Convenient stereocontrolled amidoglycosylation of alcohols with acetylated glycals and trichloroethoxysulfonamide

Article abstract of DOI:10.1016/j.carres.2016.09.001

A regio- and stereo-controlled, rhodium(II)-catalyzed amidoglycosylation of alcohols has been developed using O-acetylated glycals, trichloroethoxysulfonamide, and iodosobenzene. This one-pot amidoglycosylation was applied to a variety of primary and secondary alcohols to afford the β-O-glycosides with acceptable yields up to 84%. The reaction would proceed via stereoselective intermolecular aziridination of the glycal from the α-face followed by S_N2 reaction with alcohol at C-1 from the β-face to give 1,2:2,3-di-trans-substituted isomer only.

Full text of DOI:10.1016/j.carres.2016.09.001

Carbohydrate Research 434 (2016) 121e131
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Convenient stereocontrolled amidoglycosylation of alcohols with
acetylated glycals and trichloroethoxysulfonamide
,
Teiichi Murakami a *, Yukari Sato b, Kyoko Yoshioka c, Mutsuo Tanaka a
a Health Research Institute, National Institute of Advanced Industrial Science and Technology (AIST) Tsukuba Central 6, Tsukuba, Ibaraki 305-8566, Japan
b Research Institute for Energy Conservation, National Institute of Advanced Industrial Science and Technology (AIST) Tsukuba Central 2, Tsukuba, Ibaraki
305-8562, Japan
c Biomedical Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 6, Tsukuba, Ibaraki 305-8566,
Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
A regio- and stereo-controlled, rhodium(II)-catalyzed amidoglycosylation of alcohols has been developed
Received 25 July 2016
Received in revised form
2 September 2016
Accepted 2 September 2016
Available online 4 September 2016
using O-acetylated glycals, trichloroethoxysulfonamide, and iodosobenzene. This one-pot amidoglyco-
sylation was applied to a variety of primary and secondary alcohols to afford the
acceptable yields up to 84%. The reaction would proceed via stereoselective intermolecular aziridination
of the glycal from the -face followed by SN2 reaction with alcohol at C-1 from the -face to give 1,2:2,3-
di-trans-substituted isomer only.
b-O-glycosides with
a
b
© 2016 Elsevier Ltd. All rights reserved.
Chemical compounds studied in this article:
Tri-O-Acetyl-D-glucal (PubChem CID:
688303)
Tri-O-Acetyl-D-galactal (PubChem CID:
640125)
Hexa-O-Acetyl-lactal (PubChem CID:
2734746)
Iodosobenzene (PubChem CID: 92125)
2,2,2-Trichloroethoxysulfonamide
(PubChem CID: 3052707)
ChloroBenzene (PubChem CID: 79645)
12-Bromo-1-dodecanol (PubChem CID:
137895)
Keywords:
Glycals
Amidoglycosylation
Stereocontrol
Aziridination
Nitrene
1. Introduction
antibodies [3]. Except D-glucosamine, most aminosugars, e.g., D-
galactosamine, D-mannosamine, disaccharide lactosamine, are
rather expensive as starting materials for the chemical synthesis of
glycoconjugates and oligosaccharides.
Glycals (1,2-dehydro-sugar derivatives) have proven to be useful
synthetic precursors of 2-amino-2-deoxy-O-glycosides by way of
N-functionalization at C-2 accompanied by addition of alcohols to
C-1 (aza-glycosylation) (Scheme 1), and a variety of methods have
been developed for the nitrogen transfer to glycals over the last few
decades [4]. The aza-glycosylation with the glycals might be clas-
sified into three types: (1) direct addition of amine precursors such
2-N-Acetamido-2-deoxyglycosides, most commonly of the D-
glucose and D-galactose series, are widely distributed in living or-
ganisms as glycoconjugates (glycolipids, glycoproteins) [1] and
glycosaminoglycans (heparin, chondroitin sulfate, hyaluronic acid)
[2]. Aminosugars on cell surfaces are assumed to play an important
role as receptor ligands for protein molecules such as lectins and
* Corresponding author.
E-mail address: t-murakami@aist.go.jp (T. Murakami).
http://dx.doi.org/10.1016/j.carres.2016.09.001
0008-6215/© 2016 Elsevier Ltd. All rights reserved.

122
T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
amidoglycosylation of alcohols via rhodium-catalyzed intermolec-
ular aziridination in a one-pot manner using simple O-acetylated
glycals (D-glucal, D-galactal, D-lactal), which are readily prepared
in 3 steps from the parent sugars [29].
2. Results and discussion
In their research on rhodium-catalyzed olefin aziridination with
PhI(OAc)2 and sulfamate esters, Du Bois and co-workers found a
stereospecific amido-acetoxylation of tri-O-acetyl-D-glucal 1a to
Scheme 1. Aza-glycosylation of alcohols with glycals.
give
2-deoxy-2-(trichloroethoxysulfonyl)amino-glucopyranosyl
in a regiospecific manner in high yield [30].
as azide [5e7] and nitro group [8] to the C-2 position along with
introduction of leaving groups at C-1 followed by reaction with
alcohols; (2) addition of amine precursors to the C-1 position along
with addition of halide (usually iodide) to C-2 followed by reaction
with alcohols (or alkoxides) to cause rearrangement of the nitrogen
to C-2; [9,10] (3) formation of aza-heterocycles followed by ring
opening with alcohols [11e14]. Among them, azido-nitration re-
actions developed by Lemieux and co-workers [5] have been widely
used since the reaction of O-protected glycals with sodium azide
and cerium(IV) ammonium nitrate provides 2-azido-2-deoxy-1-O-
nitro-glycoses regioselectively. However, the stereoselectivities are
dependent on the structure of the glycal substrate; the azidoni-
trations of acetylated glucal and lactal often proceed non-
stereoselectively to give both epimers of the azido group at C-2
(gluco-N and manno-N isomers) [15]. In addition, two more steps
(C-1 activation and glycosylation) are needed for synthesis of the
glycosides.
In recent years, transition metal-catalyzed inter- and intra-mo-
lecular aziridinations of alkenes have been developed by using
nitrenes as a nitrogen source [16]. The highly reactive nitrene
species are generated in situ from several types of precursors, e.g.,
sulfonyliminoiodinanes [17], sulfonamides [18]/sufamate esters
[19]/carbamate esters [20]/N-substituted hydrazines [21] with
iodine(III) compounds, N-(sulfonyloxy)carbamates with base [22],
chloramine-T [23], and azido-compounds [24]. When the aziridi-
nation reactions are applied to glycal derivatives, the corresponding
1,2-aziridines would be formed. The anomeric C-1 position of N-
sulfonyl or N-carbonyl 1,2-aziridino-glycosides would be highly
electrophilic to react readily with nucleophiles providing 2-amino-
2-deoxy-glycoside derivatives [16c]. There have been several re-
ports on such aminoglycosylation reactions via aziridine in-
termediates. Rojas and co-workers reported intramolecular
aziridinations of 3-O-azidoformyl- [25a] and 3-O-carbamoyl-D-
allal derivatives [25b] and subsequent reactions with alcohols to
1b
-O-acetate 2a-b
However, they have not described the reaction in detail and not
presented other sugar-derived substrates. We were interested in
this amido-acetoxylation, and confirmed that the reaction of 1a
with Cl3CCH2OSO2NH2 (TcesNH2), PhI(OAc)2, MgO in the presence
of a Rh(II) catalyst [Rh2(NHCOCF3)4] afforded the
[31] with a small amount of the -acetate 2a- [32]. The amidoa-
cetoxylation was applied to acetyl-protected galactal 1b and lactal
1c under identical conditions. As shown in Table 1, Ac-galactal 1b
gave a 2:1 mixture of the
b-acetate 2a-b
a
a
a- and
b-acetates (entry 2), whereas Ac-
lactal 1c gave the -acetate 2c-
b
b
predominantly (entry 3). We tried
the amidoacetoxylation with more common sulfonamides and a
carbamate ester in place of TcesNH2. The reaction of the glucal 1a
and p-nitrobenzenesulfonamide (NsNH2) gave the product 3a in
lower yield with lower b/a selectivity (entry 4). The reaction of
galactal 1b with NsNH2 gave a comparable result to that with
TcesNH2 (entry 5 vs 2). The reaction of 1a with p-toluenesulfona-
mide gave the product 4a in low yield (entry 6). The reaction of 1a,b
with 2,2,2-trichloroethyl carbamate (TrocNH2) was also examined.
The N-trichloroethoxycarbonyl (Troc) glucosamines have been
utilized as glycosyl donors because they would give b-glycosides
stereoselectively by neighboring group participation and the Troc
Table 1
Amidoacetoxylation of acetylated glycals 1a,b,ca.
access 2-amino-2-deoxy-b-D-allopyranosides stereoselectively.
Later they applied the reactions to 3-O-carbamoyl-D-glucal de-
rivatives to prepare mannosamine derivatives [25c]. Liu and co-
workers reported stereoselective synthesis of 1,2-trans-2-amino-
2-deoxy-1-(O or S)-glycoside derivatives via rhodium-catalyzed,
substrate-controlled aziridination of 4-O- or 6-O-sulfamoyl-D-
glucal derivatives [26]. However, these precedents require prepa-
ration of the appropriate substrates for intramolecular aziridina-
tions. Stereoselective synthesis of 2-amino-2-deoxy-1-O-glycosides
from glycals via intermolecular aziridination [27] should be more
challenging since it would likely afford a mixture of stereoisomers.
Indeed, Descotes and co-workers reported that addition of photo-
chemically generated N-ethoxycarbonyl-nitrenes to acetylated
glycals in methanol gave the methyl 2-amino-glycosides as a
mixture of three stereoisomers [28]. Carreira and co-workers re-
ported a stereoselective synthesis of 2-trifluoroacetylamino-sugars
by a metal-mediated glycal amination reaction, but minor stereo-
isomers at C-2 were always detected and the glycosides of alcohols
have not been prepared [12].
Entry Glycal
R
Product Yield (%)b
b/a
ratioc Recovery of 1 (%)
1
2
3
4
5
6
7
8
1a
1b
1c
1a
1b
1a
1a
1b
Tces 2a
Tces 2b
Tces 2c
Ns
Ns
Ts
91
94
92
55
90
25
12e
44f
17:1
1:1.8d
10:1
5:1
3a
3b
4a
18
1:1.3d
4:1
Troc 5a
Troc 5b
6:1
3:1
56
28
a
Reagents and conditions: R-NH2 (1.8 equiv.), PhI(OAc)2 (1.8 equiv.),
Rh2(NHCOCF3)4 (0.1 equiv.), MgO (4 equiv.) in PhCl, 5 ꢀC, 2 h to rt, 10 h.
b
Isolated yield by silica gel chromatography.
c
The ratios were determined by 1H NMR integration of the
a/b mixture unless
otherwise noted.
d
The isomers were separated by chromatography.
1-O-Deacetylated 5a was also obtained in 13% yield.
1-O-Deacetylated 5b was obtained in 12% yield.
e
We
report
here
a
regio-
and
stereo-controlled
f

T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
123
Table 2
Lewis acid-promoted glycosylation with glucosyl b-acetates.
R
Conditions
Product
Yield(%)a
2a
5a
6a
Tces
Troc
Ac
95 ꢀC, 6 h
55 ꢀC, 1 h
70 ꢀC, 3 hd
7a
8a
9a
56b
74c
67
a
Isolated yield by silica gel chromatography.
