A flexible 1,2-cis α-glycosylation strategy based on in situ adduct transformation

Article abstract of DOI:10.1039/c7ob00839b

A flexible 1,2-cis α-selective glycosylation strategy for a wide range of glycosyl donors and acceptors has been developed, which is based on an in situ adduct transformation protocol. Based on this strategy, both NFM-derived and iodide covalent adducts c

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Flexible 1,2-cis α-Glycosylation Strategy Based on in situ
Adduct Transformation
Cite this: DOI: 10.1039/x0xx00000x
Jhe-Cyuan Hu,a Ai-Fen Wendy Feng,a Bo-Yao Chang,a Chun-Hung Lin,*,b and
Kwok-Kong Tony Mong*a
Received 00th January 2012,
Accepted 00th January 2012
A flexible 1,2-cis α-selective glycosylation strategy for a wide range of glycosyl donors and
acceptors was developed, which features an in situ adduct transformation protocol. Based on this
strategy, both NFM-derived and iodide covalent adducts can be accessed for glycosylation. With
the low temperature NMR spectroscopy, the aforementioned glycosyl adducts were detected.
DOI: 10.1039/x0xx00000x
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which can be coupled with an acceptor to form a glycosylation
product.18,19 Among the formamide additives, NFM is the most
1 Introduction
Most efforts toward the chemical synthesis of oligosaccharides
are devoted to protecting group manipulation, which is
performed to control regio- and stereochemistry during
glycosidic bond formation.1,2 The typical strategy used for this
type of stereochemical control relies on a specialized protecting
group that acts to direct the attack of the acceptor along a specific
route.3,4 Unfortunately, the introduction and removal of the
specialized protecting group often demand additional steps,
leading to a lengthy synthetic process. Thus, a simple, more step-
economical approach to synthesizing oligosaccharides would be
greatly beneficial such as the one-pot regioselective protection
of sugars5,6 and one-pot oligosaccharide synthesis.7-9
The use a nucleophile additive as the stereo-directing agent
during glycosylation is step-economical, whereby no additional
protecting group manipulation is required and the additive can
be easily removed after the reaction.10 Lemieux explored the use
of tetra-butylammonium bromide (TBAB)11 to effect 1,2-cis α-
glycosidic bond formation. This seminal work sparked the
development of other additives for glycosylation, including
tetrabutyl ammonium iodide (TBAI),12,13 lithium iodide (LiI),14
dimethylacetamide (DMA),15 phosphine oxides (R3P=O),16
thioethers (RSRʹ),17 dimethylformamide (DMF),18 and N-
formylmorpholine (NFM).19 However, the nucleophile-
modulated glycosylation generally suffers from a limited scope
of application as the coupling efficiency depends heavily on the
structure of the substrate. Because carbohydrates are structurally
diverse compounds, a general 1,2-cis α-glycosylation strategy
that is wholely based on the use of external agents is desirable
and necessary.
reactive in glycosylation and it can be used for less reactive 2-
azido-2-deoxyglycosyl donors. However, the α-selectivity of the
NFM imidinium ion formed from the NFM additive is practical
for less reactive acceptors, but is modest for more reactive
primary acceptors.19 In term of reactivity and selectivity, the
NFM imidinium adduct is complementary to the glycosyl iodide.
Base on such perception, we speculate that the reactive NFM
imidinium adduct may be substituted with an iodide nucleophile
to furnish a presumably more selective iodide donor. As such,
the selectivity of the glycosyl adducts can be improved by simply
in situ adduct transformation. The key to this strategy is finding
suitable sets of conditions for substitution of NFM derived
adduct with iodide nucleophile and subsequent glycosylation
(Scheme 1). An advantage of the proposed method is that it can
be modified according to the reactivity of the acceptor. For less
reactive acceptors, the in situ substitution can be skipped and the
more reactive NFM imidinium adduct is deployed for
glycosylation.
In previous studies, we found that glycosyl oxacarbenium
ions can be trapped by formamide nucleophiles such as DMF and
diisopropylformamide to form a glycosyl imidinium adduct,
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Figure
glycosylation.
1 Working concept of in situ transformation of glycosyl adduct in
In the absence of TBAI and DTBP, the glycosylation of
3
with produced a 1.5:1 α:β ratio of , but in the presence of 2.0
1
5
equiv. of TBAI and DTBP, the α:β ratio was improved to 5:1
(Entries 1 vs. 2). Increased α-selectivity (ca 12:1 α:β ratio) was
achieved by using 5.0 or 10.0 equiv. of TBAI (Entries 3 and 4).
Interestingly, addition of 4.0 equiv. of NFM eroded the α-
selectivity of the glycosylation, indicating the need of excessive
amount of TBAI (Entry 5). In addition to NFM, DMF (2 equiv.)
was also used for the glycosylation study, but the reaction was
sluggish with a moderate α-selectivity (Entries 2 vs 6). In
consideration of the α-selectivity and the yield of reaction, 2.0
equiv. of NFM and 5.0 equiv. of TBAI (with respect to the donor)
would be used in subsequent glycosylations.
2 Results and discussion
2.1 Optimization of Conditions for in situ Adduct
Transformation
To elucidate the optimal conditions for one-pot in situ adduct
transformation and glycosylation, thioglucosides
used as donors for the reaction along with acceptors
(Table 1). TBAI was used as the iodide additive because TBAI
is used as the iodide additive because it is readily available and
has widely been used in preparation of glycosyl iodide.12a-d First,
1
and
2
and
were
3
4
1.0 equiv. of thioglucoside 1 and 2.0 equiv. of NFM were treated
Next, we examined the effect of temperature (Entries 79).
with 1.5 equiv. of N-iodosuccinimide (NIS) and 1.0 equiv. of
trimethylsilyltrifluoromethane sulfonate (TMSOTf) at 0 ºC.20
After the formation of the NFM imidinium adduct (ca 1.0 h),
TBAI was added to substitute the NFM leaving group of the
NFM imidinium adduct (Entries 24). The substitution reaction
was monitored by TLC. Then, 2.0 equiv. of di-tert-
Since the sn-glycerol acceptor
racemization at a higher reaction temperature (≥ 50
therefore glycosyl acceptor and perbenzyl thioglucoside donor
were used. At either 15 ºC or 30 ºC, the α-selectivity of the
glycosylation of with was excellent, but the yield of the
reaction was lower at 15 ºC (Entry 7). Higher reaction
temperature (50 ºC) was detrimental to present glycosylation
protocol (Entry 9).21
Addition of the base is necessary in our method as indicated
by the erosion of α-selectivity (α:β 5:1) without the base addition
(Entry 10). Common organic bases such as diisopropylethyl
amine (DIEA) and lutidine were effective in addition to DTBP
(Entries 11 and 12). Amidine base such as diazabicyclo-[5.4.0]-
undec-7-ene (DBU) spoiled the glycosylation, but the reason is
3
was found to undergo
°
C),
4
2
4
2
butylmethylpyridine (DTBP) and 1.5 equiv. of acceptor
3 were
added, and the reaction temperature was raised to 30 ºC to initiate
the coupling reaction. For comparison, the glycosylation was
