, J = 12.0,
4.4 Hz, 1H), 3.94–4.06 (m, 2H), 3.82–3.84 (m, 1H), 3.65–3.69 (m,
2H), 2.91–2.94 (m, 2H), 2.41 (s, 3H), 2.05 (s, 3H), 2.00 (s, 3H),
1.71 (dt, J = 9.6, 3.6 Hz, 1H), 1.39 (dd, J = 14.4, 2.4 Hz, 1H);
13C NMR (CDCl3, 100 MHz): d 170.7, 170.4, 143.3, 138.6, 138.1,
129.7, 128.8, 128.3, 126.9, 126.6, 97.0, 68.9, 68.5, 66.7, 62.6, 47.9,
36.1, 32.9, 21.5, 20.9, 20.8; IR (CHCl3): 3421, 1740, 1647, 1340,
1240, 1163, 752, 492 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for
C25H31NO8SNa 528.1668, found 528.1664.
(E)-But-2-enyl
3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-
2¢-(Allyloxy)ethyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-
dideoxy-a-D-glucopyranoside (4l). Compound 4l (64 mg, 76%
yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glucal 1a (50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg,
0.2 mmol), and 2-(allyloxy)ethanol 3l (22 mL, 0.2 mmol) and
purified by column chromatography (hexane–ethyl acetate = 5 : 1).
[a]2D0 = +49.9 (c 1.0 CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.71
(d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 6.20 (d, J = 9.2 Hz,
1H), 5.91–6.02 (m, 1H), 5.32 (dd, J = 16.4 Hz, 1H), 5.24 (d, J =
10.0 Hz, 1H), 4.89 (d, J = 3.2 Hz, 1H), 4.64 (dd, J = 10.4, 3.6 Hz,
1H), 4.30 (dd, J = 12.0, 4.8 Hz, 1H), 4.16–4.21 (m, 2H), 4.07–4.09
(m, 2H), 3.93 (q, J = 3.6 Hz, 1H), 3.83–3.85 (m, 1H), 3.62–4.65
(m, 2H), 3.57–3.58 (m, 1H), 2.41 (s, 3H), 2.07 (s, 3H), 2.04 (s,
3H), 1.80 (dt, J = 10.8, 4.0 Hz, 1H), 1.54 (dd, J = 14.2, 2.8 Hz,
1H); 13C NMR (CDCl3, 100 MHz): d 170.7, 170.4, 143.2, 138.3,
134.5, 129.8, 126.8, 117.5, 96.9, 72.4, 68.6, 67.0, 66.4, 64.4, 62.7,
48.1, 32.7, 21.5, 20.9, 20.8; IR (CHCl3): 3325, 2924, 1740, 1340,
dideoxy-a-D-glucopyranoside (4n). Compound 4n (68 mg, 83%
yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glucal 1a (50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg,
0.2 mmol), and (E)-but-2-en-1-ol 3n (17 mL, 0.2 mmol) and
purified by column chromatography (hexane–ethyl acetate = 5 : 1).
[a]2D0 = +118.4 (c 1.0 CHCl3); 1H NMR (CDCl3, 300 MHz): d 7.71
(d, J = 8.1 Hz, 2H), 7.29 (d, J = 8.1 Hz, 2H), 6.04 (d, J = 8.7 Hz,
1H), 5.70–5.75 (m, 1H), 5.54–5.57 (m, 1H), 4.86 (d, J = 3.3 Hz,
1H), 4.63 (dd, J = 10.5, 3.9 Hz, 1H), 4.32 (dd, J = 12.3, 4.5 Hz,
1H), 4.11–4.20 (m, 3H), 3.88–3.94 (m, 2H), 2.42 (s, 3H), 2.08 (s,
3H), 2.07 (s, 3H), 1.82 (dt, J = 10.8, 3.9 Hz, 1H), 1.76 (d, J =
6.9 Hz, 3H), 1.44 (dd, J = 14.4, 2.1 Hz, 1H); 13C NMR (CDCl3,
100 MHz): d 170.8, 170.5, 143.4, 138.0, 131.2, 129.8, 126.9, 125.9,
95.8, 68.4, 67.1, 64.4, 62.8, 48.1, 32.9, 21.6, 21.1, 20.9, 17.9; IR
(neat): 3419, 1741, 1643, 1240, 1163, 1091, 669 cm-1; HRMS
(ESI) m/z [M + Na]+ calcd for C21H29NO8SNa 478.1512, found
478.1526.