Unreacted 2a was recovered (19%) as an anomeric mixture.
b
c
The
The
a
-anomer 8a-
a and 1-O-deacetylated 5a were also obtained in 4% and 18% yields, respectively.
d
b
-acetate 6a soon disappeared to form the corresponding oxazoline intermediate.
group can be easily and selectively removed under mild conditions
(Zn-AcOH) [33]. The reaction of 1a with TrocNH2 gave the product
5a in poor yield, and 1b with TrocNH2 gave 5b in fair yield. In both
cases, substantial amount of glycal remained and the anomeric
hydrolyzed products (1-O-deacetylated 5a,b) were obtained. In all
cases examined, the stereoisomers at C-2 were not detected.
Therefore, for the amidoacetoxylation of acetylated glycals under
Du Bois' reaction conditions, TcesNH2 showed the highest reac-
tivity. Ac-galactal 1b would be more reactive than Ac-glucal 1a, but
Table 4
Amidoglycosylation of alcohols with acetylated glycal 1a,b,c and TcesNH2.a
the
later.
Glycosyl 1-O-
sponding -acetates, and can be employed as glycosyl donors [34].
With anomerically -riched (
examined the reactivity in Lewis acid (ZnCl2)-promoted glycosyl-
ation with 12-bromododecanol [35]. As shown in Table 2, N-Tces-
glucosaminyl b-acetate 2a was found to be much less reactive than
b/a-selectivities were lower. The reaction pathway is discussed
Entry
Glycal
ReOH
Product
Yield (%)b
b
-acetates are more reactive than the corre-
1
2
3
4
5
6
7
8
9
1a
1b
1c
1b
1a
1b
1b
1a
1b
1a
Br(CH2)12eOH
Br(CH2)12eOH
Br(CH2)12eOH
AcS(CH2)12eOH
Ph(CH2)2eOH
PhCH2eOH
H2C]CHe(CH2)3eOH
cyclohexanol
cyclohexanol
7a
7b
7c
11b
12a
13b
14b
15a
15b
16a
77
84
70
11
75
62
63
57
78
74
a
b
b/
a
¼ 17) acetate 2a in hand, we
Table 3
10
Amidoglycosylation of tetradecanol with acetylated glucal 1a and TcesNH2.
11
12
13
1b
1c
1b
L(ꢁ)-menthol
L(ꢁ)-menthol
16b
16c
17b
76
67
74
Entry
Equiv. of C14H29OH
Oxidanta
Catalyst
Yield (%)b
1c
2
3
4
5
4
4
2
4
2
2
2
PhI(OAc)2
PhI¼O
PhI¼O
PhI¼O
PhI¼O
PhI¼O
PhI¼O
Rh2(NHCOCF3)4
Rh2(NHCOCF3)4
Rh2(NHCOCF3)4
Rh2(OAc)4
Cu(CH3CN)PF6
AgNO3, tBu3tpye
Rh2(NHCOCF3)4
58d
66
78
45
17
25
39
14
15
1b
1b
18b
19b
21
56
6
7f
a
The oxidant (solid, 1.8 equiv.) was added in several portions to the mixture of
other reactants for ca. 1 h at 5 ꢀC.
b
Isolated yield by silica gel chromatography.
MgO (4 equiv.) was used in place of MS4A.
c
d
a
1-Acetate 2a-
b
was obtained in 22% yield.
Reagents and conditions: R-OH (2.0 equiv.), TcesNH2 (1.7 equiv.), PhI(OAc)2 (1.8
equiv.), Rh2(NHCOCF3)4 (0.1 equiv.), MS4A in PhCl, 5 ꢀC, 2 h to rt.
e
f
tBu3tpy: 4,40,400-tri-tert-butyl-2,2’:60,200-terpyridine.
b
The reaction was carried out in toluene.
Isolated yield by silica gel chromatography.

124
T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
N-Troc derivative 5a [36] and the yield of
b-glycoside 7a was lower
corresponding b-glycosides in good yields. Ac-galactal 1b appeared
than those of the N-Troc 8a and N-Ac 9a glycosides. Starting ma-
terial 2a was recovered (19%) as a 3:1 mixture of - and -acetates,
to be more reactive and gave the glycosides in better yields than 1a
and 1c (entries 8e12 and 1e3). For sugar-derived alcohols, 1,2:3,4-
a
b
indicating that anomerization occurred during the reaction.
Anomeric O-acetates can be converted to more reactive leaving
groups such as halides and O-trichloroacetimidate. Yu and a co-
worker reported the conversion of 2a to the 1-O-tri-
chloroacetimidate and the reaction with several alcohols including
di-O-isopropylidene-
17b in good yield, whereas methyl 2,3,4-tri-O-benzyl-
pyranoside gave the galactoside 18b in low yield, and substantial
amounts of some byproducts: de-O-benzylated glucoses and
benzaldehyde were obtained. The reaction of 1b with methyl 2,3,6-
a
-D-galactopyranose afforded the galactoside
-D-gluco-
a
protected sugars affording the
b-glucosides in good yields [31a].
tri-O-benzyl-a-D-glucopyranoside did not give the glycoside (data
However, the whole process would become lengthy. We next
examined a direct synthesis of 2-sulfonamido-1-O-glycosides [37]
from glycals by adding alcohols in the reaction mixture. As shown
in Table 3, the reaction of 1a and tetradecanol (4 equiv.) with
TcesNH2 in the presence of PhI(OAc)2 and catalytic Rh2(NHCOCF3)4
not shown). In all the cases examined, no a-anomer was detected
by 1H and 13C NMR. Small amounts (3e8%) of hydrolyzed products
(1-OH) were formed when using less reactive alcohols.
Danishefsky and co-workers reported
a
sulfonamido-
glycosylation from glycals, and they succeeded in applying the
methodology to the syntheses of oligosaccharides and glyco-
conjugates [10]. Their glycosylation method requires two reaction
in chlorobenzene afforded the desired tetradecyl-
b-glucoside 10a
in 58% yield with no -glucoside. However, the 1-O-acetate 2a-
a
b
was also formed (entry 1). Formation of 2a was suppressed by using
iodosobenzene with 4 Å molecular sieves (as dehydration agent) in
place of PhI(OAc)2 with MgO (entry 2). Reducing the amount of
alcohol improved the yield of 10a (entry 3). For the aziridination
catalyst, Rh2(OAc)4 was less effective than Rh2(NHCOCF3)4, and
copper(I) [18a] and silver [17c] catalysts were much less effective
(entries 4e6). When the reaction was carried out in toluene, the
yield of 10a decreased and 60% of 1a was recovered [38] (entry 7).
With the optimized reaction conditions in hand, we investigated
the scope and generality of this Rh-catalyzed one-pot amidogly-
cosylation [39] (amido-alkoxylation of glycals [40]), and the results
are summarized in Table 4. Reactions of 12-bromododecanol and 2-
phenylethanol with the glycals 1a,b,c proceeded smoothly to afford
steps: (1) addition of iodonium reagent [usually I(sym-collidine)2
-
ClO4] and benzenesulfonamide to glycals to form 1,2-trans-2-iodo-
1-sulfonamido-glycoses, and (2) reaction with the metal alkoxide of
a glycosyl acceptor and silver salt (AgOTf or AgBF4) to cause rear-
rangement of the sulfonamide to C-2. The latter step usually re-
quires either rather basic alkali-metal (Li, K) alkoxide, with which
O-acyl protecting groups could be incompatible, or toxic tributyltin
alkoxide [42]. In addition, excess amounts (from 1.4 [10a] to 10 [42]
equiv.) of expensive silver salts are necessary not only for the
abstraction of iodine atom in the latter step but also for the prep-
aration of I(collidine)2ClO4 (from AgClO4). Our one-pot sulfona-
mido-glycosylation described above would be more convenient
and economical than Danishefsky's method. However, it might be
difficult to apply this one-pot glycosylation to oligosaccharide
synthesis because secondary alcohols of protected sugars having
low nucleophilic and/or steric hindrance did not react well with the
adduct of nitrenoid addition to acetylated glycals.
the corresponding b-glycosides 7a,b,c, 12a in good yields (entries
1,2,3,5). In contrast, 12-acetylthio-1-dodecanol gave the galactoside
11b in poor yield under identical conditions, indicating that the
acetylthio group would suppress the reaction (entry 4). Reaction of
1b with 4-penten-1-ol gave the
b
-galactoside 14b in somewhat
The reaction would proceed via the generation of rhodium-
lower yield along with a byproduct [41] derived from 4-pentenol,
indicating that 4-pentenol was also aziridinated, but would be less
reactive than 1b (entry 7). Cyclic secondary alcohols: cyclohexanol
and L(ꢁ)-menthol reacted with the glycals 1a-c to give the
nitrenoid followed by formation of the
mediate (20) presumably due to the presence of
adjacent C-3 [11e13] (Scheme 2). The aziridine would be opened
with the alcohol at C-1 from the -face (SN2 reaction) to afford 1,2-
a
-oriented aziridine inter-
b
-acetoxy group at
b
Scheme 2. Proposed reaction pathway.

T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
125
and 2,3-di-trans-product 21 [16c,43]. For the amidoacetoxylation
4. Experimental
(in the absence of alcohol and the presence of AcOH generated in
situ), since AcOH is less nucleophilic than alcohol, the aziridine
would tend to open to oxocarbenium intermediate 22. The acetate
4.1. General methods
can add to C-1 from both faces to form a mixture of
tates (23- and e ) [43a,b].
-Acetoxy group at C-4 (R2) of Ac-
-face to give C-1 -acetate as a ma-
a
- and
b
-ace-
Melting points were determined with a Yanaco melting point
apparatus MP-500D. Optical rotations were measured with a JASCO
a
b
b
galactal 1b might cover the
b
a
DIP-1000 polarimeter and [a] .
D values are given in 10ꢁ1 deg cm2 gꢁ1
jor product.
1H and 13C NMR spectra were recorded on a Varian INOVA 400
(400 MHz for 1H and 100 MHz for 13C) spectrometer or on a Bruker
Avance III-500 (500 MHz for 1H and 125.8 MHz for 13C) spec-
The trichloroethoxysulfonamide in 10a is converted to either
sulfaminic acid or free amine by tuning the reaction conditions
(Scheme 3). When 10a was treated with zinc and acetic acid in
methanol, only trichloroethyl group was removed to give the sul-
faminic acid 24 in 95% yield. N-Sulfated glucosamine is a key
structural unit in heparin, a bioactive polysaccharide having anti-
coagulant and antithrombotic properties [44]. The whole Tces
group was removed by treatment with zinc and acetic acid in the
presence of CuSO4 in THF to give the amine 25. This deprotection
process might be more convenient than that by zinc-copper couple
reported by Du Bois [19a]. The amine 25 reacted with benzoyl
chloride to give the benzamide 26. When the desulfonylation was
carried out in the presence of acetic anhydride, the acetamide 27
was obtained in good yield. We previously prepared 12-
trometer at 25 ꢀC. 1H chemical shifts (
internal (CH3)4Si (
given in ppm relative to CDCl3
d
) are given in ppm relative to
0.00) in CDCl3 and 13C chemical shifts (
) are
77.0). Elemental analyses and
d
d
(
d
high-resolution mass spectrometry (HRMS) analyses were per-
formed in the analytical section in this Institute (AIST). Mass
spectra (MS) were recorded on a Waters micromass ZQ spectrom-
eter with electrospray ionization (ESI) in the positive ion mode.