also performed in the absence of TBAI and DTBP.
Table 1. Elucidation conditions for the in situ adduct transformation.
unclear (Entry 13). For comparison, the glycosylation of
4 with
2
was repeated in the absence of (i) NFM (Entry 14), (ii) in the
absence of TBAI and lutidine (Entry 15), or (iii) in the absence
of NFM, TBAI and base (Entry 16). Under the conditions of
entries 14 and 15, no glycosylation product was produced. In the
absence of any additive and base (i.e. entry 16), the glycosylation
product was found but with no α-selectivity.
Entry
Donor,
acceptor
Formamide
and TBAI
(equiv)
Base
a
T
̊
Product 5 or 6
Yield
(%)
α:βb
1
2
3
4
1, 3
1, 3
1, 3
1, 3
NFM (2), 0
NFM (2), 2
NFM (2), 5
NFM (2),
-
0
5, 75
5, 44
5, 60
5, 48
1.5:1
5:1
11:1
13:1
A
A
A
30
30
30
10
5
6
7
8
1, 3
1, 3
2, 4
2, 4
2, 4
2, 4
2, 4
2, 4
2, 4
2, 4
2, 4
2, 4
NFM (4), 5
DMF (2), 5
NFM (2), 5
NFM (2), 5
NFM (2), 5
NFM (2), 5
NFM (2), 5
NFM (2), 5
NFM (2), 5
NFM (0), 5
NFM (2), 0
NFM (0), 0
A
A
A
A
A
-
B
C
D
B
A
-
30
30
15
30
50c
30
30
30
30
30
0
5, 63
5, 40
6, 47
6, 55
6, 23
6, 66
6, 76
6, 76
-
6:1
4:1
>19:1
>19:1
3:1
5:1
>19:1
>19:1
-
9
10
11
12
13
14
15
16
-
-
-
-
1:1
d
0
6, 75
a Base used in present study: A = DTBP, B = lutidine, C = DIEA, and D =
DBU. b Ratio of α- and β-isomers was estimated from HPLC analysis or
NMR spectroscopy. c 1,2-Dichloroethane (C2H4Cl2) was used as solvent. d
Only α-glucosyl formate, the hydrolysed product of the NFM imidinium
adduct, was produced.
Figure 2. Representative 1H NMR spectra (500 MHz) for samples taken after the
activation of donor
TBAI (b)
2
in the presence of NFM (a) and after the substitution with
.
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Having established the one-pot in situ adduct transformation method (Table 2). In the beginning, per-O-benzyl protected
and glycosylation, we applied the low temperature NMR thioglycoside donors
spectroscopy to detect the glycosylation adducts. To this end, thioglucoside donors
2
,
13
10 11
15-18. The glycosylation of rhamnosyl acceptor 16
TMSOTf in the presence of NFM, followed by the iodide diosgenin 17, and thioglucosyl acceptor 18 with thioglucoside
substitution at 0 ºC. At different time points, an aliquot of the donor produced the desired products 19 20, and 21 at practical
70% yields.
,
14 and orthogonally protected
9
,
,
,
12 were coupled with various
thioglucoside
2
in CDCl3 solution was activated by NIS and acceptors
4
,
,
2
,
reaction mixture was taken for NMR analysis (Figure 2).
For the samples taken following the activation of donor
60%‒
2
, α-
Table 2. Scope of application for non-amino thioglycoside donors 2, 912.
glucosyl NFM imidinium
7 was observed as the major
intermediate. The identity of this intermediate is supported by
the observed chemical shifts (δ) of the proton signals at 6.45 and
9.02 ppm, respectively, which correspond to the anomeric and
imidinum protons of
7
(Figure 2a).18 In the samples taken after
the substitution reaction, these anomeric and imidinum proton
signals were diminished, and a new downfield signal appeared at
6.79 ppm with a corresponding 13C signal at 80.6 ppm (see 1D
13C, 2D-COSY, and 2D-HSQC NMR spectra). In the literature,
1
similar signals have been identified as the anomeric H and 13C
signals of α-glucosyl iodide
revealed a tiny proton signal at 5.95 ppm with a JH-H value of
8.0 Hz, which is likely to be the anomeric H signal of the β-
iodide.23
8
(Figure 2b).22 Closer examination
3
1
From above NMR studies, we propose the reaction
mechanism to account for the α-selectivity obtained in
glycosylation (Scheme 1). The thioglycoside donor is first
activated by the NIS to give the glycosyl oxacarbenium ion,
which is reacted with NFM additive to form a mixture α- and β-
imidinium adducts. Thermodynamically, the α-imidinium adduct
is more stable than its β-counterpart, but the β-imidinium is more
reactive in glycosylation. When TBAI is added, the iodide
nucleophile attacks the β-imidinium adduct via a SN2-like
mechanism forming the α-glycosyl iodide as the major pathway.
Trace amount of the β-iodide anomer detected may be formed
through a minor SN1 reaction pathway and or through
equilibrium with the α-iodide counterpart. Subsequent coupling
of the β-iodide with an alcohol acceptor affords the α-
glycosylation product.
Entry
Donor,
acceptor
2, 16
2, 17
2, 18
9, 15
9, 15
9, 4
10, 4
11, 4
12, 4
13, 4
13, 15
14, 15
Base
Product
no
19
20
21
22
22
23
24
25
26
27
28
Yield (%)
α:β
1
2
3
4
5
6
7
8
9
DIEA
70
60
68
34
70
70
60
19:1a
14:1a
9:1a
lutidine
lutidine
DIEA
lutidine
lutidine
lutidine
lutidine
lutidine
DIEA
>19:1a
>19:1a
>19:1a
>19:1b
>19:1a
10:1b
>19:1a
13:1a
5:1b
65
60
69
65
77
10
11
12
lutidine
lutidine
29
a α:β Anomer ratio was determined by HPLC analysis. b α:β Anomer ratio
was determined by NMR analysis.
Scheme 1 Proposed mechanism for one-pot in situ adduct transformation and
glycosylation.
with good to excellent α:β ratios (Entries 1-3). For glycosylation
of 15 with 6-O-acetyl (Ac)-protected thioglucosyl donor
9,
2.2 Scope of Application to Thioglycosyl Donors
DIEA was initially used as the base, but the yield of the product
With the one-pot in situ adduct transformation and glycosylation
protocol established, we next explored the substrate scope of this
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15 was modest (34%) (Entry 4). Nonetheless, when lutidine was and 41 were produced as a single anomer at 76% and 70% yield,
used, the yield of 15 was improved to 70% (Entry 5). respectively.
Next, we examined the glycosylation of with orthogonally As mentioned earlier, the in situ adduct transformation and
protected donors including 6-O-acetyl (Ac) thioglucoside , 6- glycosylation protocol can be modified in accordance with the
4
9
O-benzoyl (Bz) thioglucoside 10, 6-O-tert-butyldiphenylsilyl reactivity of the glycosyl acceptor. For illustration, the hindered
(TBDP) thioglucoside 11, and 4-O-Ac thioglucoside 12 (Entries secondary glucosyl and mannosyl acceptors 42 and 44 were
69). It should be noted that glycosyl donors containing either employed for glycosylation with
2 (Scheme 2). When the
an electron-withdrawing (Ac or Bz) or sterically bulky (TBDP) unmodified in situ adduct transformation and glycosylation
protecting group have been shown be less reactive. For example, protocol was used to couple the hindered glucosyl acceptor 42
the glycosylation of acetonide protected sn-glycerol acceptor with
2, the reaction was sluggish and the yield of the
with 6-O-Ac glucosyl iodide required 6 days for completion.24
A
glycosylation was poor (Scheme 2a). To improve the conditions,
higher temperature25 or microwave irradiation26 was required to
Table 3. Scope of application for azido thioglycoside donors 2628.
accelerate the reaction.
Our protocol was effective for the glycosylation of acceptor
4
with protected thioglycosides
disaccharides 23 24 25, and 26 were obtained in satisfactory
60%70% yields with high α-selectivity (Entries 6 9). It should
be noted that during the glycosylation with donors 10 and 12
small amounts (~5%10%) of glycosyl chlorides 10 and 12
9, 10, 11, and 12, and the desired
,
,
‒
,