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Benzylthio 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4o). Compound 4o (65 mg, 71% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and benzylthiol 3o (20 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +8.8 (c 0.5
(50 mg, 0.18 mmol), benzenesulfonamide 2b (32 mg, 0.2 mmol),
and benzyl alcohol 3a (21 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +70.1 (c 0.25
CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.80 (d, J = 10.0 Hz, 2H),
7.27–7.41 (m, 8H), 6.03 (d, J = 9.2 Hz, 1H), 4.88 (d, J = 2.8 Hz,
1H), 4.72 (d, J = 12 Hz, 1H), 4.64 (dd, J = 10.4, 4.0 Hz, 1H), 4.51
(d, J = 12 Hz, 1H), 4.28–4.33 (m, 1H), 4.13–4.28 (m, 2H), 3.92
(q, J = 3.6 Hz, 1H), 2.08 (s, 3H), 2.05 (s, 3H), 1.81 (dt, J = 9.6,
3.6 Hz, 1H), 1.47 (dd, J = 14.4, 2.0 Hz, 1H); 13C NMR (CDCl3,
100 MHz): d 170.7, 170.4, 143.3, 138.0, 136.4, 129.8, 128.7, 128.3,
127.9, 126.9, 96.2, 69.7, 67.0, 64.6, 62.7, 48.0, 32.9, 21.0, 20.8; IR
(CHCl3): 3420, 1740, 1647, 1217, 1165, 505 cm-1; HRMS (ESI) m/z
[M + Na]+ calcd for C23H27NO8SNa 500.1355, found 500.1354.
1
CHCl3); H NMR (CDCl3, 400 MHz): d 7.77 (d, J = 8.0 Hz,
2H), 7.27–7.32 (m, 7H), 5.18 (d, J = 10.0 Hz, 1H), 4.74–4.84 (m,
2 H), 3.99 (dd, J = 12.0, 4.4 Hz, 1H), 3.68–3.78 (m, 3H), 3.33–
3.48 (m, 1H), 2.70–2.75 (m, 1H), 2.41 (s, 3H), 2.27 (dt, J = 6.4,
2.4 Hz, 1H), 2.07 (s, 3H), 2.04 (dd, J = 14.4, 2.0 Hz, 1H), 2.01 (s,
3H); 13C NMR (CDCl3, 100 MHz): d 170.6, 169.8, 143.8, 138.4,
137.2, 129.4, 128.9, 128.7, 127.4, 127.3, 81.6, 75.9, 68.3, 62.6, 44.6,
38.5, 34.7, 21.5, 20.8, 20.7; IR (CHCl3): 3420, 1637, 1238, 1163,
524 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for C24H29NO7S2Na
530.1283, found 530.1285.
Benzyl 3-p-fluorophenylsulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-glucopyranoside (4rc). Compound 4rc (81 mg, 91%
yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glucal 1a (50 mg, 0.18 mmol), p-fluorobenzenesulfonamide 2c
(35 mg, 0.2 mmol), and benzyl alcohol 3a (21 mL, 0.2 mmol)
and purified by column chromatography (hexane–ethyl acetate =
5 : 1). [a]2D0 = +69.1 (c 1.0 CHCl3); 1H NMR (CDCl3, 400 MHz): d
7.79–7.82 (m, 2H), 7.30–7.40 (m, 7H), 6.10 (d, J = 8.8 Hz, 1H),
4.91 (d, J = 3.2 Hz, 1H), 4.73 (d, J = 12 Hz, 1H), 4.65 (dd, J =
10.4, 3.6 Hz, 1H), 4.52 (d, J = 12 Hz, 1H), 4.31 (dd, J = 12.4,
4.4 Hz, 1H), 4.13–4.17 (m, 2H), 3.95 (q, J = 3.6 Hz, 1H), 2.09 (s,
3H), 2.06 (s, 3H), 1.86 (dt, J = 14.4, 4.0 Hz, 1H), 1.49 (dd, J =
14.4, 2.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz): d 170.8, 170.5,
136.4, 129.6, 129.5, 128.9, 128.5, 128.0, 116.5, 116.4, 96.2, 69.9,
67.0, 64.7, 62.7, 48.2, 33.0, 21.0, 20.9; IR (CHCl3): 3404, 1740,
1494, 1344, 1234, 1169, 1051, 754, 498 cm-1; HRMS (ESI) m/z
[M + Na]+ calcd for C23H26NO8SFNa 518.1261, found 518.1253.
tert-Butyl hydrosulfide 3-p-toluenesulfonamido-4,6-di-O-acetyl-
2,3-dideoxy-a-D-glucopyranoside (4p). Compound 4p (64 mg,
75%) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glucal 1a (50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg,
0.2 mmol), and tert-butyl hydrosulfide 3p (23 mL, 0.2 mmol) and
purified by column chromatography (hexane–ethyl acetate = 5 : 1).