Thin layer chromatography (TLC) and column chromatography
were performed on Merck pre-coated silica gel 60F254 plates and
silica gel (Kanto Chemicals, neutral, 100e210
mm, or Wakogel C-
300, 45e75 m), respectively. Rh2(NHCOCF3)4 was prepared from
m
Rh2(OAc)4 and CF3CONH2 in chlorobenzene according to ref. [19a];
Supporting information, p. 2. TcesNH2 was obtained commercially
from Sigma-Aldrich.
mercaptododecyl N-acetyl-
Ac-lactal 1c, and the synthetic
binding activity to some galectins evaluated by surface plasmon
resonance (SPR) method [15d]. For the synthesis of the -anomer,
bromododecyl -lactoside 7c was converted to the acetylthio de-
rivative 28. Treatment of 28 with zinc and acetic anhydride in the
a
-lactosaminide via azidonitration of
a-lactosaminide showed high
b
4.2. General procedure for amidoacetoxylation
b
To a mixture of glycal 1a,b,c (0.2 mmol), R-NH2 (R ¼ Tces, Ns, Ts,
or Troc) (0.35 mmol), Rh2(NHCOCF3)4 (12 mg, 0.02 mmol), and MgO
(32 mg, 0.8 mmol) under nitrogen was added PhCl (3 mL), and the
presence of CuSO4 in THF afforded the acetylated b-lactosaminide
29 in good yield.
Scheme 3. Conversions of the trichloroethoxysulfonyl group.
3. Conclusions
resulting light-purple suspension was cooled with an ice-water
bath. PhI(OAc)2 (80 mg, 0.36 mmol) was added in several por-
tions for 1 h, and the resulting light-brown suspension was stirred
at 5 ꢀC for 1 h and then at rt for 10 h. The reaction mixture was
filtered, washed with CH2Cl2, and the combined filtrates were
concentrated under reduced pressure. The residue was purified by
silica gel chromatography eluting with hexane-EtOAc mixture.
In conclusion, we have developed a regio- and stereo-selective
synthesis of 2-amino-2-deoxy-1-O-b-glycosides from acetylated
glycals via rhodium(II)-catalyzed intermolecular aziridination with
trichloroethoxysulfonamide and iodosobenzene. This amidoglyco-
sylation proceeds smoothly under mild conditions without the use
of usual O-glycosylation promoters such as Lewis acids, and is
applicable to a variety of primary and secondary alcohols with
appropriate nucleophilicity. In the absence of alcohol and the
presence of diacetoxyiodobenzene, 2-amino-2-deoxy-glycose-1-O-
acetates are formed as anomeric mixture. On the basis of the ste-
reochemical results, the reaction pathway has been proposed. The
N-Tces group can be directly converted to either N-sulfate, free
amine, or acetamide by tuning reaction conditions.
4.2.1. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido-b-D-glucopyranose (2a-b)
Obtained in 91% yield (
b
/
a
¼ 17) as a colorless foam: Rf 0.28 (3:2
hexane/EtOAc); [
a]
D [25] þ9.0 (c 1.0, CHCl3); 1H NMR (CDCl3):
d 2.06
(s, 3H), 2.10 (s, 3H), 2.15 (s, 3H), 2.22 (s, 3H), 3.78 (dt, 1H, J ¼ 10.4,
9.0 Hz), 3.87 (ddd, 1H, J ¼ 2.2, 4.5, 9.9 Hz), 4.12 (dd, 1H, J ¼ 2.2,
12.5 Hz), 4.28 (dd, 1H, J ¼ 4.5, 12.5 Hz), 4.61 (d, 1H, J ¼ 11.0 Hz), 4.64

126
T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
(d, 1H, J ¼ 11.0 Hz), 5.11 (t, 1H, J ¼ 9.7 Hz), 5.20 (t, 1H, J ¼ 9.9 Hz), 5.71
(d, 1H, J ¼ 8.7 Hz), 5.81 (d, 1H, J ¼ 9.0 Hz) ppm; 13C NMR (CDCl3):
4.2.6. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(p-nitrobenzenesulfonyl)
amido- -D-galactopyranose (3b-
a
a)
d
20.5, 20.7, 20.8, 21.0, 57.9, 61.5, 67.9, 72.4, 72.6, 78.6, 92.0, 93.2,
Obtained in 51% yield as a colorless foam: Rf 0.29 (1:1 hexane/
169.4, 169.7, 170.7, 171.8 ppm. These data are consistent with those
reported. [ref. [31b]; Supporting information, p.11].
EtOAc); [
a
]
[25] þ44.1 (c 1.2, CHCl3); 1H NMR (CDCl3):
d 1.84 (s,
D
3H), 2.01 (s, 3H), 2.13 (s, 3H), 2.17 (s, 3H), 4.04 (m, 3H), 4.21 (dt, 1H,
J ¼ 0.6, 6.7 Hz), 5.19 (dd, 1H, J ¼ 3.3, 11.2 Hz), 5.35 (d, 1H, J ¼ 9.0 Hz),
5.39 (dd, 1H, J ¼ 0.6, 3.2 Hz), 6.03 (d, 1H, J ¼ 3.6 Hz), 8.04 (m, 2H),
4.2.2. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido-
a
-D-galactopyranose (2b-
a)
8.37 (m, 2H) ppm; 13C NMR (CDCl3):
d
¼ 20.5, 20.6, 20.7, 51.4, 61.0,
Obtained in 61% yield as a colorless foam: Rf 0.24 (3:2 hexane/
66.8, 67.4, 68.5, 90.9, 124.5, 128.1, 146.5, 150.2, 168.6, 169.8, 170.3,
170.6 ppm; Anal. Calcd for C20H24N2O13S: C, 45.11; H, 4.54; N, 5.26;
S, 6.02. Found: C, 44.87; H, 4.51; N,5.14; S, 5.90.
EtOAc); [
a
]
D [25] þ105.4 (c 1.92, CHCl3); 1H NMR (CDCl3):
d 2.03 (s,
3H), 2.10 (s, 3H), 2.17 (s, 3H), 2.21 (s, 3H), 4.07 (dd, 1H, J ¼ 6.7,
11.2 Hz), 4.10 (dd, 1H, J ¼ 6.7, 11.2 Hz), 4.15 (ddd, 1H, J ¼ 3.6, 9.6,
11.2 Hz), 4.25 (dt, 1H, J ¼ 0.9, 6.7 Hz), 4.61 (d, 1H, J ¼ 10.8 Hz), 4.66
(d, 1H, J ¼ 10.8 Hz), 5.14 (d, 1H, J ¼ 9.6 Hz), 5.24 (dd, 1H, J ¼ 3.2,
11.3 Hz), 5.45 (dd, 1H, J ¼ 1.0, 3.1 Hz), 6.40 (d, 1H, J ¼ 3.6 Hz) ppm;
4.2.7. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(p-nitrobenzenesulfonyl)
amido-b-D-galactopyranose (3b-b)
Obtained in 39% yield as a colorless foam: Rf 0.37 (1:1 hexane/
13C NMR (CDCl3):
d
20.57, 20.60, 20.78, 20.84, 52.0, 61.1, 66.9, 67.4,
EtOAc); [
a
]
D [25] ꢁ2.0 (c 0.7, CHCl3); 1H NMR (CDCl3):
d 1.85 (s, 3H),
68.5, 78.3, 90.9, 93.1, 169.0, 170.0, 170.4, 171.0 ppm; MS (ESI): m/z
1.86 (s, 3H), 2.03 (s, 3H), 2.18 (s, 3H), 3.88 (dt, 1H, J ¼ 10.8, 9.0 Hz),
4.11 (m, 3H), 5.11 (dd, 1H, J ¼ 3.4, 11.0 Hz), 5.37 (d, 1H, J ¼ 3.3 Hz),
5.71 (d,1H, J ¼ 8.7 Hz), 5.80 (br,1H), 8.06 (m, 2H), 8.36 (m, 2H) ppm.
35
calcd for C
H
Cl3NO12S 556.99; found (%) 579.85 ([M(35Cl3)þ
16 22
Na]þ,
94),
581.96
([M(35Cl2þ37Cl)þNa]þ, 100),
583.95
([M(35Clþ37Cl2)þNa]þ, 39).
4.2.8. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(p-toluenesulfonyl)amido-
4.2.3. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido- -D-galactopyranose (2b-
b
/
a
-D-glucopyranose (4a-
Obtained in 25% yield (
hexane/EtOAc); 1H NMR (CDCl3) for
b/a)
b
b
)
b/
a
¼ 4) as a colorless solid: Rf 0.33 (1:1
-anomer: 1.83 (s, 3H),1.85 (s,
Obtained in 33% yield as a colorless foam: Rf 0.33 (3:2 hexane/
b
d
EtOAc); [
a
]
[25] þ8.3 (c 0.6, CHCl3); 1H NMR (CDCl3):
d
¼ 2.05 (s,
3H), 2.02 (s, 3H), 2.08 (s, 3H), 2.41 (s, 3H), 3.70 (q, 1H, J ¼ 8.4 Hz),
3.79 (ddd, 1H, J ¼ 2.4, 4.6, 9.6 Hz), 4.08 (dd, 1H, J ¼ 2.2,12.5 Hz), 4.26
(dd, 1H, J ¼ 4.5, 12.5 Hz), 5.08 (m, 2H), 5.23 (d, 1H, 9.3 Hz), 5.61 (d,
1H, J ¼ 8.6 Hz), 7.30 (m, 2H), 7.72 (m, 2H) ppm.
D
3H), 2.11 (s, 3H), 2.17 (s, 3H), 2.23 (s, 3H), 3.95 (dt, 1H, J ¼ 8.9,
11.1 Hz), 4.06 (dt, 1H, J ¼ 0.9, 6.5 Hz), 4.12 (dd, 1H, J ¼ 6.3, 11.2 Hz),
4.16 (dd, 1H, J ¼ 6.7, 11.2 Hz), 4.64 (s, 2H), 5.08 (dd, 1H, J ¼ 3.3,
11.1 Hz), 5.40 (d, 1H, J ¼ 3.3 Hz), 5.67 (d, 1H, J ¼ 9.0 Hz), 5.72 (d, 1H,
J ¼ 8.8 Hz) ppm; 13C NMR (CDCl3):
d
20.58, 20.64, 20.78, 21.0, 54.9,
4.2.9. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(2,2,2-
61.2, 66.5, 70.4, 71.7, 78.4, 92.5, 93.3, 169.93, 170.06, 170.5,
trichloroethoxycarbonyl)amido-
Obtained in 44% yield (
hexane/EtOAc); 1H NMR (CDCl3) for
b
/
a
-D-galactopyranose (5b-
¼ 3) as a colorless oil: Rf 0.36 (3:2
-anomer: 2.01 (s, 3H), 2.05
b/a)
35
171.1 ppm; HRMS (FAB): calcd. for C
497.9796; found 497.9789.