were detected (see inset) that were inseparable from their iodide
counterparts. The identities of the chloride intermediates 10 and
12 were tentatively inferred from the mass spectrometry of the


crude reaction mixtures. Such chloride byproducts have been
reported in previous studies and was presumably derived from
the solvent, i.e. CH2Cl2.12a For thiogalactoside donor 13, the in
situ prepared galactosyl iodide was not detectable during TLC
examination due to the instability of the galactosyl iodide
(Entries 10 and 11). For thioxylopyranosyl donor 14, significant
stereocontrol was obtained regardless of the lack of a substituent
at C5 (Entry 12).27
2-Azido-2-deoxythioglycosides are common building blocks
for construction of 2-acetamido-2-deoxy-α-glycosides and
related oligosaccharide structures.28,29 Therefore, it is practical to
investigate the suitability of the present glycosylation protocol
with 2-azido-2-deoxythioglycoside donors (Table 3). Thus,
Entry
Donor,
acceptor
(equiv.)
Base
(equiv.)
TBAI
(equiv.)
Product
no., %
glucosyl acceptor
4 and cholesterol 33 were coupled with 2-
α:β
azido-2-deoxythiogalactoside 30. These reactions formed the
desired products 35 and 36 at 65% and 60% yields, respectively,
with high α:β ratios of >14:1 (Table 3, entries 1 and 2).
1
2
3
4
5
6
7
30, 4 (1, 1.5)
DTBP
(2.0)
5.0
35, 65
36, 60
37, 62
38, 84
39, 58
40, 76
41, 70
>19:1a
>19:1a
9:1a,b
30, 33 (1, 1.5) DTBP
5.0
For the less reactive 2-azido-2-deoxythioglucoside donor 31
,
(2.0)
lutidine
(4.0)
lutidine
(4.0)
lutidine
(4.0)
2.0 equiv. of the donor was used to couple with 1.0 equiv. of the
acceptor. The stoichiometric amounts of NFM and TBAI used
were 4 and 10 equiv., respectively. The glycosylation of
31, 4 (2, 1)
31, 15 (2, 1)
31, 33 (2, 1)
10.0
10.0
10.0
5.0
15:1a,b
>19:1a,b
α onlyc
α onlyc
acceptors
expected products 37
4
,
15, and 33 with the azido donor 31 produced the
38, and 39, respectively, in 58-84% yields
,
32, 15 (1, 1.5) lutidine
with practical α-selectivity (Table 3, Entries 3-5).
(2.0)
32, 34 (1, 1.5) lutidine
(2.0)
In addition to 2-azido-2-deoxythioglycosides 30 and 31, we
applied the glycosylation protocol to 4-azido-4,6-dideoxy
thiogalactoside 32. Thioglycoside 32 can serve as a building
block for the synthesis of 4-amino-4-deoxy-D-fucoside (Fuc4N),
which is present in the cell wall of Mycobacterium marinum and
various plants.30 The galactosyl acceptor 15 and 2-deoxy
glycosyl acceptor 34 were coupled with the 4-azido donor 32
using the one-pot in situ adduct transformation and glycosylation
protocol (Entries 6 and 7).31 As expected, the disaccharides 40
5.0
a
α:β Anomer ratio was determined by HPLC analysis with α-anomer as
b
standard. 10.0 equiv of TBAI, 3.0 equiv of NIS, and 2.6 equiv of TMSOTf,
were used (see the procedure in SI). cα:β Anomer ratio was determined by
NMR spectroscopy.
, the iodide substitution step of the original protocol was skipped
and the glucosyl NFM adduct could be used directly for coupling
with the acceptor 42. By optimizing the amount of NFM to 4
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equiv., the glycosylation of 42 with
at a 70% yield and α:β ratio of 16:1 (Scheme 2b). Using the same
2 produced disaccharide 43
3. Conclusion
In summary, a flexible glycosylation strategy was developed
for the construction of 1,2-cis α-glycosidic bonds utilizing the
theory underlying in situ transformation of glycosyl imidinium
adduct to glycosyl iodide. The protocol is effective for reactive
hydroxyl acceptors, and can also be modified for reactions with
hindered acceptors. Further NMR studies were performed to
confirm the presence of the glycosyl adducts.
modified protocol and 8.0 equiv. of NFM additive, the
glycosylation of secondary mannosyl acceptor 44 with
2 formed
disaccharide 45 at a practical 60% yield with excellent α-
selectivity (Scheme 2b).
Scheme 3. Synthesis of trisaccharide 48 from perbenzyl protected glucosyl
building blocks
bonds.
2, 4, and 12 with hindered and unhindered 1,2-cis α-glycosidic
Scheme 2. a) Glycosylation of less reactive acceptor 42 with one-pot in situ adduct
transformation and glycosylation protocol. b) Glycosylation of the less reactive
acceptors 42 and 44 using the imidinium adduct
4. Experimental
2.3 Application to Oligosaccharide Synthesis
4.1 One-pot in situ adduct transformation and glycosylation
protocol for thioglycoside donors (1, 2, 9-14, 30, and 32).
Thioglycoside donor (1.0 equiv), N-formylmorpholine (2.0
equiv), and activated 4Å molecular sieve (MS) were added to
dried CH2Cl2 such that final concentration of the donor was 50
mM. Resulting mixture was stirred at room temperature for 10
The utility of the present in situ adduct transformation and
glycosylation protocol was demonstrated by the synthesis of the
trisaccharide compound 48. As the target contains both a
hindered α-(14) and an unhindered α-(16)-glycosidic bond,
it should be constructed via the joined use of glycosyl NFM and
iodide adducts (Scheme 3). Thus, the glycosylation of the methyl
min and at 0 °C (for 1, 2, 9-13, 30) or at -20 °C (for 14, 32) for
additional 20-30 min. Subsequently, NIS (1.5 equiv.) and
TMSOTf (1.0 equiv.) were added, and the reaction progress was
monitored by TLC. Upon the complete formation of the NFM
imidinium ion (by TLC examination), TBAI (5.0 equiv.) was
added. The mixture was stirred at 0 °C for 0.5 to 2 h. Glycosyl
glucosyl acceptor 4 with the thioglucosyl donor 12 using the one-
pot in situ adduct transformation and glycosylation protocol
produced the α-(16)-linked disaccharide 26 at a 60% isolated
yield and a high 12:1 α:β ratio (Scheme 3a).
Removal of the acetyl group of 26 produced a hindered
disaccharide acceptor 46. As 46 was a secondary acceptor, the
iodide substitution step in the one-pot adduct transformation and
glycosylation protocol was skipped and the glucosyl imidinium
iodides from donors
1
,
2
,
9
-
12 were detectable by TLC, but
glycosyl iodides from 13
,
14, 30 and 32 were not detectable.
After 0.5 - 2 h, an acceptor (1.5 equiv.) and a base (DTBP, DIEA,
or lutidine) (2.0 equiv.) were added to the reaction mixture. The
reaction temperature was then raised to 30 °C and the resulting
mixture was continuously stirred for ~ 18 - 24 h (for 14, a lower
15 ºC was applied), followed by the addition of satd. NaHCO3
and Na2S2O3(s). The mixture was vigorously stirred until the red
color of the solution changed to the pale yellow. The mixture was
diluted with CH2Cl2, followed by filtration, and concentrated for
flash chromatography purification over silica gel to furnish the
glycosylation product.
adduct derived from the donor
2 and NFM could directly react
with the acceptor 46. As such, a fully protected trisaccharide 47
was produced in 60% yield as the sole anomer (Scheme 3b).
Global deprotection 47 to 48 was straightforward because only
benzyl ether protecting groups are present in 47 and they could
be removed cleanly by a single hydrogenolysis process.
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75.4, 74.9, 74.8, 73.3, 73.3, 72.3, 70.3, 70.2, 68.4, 66.0, 55.1