[a]2D0 = +54.9 (c 1.0 CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.79
(d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 5.17–5.19 (m, 2H),
4.68 (dd, J = 10.0, 4.8 Hz, 1H), 4.03 (dd, J = 12.0, 4.4 Hz, 1H),
3.70–3.82 (m, 2H), 3.41 (q, J = 3.6 Hz, 1H), 2.41 (s, 3H), 2.12 (dt,
J = 6.4, 2.4 Hz, 1H), 2.09 (s, 3H), 2.04 (dd, J = 14.4, 2.0 Hz, 1H),
2.01 (s, 3H), 1.27 (s, 9H); 13C NMR (CDCl3, 100 MHz): d 170.5,
170.1, 143.6, 138.5, 129.3, 127.3, 79.5, 76.7, 72.4, 68.4, 62.7, 44.1,
40.3, 40.2, 21.5, 21.1, 20.7; IR (CHCl3): 3421, 1740, 1636, 1334,
1238, 1163, 1057, 492 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for
C21H31NO7S2Na 496.1440, found 496.1436.
Benzyl 3-p-chlorophenylsulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-glucopyranoside (4rd). Compound 4rd (78 mg, 85%
yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glucal 1a (50 mg, 0.18 mmol), p-chlorobenzenesulfonamide
2d (38 mg, 0.2 mmol), and benzyl alcohol 3a (21 mL, 0.2 mmol)
and purified by column chromatography (hexane–ethyl acetate =
L-menthol 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4q). Compound 4q (75 mg, 77% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and L-menthol 3q (32 mg, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +38.9 (c 1.0
CHCl3); 1H NMR (CDCl3, 300 MHz): d 7.68 (d, J = 8.4 Hz, 2H),
7.28 (d, J = 8.0 Hz, 2H), 6.14 (d, J = 9.0 Hz, 1H), 4.88 (d, J =
3.3 Hz, 1H), 4.61 (dd, J = 10.5, 3.6 Hz, 1H), 4.18–4.32 (m, 3H),
3.89 (q, J = 3.6 Hz, 1H), 3.28 (td, J = 4.5 Hz, 1H), 2.42 (s, 3H),
2.17–2.21 (m, 1H), 2.10 (s, 3H), 2.08 (s, 3H), 1.87–1.90 (m, 1H),
1.63–1.75 (m, 4H), 1.04–1.39 (m, 5H), 0.97 (d, J = 7.2 Hz, 3H), 0.93
(d, J = 6.6 Hz, 3H), 0.69 (d, J = 6.9 Hz, 3H); 13C NMR (CDCl3,
100 MHz): d 170.9, 170.5, 143.4, 138.2, 129.7, 126.8, 99.4, 82.8,
67.3, 64.7, 48.8, 43.0, 34.1, 33.1, 31.7, 26.1, 23.2, 22.3, 21.6, 21.3,
21.1, 20.9, 16.2; IR (neat): 3419, 1743, 1653, 1230, 1172, 1042,
561 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for C27H41NO8SNa
562.2451, found 562.2471.
1
5 : 1). [a]2D0 = +64.3 (c 1.0 CHCl3); H NMR (CDCl3, 400 MHz):
d 7.72 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H), 7.29–7.40
(m, 5H), 6.11 (d, J = 8.8 Hz, 1H), 4.91 (d, J = 2.8 Hz, 1H), 4.73
(d, J = 12 Hz, 1H), 4.65 (dd, J = 10.4, 3.6 Hz, 1H), 4.51 (d,
J = 12 Hz, 1H), 4.30 (dd, J = 12.4, 4.4 Hz, 1H), 4.11–4.16 (m,
2H), 3.94 (q, J = 3.6 Hz, 1H), 2.08 (s, 3H), 2.05 (s, 3H), 1.85
(dt, J = 14.4, 4.0 Hz, 1H), 1.49 (dd, J = 14.8, 2.4 Hz, 1H); 13C
NMR (CDCl3, 100 MHz): d 170.7, 170.4, 139.6, 139.1, 136.3,
129.5, 128.8, 128.4, 128.3, 127.9, 96.1, 69.8, 66.9, 64.6, 62.6, 48.2,
32.9, 20.9, 20.8; IR (CHCl3): 3422, 1740, 1647, 1344, 1240, 1165,
1051, 754, 497 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for
C23H26NO8SClNa 534.0965, found 534.0958.