H
Cl3NO10S [M - OAc]þ
b/a
14 19
b
d
(s, 3H), 2.13 (s, 3H), 2.18 (s, 3H), 4.05 (t, 1H, J ¼ 6.6 Hz), 4.11 (m, 1H),
4.13 (dd, 1H, J ¼ 6.4, 11.3 Hz), 4.17 (dd, 1H, J ¼ 6.8, 11.3 Hz), 4.73 (s,
2H), 5.15 (dd, 1H, J ¼ 3.1, 11.2 Hz), 5.15 (1H, NH), 5.41 (d, 1H,
4.2.4. 1,3,6-Tri-O-Acetyl-4-O-(2,3,4,6-tetra-O-acetyl-
galactopyranosyl)-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-
-D-glucopyranose (2c-
Obtained in 92% yield (
hexane/EtOAc); 1H NMR (CDCl3):
b-D-
b
b)
J ¼ 3.0 Hz), 5.76 (d, 1H, J ¼ 8.8 Hz) ppm; HRMS (FAB): calcd. for
35
b/a
¼ 10) as a colorless foam: Rf 0.27 (1:1
1.98 (s, 3H), 2.07 (s, 3H), 2.08 (s,
C H
Cl3NO9S [M - OAc]þ 462.0126; found 462.0120.
15 19
d
3H), 2.13 (s, 3H), 2.17 (s, 6H), 2.18 (s, 3H), 2.23 (s, 3H), 3.73 (q, 1H,
J ¼ 8.7 Hz), 3.86 (m, 2H), 3.91 (t, 1H, J ¼ 7.2 Hz), 4.10 (dd, 1H, J ¼ 7.1,
11.2 Hz), 4.14 (m, 1H), 4.18 (dd, 1H, J ¼ 6.3, 11.0 Hz), 4.45 (dd, 1H,
J ¼ 1.9, 12 Hz), 4.49 (d, 1H, J ¼ 7.8 Hz), 4.65 (s, 2H), 5.00 (dd, 1H,
J ¼ 2.5, 10.5 Hz), 5.10 (dd, 1H, J ¼ 7.8, 10.5 Hz), 5.17 (t, 1H), 5.38 (dd,
1H, J ¼ 0.8, 3.3 Hz), 5.74 (d, 1H, J ¼ 7.8 Hz), 6.02 (d, 1H, J ¼ 9.4 Hz)
4.3. General procedure for ZnCl2-promoted glycosylation
To a mixture of glucosaminyl -acetate (2a- , 5a-b, or 6a)
b
b
(0.30 mmol),12-bromo-1-dodecanol (108 mg, 0.4 mmol), and ZnCl2
(56 mg, 0.4 mmol, dried in vacuo at 110 ꢀC for 1 h prior to use) was
added dichloroethane (4 mL), and the suspension was stirred upon
heating with monitoring the reaction by TLC. The resulting mixture
was diluted with EtOAc (20 mL) and aq. NaHCO3 (20 mL), and the
mixture was stirred for 10 min, filtered through Celite, and washed
thoroughly with EtOAc (10 mL). The combined filtrate and wash-
ings were successively washed with H2O and brine. The aqueous
phase was extracted with EtOAc (2 ꢂ 20 mL), and the combined
organic layers were dried over Na2SO4. Removal of the solvent gave
a residue, which was purified by silica gel column chromatography
eluting with hexane-EtOAc mixture.
ppm; 13C NMR (CDCl3):
d 20.49, 20.63 (3C), 20.81, 20.91, 21.01, 57.2,
60.9, 61.9, 66.6, 69.0, 70.7, 70.9, 71.7, 73.5, 74.5, 78.6, 91.9, 93.3,
100.7, 169.2, 169.6, 170.07, 170.13, 170.32, 170.38, 170.9 ppm; MS
35
(ESI): m/z calcd for C
H Cl3NO20S 845.08; found (%) 868.08
28 38
([M(35Cl3)þNa]þ, 91), 870.07 ([M(35Cl2þ37Cl)þNa]þ, 100), 872.00
([M(35Clþ37Cl2)þNa]þ, 38).
4.2.5. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(p-nitrobenzenesulfonyl)
amido-
Obtained in 55% yield (
hexane/EtOAc); m.p. 155e158 ꢀC; [
NMR (CDCl3):
b-D-glucopyranose (3a-b)
b
/a
¼ 5) as a colorless solid: Rf 0.35 (1:1
a
]
[25] þ2.8 (c 1.1, CHCl3); 1H
4.3.1. 12-Bromododecyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
D
d
1.84 (s, 3H), 1.88 (s, 3H), 2.04 (s, 3H), 2.09 (s, 3H),
trichloroethoxysulfonyl)amido-b-D-glucopyranoside (7a)
3.74 (q, 1H, J ¼ 9.5 Hz), 3.87 (ddd, 1H, J ¼ 2.1, 4.4, 10.0 Hz), 4.10 (dd,
1H, J ¼ 2.1, 12.6 Hz), 4.27 (dd, 1H, J ¼ 4.4, 12.6 Hz), 5.09 (t, 1H,
J ¼ 9.7 Hz), 5.20 (t, 1H, J ¼ 9.9 Hz), 5.68 (d, 1H, J ¼ 8.7 Hz), 5.90 (d,
1H, J ¼ 9.4 Hz), 8.06 (m, 2H), 8.36 (m, 2H) ppm; 13C NMR (CDCl3):
Obtained in 56% yield as a colorless solid: m.p. 71e73 ꢀC; Rf 0.33
(2:1 hexane/EtOAc); [
(CDCl3):
a
]
[25] ꢁ17.8 (c 2.50, CHCl3); 1H NMR
D
d
1.26 (s-like, 14H), 1.42 (m, 2H), 1.66 (m, 2H), 1.85 (quint,
2H, J ¼ 7.3 Hz), 2.05 (s, 3H), 2.10 (s, 3H), 2.13 (s, 3H), 3.41 (t, 2H,
J ¼ 6.9 Hz), 3.57 (dt, 1H, J ¼ 9.4, 7.0 Hz), 3.58 (q, 1H, J ¼ 9.0 Hz), 3.71
(ddd, 1H, J ¼ 2.3, 4.8, 9.4 Hz), 3.88 (dt, 1H, J ¼ 9.4, 7.3 Hz), 4.14 (dd,
1H, J ¼ 2.3, 12.3 Hz), 4.28 (dd, 1H, J ¼ 4.8, 12.3 Hz), 4.44 (d, 1H,
J ¼ 8.2 Hz), 4.68 (d, 1H, J ¼ 10.9 Hz), 4.72 (d, 1H, J ¼ 10.9 Hz), 5.08 (t,
d
20.5 (3C), 20.7, 57.3, 61.4, 67.8, 72.5, 72.6, 92.1, 124.2 (2C), 128.2
(2C), 147.0, 150.0, 169.2, 169.3, 170.6, 171.3 ppm; Anal. Calcd for
20H24N2O13S: C, 45.11; H, 4.54; N, 5.26; S, 6.02. Found: C, 44.65; H,
4.49; N,5.11; S, 6.00.
C

T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
127
1H, J ¼ 9.5 Hz), 5.13 (t, 1H, J ¼ 9.5 Hz), 5.52 (d, 1H, J ¼ 9.0 Hz, 1H)
ppm; 13C NMR (CDCl3):
20.58, 20.73, 20.85, 25.8, 28.1, 28.7, 29.34,
J ¼ 9.5 Hz), 5.36 (d, 1H, J ¼ 8.9 Hz) ppm; 13C NMR (CDCl3):
d
14.1,
d
20.6, 20.7, 20.8, 22.7, 25.8, 29.34, 29.36, 29.49, 29.58, 29.64, 31.9,
29.39, 29.47, 29.49, 32.8, 34.1, 59.0, 62.0, 68.4, 70.6, 71.8, 72.9, 78.6,
93.4, 100.7, 169.3, 170.7, 171.6 ppm; Anal. Calcd for
59.0, 62.0, 68.4, 70.6, 71.8, 72.8, 78.7, 93.4, 100.8, 169.3, 170.7,
35
171.6 ppm; MS (ESI): m/z calcd for C
H Cl3NO11S 711.20; found (%)
28 48
C
26H43BrCl3NO11S: C, 40.88; H, 5.67; N,1.83; S, 4.20. Found: C, 41.16;
734.21 ([M(35Cl3)þNa]þ, 97), 736.21 ([M(35Cl2þ37Cl)þNa]þ, 100),
H, 5.63; N, 1.84; S, 4.39.
738.16 ([M(35Clþ37Cl2)þNa]þ, 43).
4.3.2. 12-Bromododecyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
4.4.2. 12-Bromododecyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxycarbonyl)amido-
b
-D-glucopyranoside (8a)
trichloroethoxysulfonyl)amido-b-D-galactopyranoside (7b)
Obtained in 74% yield as a colorless solid: m.p. 75e77 ꢀC; Rf 0.25
Obtained in 84% yield as a colorless foam: Rf 0.33 (2:1 hexane/
(3:1 hexane/EtOAc); [
a
]
D [25] þ0.4 (c 2.1, CHCl3); 1H NMR (CDCl3):
EtOAc); [
a
]
D [25] ꢁ35.5 (c 1.92, CHCl3); 1H NMR (CDCl3):
d 1.27 (s-
d
1.24e1.34 (m, 14H), 1.42 (m, 2H), 1.57 (m, 2H), 1.85 (quint, 2H,
like,14H), 1.42 (m, 2H), 1.68 (m, 2H), 1.85 (quint, 2H, J ¼ 7.2 Hz), 2.06
(s, 3H), 2.10 (s, 3H), 2.18 (s, 3H), 3.41 (t, 2H, J ¼ 6.9 Hz), 3.58 (dt, 1H,
J ¼ 9.3, 7.2 Hz), 3.73 (q, 1H, J ¼ 9.0 Hz), 3.90 (dt, 1H, J ¼ 9.4, 7.3 Hz),
3.93 (t, 1H, J ¼ 6.6 Hz), 4.12 (dd, 1H, J ¼ 6.7, 11.2 Hz), 4.20 (dd, 1H,
J ¼ 6.5, 11.2 Hz), 4.46 (d, 1H, J ¼ 8.4 Hz), 4.71 (s, 2H), 5.07 (dd, 1H,
J ¼ 3.5, 10.9 Hz), 5.37 (d, 1H, J ¼ 3.5 Hz), 5.44 (br, 1H) ppm; 13C NMR
J ¼ 7.2 Hz), 2.029 (s, 3H), 2.032 (s, 3H), 2.09 (s, 3H), 3.41 (t, 2H,
J ¼ 6.9 Hz), 3.47 (dt, 1H, J ¼ 9.6, 6.9 Hz), 3.61 (dt, 1H, J ¼ 10.7, 8.6 Hz),
3.70 (m, 1H), 3.88 (dt, 1H, J ¼ 9.6, 6.6 Hz), 4.13 (dd, 1H, J ¼ 2.3,
12.3 Hz), 4.29 (dd, 1H, J ¼ 4.7, 12.3 Hz), 4.64 (d, 1H, J ¼ 8.6 Hz), 4.67
(d, 1H, J ¼ 11.9 Hz), 4.77 (d, 1H, J ¼ 11.9 Hz), 5.07 (t, 1H, J ¼ 9.7 Hz),
5.19 (d, 1H, J ¼ 8.6 Hz), 5.32 (t, 1H, J ¼ 10.0 Hz) ppm; 13C NMR
(CDCl3):
d 20.68 (2C), 20.82, 25.8, 28.1, 28.7, 29.39, 29.47, 29.50,
(CDCl3):
d
20.62, 20.64, 20.75, 25.8, 28.1, 28.7, 29.34, 29.38, 29.41,
32.8, 34.0, 56.1, 61.3, 66.9, 70.66, 70.71, 78.6, 93.4,101.0, 170.2, 170.5,
79
29.48, 29.50, 32.8, 34.1, 56.3, 62.1, 68.7, 70.4, 71.7, 71.8, 74.4, 95.4,
100.7, 153.9, 169.5, 170.64, 170.73 ppm; Anal. Calcd for
171.2 ppm; HRMS (FAB): calcd. for C
762.0884; found 762.0898.