(OCH3).
4.2 One-pot in situ adduct transformation and glycosylation
procedure for 2-azido-2-deoxythioglucoside donor (31).
Mixture of 2-azido-2-deoxythioglucoside donor 31 (2.0 equiv.),
N-formylmorpholine (4.0 equiv.), and activated 4Å molecular
sieve (MS) was suspended in dried CH2Cl2 ([31] = 50 mM). Then,
the resulting mixture was stirred at room temperature for 10 min
and at 0 °C for an additional 20 min, followed by addition of NIS
(3.0 equiv.) and TMSOTf (2.6 equiv.). The formation of the
NFM imidinium ion intermediate was monitored by TLC. Upon
complete formation of the imidinium ion, TBAI (10.0 equiv.)
was added and the mixture was stirred ng mixture was stirred at
room temperature for 10 min and at 0 °C until the formation of
glycosyl iodide (detectable by TLC). At this stage, acceptor (1.0
equiv.) and lutidine (5.2 equiv.) were added and the reaction
temperature was raised to 30 °C. After 24 h reaction, satd.
NaHCO3 and Na2S2O3(s) were added to the mixture, followed by
vigorous stirring until the color of the solution changed from the
deep red to pale yellow. The resulting mixture was dried (over
MgSO4), filtered, and concentrated for flash chromatography
purification over silica gel to furnish the glycosylation product.
4.5 Methyl 2,3,4,6-Tetra-
4)-2,3- -isopropylidene-α-
Anomer of disaccharide 19 was (78 mg, 70%) synthesized from
glycosylation of -rhamnoside acceptor 16 (46 mg, 0.23 mmol)
with thioglucoside donor (100 mg, mmol) using the one-pot in
O
L
-benzyl-α-
D-glucopyranosyl-(1
O
-rhamnopyranoside (19).17 α-
L
2
situ adduct transformation and glycosylation procedure (Table 2,
entry 1 in main text). For α-anomer of 19, 1H NMR (600 MHz,
CDCl3): δ 7.36 – 7.23 (m, 18H, Ar-H), 7.19 – 7.15 (m, 2H, Ar-
H), 4.97 (d, J = 3.5 Hz, 1H, H-1), 4.95 (d, J = 10.1 Hz, 1H), 4.88
– 4.81 (m, 3H, including H-1), 4.79 (d, J = 11.6 Hz, 1H), 4.70 (d,
J = 11.7 Hz, 1H), 4.61 (d, J = 12.1 Hz, 1H), 4.53 (d, J = 10.7 Hz,
1H), 4.49 (d, J = 12.1 Hz, 1H), 4.12 – 4.08 (m, 1H), 4.08 – 4.04
(m, 2H), 3.98 (t, J = 9.4 Hz, 1H), 3.82 – 3.71 (m , 3H), 3.67 –
3.62 (m, 1H), 3.59 (dd, J = 9.8, 3.6 Hz, 1H), 3.33 (m, 4H), 1.43
(s, 3H, isopropylidene-CH3), 1.31 (d, J = 6.3 Hz, 3H, CH3), 1.25
(s, 3H, isopropylidene-CH3); 13C NMR (150 MHz, CDCl3): δ
138.8, 138.4, 138.0, 137.9, 128.4, 128.4, 128.3, 128.3, 128.2,
127.9, 127.9, 127.9, 127.8, 127.6, 127.6, 127.5, 108.9, 98.3 (C-
1, JCH = 167.9 Hz,), 97.8 (C-1, JCH = 167.4 Hz), 82.2, 80.9, 79.9,
77.9, 76.8, 75.9, 75.5, 75.1, 74.2, 73.5, 70.3, 68.0, 64.7, 54.6,
28.1, 26.3, 17.4; HRMS-ESI (m/z): [M + Na]+ calcd for
C44H52NaO10+, 763.3453; found 763.3450.
4.3
glucopyranosyl]-1,2-
Glucopyranoside
glycosylation of sn-glycerol acceptor
thioglucoside (200 mg, 0.28 mmol) using the one-pot in situ
adduct transformation and glycosylation procedure (with DTBP
as the base, Table 1, entry 3). For
, 1H NMR (500 MHz, CDCl3)
3-
O
-[3,4,6-Tri-
O
-benzyl-2-
-cyclohexylidene-sn-glycerol (5).32 α-
was (126 mg, 60%) prepared from
(72 mg, 0.42 mmol) with
O-(2-naphthylmethyl)-α-D-
O
5
3
1
4.6 Diosgeninyl 2,3,4,6-Tetra-O-benzyl-α-D-glucopyranoside
(20). Diogeninyl α-glucoside 20 was (75 mg, 60%) synthesized
from glycosylation of diosgenine acceptor 17 (94 mg, 0.225
5
δ 7.84 – 7.73 (m, 4H), 7.51 – 7.44 (m, 3H), 7.39 – 7.21 (m, 13H),
7.16 – 7.12 (m, 2H), 5.00 (d, J = 10.9 Hz, 1H, benzyl-H), 4.93 –
4.89 (m, 2H, including H-1), 4.86 – 4.80 (m, 3H), 4.58 (d, J =
12.1 Hz, 1H, benzyl-H), 4.49 – 4.44 (m, 2H), 4.40 – 4.34 (m, 1H),
4.06 (dd, J = 8.3, 6.4 Hz, 1H), 3.98 (t, J = 9.3 Hz, 1H), 3.81 –
3.76 (m, J = 8.9 Hz, 1H), 3.75 – 3.68 (m, 2H), 3.66 – 3.55 (m,
5H), 1.64 – 1.56 (m, 10H) ); 13C NMR (125 MHz, CDCl3) δ
138.8, 138.3, 137.9, 135.6, 133.2, 133.1, 128.4, 128.3, 128.2,
127.90, 127.86, 127.8, 127.7, 127.6, 127.5, 126.8, 126.1, 126.0,
125.9, 110.1, 97.3 (C-1, JCH = 167.8 Hz), 81.9, 79.9, 77.6, 75.7,
75.0, 74.3, 73.5, 73.1, 70.4, 69.0, 68.5, 66.6, 36.5, 35.0, 25.1,
24.0, 23.9.
mmol) with thioglucoside donor
2 (100 mg, 0.15 mmol) using
the one-pot in situ adduct transformation and glycosylation
procedure (Table 2, entry 2 in main text). For α-glucoside 20, Rf
[ ]35
+150 (c 0.08, CHCl3); 1H
D
0.54 (hexanes/EtOAc 3/1);
훼
NMR (500 MHz, CDCl3): δ 7.34 – 7.25 (m, 18H, Ar-H), 7.13
(dd, J = 2.0, 7.5 Hz, 2H, Ar-H), 5.28 (d, J = 5.0 Hz, 1H), 5.00 (d,
J = 11.0 Hz, 1H), 4.93 (d, J = 3.5 Hz, 1H, H-1), 4.82 (dd, J = 8.0,
10.5 Hz, 2H), 4.76 (d, J = 12.0 Hz, 1H), 4.65 (d, J = 12.0 Hz,
1H), 4.60 (d, J = 12.0 Hz, 1H), 4.47 (d, J = 6.5 Hz, 1H), 4.44 (d,
J = 8.0 Hz, 1H), 4.41 (q, J = 15.5 Hz, 1H), 3.99 (t, J = 9.5 Hz,
1H), 3.87 (d, J = 10.5 Hz, 1H), 3.73 (dd, J = 4.0, 11.0 Hz, 1H),
3.64 – 3.61 (m, 2H), 3.55 (dd, J = 4.0, 10.0 Hz, 1H), 3.48 – 3.43
(m, 2H), 3.37 (t, J = 10.5 Hz, 1H), 2.42 (t, J = 11.0 Hz, 1H) , 2.28
(dd, J = 3.0, 13.0 Hz, 1H), 2.00 – 1.95 (m, 2H), 1.88 – 1.84 (m,
3H), 1.79 – 1.72 (m, 2H), 1.68 – 1.60 (m, 5H), 1.54 – 1.50 (m,
3H), 1.48 – 1.42 (m, 2H), 1.31 – 1.27 (m, 2H), 1.20 – 1.07 (m,
3H), 1.04 – 1.01 (m, 4H), 0.97 (d, J = 7.0 Hz, 3H), 0.93 (dd, J =
5.0, 11.5 Hz, 1H), 0.78 (t, J = 3.5 Hz, 6H); 13C NMR (125 MHz,
CDCl3): δ 140.95, 139.04, 138.35, 138.33, 138.05, 128.49,
128.46, 128.45, 128.41, 128.22, 128.05, 127.99, 127.93, 127.89,
127.84, 127.78, 127.71, 127.63, 127.61, 121.51, 109.36, 94.74,
82.20, 80.91, 80.03, 77.97, 76.57, 75.75, 75.21, 73.51, 73.17,
70.15, 68.69, 66.93, 62.20, 56.61, 50.12, 41.70, 40.36, 39.95,
39.87, 37.16, 37.02, 32.17, 31.94, 31.52, 31.48, 30.39, 29.78,
28.89, 27.57, 20.94, 19.50, 17.22, 16.37, 14.61; HRMS-ESI
4.4 Methyl 2,3,4,6-Tetra-
6)-2,3,4-tri- -benzyl-α-
-glucopyranoside (6).33 α-Anomer of
disaccharide was synthesized from glycosylation of glucoside
acceptor (105 mg, 0.23 mmol) with thioglucoside donor (100
O-benzyl-α-D-glucopyranosyl-(1
O
D
6
4
2
mg, 0.15 mmol) using the one-pot in situ adduct transformation
and glycosylation procedure (55% yield from DTBP as the base,
76% yield from either DIEA or LTD as the base) (Table 1, entries
1
7, 10, and 11 in main text). For α-anomer of
6
, H NMR (500
MHz, CDCl3): δ 7.37 – 7.20 (m, 33H, Ar-H), 7.15 – 7.10 (m, 2H,
Ar-H), 5.00 – 4.89 (m, 4H, including H-1), 4.85 – 4.75 (m, 3H),
4.70 (d, J = 12.1 Hz, 1H, benzyl-H), 4.68 – 4.62 (m, 3H), 4.58
(d, J = 3.7 Hz, 1H), 4.55 (d, J = 3.7 Hz, 2H, including H-1), 4.45
(d, J = 11.0 Hz, 1H), 4.41 (d, J = 12.1 Hz, 1H, benzyl-H), 4.02 –
3.93 (m, 2H), 3.82 (dd, J = 11.5, 4.4 Hz, 1H), 3.80 – 3.76 (m,
2H), 3.71 (d, J = 11.1 Hz, 1H, benzyl-H), 3.68 – 3.59 (m, 3H),
3.57 – 3.52 (m, 2H, including H-2), 3.44 (dd, J = 9.6, 3.5 Hz,
1H, H-2), 3.35 (s, 3H, OCH3); 13C NMR (125 MHz, CDCl3): δ
138.8, 138.7, 138.41, 138.37, 138.36, 138.1, 137.9, 128.38,
128.35, 128.30, 128.26, 128.24, 128.21, 128.0, 127.94, 127.91,
127.88, 127.81, 127.78, 127.66, 127.65, 127.57 127.56, 127.54,
127.52, 127.49, 127.47, 127.4, 97.9 (C-1, 1JCH = 166.3 Hz), 97.2
(C-1, 1JCH = 167.8 Hz), 82.1, 81.6, 80.1, 79.9, 77.7, 77.6, 75.7,
(m/z): [M + Na]+ calcd for C61H76NaO8 , 959.5438; found,
959.5437.
+
4.5
p
-Tolyl 2,3,4,6-Tetra- -glucopyranosyl-(1
O
-benzyl-α-
D