Benzyl 3-p-nitrophenylsulfonamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4re). Compound 4re (82 mg, 88% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), p-nitrobenzenesulfonamide 2e (41 mg,
0.2 mmol), and benzyl alcohol 3a (21 mL, 0.2 mmol) and
purified by column chromatography (hexane–ethyl acetate = 5 : 1).
Benzyl 3-benzenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-a-D-
glucopyranoside (4rb). Compound 4rb (73 mg, 85% yield) was
prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
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[a]2D0 = +68.4 (c 0.5 CHCl3); 1H NMR (CDCl3, 400 MHz): d 8.33
(d, J = 8.4 Hz, 2H), 7.96 (d, J = 8.4 Hz, 2H), 7.29–7.43 (m, 5H),
6.28 (d, J = 8.8 Hz, 1H), 4.93 (d, J = 3.2 Hz, 1H), 4.74 (d, J =
12.0 Hz, 1H), 4.68 (dd, J = 10.4, 3.6 Hz, 1H), 4.52 (d, J = 11.6 Hz,
1H), 4.31 (dd, J = 12.4, 4.4 Hz, 1H), 4.13–4.18(m, 2H), 4.01 (q,
J = 4.0 Hz, 1H), 2.09 (s, 3H), 2.07 (s, 3H), 1.90 (dt, J = 14.8,
4.0 Hz, 1H), 1.50 (dd, J = 14.8, 2.4 Hz, 1H); 13C NMR (CDCl3,
100 MHz): d 170.7, 170.3, 147.6, 147.0, 136.2, 128.9, 128.6, 128.0,
127.9, 124.5, 96.0, 69.9, 66.8, 64.6, 62.5, 48.5, 33.0, 20.9, 20.8; IR
(CHCl3): 3323, 1740, 1529, 1350, 1240, 1166, 503 cm-1; HRMS
(ESI) m/z [M + Na]+ calcd for C23H26N2O10SNa 545.1206, found
545.1207.
4.54 (d, J = 12.0 Hz, 1H), 4.42–4.45 (m, 1H), 4.43 (dd, J = 10.8,
4.0 Hz, 1H), 4.09–4.16 (m, 2H), 2.10 (s, 3H), 1.95–2.06 (m, 2H),
1.93 (s, 3H); 13C NMR (CDCl3, 100 MHz): d 170.8, 170.0, 156.2,
136.8, 136.7, 128.7, 128.5, 128.1, 128.0, 127.9, 127.8, 96.0, 69.4,
67.7, 66.5, 64.4, 62.9, 45.2, 33.0, 20.8, 20.7; IR (CHCl3): 3420,
1734, 1638, 1508, 1223, 1047, 752, 513 cm-1; HRMS (ESI) m/z
[M + Na]+ calcd for C25H29NO8Na 494.1791, found 494.1795.