H
Br35Cl3NO11S [MþH]þ
26 44
C
27H43BrCl3NO10: C, 44.55; H, 5.95; N,1.92. Found: C, 44.95; H, 5.98;
N, 1.67.
4.4.3. 12-Bromododecyl 3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-
acetyl- -D-galactopyranosyl)-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido- -D-glucopyranoside (7c)
b
4.3.3. 12-Bromododecyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-
b
-
b
D-glucopyranoside (9a)
Obtained in 70% yield as a colorless foam: Rf 0.24 (3:2 hexane/
Obtained in 67% yield as a colorless solid: m.p. 107e109 ꢀC; Rf
EtOAc); [
a]
D [25] ꢁ13.0 (c 2.1, CHCl3); 1H NMR (CDCl3):
d 1.24e1.35
0.40 (1:2 hexane/EtOAc); [
(CDCl3):
a
]
D
[25] ꢁ9.9 (c 2.7, CHCl3); 1H NMR
(m, 14H), 1.42 (m, 2H), 1.64 (m, 2H), 1.85 (quint, 2H, J ¼ 7.2 Hz), 1.98
(s, 3H), 2.06 (s, 3H), 2.07 (s, 3H), 2.13 (s, 3H), 2.157 (s, 3H), 2.164 (s,
3H), 3.41 (t, 2H, J ¼ 6.9 Hz), 3.52 (dt, 1H, J ¼ 9.5, 6.9 Hz), 3.55 (dt, 1H,
J ¼ 7.5, 9.0 Hz), 3.67 (ddd, 1H, J ¼ 2.5, 5.2, 8.4 Hz), 3.80 (t, 1H,
J ¼ 8.5 Hz), 3.83 (dt, 1H, J ¼ 9.5, 7.2 Hz), 3.91 (t, 1H, J ¼ 6.7 Hz), 4.10
(dd, 1H, J ¼ 7.1, 11.1 Hz), 4.14 (dd, 1H, J ¼ 5.2, 12.2 Hz), 4.17 (dd, 1H,
J ¼ 6.5,11.1 Hz), 4.44 (d,1H, J ¼ 7.6 Hz), 4.49 (dd,1H, J ¼ 2.5,12.0 Hz),
4.50 (d, 1H, J ¼ 7.8 Hz), 4.69 (d, 1H, J ¼ 10.9 Hz), 4.72 (d, 1H,
J ¼ 10.9 Hz), 4.99 (dd, 1H, J ¼ 3.4, 10.5 Hz), 5.08 (dd, 1H, J ¼ 8.4,
9.4 Hz), 5.10 (dd, 1H, J ¼ 7.8, 10.5 Hz), 5.37 (dd, 1H, J ¼ 0.9, 3.4 Hz),
d
1.26 (s-like, 14H), 1.42 (m, 2H), 1.56 (m, 2H), 1.85 (quint,
2H, J ¼ 7.2 Hz), 1.95 (s, 3H), 2.02 (s, 3H), 2.03 (s, 3H), 2.09 (s, 3H),
3.41 (t, 2H, J ¼ 6.9 Hz), 3.47 (dt, 1H, J ¼ 9.6, 6.9 Hz), 3.70 (ddd, 1H,
J ¼ 2.5, 4.7, 10.0 Hz), 3.81 (dt, 1H, J ¼ 10.6, 8.5 Hz), 3.86 (dt, 1H,
J ¼ 9.6, 6.5 Hz), 4.13 (dd, 1H, J ¼ 2.5, 12.2 Hz), 4.27 (dd, 1H, J ¼ 4.8,
12.2 Hz), 4.68 (d, 1H, J ¼ 8.3 Hz), 5.07 (t, 1H, J ¼ 9.6 Hz), 5.31 (dd, 1H,
J ¼ 9.3, 10.6 Hz), 5.54 (d, 1H, J ¼ 8.7 Hz) ppm; 13C NMR (CDCl3):
d
20.45, 20.53, 20.56, 23.0, 25.7, 27.9, 28.5, 29.16, 29.20, 29.25,
29.30, 29.34, 29.39, 32.6, 33.9, 54.5, 62.1, 68.7, 69.7, 71.4, 72.3, 100.5,
169.3, 170.2, 170.54, 170.59 ppm; Anal. Calcd for C26H44BrNO9: C,
52.52; H, 7.46; N, 2.36. Found: C, 52.85; H, 7.47; N, 2.11.
5.71 (d, 1H, J ¼ 9.0 Hz) ppm; 13C NMR (CDCl3):
d 20.51, 20.65 (3C),
20.85, 20.97, 25.8, 28.1, 28.7, 29.35, 29.39, 29.47, 32.8, 34.1, 58.3,
60.9, 62.2, 66.6, 69.1, 70.4, 70.7, 70.8, 72.4, 72.6, 75.6, 78.6, 93.4,
4.4. General procedure for one-pot amidoglycosylation
100.5, 100.9, 169.5, 170.06, 170.12, 170.36, 170.42, 171.2 ppm; MS
79
(ESI): m/z calcd for C
H
Br35Cl3NO19S 1049.17; found (%) 1072.16
38 59
To a mixture of glycal 1a,b,c (0.2 mmol), alcohol (0.4 mmol),
TcesNH2 (80 mg, 0.35 mmol), Rh2(NHCOCF3)4 (12 mg, 0.02 mmol),
and activated powdered molecular sieves 4 Å (160 mg) under ni-
trogen was added PhCl (3 mL), and the resulting light-purple sus-
pension was cooled with an ice-water bath. PhIO (80 mg,
0.36 mmol) was added in several portions for 1 h, and the resulting
light-brown suspension was stirred at 5 ꢀC for 1 h and then at rt for
5e15 h with monitoring the reaction by TLC. The reaction mixture
was filtered, washed with CH2Cl2, and the combined filtrates were
concentrated under reduced pressure to remove CH2Cl2. The res-
idue was purified by silica gel chromatography, usually eluting with
hexane-EtOAc mixture.
([M(79Brþ35Cl3)þNa]þ, 54), 1074.21 ([M(35Cl2þ37Cl)þNa]þ, 100),
1076.13 ([M(35Clþ37Cl2)þNa]þ, 78).
4.4.4. 2-Phenylethyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido-b-D-glucopyranoside (12a)
Obtained in 75% yield as a colorless foam: Rf 0.34 (3:2 hexane/
EtOAc); [
a]
[25] ꢁ14.4 (c 0.90, CHCl3); 1H NMR (CDCl3):
d 2.04 (s,
D
3H), 2.09 (s, 3H), 2.12 (s, 3H), 2.99 (t, 2H, J ¼ 7.6 Hz), 3.60 (q, 1H,
J ¼ 9.0 Hz), 3.69 (ddd, 1H, J ¼ 2.5, 4.9, 9.6 Hz), 3.80 (dt, 1H, J ¼ 10.2,
7.7 Hz), 4.11 (dt, 1H, J ¼ 10.1, 7.6 Hz), 4.13 (dd, 1H, J ¼ 2.5, 12.3 Hz),
4.26 (dd, 1H, J ¼ 4.9, 12.3 Hz), 4.46 (d, 1H, J ¼ 8.2 Hz), 4.64 (d, 1H,
J ¼ 10.9 Hz), 4.68 (d, 1H, J ¼ 10.9 Hz), 5.07 (t, 1H, J ¼ 9.4 Hz), 5.12 (t,
1H, J ¼ 9.6 Hz), 5.52 (d, 1H, J ¼ 9.0 Hz) ppm; 13C NMR (CDCl3):
4.4.1. Tetradecyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
d 20.6, 20.7, 20.9, 36.0, 58.9, 61.9, 68.4, 70.9, 71.9, 72.8, 78.6, 93.4,
trichloroethoxysulfonyl)amido-
b
-D-glucopyranoside (10a)
100.7, 126.7, 128.6 (2C), 128.9 (2C), 137.6, 169.4, 170.7, 171.6 ppm;
35
Obtained in 78% yield as a colorless foam: Rf 0.35 (2:1 hexane/
HRMS (FAB): calcd. for C
620.0536.
H
22 28
Cl3NO11S [MþH]þ 620.0527; found
EtOAc); [
a]
D [25] ꢁ18.0 (c 2.2, CHCl3); 1H NMR (CDCl3):
d 0.88 (t, 3H,
J ¼ 6.9 Hz), 1.25 (s-like, 20H), 1.32 (m, 2H), 1.66 (quint, 2H,
J ¼ 7.3 Hz), 2.04 (s, 3H), 2.10 (s, 3H), 2.13 (s, 3H), 3.56 (dt, 1H, J ¼ 9.3,
7.1 Hz), 3.58 (q, 1H, J ¼ 9.0 Hz), 3.69 (ddd, 1H, J ¼ 2.3, 4.9, 8.8 Hz),
3.88 (dt, 1H, J ¼ 9.4, 7.3 Hz), 4.14 (dd, 1H, J ¼ 2.3, 12.3 Hz), 4.27 (dd,
1H, J ¼ 4.9, 12.3 Hz), 4.43 (d, 1H, J ¼ 8.2 Hz), 4.68 (d, 1H, J ¼ 10.9 Hz),
4.72 (d, 1H, J ¼ 10.9 Hz), 5.08 (t, 1H, J ¼ 9.5 Hz), 5.12 (t, 1H,
4.4.5. Benzyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido- -D-galactopyranoside (13b)
b
Obtained in 62% yield as a colorless foam: Rf 0.28 (3:2 hexane/
EtOAc); [
a
]
[25] ꢁ44.4 (c 1.45, CHCl3); 1H NMR (CDCl3):
d 2.05 (s,
D
3H), 2.08 (s, 3H), 2.18 (s, 3H), 3.80 (dt, 1H, J ¼ 10.9, 8.6 Hz), 3.90 (dt,

128
T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
1H, J ¼ 0.9, 6.6 Hz), 4.15 (dd,1H, J ¼ 6.5,11.3 Hz), 4.22 (dd,1H, J ¼ 6.7,
11.3 Hz), 4.49 (d,1H, J ¼ 8.3 Hz), 4.56 (s, 2H), 4.68 (d,1H, J ¼ 11.6 Hz),
4.94 (d, 1H, J ¼ 11.0 Hz), 5.01 (dd, 1H, J ¼ 3.4, 10.9 Hz), 5.21 (d, 1H,
J ¼ 8.7 Hz), 5.36 (d,1H, J ¼ 3.4 Hz), 7.30e7.40 (m, 5H) ppm; 13C NMR
J ¼ 9.5 Hz), 5.13 (t, 1H, J ¼ 9.5 Hz), 5.38 (d, 1H, J ¼ 9.0 Hz) ppm; 13
C
NMR (CDCl3): d 15.3, 20.58, 20.66, 20.80, 20.88, 22.2, 23.1, 25.1, 31.5,
34.2, 40.0, 47.6, 58.9, 62.4, 68.7, 71.5, 73.2, 77.6, 78.8, 93.4, 97.3,
169.4, 170.7, 171.7 ppm.
(CDCl3): d 20.7 (2C), 20.8, 56.0, 61.4, 66.9, 70.7, 70.9, 71.0, 78.6, 93.3,
99.2, 128.5, 128.6, 128.7, 135.8, 170.2, 170.5, 171.2 ppm; MS (ESI): m/z
35
4.4.10. L-menthyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido-b-D-galactopyranoside (16b)
calcd for C H
21 26
Cl3NO11S 605.03; found (%) 627.96 ([M(35Cl3)þNa]þ,
92), 629.94 ([M(35Cl2þ37Cl)þNa]þ, 100), 631.93 ([M(35Clþ37Cl2)þ
Na]þ, 41).