6)-2,3-di-
O
-benzoyl-4- -benzyl-thio-β-D-glucopyranoside
O
(21). α-Anomer of disaccharide 21 was (101 mg, 68%)
synthesized from glycosylation of thioglucoside acceptor 18
(132 mg, 0.23 mmol) with thioglucosyl donor
mmol) and using the one-pot in situ adduct transformation and
glycosylation procedure (Table 2, entry 3 in main article). For α-
2 (100 mg, 0.15
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

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DOI: 10.1039/C7OB00839B
Page 7 of 12
Journal Name
Organic & Biomolecular Chemistry
ARTICLE
[ ]35
+49.8 (c
D
77.1, 75.7, 75.5, 74.9, 74.8, 73.3, 72.3, 70.3, 68.7, 66.0, 63.0,
55.1 (OCH3), 20.76 (CH3CO). HRMS-ESI (m/z): [M + Na]+
calcd for C57H62NaO12+, 961.4134; found, 961.4135.
anomer of 21, Rf 0.35 (hexanes/EtOAc 3/1);
훼
1
0.610, CHCl3); H NMR (500 MHz, CDCl3): δ 7.95 (d, J = 7.2
Hz, 2H, Ar-H), 7.77 (d, J = 7.2 Hz, 2H, Ar-H), 7.52 – 7.46 (m, J
= 7.4, 13.7 Hz, 2H, Ar-H), 7.40 – 7.24 (m, 25H, Ar-H), 7.15 –
7.12 (m, 2H, Ar-H), 7.11 – 7.08 (m, 2H, Ar-H), 7.06 – 7.03 (m,
4H, Ar-H), 5.65 (t, J = 9.4 Hz, 1H), 5.29 (t, J = 9.7 Hz, 1H), 5.11
(d, J = 3.5 Hz, 1H, H-1), 5.01 (d, J = 10.9 Hz, 1H), 4.86 (d, J =
10.9 Hz, 1H), 4.83 (d, J = 10.9 Hz, 1H), 4.80 (d, J = 10.0 Hz,
1H), 4.73 – 4.68 (m, 2H), 4.65 (d, J = 12.2 Hz, 1H), 4.54 – 4.49
(m, 4H), 4.02 (t, J = 9.3 Hz, 1H), 3.92 – 3.87 (m, 4H), 3.75 –
3.66 (m, 4H), 3.62 (dd, J = 9.6, 3.5 Hz, 1H, H-2), 2.20 (s, 3H);
13C NMR (125 MHz, CDCl3): δ165.6, 165.2, 138.8, 138.5, 138.4,
138.2, 138.0, 137.3, 134.0, 133.1, 133.0, 129.83, 129.77, 129.75,
129.5, 129.4, 128.5, 128.4, 128.29, 128.27, 128.19, 128.17,
127.91, 127.90, 127.84, 127.79, 127.71, 127.70, 127.63, 127.55,
97.1 (C-1, JCH = 168.8), 86.6, 81.9, 80.3, 79.6, 77.7, 76.3, 75.7,
75.6, 75.1, 74.6, 73.4, 72.9, 71.0, 70.3, 68.6, 65.2, 21.1 (CH3);
HRMS-ESI (m/z): [M + Na]+ calcd for C68H66NaO12S+,
1129.4167; found, 1129.4162.
4.8 Methyl 6-
syl-(1 6)-2,3,4-tri-
Anomer of disaccharide 24 was (75 mg, 60%) synthesized from
glycosylation of glucoside acceptor (105 mg, 0.225 mmol) with
O
-Benzoyl-2,3,4-tri-
O-benzyl-α-D-glucopyrano