Benzyl
3-amido-4,6-di-O-acetyl-2,3-dideoxy-a-D-glucopyra-
noside (4u). Compound 4u (33 mg, 54% yield) was prepared
according to the general procedure for synthesis of 3-amino-
2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a (50 mg,
0.18 mmol), tert-Butyl carbamate 2i (23 mg, 0.2 mmol), and
benzyl alcohol 3a (21 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +82.0 (c
Benzyl
3-p-methoxyphenylsulfonamido-4,6-di-O-acetyl-2,3-
dideoxy-a-D-glucopyranoside (4rf). Compound 4rf (67 mg,
74% yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glucal 1a (50 mg, 0.18 mmol), p-methoxybenzenesulfonamide
2f (38 mg, 0.2 mmol), and benzyl alcohol 3a (21 mL, 0.2 mmol)
and purified by column chromatography (hexane–ethyl acetate =
5 : 1). [a]2D0 = +102.4 (c 1.0 CHCl3); 1H NMR (CDCl3, 400 MHz):
d 7.73 (d, J = 8.8 Hz, 2H), 7.32–7.41 (m, 5H), 6.95 (d, J = 8.0 Hz,
2H), 6.00 (d, J = 8.8 Hz, 1H), 4.89 (d, J = 3.2 Hz, 1H), 4.73 (d,
J = 12.0 Hz, 1H), 4.65 (dd, J = 10.0, 3.6 Hz, 1H), 4.52 (d, J =
12.0 Hz, 1H), 4.32 (dd, J = 12.4, 5.2 Hz, 1H), 4.13–4.16 (m, 2H),
3.91 (q, J = 4.0 Hz, 1H), 3.89 (s, 3H), 2.09 (s, 3H), 2.07 (s, 3H),
1.90 (dt, J = 14.8, 3.6 Hz, 1H), 1.48 (dd, J = 14.8, 2.4 Hz, 1H);
13C NMR (CDCl3, 100 MHz): d 170.7, 170.4, 162.8, 136.4, 132.6,
128.9, 128.8, 128.3, 127.9, 114.3, 96.2, 69.8, 67.0, 64.6, 62.7, 55.6,
48.0, 32.9, 21.0, 20.8; IR (CHCl3): 3335, 1740, 1597, 1499, 1257,
1157 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for C24H29NO9SNa
530.1461, found 530.1454.
1
1.0 CHCl3); H NMR (CDCl3, 400 MHz): d 7.28–7.37 (m, 5H),
5.75–5.95 (m, 2H), 5.35 (d, J = 9.2 Hz, 1H), 5.15–5.31 (m, 2H),
4.87 (d, J = 12.0 Hz, 1H), 4.61 (d, J = 11.6 Hz, 1H), 4.12–4.31 (m,
3H), 2.10 (s, 3H), 2.06 (s, 3H), 1.28–1.44 (m, 1H), 0.87–0.99 (m,
1H); 13C NMR (CDCl3, 100 MHz): d 170.8, 170.3, 137.6, 129.3,
128.3, 128.1, 127.9, 127.8, 93.7, 70.3, 67.1, 65.3, 62.9, 41.4, 21.0,
20.9; IR (CHCl3): 3443, 1742, 1643, 1369, 1231, 1153, 1038 cm-1;
HRMS (ESI) m/z [M + H]+ calcd for C17H24NO6 338.1604, found
338.1605.
Benzyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dideoxy-a-
D-galactopyranoside (4v). Compound 4v (77 mg, 87% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glacal 1b
(50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg, 0.2 mmol),
and benzyl alcohol 3a (21 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +41.6 (c 0.5
CHCl3); 1H NMR (CDCl3, 300 MHz): d 7.81 (d, J = 8.4 Hz, 2H),
7.31–7.75 (m, 7H), 6.06 (d, J = 8.1 Hz, 1H), 4.92 (d, J = 3.0 Hz,
1H), 4.78 (d, J = 2.7 Hz, 1H), 4.74 (d, J = 12 Hz, 1H), 4.51 (d,
J = 12 Hz, 1H), 4.26–4.30 (m, 1H), 3.99–4.10 (m, 2H), 3.63 (q,
J = 2.7 Hz, 1H), 2.42 (s, 3H), 2.07 (s, 3H), 2.05 (s, 3H), 1.95–2.04
(m, 1H), 1.18–1.27 (m, 1H); 13C NMR (CDCl3, 75 MHz): d 170.5,
169.5, 143.5, 137.8, 136.5, 129.8, 128.7, 128.3, 128.1, 127.1, 95.7,
69.4, 67.9, 63.4, 62.9, 47.6, 28.6, 21.6, 20.8, 20.7; IR (neat): 3417,
1643, 1214, 1175, 1042, 665 cm-1; HRMS (ESI) m/z [M + Na]+
calcd for C24H29NO8SNa 514.1512, found 514.1516.