Obtained in 76% yield as a colorless foam: Rf 0.40 (2:1 hexane/
EtOAc); [
a
]
D [25] ꢁ54.3 (c 0.84, CHCl3); 1H NMR (CDCl3):
d 0.74 (d,
3H, J ¼ 6.8 Hz), 0.82 (m, 1H), 0.88 (d, 3H, J ¼ 7.0 Hz), 0.93 (d, 3H,
J ¼ 6.5 Hz), 0.98 (m, 1H), 1.00 (q, 1H, J ¼ 11.7 Hz), 1.30 (m, 2H), 1.67
(m, 2H), 2.04 (s, 3H), 2.07 (m, 1H), 2.11 (s, 3H), 2.20 (s, 3H), 2.27 (m,
1H), 3.53 (dt, 1H, J ¼ 4.1, 10.7 Hz), 3.66 (q, 1H, J ¼ 9.4 Hz), 3.92 (t, 1H,
J ¼ 6.7 Hz), 4.08 (dd, 1H, J ¼ 6.6, 11.2 Hz), 4.20 (dd, 1H, J ¼ 6.8,
11.2 Hz), 4.54 (d, 1H, J ¼ 8.2 Hz), 4.75 (s, 2H), 5.08 (dd, 1H, J ¼ 3.5,
10.7 Hz), 5.35 (d, 1H, J ¼ 3.5 Hz), 5.50 (d, 1H, J ¼ 9.0 Hz) ppm; 13C
4.4.6. 4-Pentenyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido-b-D-galactopyranoside (14b)
Obtained in 63% yield as a colorless solid: m.p. 84e86 ꢀC; Rf 0.36
(3:2 hexane/EtOAc); [
(CDCl3):
a
]
[25] ꢁ23.1 (c 1.45, CHCl3); 1H NMR
D
d
1.79 (quint, 2H, J ¼ 7.2 Hz), 2.06 (s, 3H), 2.10 (s, 3H), 2.15
(m, 2H), 2.18 (s, 3H), 3.61 (dt,1H, J ¼ 9.6, 7.0 Hz), 3.74 (dt,1H, J ¼ 11.1,
8.4 Hz), 3.91 (t, 1H, J ¼ 7.0 Hz), 3.92 (dt, 1H, J ¼ 9.5, 7.0 Hz), 4.12 (dd,
1H, J ¼ 6.7, 11.3 Hz), 4.19 (dd, 1H, J ¼ 6.7, 11.3 Hz), 4.46 (d, 1H,
J ¼ 8.2 Hz), 4.68 (d, 1H, J ¼ 11.0 Hz), 4.71 (d, 1H, J ¼ 11.0 Hz), 4.99 (m,
1H), 5.04 (m, 1H), 5.05 (dd, 1H, J ¼ 3.4, 11.0 Hz), 5.20 (d, 1H,
J ¼ 8.4 Hz), 5.37 (d, 1H, J ¼ 3.3 Hz), 5.80 (ddt, 1H, J ¼ 17.0, 10.2,
NMR (CDCl3):
d 15.3, 20.64, 20.75, 20.88, 22.2, 23.0, 25.0, 31.5, 34.2,
40.2, 47.6, 56.0, 61.5, 67.1, 70.5, 71.1, 77.9, 78.7, 93.4, 97.9, 170.4,
35
170.6, 171.4 ppm; MS (ESI): m/z calcd for C
H Cl3NO11S 653.12;
24 38
found (%) 676.09 ([M(35Cl3)þNa]þ, 95), 678.05 ([M(35Cl2þ37Cl)þ
Na]þ, 100), 680.07 ([M(35Clþ37Cl2)þNa]þ, 40).
6.7 Hz) ppm; 13C NMR (CDCl3):
d 20.7 (2C), 20.8, 28.6, 29.9, 56.1,
61.4, 66.9, 69.9, 70.7, 78.6, 93.4, 101.0, 115.2, 137.6, 170.2, 170.5,
171.3 ppm; Anal. Calcd for C19H28Cl3NO11S: C, 39.02; H, 4.83; N,
2.39; S, 5.48. Found: C, 38.83; H, 4.86; N, 2.34; S, 5.39.
4.4.11. L-menthyl 3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-
galactopyranosyl)-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-
b-D-
b
-D-glucopyranoside (16c)
4.4.7. Cyclohexyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido-b-D-glucopyranoside (15a)
Obtained in 67% yield as a colorless foam: Rf 0.30 (3:2 hexane/
EtOAc); [
a
]
[25] ꢁ32.7 (c 1.0, CHCl3); 1H NMR (CDCl3):
d 0.72 (d,
D
Obtained in 57% yield as a colorless foam: Rf 0.35 (3:2 hexane/
3H, J ¼ 6.8 Hz), 0.80 (m, 1H), 0.86 (d, 3H, J ¼ 7.0 Hz), 0.93 (d, 3H,
J ¼ 6.4 Hz), 0.96 (m, 1H), 0.99 (q, 1H, J ¼ 11.6 Hz), 1.30 (m, 2H), 1.66
(m, 2H), 1.98 (s, 3H), 2.05 (m, 1H), 2.05 (s, 3H), 2.08 (s, 3H), 2.10 (s,
3H), 2.15 (m, 1H), 2.16 (s, 6H), 3.47 (q, 1H, J ¼ 9.2 Hz), 3.53 (dt, 1H,
J ¼ 3.9, 10.7 Hz), 3.69 (m, 1H), 3.79 (t, 1H, J ¼ 9.7 Hz), 3.91 (t, 1H,
J ¼ 6.7 Hz), 4.10 (dd, 1H, J ¼ 7.0, 10.5 Hz), 4.10 (m, 1H), 4.16 (dd, 1H,
J ¼ 6.4, 11.1 Hz), 4.52 (d, 1H, J ¼ 7.8 Hz), 4.55 (d, 1H, J ¼ 8.2 Hz), 4.74
(s, 2H), 5.00 (dd,1H, J ¼ 3.4,10.4 Hz), 5.09 (t,1H, J ¼ 9.0 Hz), 5.10 (dd,
1H, J ¼ 7.8, 10.4 Hz), 5.37 (d, 1H, J ¼ 3.4 Hz), 5.76 (d, 1H, J ¼ 9.1 Hz,
EtOAc); [
a
]
D [25] ꢁ21.8 (c 2.0, CHCl3); 1H NMR (CDCl3):
d 1.10e1.50
(m, 5H), 1.57 (m, 1H), 1.78 (m, 2H), 1.98 (m, 2H), 2.05 (s, 3H), 2.09 (s,
3H), 2.13 (s, 3H), 3.57 (q, 1H, J ¼ 9.1 Hz), 3.70 (m, 2H), 4.12 (dd, 1H,
J ¼ 2.5, 12.3 Hz), 4.28 (dd, 1H, J ¼ 5.1, 12.3 Hz), 4.58 (d, 1H,
J ¼ 8.2 Hz), 4.72 (s, 2H), 5.07 (t,1H, J ¼ 9.5 Hz), 5.14 (t,1H, J ¼ 9.7 Hz),
5.55 (d, 1H, J ¼ 9.0 Hz) ppm; 13C NMR (CDCl3):
d 20.58, 20.73, 20.88,
24.2, 24.3, 25.4, 31.7, 33.5, 59.0, 62.1, 68.6, 71.7, 73.0, 78.4, 78.7, 93.4,
35
98.7, 169.4,170.8, 171.7 ppm; MS (ESI): m/z calcd for C
H Cl3NO11S
20 30
597.06; found (%) 619.95 ([M(35Cl3)þNa]þ, 100), 622.00
1H) ppm; 13C NMR (CDCl3):
d 15.3, 20.52, 20.59, 20.63, 20.73, 20.77,
([M(35Cl2þ37Cl)þNa]þ, 97), 623.92 ([M(35Clþ37Cl2)þNa]þ, 39).
20.98, 22.3, 23.1, 25.1, 31.5, 34.2, 40.0, 47.6, 59.0, 60.9, 62.1, 66.7, 69.1,
70.76, 70.84, 72.3, 73.2, 76.4, 77.3, 78.7, 93.5, 97.0, 101.1, 169.4, 170.1
(2C), 170.35, 170.43, 171.4 ppm; MS (ESI): m/z calcd for
4.4.8. Cyclohexyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
Cl3NO19S 941.21; found (%) 964.26 ([M(35Cl3)þNa]þ, 81),
trichloroethoxysulfonyl)amido-
b-D-galactopyranoside (15b)
35
C
H
36 54
966.27 ([M(35Cl2þ37Cl)þNa]þ, 100), 968.27 ([M(35Clþ37Cl2)þNa]þ,
Obtained in 78% yield as a colorless foam: Rf 0.31 (2:1 hexane/
EtOAc); [
a
]
D [25] ꢁ30.2 (c 1.1, CHCl3); 1H NMR (CDCl3):
d 1.10e1.50
41).
(m, 5H), 1.57 (m, 1H), 1.79 (m, 2H), 2.01 (m, 2H) 2.06 (s, 3H), 2.10 (s,
3H), 2.18 (s, 3H), 3.69 (dt, 1H, J ¼ 3.3, 10.0 Hz), 3.72 (dt, 1H, J ¼ 10.9,
8.6 Hz), 3.93 (t,1H, J ¼ 6.7 Hz), 4.10 (dd,1H, J ¼ 6.7,11.2 Hz), 4.21 (dd,
1H, J ¼ 6.6,11.3 Hz), 4.60 (d,1H, J ¼ 8.3 Hz), 4.73 (s, 2H), 5.07 (dd,1H,
J ¼ 3.5, 10.7 Hz), 5.36 (d, 1H, J ¼ 3.5 Hz), 5.53 (d, 1H, J ¼ 9.0 Hz) ppm;
4.4.12. 6-O-[3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido-
isopropylidene- -D-galactopyranose (17b)
b-D-galactopyranosyl]-1,2:3,4-di-O-
a
13C NMR (CDCl3):
d
20.65, 20.71, 20.85, 24.2, 24.4, 25.4, 31.7, 33.6,
Obtained in 74% yield as a colorless foam: Rf 0.27 (3:2 hexane/
56.2, 61.3, 66.9, 70.6, 70.9.1, 78.5, 78.6, 93.4, 99.1, 170.3, 170.5,
EtOAc); [
a
]
D
[25] ꢁ46.4 (c 2.0, CHCl3); 1H NMR (CDCl3):
d 1.32 (s,
35
171.3 ppm; MS (ESI): m/z calcd for C
H
Cl3NO11S 597.06; found
3H), 1.34 (s, 3H), 1.46 (s, 3H), 1.60 (s, 3H), 2.05 (s, 3H), 2.07 (s, 3H),
2.15 (s, 3H), 3.72 (ddd, 1H, J ¼ 7.2, 8.2, 10.9 Hz), 3.92 (dd, 1H, J ¼ 8.8,
12.7 Hz), 3.95 (dt, 1H, J ¼ 0.8, 6.7 Hz), 4.00 (dd, 1H, J ¼ 2.5, 12.6 Hz),
4.12 (dd, 1H, J ¼ 6.7, 11.2 Hz), 4.17 (dd, 1H, J ¼ 2.0, 8.0 Hz), 4.19 (dd,
1H, J ¼ 6.6, 11.2 Hz), 4.34 (dd, 1H, J ¼ 2.3, 5.2 Hz), 4.59 (dd, 1H,
J ¼ 2.3, 7.9 Hz), 4.71 (d, 1H, J ¼ 11 Hz), 4.74 (d, 1H, J ¼ 11 Hz), 4.83 (d,
1H, J ¼ 8.4 Hz), 5.04 (dd, 1H, J ¼ 3.3, 10.9 Hz), 5.37 (dd, 1H, J ¼ 0.8,
20 30
(%) 620.02 ([M(35Cl3)þNa]þ, 94), 622.00 ([M(35Cl2þ37Cl)þNa]þ,
100), 623.99 ([M(35Clþ37Cl2)þNa]þ, 39).