O
-benzyl-α- -glucopyranoside (24). α-
D
4
6-O-Bz protected thioglucosyl donor 10 (100 mg, 0.125 mmol)
using the one-pot in situ adduct transformation and glycosylation
procedure (Table 2, entry 7 in main text). The resulting mixture
was dried (over MgSO4), filtered, and concentrated for flash
chromatography purification over silica gel (Elution:
hexanes/EtOAc 1/0 to 7/1) to furnish the glycosylation product.
[ ]35
For α-disaccharide 24, Rf 0.34 (hexanes/EtOAc 3/1);
훼
D
+59.75 (c 0.569, CHCl3); 1H NMR (400 MHz, CDCl3): δ 7.90 –
7.88 (m, 2H, Ar-H), 7.45 (t, J = 7.6 Hz, 1H, Ar-H), 7.32 – 7.22
(m, 13H, Ar-H), 7.20 – 7.15 (m, 19H, Ar-H), 4.90 (d, J = 3.2 Hz,
1H), 4.87 (t, J = 2.8 Hz, 2H), 4.84 (d, J = 5.6 Hz, 1H), 4.82 (d, J
= 5.2 Hz, 1H), 4.72 (dd, J = 3.2, 10.8 Hz, 2H), 4.59 (t, J = 13.6
Hz, 4H), 4.53 (s, 1H), 4.50 (d, J = 2.0 Hz, 1H), 4.47 (d, J = 3.2
Hz, 1H), 4.42 (dd, J = 2.0, 12.0 Hz, 1H), 4.30 (dd, J = 4.4, 12.0
Hz, 1H), 3.96 – 3.88 (m, 3H), 3.75 – 3.69 (m, 2H), 3.62 (d, J =
10.0 Hz, 1H), 3.54 – 3.45 (m, 3H), 3.32 (dd, J = 3.6, 9.6 Hz, 1H),
3.27 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3): δ 166.2 (C=O),
138.9, 138.6, 138.38, 138.37, 138.2, 138.0, 133.1, 130.0, 129.7,
128.47, 128.46, 128.41, 128.39, 128.2, 128.04, 128.03, 127.97,
127.90, 127.84, 127.78, 127.75, 127.72, 127.65, 127.63, 98.0
(1JCH = 165.4 Hz), 97.0 (1JCH = 168.4 Hz), 82.2, 81.8, 80.24,
4.6 6-
O
-Acetyl-2,3,4-tri-
O
-benzyl-α-
D-glucopyranosyl-(1
6)-1,2:3,4-
O
-diisopropylidene-α-
D
-galactopyranose (22).34 α-
Anomer of disaccharide 22 was (41 mg, 70%) synthesized from
glycosylation of galactosyl acceptor 15 (31 mg, 0.12 mmol with
thioglucosyl donor
9 (50 mg, 0.08 mmol) using the one-pot in
situ adduct transformation and glycosylation procedure (Table 2,
entry 5 in main text). For α-anomer of 22, 1H NMR (500 MHz,
CDCl3): δ 7.39 – 7.24 (m, 15H, Ar-H), 5.52 (d, J = 5.0 Hz, 1H,
H-1), 5.00 (d, J = 10.8 Hz, 1H), 4.94 (d, J = 3.6 Hz, 1H, H-1),
4.86 (d, J = 10.9 Hz, 1H), 4.81 (d, J = 10.8 Hz, 1H), 4.72 (q, J =
11.9 Hz, 2H), 4.60 (dd, J = 2.4, 7.9 Hz, 1H), 4.56 (d, J = 10.9 Hz,
1H), 4.35 – 4.29 (m, 3H), 4.23 (dd, J = 2.1, 12.0 Hz, 1H), 4.06 –
3.99 (m, 2H), 3.94 (ddd, J = 2.1, 4.1, 10.1 Hz, 1H), 3.80-3.70 (m,
2H), 3.55 (dd, J = 3.6, 9.6 Hz, 1H), 3.49 (dd, J = 9.1, 9.9 Hz, 1H),
2.02 (s, 3H, COCH3), 1.54 (s, 3H, isopropylidene-CH3), 1.45 (s,
3H, isopropylidene-CH3), 1.33 (s, 3H, isopropylidene-CH3),
1.31 (s, 3H, isopropylidene-CH3); 13C NMR (125 MHz, CDCl3):
δ 170.8 (C=O), 138.7, 138.1, 137.9, 128.41, 128.37, 128.36,
128.1, 127.9, 127.83, 127.78, 127.75, 127.6, 109.2, 108.6, 97.0
80.20, 77.9, 77.6, 75.8, 75.1, 73.4, 72.5, 70.4, 68.9, 66.1, 63.5,
+
55.2; HRMS-ESI (m/z): [M + Na]+ calcd for C62H64NaO12
,
1023.4290; found, 1023.4332.
4.9 Methyl 6-
-glucopyranosyl-(1
glucopyranoside (25).
(80 mg, 55%) synthesized from glycosylation of glucosyl
acceptor (87 mg, 0.188 mmol) with thioglucoside donor 11
O
-
tert-Butyl-diphenylsilyl-2,3,4-tri-
6)-2,3,4-tri- -benzyl-α-
-Anomer of disaccharide 25 was
O-benzyl-α-
D

O
D-
4
(100 mg, 0.125 mmol) using the one-pot in situ adduct
transformation and glycosylation procedure (Table 2, entry 8 in
main text). For -disaccharide 25, Rf 0.42 (hexanes/EtOAc 3/1);
(C-1, JCH = 168.0 Hz), 96.3 (C-1, JCH = 178.4 Hz), 81.8, 79.8,

77.2, 75.6, 74.8, 72.4, 70.9, 70.6, 70.6, 68.6, 66.6, 65.9, 63.1,
26.1, 26.0, 24.9, 24.6, 20.8 (CH3CO); HRMS-ESI (m/z): [M +
Na]+ calcd for C41H50NaO12+, 757.3195; found, 757.3197.
[ ]28
훼
+52.1 (c 2.07, CHCl3); 1H NMR (400 MHz, CDCl3): δ 7.70
D
– 7.63 (m, 4H, Ar-H), 7.38 – 7.23 (m, 34H, Ar-H), 7.15 – 7.12
(m, 2H, Ar-H), 5.01 (t, J = 3.6 Hz, 1H; H-1), 4.95 – 4.87 (m,
-Acetyl-2,3,4-tri- -glucopyran- 4H), 4.83 – 4.77 (m, 2H), 4.71 – 4.53 (m, 7H including H-1),
-benzyl-α-D
-glucopyranoside (23).33 α-
4.02 – 3.95 (m, 2H), 3.82 – 3.64 (m, 9H), 3.57 – 3.52 (m, 1H),
4.7 Methyl 6-
O
O
-benzyl-α-
D
osyl-(1 6)-2,3,4-tri-

O
3.44 – 3.40 (m, 1H), 3.35 (s, 3H; CH3), 1.02 (s, 9H; tbutyl-H);
13C NMR (100 MHz, CDCl3) δ 138.9, 138.8, 138.64, 138.57,
138.4, 138.3, 135.9, 135.7, 133.7, 133.4, 129.62, 129.58, 128.5,
128.43, 128.41, 128.35, 128.2, 128.06, 128.03, 127.9, 127.8,
127.73, 127.69, 127.66, 127.60, 127.57, 98.02 (1JCH = 168.5 Hz),
97.00 (1JCH = 167.1 Hz), 82.2, 81.9, 80.5, 80.2, 77.84, 77.79,
75.75, 75.7, 75.1, 75.0, 73.4, 72.4, 71.7, 70.6, 65.7, 63.0, 55.2,
Anomer of disaccharide 23 was (1.1 g, 70%) prepared from
glycosylation of glucosyl acceptor (1.2 g, 2.51 mmol) with
thioglucoside donor (1.0 g, 1.67 mmol) using the one-pot in
4
9
situ adduct transformation and glycosylation procedure (Table 2,
entry 6 in main text). For α-anomer of 23, 1H NMR (500 MHz,
CDCl3): δ 7.34 – 7.23 (m, 30H, ArH), 4.98 (d, J = 1.4 Hz, 1H),
4.96 – 4.94 (m, 2H including H-1), 4.93 (d, J = 11.4 Hz, 1H),
4.87 (d, J = 11.0 Hz, 1H), 4.81 (d, J = 10.8 Hz, 1H), 4.78 (d, J =
10.9 Hz, 1H), 4.71 (d, J = 12.0 Hz, 1H), 4.67 – 4.62 (m, 3H),
4.60 – 4.52 (m, 3H including H-1), 4.19 (d, J = 3.1 Hz, 2H), 3.98
(td, J = 9.2, 6.2 Hz, 2H), 3.85 (dt, J = 10.1, 3.0 Hz, 1H), 3.82 –
3.76 (m, 2H), 3.70 (d, J = 10.4 Hz, 1H), 3.64 (t, J = 9.4 Hz, 1H),
3.51 (dd, J = 9.6, 3.4 Hz, 1H, H-2), 3.48 – 3.42 (m, 2H, including
H-2), 3.36 (s, 3H, OCH3), 1.96 (s, 3H, COCH3); 13C NMR (125
MHz, CDCl3): δ 170.6 (C=O), 138.7, 138.5, 138.3, 138.2, 138.1,
138.0, 128.4 128.3, 128.3, 128.1, 128.0, 127.9, 127.9, 127.8,
127.7, 127.7, 127.6, 127.6, 127.6, 127.5, 97.9 (C-1, JCH = 168.5
Hz), 97.0 (C-1, JCH = 167.1 Hz), 82.1, 81.5, 80.1, 79.9, 77.7,
26.9, 19.4; HRMS-ESI (m/z): [M
+
Na]+ calcd for
C71H78NaO11Si+, 1157.5206; found, 1157.5227.
4.10 Methyl 4-
syl-(1 6)-2,3,4-tri-
α-Anomer of disaccharide 26 was (0.98 g, 60%) synthesized
from glycosylation of glucoside acceptor (1.17 g, 2.51 mmol)
O
-Acetyl-2,3,6-tri-
O
-benzyl-α-
D
-glucopyrano-