Benzyl 3-methylsulfonamido-4,6-di-O-acetyl-2,3-dideoxy-a-D-
glucopyranoside (4s). Compound 4s (69 mg, 92% yield) was
prepared according to the general procedure for synthesis of
3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), methanesulfonamide 2g (19 mg, 0.2 mmol),
and benzyl alcohol 3a (21 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +58.6 (c 1.0
CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.32–7.39 (m, 5H), 5.84
(d, J = 8.4 Hz, 1H), 5.01 (d, J = 3.2 Hz, 1H), 4.77 (dd, J = 10.8,
3.6 Hz, 1H), 4.73 (d, J = 12.4 Hz, 1H), 4.52 (d, J = 11.6 Hz,
1H), 4.32 (dd, J = 12.0, 4.4 Hz, 1H), 4.11–4.15 (m, 3H), 2.94 (s,
3H), 2.05–2.17 (m, 8H); 13C NMR (CDCl3, 100 MHz): d 170.7,
170.1, 136.3, 128.8, 128.4, 128.1, 95.8, 69.7, 67.2, 64.5, 62.6, 48.4,
41.6, 34.0, 21.0, 20.8; IR (CHCl3): 3421, 1740, 1647, 1327, 1232,
1153, 1049, 754, 499 cm-1; HRMS (ESI) m/z [M + Na]+ calcd for
C18H25NO8SNa 438.1199, found 438.1193.
Isopentanyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-galactopyranoside (4w). Compound 4w (70 mg, 83%
yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glacal 1b (50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg,
0.2 mmol), and 3-pentanol 3h (22 mL, 0.2 mmol) and purified
Benzyl 3-benzyloxycarbonylamido-4,6-di-O-acetyl-2,3-dideoxy-
a-D-glucopyranoside (4t). Compound 4t (61 mg, 72% yield)
was prepared according to the general procedure for synthesis
of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-D-glucal 1a
(50 mg, 0.18 mmol), benzyl carbamate 2h (31 mg, 0.2 mmol),
and benzyl alcohol 3a (21 mL, 0.2 mmol) and purified by column
chromatography (hexane–ethyl acetate = 5 : 1). [a]2D0 = +43.3 (c 1.0
CHCl3); 1H NMR (CDCl3, 400 MHz): d 7.31–7.35 (m, 10H), 6.23
(d, J = 8.8 Hz, 1H), 5.07 (q, J = 12.4 Hz, 2H), 4.99 (d, J = 3.2 Hz,
1H), 4.82 (dd, J = 10.8, 4.0 Hz, 1H), 4.75 (d, J = 12.0 Hz, 1H),
by column chromatography (hexane–ethyl acetate = 5 : 1). [a]D20
=
+38.0 (c 0.5 CHCl3); 1H NMR (CDCl3, 300 MHz): d 7.78 (d, J =
8.1 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.21 (d, J = 8.1 Hz, 1H),
4.98 (d, J = 3.0 Hz, 1H), 4.75 (d, J = 3.0 Hz, 1H), 4.32– 4.37 (m,
1H), 4.01– 4.04 (m, 2H), 3.61 (q, J = 3.3 Hz, 1H), 3.49–3.57 (m,
1H), 2.42 (s, 3H), 2.07 (s, 3H), 2.05 (s, 3H), 1.96–2.04 (m, 1H),
1.49–1.66 (m, 4H), 1.39 (d, J = 14.1, 1H), 1.00 (q, J = 7.2 Hz, 1H),
0.88 (q, J = 7.2 Hz, 1H); 13C NMR (CDCl3, 75 MHz): d 170.5,
169.6, 143.5, 137.9, 129.8, 127.1, 95.9, 81.0, 68.0, 63.5, 63.1, 47.7,
28.9, 26.7, 25.0, 21.6, 20.8, 20.7, 9.9, 9.1; IR (neat): 3419, 1635,
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1230, 1161, 1025, 748 cm-1; HRMS (ESI) m/z [M + Na]+ calcd
for C22H33NO8SNa 494.1825, found 494.1815.
Acknowledgements
We thank Prof. Narasaka Koichi for invaluable discussion on
mechanism. We gratefully acknowledge Nanyang Technological
University (RG50/08) and the Ministry of Education, Singapore
(MOE 2009-T2-1-030) for the funding support of this research.
Cyclopentyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-galactopyranoside (4x). Compound 4x (66 mg, 78%
yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glacal 1b (50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg,
0.2 mmol), and cyclopentanol 3i (18 mL, 0.2 mmol) and purified
Notes and references
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by column chromatography (hexane–ethyl acetate = 5 : 1). [a]D20
=
1
+29.7 (c 1.0 CHCl3); H NMR (CDCl3, 400 MHz): d 7.77 (d,
J = 8.4 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 6.17 (d, J = 8.4 Hz,
1H), 4.94 (d, J = 3.2 Hz, 1H), 4.76 (d, J = 3.2 Hz, 1H), 4.27 (t,
J = 6.0 Hz, 1H), 4.18–4.20 (m, 1H), 4.03–4.06 (m, 2H), 3.58–3.63
(m, 1H), 2.43 (s, 3H), 2.07 (s, 3H), 2.05 (d, J = 1.6 Hz, 1H), 2.03
(s, 3H), 1.71–1.98 (m, 8H), 1.34 (dd, J = 13.2, 1.2 Hz, 1H); 13C
NMR (CDCl3, 100 MHz): d 170.5, 169.6, 143.4, 137.9, 129.8,
127.0, 95.9, 79.9, 68.0, 63.3, 62.9, 47.8, 33.4, 31.9, 28.9, 23.4, 23.0,
21.6, 20.8, 20.7; IR (neat): 3419, 1745, 1227, 1161, 1047, 665 cm-1;
HRMS (ESI) m/z [M + Na]+ calcd for C22H31NO8SNa 492.1668,
found 492.1659.
Cyclohexyl
3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-galactopyranoside (4y). Compound 4y (67 mg, 77%
yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glacal 1b (50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg,
0.2 mmol), and cyclohexanol 3j (21 mL, 0.2 mmol) and purified
by column chromatography (hexane–ethyl acetate = 5 : 1). [a]D20
=
1
+34.5 (c 1.0 CHCl3); H NMR (CDCl3, 400 MHz): d 7.77 (d,
J = 7.6 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 6.27 (d, J = 8.0 Hz,
1H), 5.02 (d, J = 2.8 Hz, 1H), 4.76 (d, J = 2.8 Hz, 1H), 4.28–4.36
(m, 1H), 4.02–4.16 (m, 2H), 2.41 (s, 3H), 2.06 (s, 3H), 2.04 (s,
3H), 1.90–1.92 (m, 1H), 1.29–2.03 (m, 11H); 13C NMR (CDCl3,
100 MHz): d 170.6, 170.4, 143.5, 138.0, 129.8, 127.1, 95.4, 76.1,
68.1, 63.4, 63.1, 47.9, 33.4, 31.5, 29.0, 25.5, 24.1, 23.5, 21.6, 20.9,
20.8; IR (neat): 3415, 1742, 1230, 1164, 1032, 714 cm-1; HRMS
(ESI) m/z [M + Na]+ calcd for C23H33NO8SNa 506.1825, found
506.1815.
(E)-But-2-enyl 3-p-toluenesulfonamido-4,6-di-O-acetyl-2,3-dide-
oxy-a-D-galactopyranoside (4z). Compound 4z (71 mg, 87%
yield) was prepared according to the general procedure for
synthesis of 3-amino-2,3-dideoxysugars from 3,4,6-tri-O-acetyl-
D-glacal 1b (50 mg, 0.18 mmol), p-toluenesulfonamide 2a (34 mg,
0.2 mmol), and (E)-but-2-en-1-ol 3n (17 mL, 0.2 mmol) and
purified by column chromatography (hexane–ethyl acetate = 5 : 1).
[a]2D0 = +32.2 (c 1.0 CHCl3); 1H NMR (CDCl3, 300 MHz): d 7.78
(d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 6.08 (d, J = 8.1 Hz,
1H), 5.58–5.75 (m, 1H), 5.52–5.57 (m, 1H), 4.91 (d, J = 3.0 Hz,
1H), 4.76 (d, J = 2.7 Hz, 1H), 4.11–4.15 (m, 1H), 3.98–4.09 (m,
3H), 3.88–3.94 (m, 1H), 3.59 (q, J = 2.7 Hz, 1H), 2.42 (s, 3H),
2.06 (s, 3H), 2.01 (s, 3H), 1.97–2.00 (m, 1H), 1.76 (d, J = 5.4 Hz,
3H), 1.42 (d, J = 14.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz): d
170.5, 169.5, 143.5, 137.8, 131.1, 129.8, 127.1, 126.0, 95.6, 68.2,
68.0, 63.2, 62.9, 47.6, 28.6, 21.6, 20.8, 20.7, 17.8; IR (neat): 3419,
1744, 1645, 1228, 1161, 1091, 645 cm-1; HRMS (ESI) m/z [M +
Na]+ calcd for C21H29NO8SNa 478.1512, found 478.1518.
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