4.4.9. L-menthyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido-b-D-glucopyranoside (16a)
Obtained in 74% yield as a colorless foam: Rf 0.40 (2:1 hexane/
EtOAc); [
a
]
D [25] ꢁ53.4 (c 0.90, CHCl3); 1H NMR (CDCl3):
d
0.74 (d,
3.3 Hz), 5.59 (d, 1H, J ¼ 5.2 Hz), 5.82 (d, 1H, J ¼ 8.4 Hz, 1H) ppm; 13
C
3H, J ¼ 6.8 Hz), 0.82 (m, 1H), 0.87 (d, 3H, J ¼ 7.0 Hz), 0.93 (d, 3H,
J ¼ 6.5 Hz), 0.98 (m, 1H), 1.00 (q, 1H, J ¼ 11.7 Hz), 1.30 (m, 2H), 1.67
(m, 2H), 2.02 (m, 1H), 2.05 (s, 3H), 2.07 (s, 3H), 2.14 (s, 3H), 2.22 (m,
1H), 3.55 (q, 1H, J ¼ 9.1 Hz), 3.56 (dt, 1H, J ¼ 3.3, 11.0 Hz), 3.70 (ddd,
1H, J ¼ 2.7, 5.3, 9.5 Hz), 4.14 (dd, 1H, J ¼ 2.7, 12.1 Hz), 4.20 (dd, 1H,
J ¼ 5.3, 12.1 Hz), 4.54 (d, 1H, J ¼ 8.3 Hz), 4.75 (s, 2H), 5.07 (t, 1H,
NMR (CDCl3): d 20.60 (2C), 20.65, 24.2, 24.7, 25.87, 25.92, 55.8, 61.2,
66.8, 68.5, 68.8, 70.0, 70.6, 70.84, 70.88, 70.95, 78.7, 93.7, 96.2,101.2,
109.2, 109.5, 170.1, 170.4, 170.6 ppm; MS (ESI): m/z calcd for
35
C
H
Cl3NO16S 757.10; found (%) 780.05 ([M(35Cl3)þNa]þ, 92),
26 38
782.04 ([M(35Cl2þ37Cl)þNa]þ, 100), 784.02 ([M(35Clþ37Cl2)þNa]þ,
39).

T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
129
4.4.13. Methyl 6-O-[3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxysulfonyl)amido- -D-galactopyranosyl]-2,3,4-tri-O-
benzyl- -D-glucopyranoside (18b)
4.5.2. Tetradecyl 3,4,6-tri-O-acetyl-2-benzamido-2-deoxy-
glucopyranoside (26)
b-D-
b
a
To a mixture of 10a (43 mg, 0.06 mmol), powdered anhydrous
CuSO4 (5 mg, 0.03 mmol), and acetic acid (0.1 mL) in tetrahydro-
furan (1 mL) was added zinc (42 mg, 0.6 mmol) in 1 portion. The
resulting dark-grey suspension was stirred at rt for 3 h. The reaction
mixture was filtered and washed with EtOAc, and the combined
filtrates were mixed with H2O, and the layers were separated. The
organic layer was washed with aq. NaCl, and the combined aqueous
layers were extracted with EtOAc. The combined organic extracts
were dried (Na2SO4), concentrated, and co-evaporated with hep-
tane (1 mL) to give crude tetradecyl 3,4,6-tri-O-acetyl-2-amino-2-
Obtained in 21% yield as a colorless foam: Rf 0.25 (3:2 hexane/
EtOAc); [
a]
[25] þ19.5 (c 0.72, CHCl3); 1H NMR (CDCl3):
d 2.01 (s,
D
3H), 2.06 (s, 3H), 2.12 (s, 3H), 3.40 (s, 3H), 3.45 (dd, 1H, J ¼ 8.9,
9.9 Hz), 3.52 (dd, 1H, J ¼ 3.5, 9.7 Hz), 3.65 (dd, 1H, J ¼ 5.8, 11.0 Hz),
3.70 (dt, 1H, J ¼ 11.0, 7.9 Hz), 3.81 (dt, 1H, J ¼ 0.9, 6.7 Hz), 3.86 (ddd,
1H, J ¼ 2.1, 5.8, 10 Hz), 4.00 (t, 1H, J ¼ 9.2 Hz), 4.10 (m, 3H), 4.28 (d,
1H, J ¼ 8.3 Hz), 4.60 (d, 1H, J ¼ 3.3 Hz), 4.64 (s, 2H), 4.64 (d, 2H,
J ¼ 12.1 Hz), 4.79 (d,1H, J ¼ 12.1 Hz), 4.80 (d,1H, J ¼ 11.0 Hz), 4.89 (d,
1H, J ¼ 11.6 Hz), 4.96 (dd, 1H, J ¼ 3.4, 11.0 Hz), 4.99 (d, 1H,
J ¼ 11.0 Hz), 5.02 (d, 1H, J ¼ 7.6 Hz), 5.34 (dd, 1H, J ¼ 0.9, 3.4 Hz),
deoxy-
b-D-glucopyranoside (25) (33 mg) as a colorless solid: Rf
7.27e7.40 (m, 15H) ppm; 13C NMR (CDCl3):
d
20.6, 20.7, 55.5, 55.6,
0.50 (EtOAc); 1H NMR (CDCl3):
d
0.88 (t, 3H, J ¼ 6.9 Hz), 1.25 (s-like,
61.1, 66.6, 68.9, 69.7, 70.3, 70.7, 73.4, 74.5, 75.6, 77.6, 78.5, 79.8, 81.9,
93.5, 98.0, 101.4, 127.6, 127.82, 127.84, 127.90, 127.93, 128.1, 128.35,
22H), 1.62 (m, 2H), 2.02 (s, 3H), 2.074 (s, 3H), 2.077 (s, 3H), 2.93 (dd,
1H, J ¼ 8.2, 9.7 Hz), 3.51 (dt, 1H, J ¼ 9.5, 7.0 Hz), 3.68 (ddd, 1H,
J ¼ 2.4, 4.9, 9.6 Hz), 3.90 (dt, 1H, J ¼ 9.5, 6.7 Hz), 4.11 (dd, 1H, J ¼ 2.4,
12.2 Hz), 4.24 (d, 1H, J ¼ 8.0 Hz), 4.29 (dd, 1H, J ¼ 4.9, 12.2 Hz), 4.98
(t, 1H, J ¼ 9.3 Hz), 5.01 (t, 1H, J ¼ 9.3 Hz) ppm.
128.44, 138.0, 138.4, 138.6, 170.0, 170.4, 170.9 ppm; MS (ESI): m/z
35
calcd for C
H
42 50
Cl3NO16S 961.19; found (%) 984.18 ([M(35Cl3)þNa]þ,
100), 986.17 ([M(35Cl2þ37Cl)þNa]þ, 95), 988.17 ([M(35Clþ37Cl2)þ
Na]þ, 32).
To a solution of the amine 25 in CH2Cl2 (1 mL) at 5 ꢀC was added
benzoyl chloride (17 mg, 0.12 mmol) in CH2Cl2 (0.2 mL) followed by
Et3N (25 mg, 0.25 mmol). The reaction mixture was stirred at 5 ꢀC
for 1 h, and then diluted with EtOAc (10 mL) and aq. NaHCO3 (5 mL),
and the layers were separated. The organic layer was washed with
aq. NaCl, and the combined aqueous layers were extracted with
EtOAc. The combined organic extracts were dried (Na2SO4) and
concentrated to give a residue, which was purified by silica gel
chromatography eluting with hexane-EtOAc (3:2) to give 26
(31 mg, 85%) as a colorless solid: m.p. 172e174 ꢀC; Rf 0.30 (3:2
4.4.14. Cholest-5-en-3
trichloroethoxysulfonyl)amido-
b
-yl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
-D-galactopyranoside (19b)
b
Obtained in 56% yield as a colorless solid: Rf 0.30 (3:1 hexane/
EtOAc); [
a
]
[25] ꢁ32.0 (c 2.0, CHCl3); 1H NMR (CDCl3):
d 0.67 (s,
D
3H), 0.86 (d, 3H, J ¼ 6.6 Hz), 0.87 (d, 3H, J ¼ 6.6 Hz), 0.91 (d, 3H,
J ¼ 6.4 Hz),1.00 (s, 3H), 0.90e2.05 (m, 26H), 2.05 (s, 3H), 2.10 (s, 3H),
2.17 (s, 3H), 2.33 (m, 1H), 2.39 (ddd, 1H, J ¼ 2.1, 4.8, 13.1 Hz), 3.62 (tt,
1H, J ¼ 4.7, 11.4 Hz), 3.74 (dt, 1H, J ¼ 11.1, 8.5 Hz), 3.90 (t, 1H,
J ¼ 7.0 Hz), 4.10 (dd, 1H, J ¼ 7.0, 11.2 Hz), 4.19 (dd, 1H, J ¼ 6.6,
11.2 Hz), 4.57 (d, 1H, J ¼ 8.2 Hz), 4.73 (s, 2H), 5.01 (dd, 1H, J ¼ 2.4,
8.8 Hz), 5.05 (dd, 1H, J ¼ 3.5, 11.0 Hz), 5.37 (d, 1H, J ¼ 3.5 Hz) ppm;
hexane/EtOAc); [
a
]
[25] þ5.8 (c 0.6, CHCl3); 1H NMR (CDCl3):
D
d
0.88 (t, 3H, J ¼ 7.0 Hz), 1.05e1.35 (m, 22H), 1.52 (m, 2H), 1.99 (s,
3H), 2.04 (s, 3H), 2.10 (s, 3H), 3.47 (dt, 1H, J ¼ 9.7, 6.8 Hz), 3.76 (ddd,
1H, J ¼ 2.5, 4.8, 9.9 Hz), 3.88 (dt, 1H, J ¼ 9.6, 6.3 Hz), 4.10 (q, 1H,
J ¼ 9.2 Hz), 4.17 (dd, 1H, J ¼ 2.4, 12.2 Hz), 4.30 (dd, 1H, J ¼ 4.8,
12.2 Hz), 4.78 (d, 1H, J ¼ 8.3 Hz), 5.15 (t, 1H, J ¼ 9.6 Hz), 5.46 (dd, 1H,
J ¼ 9.6,10.4 Hz), 6.22 (m,1H), 7.41 (m, 2H), 7.50 (m,1H), 7.70 (m, 2H)
13C NMR (CDCl3):
d 11.8,18.7,19.3, 20.68, 20.71, 20.9, 21.0, 22.5, 22.8,
23.8, 24.3, 28.0, 28.2, 29.6, 31.8, 31.9, 35.8, 36.2, 36.7, 37.2, 38.5, 39.5,
39.7, 42.3, 50.1, 56.1, 56.7, 61.3, 66.9, 70.7, 70.9, 78.7, 79.7, 93.4, 99.2,
122.5, 139.9, 170.2, 170.4, 171.2 ppm; MS (ESI): m/z calcd for
ppm; 13C NMR (CDCl3):
d 14.1, 20.63, 20.65, 20.74, 22.6, 25.8, 29.31,
35
C
H
Cl3NO11S 883.33; found (%) 906.33 ([M(35Cl3)þNa]þ, 94),
41 64
29.40, 29.49, 29.53, 29.60, 29.65, 31.9, 55.0, 62.2, 68.7, 70.0, 71.9,
72.4, 101.0, 126.9 (2C), 128.6 (2C), 131.6, 134.2, 167.5, 169.4, 170.7,
171.1 ppm; Anal. Calcd for C33H51NO9: C, 65.43; H, 8.49; N, 2.31.