O
-benzyl-α- -glucopyranoside
D
(26).
4
with 4-O-acetyl protected thioglucosyl donor 12 (1.0 g, 1.67
mmol) using one-pot in situ adduct transformation and
glycosylation procedure (Table 2, entry 9 in main text). For α-
[ ]30
disaccharide 26, Rf 0.16 (hexanes/EtOAc 3/1);
훼
+76.19 (c
D
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J. Name., 2012, 00, 1-3 | 7

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ARTICLE
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1
0.315, CHCl3); H NMR (500 MHz, CDCl3): δ 7.34 – 7.22 (m,
30H, Ar-H), 5.02 (d, J = 10.0 Hz, 1H) , 4.99 (d, J = 5.0 Hz, 1H) ,
4.95 (d, J = 3.5 Hz, 2H, including H-1), 4.92 (d, J = 10.5 Hz,
1H), 4.82 (t, J = 11.5 Hz, 2H) , 4.71 (d, J = 12.5 Hz, 1H) , 4.66
(d, J = 5.0 Hz, 2H) , 4.63 (d, J = 8.0 Hz, 1H) , 4.59 (d, J = 1.5
Hz, 1H) , 4.57 (d, J = 3.0 Hz, 1H; H-1) , 4.45 (q, J = 12.0 Hz,
2H) , 3.99 (t, J = 9.0 Hz, 1H) , 3.87 (t, J = 12.5 Hz, 1H) , 3.84 –
3.77 (m, 3H), 3.71 (d, J = 11.5 Hz, 1H) , 3.65 (t, J = 9.5 Hz, 1H) ,
3.56 (dd, J = 3.0, 9.5 Hz, 1H), 3.45 (dd, J = 3.5, 9.5 Hz, 1H), 3.41
(dd, J = 3.0, 11.0 Hz, 1H), 3.37 (d, J = 5.0 Hz, 1H) , 3.35 (s, 3H,
CH3), 1.80 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ 169.7
(C=O), 138.9, 138.7, 138.5, 138.3, 138.2, 137.9, 128.51, 128.47,
128.46, 128.36, 128.34, 128.11, 128.07, 128.03, 127.94, 127.91,
CDCl3): δ 138.79, 138.77, 138.1, 136.5, 133. 5, 132.9, 128.4,
128.30, 128.23, 128.17, 128.0, 127.94, 127.85, 127.8, 127.7,
127.54, 127.53, 126.03, 126.00, 125.8, 125.7, 109.2, 108.6, 97.6
(C-1, 1JCH = 168.5 Hz), 96.4 (C-1 , 1JCH = 176.2 Hz), 79.0, 76.5,
ʹ
75.1, 74.9, 73.4, 73.1, 72.7, 70.9, 70.71, 70.67, 69.2, 68.7, 66.4,
65.9, 26.2, 26.1, 24.5, 24.6.
4.13 2,3,4-Tri-
O
-benzyl-α-
D-xylopyranosyl-(16)-1,2:3,4-di-
O
-isopropylidene-α-
D
-galactopyranose (29).36 α-Anomer of
disaccharide 29 was (47 mg, 75%) obtained from glycosylation
of galactosyl acceptor 15 (36 mg, 0.14 mmol) with thioxyloside
donor 14 (50 mg, 0.09 mmol) using the one-pot in situ adduct
127.77, 127.76, 127.73, 127.69, 127.65, 127.58, 98.1 (1JCH
=
165.0 Hz), 97.2 (1JCH = 168.6 Hz), 82.22 80.3, 79.7, 78.6, 77.9, transformation and glycosylation procedure (Table 2, entry 12 in
1
75.8, 75.1, 74.9, 73.6, 73.5, 72.6, 70.5, 70.4, 68.94, 68.89, 66.3,
main article). For α-anomer of disaccharide 29, H NMR (500
MHz, CDCl3): δ 7.38 – 7.26 (m, 15H, Ar-H), 5.53 (d, J = 5.0 Hz,
1H, H-1), 4.92 (d, J = 10.9 Hz, 1H), 4.89 – 4.86 (m, 2H including
H-1), 4.75 – 4.70 (m, 3H), 4.64 – 4.59 (m, 2H), 4.36 (dd, J = 1.8,
7.9 Hz, 1H), 4.31 (dd, J = 2.3, 5.0 Hz, 1H), 4.07 – 4.03 (m, 1H),
3.93 – 3.87 (m, 1H), 3.77 (dd, J = 6.0, 10.2 Hz, 1H), 3.71 (dd, J
= 7.7, 10.2 Hz, 1H), 3.62-3.55 (m, 3H), 3.46 (dd, J = 3.6, 9.5 Hz,
1H), 1.54 (s, 3H, CH3), 1.45 (s, 3H, CH3), 1.33 (s, 3H, CH3), 1.31
(s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ 139.0, 138.4, 138.3,
128.39, 128.37, 128.30, 128.27, 128.25, 128.17, 127.94, 127.91,
127.80, 127.78, 127.75, 127.71, 127.6, 127.48, 127.46, 127.43,
109.1, 108.6, 97.2 (C-1, JCH = 167.6 Hz), 96.3 (C-1, JCH = 178.6
Hz), 81.2, 79.6, 78.0, 75.6, 73.4, 72.5, 70.8, 70.7, 70.6, 66.3, 65.
8, 60.0, 26.1, 26.0, 24.9, 24.6.
55.2, 20.9. HRMS-ESI (m/z): [M + Na]+ calcd for C57H62NaO12
,
+
961.4133; found, 961.4150.
4.11 Methyl 2,3,4,6-Tetra- -benzyl-α-
O
D-galactopyranosyl-
-glucopyranoside (27).34 α-
(1 6)-2,3,4-tri- -benzyl-α-D