Found: C, 65.15; H, 8.29; N, 2.07.
908.25 ([M(35Cl2þ37Cl)þNa]þ, 100), 910.30 ([M(35Clþ37Cl2)þNa]þ,
34).
4.5. Conversions of N-Tces group
4.5.3. Tetradecyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-b-D-
4.5.1. Tetradecyl 3,4,6-tri-O-acetyl-2-deoxy-2-sulfoamino-
b
-D-
glucopyranoside (27)
glucopyranoside (24)
To a mixture of 10a (43 mg, 0.06 mmol) and powdered anhy-
drous CuSO4 (5 mg, 0.03 mmol) in tetrahydrofuran (1 mL) was
added acetic acid (0.1 mL) and acetic anhydride (0.1 mL). Zinc dust
(42 mg, 0.6 mmol) was added in 2 portions for 10 min, and the
resulting dark-grey suspension was stirred at rt for 3 h. The reaction
mixture was filtered and washed with EtOAc, and the combined
filtrates were mixed with H2O, and the layers were separated. The
organic layer was washed with aq. NaCl, and the combined aqueous
layers were extracted with EtOAc. The combined organic extracts
were dried (Na2SO4) and concentrated to give a residue, which was
purified by silica gel chromatography eluting with hexane-EtOAc
To a mixture of 10a (66 mg, 0.092 mmol) and acetic acid (60 mg,
1.0 mmol) in methanol (1.5 mL) was added zinc (35 mg, 0.5 mmol),
and the resulting dark-grey suspension was stirred at 5 ꢀC for
30 min. The reaction mixture was diluted with CH2Cl2 (5 mL),
filtered and washed with CH2Cl2-methanol (10:1). The combined
filtrates were concentrated and co-evaporated with heptane (1 mL)
to give a residue, which was purified by silica gel chromatography
eluting with CH2Cl2-methanol (7 / 6) to give 24 (50 mg, 93%) as a
colorless solid: m.p. 138e140 ꢀC; Rf 0.30 (6:1 CH2Cl2/MeOH); [
a]
D
[25] þ7.7 (c 1.1, CHCl3); 1H NMR (CD3OD-CDCl3):
d 0.88 (t, 3H,
J ¼ 6.7 Hz), 1.26 (s-like, 20H), 1.34 (m, 2H), 1.64 (m, 2H), 2.03 (s, 3H),
2.07 (s, 3H), 2.08 (s, 3H), 3.36 (t, 1H, J ¼ 9.8 Hz), 3.63 (dt, 1H, J ¼ 9.3,
7.2 Hz), 3.75 (ddd, 1H, J ¼ 2.3, 4.8, 9.7 Hz), 3.85 (dt, 1H, J ¼ 9.0,
7.3 Hz), 4.13 (dd, 1H, J ¼ 2.3, 12.2 Hz), 4.27 (dd, 1H, J ¼ 4.8, 12.2 Hz),
4.57 (d, 1H, J ¼ 8.0 Hz), 4.99 (dd, 1H, J ¼ 9.3, 9.7 Hz), 5.24 (t, 1H,
(1:2) to give 27 (26 mg, 80%) as
126e129 ꢀC; Rf 0.30 (1:2 hexane/EtOAc); [
CHCl3); 1H NMR (CDCl3):
a
colorless solid: m.p.
a]
[25] ꢁ6.3 (c 1.0,
D
d
0.88 (t, 3H, J ¼ 6.9 Hz), 1.25 (s-like, 22H),
1.57 (m, 2H), 1.95 (s, 3H), 2.03 (s, 3H), 2.04 (s, 3H), 2.09 (s, 3H), 3.47
(dt, 1H, J ¼ 9.6, 6.9 Hz), 3.71 (ddd, 1H, J ¼ 2.5, 4.7, 10.0 Hz), 3.82 (dt,
1H, J ¼ 10.4, 8.5 Hz), 3.86 (dt,1H, J ¼ 9.6, 6.8 Hz), 4.13 (dd,1H, J ¼ 2.3,
12.3 Hz), 4.27 (dd, 1H, J ¼ 4.7, 12.3 Hz), 4.69 (d, 1H, J ¼ 8.2 Hz), 5.07
(t, 1H, J ¼ 9.6 Hz), 5.32 (dd, 1H, J ¼ 9.4, 10.5 Hz), 5.64 (d, 1H,
J ¼ 9.3, 9.8 Hz) ppm; 13C NMR (CDCl3):
d 14.1, 20.60, 20.66, 21.3,
22.6, 25.8, 29.35, 29.53, 29.61, 29.67, 29.74, 29.77, 29.80, 29.84, 31.9,
58.2, 62.5, 69.1, 70.4, 71.3, 74.2, 101.0, 169.5, 170.6, 171.5 ppm; Anal.
Calcd for C26H47NO11S: C, 53.68; H, 8.14; N, 2.41; S, 5.51. Found: C,
53.50; H, 8.25; N, 2.53.
J ¼ 8.5 Hz) ppm; 13C NMR (CDCl3):
d 14.1, 20.6, 20.7, 20.8, 22.7, 25.8,
29.34, 29.36, 29.49, 29.58, 29.64, 31.9, 59.0, 62.0, 68.4, 70.6, 71.8,

130
T. Murakami et al. / Carbohydrate Research 434 (2016) 121e131
72.8, 78.7, 93.4, 100.8, 169.3, 170.7, 171.6 ppm; Anal. Calcd for
28H49NO9: C, 61.86; H, 9.08; N, 2.58. Found: C, 61.50; H, 8.95; N,
(compound16c.mol).
C
2.53.
Appendix A. Supplementary data
4.5.4. 12-Acetylthiododecyl 3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.carres.2016.09.
001. These data include MOL files and InChiKeys of the most
important compounds described in this article.
acetyl-
trichloroethoxysulfonyl)amido-
To a solution of the lactoside 7c (105 mg, 0.10 mmol) in DMF
(1 mL) at
ꢀC was added potassium thioacetate (36 mg,
b-D-galactopyranosyl)-2-deoxy-2-(2,2,2-
b-D-glucopyranoside (28)
5
0.30 mmol). The reaction mixture was stirred at 5 ꢀC for 0.5 h, and
then at rt for 3 h. The mixture was diluted with hexane-EtOAc (1:1,
10 mL) and H2O (5 mL), and the layers were separated. The organic
layer was washed with aq. NaCl, and the combined aqueous layers
were extracted with hexane-EtOAc (1:1). The combined organic
extracts were dried (Na2SO4) and concentrated to give a brown
residue, which was purified by silica gel chromatography eluting
with hexane-EtOAc (3:2 to 1:1) to give 27 (98 mg, 93%) as a
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[25] ꢁ13.2 (c 1.7,
D
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3H), 2.07 (s, 3H), 2.12 (s, 3H), 2.155 (s, 3H), 2.160 (s, 3H), 2.32 (s, 3H),
2.86 (t, 2H, J ¼ 7.4 Hz), 3.53 (dt, 1H, J ¼ 9.5, 7.0 Hz), 3.55 (q, 1H,
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3.83 (dt,1H, J ¼ 9.5, 7.2 Hz), 3.90 (dt,1H, J ¼ 0.8, 6.8 Hz), 4.10 (dd,1H,
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1H, J ¼ 7.4 Hz), 4.48 (dd, 1H, J ¼ 2.9, 11.9 Hz), 4.50 (d, 1H, J ¼ 7.8 Hz),
4.69 (d, 1H, J ¼ 10.9 Hz), 4.72 (d, 1H, J ¼ 10.9 Hz), 4.99 (dd, 1H,
J ¼ 3.4, 10.4 Hz), 5.08 (dd, 1H, J ¼ 8.2, 9.1 Hz), 5.11 (dd, 1H, J ¼ 7.8,
10.4 Hz), 5.37 (dd, 1H, J ¼ 0.7, 3.3 Hz), 5.50 (d, 1H, J ¼ 9.0 Hz) ppm.
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acetyl-b-D-galactopyranosyl)-2-acetamido-2-deoxy-b-D-
glucopyranoside (29)
To a mixture of 28 (78 mg, 0.074 mmol) and powdered anhy-
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added acetic acid (0.1 mL) and acetic anhydride (0.1 mL). Zinc dust
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mixture was filtered and washed with EtOAc, and the combined
filtrates were mixed with H2O, and the layers were separated. The
organic layer was washed with aq. NaCl, and the combined aqueous
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114e117 ꢀC; Rf 0.24 (1:2 hexane/EtOAc); [
CHCl3); 1H NMR (CDCl3):
1.25 (s-like, 12H), 1.34 (m, 4H), 1.56 (m,
a
colorless solid: m.p.
a]
[25] ꢁ16.9 (c 1.0,
D
d
4H), 1.96 (s, 3H), 1.97 (s, 3H), 2.06 (s, 6H), 2.07 (s, 3H), 2.11 (s, 3H),
2.15 (s, 3H), 2.32 (s, 3H), 2.86 (t, 2H, J ¼ 7.4 Hz), 3.41 (dt, 1H, J ¼ 9.5,
6.8 Hz), 3.62 (ddd, 1H, J ¼ 3.0, 5.2, 8.5 Hz), 3.78 (t, 1H, J ¼ 8.2 Hz),
3.81 (dt,1H, J ¼ 9.5, 6.8 Hz), 3.88 (dt,1H, J ¼ 0.8, 6.9 Hz), 4.02 (dt,1H,
J ¼ 7.5, 9.4 Hz), 4.09 (dd, 1H, J ¼ 7.4, 11.2 Hz), 4.13 (dd, 1H, J ¼ 5.3,
11.9 Hz), 4.14 (dd, 1H, J ¼ 6.4, 11.2 Hz), 4.44 (d, 1H, J ¼ 7.5 Hz), 4.49
(dd, 1H, J ¼ 2.9, 11.9 Hz), 4.50 (d, 1H, J ¼ 8.0 Hz), 4.98 (dd, 1H, J ¼ 3.4,
10.5 Hz), 5.08 (dd, 1H, J ¼ 8.2, 9.4 Hz), 5.12 (dd, 1H, J ¼ 7.9, 10.5 Hz),
5.36 (dd, 1H, J ¼ 0.6, 3.3 Hz), 5.62 (d, 1H, J ¼ 9.3 Hz) ppm; 13C NMR
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29.37, 29.42, 29.47, 30.5, 53.1, 60.7, 62.3, 66.5, 69.0, 69.6, 70.6, 70.7,
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Key compounds in this article (Chemical compound viewer)
Compound 7b (compound7b.mol), 10a (compound10a.mol), 16c

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