O
Anomer of disaccharide 27 (54.4 mg, 69%) was obtained from
glycosylation of thiogalactoside donor 13 (50 mg, 0.08 mmol)
with glucoside acceptor
4 (56 mg, 0.12 mmol) using the one-pot
in situ adduct transformation and glycosylation procedure (Table
2, entry 10 in main text). For α-anomer of 27, 1H NMR (500 MHz,
CDCl3): δ 7.38 – 7.17 (m, 35H, Ar-H), 4.99 (d, J = 3.5 Hz, 1H,
H-1), 4.95 (d, J = 8.7 Hz, 1H), 4.93 (d, J = 9.2 Hz, 1H), 4.84 (d,
J = 11.0 Hz, 1H), 4.80 (d, J = 4.8 Hz, 1H, H-1), 4.78 (d, J = 5.9
Hz, 1H), 4.72 – 4.67 (m, 4H), 4.60 – 4.56 (m, 2H), 4.54 (d, J =
4.2 Hz, 1H), 4.53 (d, J = 3.5 Hz, 1H, H-1), 4.42 (d, J = 11.8 Hz,
1H), 4.36 (d, J = 11.8 Hz, 1H), 4.03 (dd, J = 3.5, 9.5 Hz, 1H),
3.99 – 3.93 (m, 2H), 3.93 – 3.88 (m, 2H), 3.82 – 3.70 (m, 3H),
3.59 (t, J = 9.3 Hz, 1H), 3.54 – 3.46 (m,2H), 3.41 (dd, J = 3.6,
9.6 Hz, 1H, H-2), 3.29 (s, 3H, OCH3); 13C NMR (125 MHz,
CDCl3): δ 138.9, 138.8, 138.71, 138.67, 138.4, 138.2, 138.1,
128.4, 128.32, 128.30, 128.25, 128.20, 128.15, 128.14, 128.09,
128.07, 128.01, 128.00, 127.93, 127.91, 127.8, 127.7, 127.60,
127.58, 127.5, 127.4, 127.3, 97.90 (C-1, 1JCH =168.3 Hz), 97.85
(C-1ʹ, 1JCH =168.3 Hz), 82.0, 80.2, 78.2, 78.0, 76.51, 75.6, 75.1,
75.0, 74.7, 73.3, 73.3, 72.8, 72.5, 70.3, 69.4, 68.9, 66.4, 55.0
(OCH3).
4.14 Methyl 2-Azido-3,4,6-tri-
pyranosyl-(1 6)-2,3,4-tri- -benzyl-α-
(35). α-Anomer of disaccharide 35 was (102 mg, 65%) obtained
from glucosyl acceptor (121 mg, 0.26 mmol) with 2-azido-2-
O
-benzyl-2-deoxy-α-
D-galacto-

O
D
-glucopyranoside
4
deoxythiogalactoside donor 30 (100 mg, 0.17 mmol) using the
one-pot in situ adduct transformation and glycosylation
procedure (Table 3, entry 1 in main text). For α-anomer of
[ ]25
+60.4 (c
D
disaccharide 35, Rf 0.4 (hexanes/EtOAc 2.5/1);
훼
1
0.345, CHCl3); H NMR (500 MHz, CDCl3): δ 7.43 – 7.20 (m,
30H, Ar-H), 5.01 – 4.96 (m, 2H including H-1), 4.90 – 4.84 (m,
2H), 4.83 – 4.75 (m, 2H), 4.72 (d, J = 10.8 Hz, 1H), 4.65 (d, J =
10.7 Hz, 2H), 4.60 – 4.50 (m, 3H including H-1), 4.44 (d, J =
11.8 Hz, 1H, benzyl-H), 4.37 (d, J = 11.1 Hz, 1H, benzyl-H),
4.03 – 3.96 (m, 2H), 3.96 – 3.91 (m, 1H), 3.91 – 3.86 (m, 1H),
3.85 – 3.73 (m, 3H), 3.69 (d, J = 11.1 Hz, 1H, H-6), 3.59 – 3.48
(m, 4H), 3.33 (s, 3H, OCH3); 13C NMR (125 MHz, CDCl3): δ
138.7, 138.2, 138.2, 138.1, 137. 8, 137.4, 128.5, 128.4, 128.3,
128.2, 128.0, 128.0, 127.9, 127.8, 127.7, 127.6, 127.6, 98.5 (C-
1, JCH = 171.0 Hz), 97.8 (C-1, JCH = 166.9 Hz), 81.9, 80.0, 77.8,
76.5, 75.7, 74.9, 74.7, 73.4, 73.3, 71.9, 69.9, 69.6, 68.5, 66.6,
4.12
1,2:3,4-di-
2,3,4,6-Tetra-
O
-benzyl-α-
D-galactopyranosyl-(16)-
-galactopyranose (28).12d α-
O
-isopropylidene-α-
D
Anomer of disaccharide 28 was (135 mg, 63%, 13:1 α:β)
synthesized from glycosylation of galactosyl acceptor 15 (117
mg, 0.45 mmol) with thiogalactoside donor 12 (200 mg, 0.30
mmol) using the one-pot in situ adduct transformation and
glycosylation procedure (Table 2, entry 11 in main text). For α-
[ ]35
anomer of 28, Rf 0.28 (hexanes/EtOAc 3/1);
훼
+48.0 (c
D
59.8, 55.0; HRMS-ESI (m/z): [M
+
Na]+ calcd for
1
0.248, CHCl3); H NMR (400 MHz, CDCl3): δ 7.83 – 7.78 (m,
3H, Ar-H), 7.75 – 7.72 (m, 1H, Ar-H), 7.50 – 7.44 (m, 3H, Ar-
H), 7.39 – 7.38 (m, 2H, Ar-H), 7.35 – 7.22 (m, 11H, Ar-H), 5.52
C55H59N3NaO10+, 944.4093; found, 944.4097.
4.15 Cholesteryl 2-Azido-3,4,6-tri-O-benzyl-2-deoxy-α-D-
(d, J = 4.8 Hz, 1H, H-1), 5.03 (d, J = 3.6 Hz, 1H, H-1ʹ), 4.97 (dd,
galactopyranoside (36). α-Anomer of cholesteryl galactoside 36
was (62 mg, 60%) obtained from glycosylation of cholesterol 33
(70 mg, 0.18 mmol) with 2-azido-2-deoxythiogalactoside donor
30 (70 mg, 0.12 mmol) using the one-pot in situ adduct
transformation and glycosylation procedure (Table 3, entry 2 in
main text) and was obtained as a white amorphous solid via
column chromatography purification (Elution: hexanes/EtOAc/
CH2Cl2 30/1/1 to 26/1/1). For α-anomer of 36, Rf 0.7
J = 4.8, 12.0 Hz, 2H), 4.87 (d, J = 12.0 Hz, 1H), 4.78 (s, 2H),
4.61 (d, J = 11.6 Hz, 1H), 4.57 (dd, J = 2.4, 8.0 Hz, 1H), 4.49 (d,
J = 12.8 Hz, 1H), 4.43 (d, J = 12.8 Hz, 2H), 4.34 – 4.29 (m, 2H),
4.12 (dd, J = 1.6, 10.8 Hz, 1H), 4.07 – 4.01 (m, 3H), 3.83 – 3.73
(m, 2H), 3.62 – 3.52 (m, 2H), 1.50 (s, 3H, CH3), 1.44 (s, 3H,
CH3), 1.32 (s, 3H, CH3), 1.30 (s, 3H, CH3); 13C NMR (100 MHz,
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

View Article Online
DOI: 10.1039/C7OB00839B
Page 9 of 12
Journal Name
Organic & Biomolecular Chemistry
ARTICLE
[ ]35
+51.0 (c 0.8, CHCl3); 1H NMR (500
D
170.0 Hz), 96.2 (C-1, JCH = 178.8 Hz), 79.9, 78.2, 75.2, 74.9,
73.5, 70.8, 70.7, 70.61, 70.55, 68.1, 66.8, 66.2, 63.4 (C-2), 26.1,
25.94, 24.92, 24.4. HRMS-ESI (m/z): [M + Na]+ calcd for
C39H47N3NaO10+, 740.3154; found, 740.3155.
(hexanes/EtOAc 5/1);
훼
MHz, CDCl3): δ 7.43 – 7.22 (m, 15H), 5.28 (d, J = 5.0 Hz, 1H),
5.05 (d, J = 3.6 Hz, 1H, H-1), 4.88 (d, J = 11.3 Hz, 1H), 4.72 (q,
J = 11.3 Hz, 2H), 4.53 (d, J = 11.0 Hz, 1H), 4.50 (d, J = 12.0 Hz,
1H), 4.43 (d, J = 11.7 Hz, 2H), 4.10 – 4.03 (m, 2H), 3.98 (dd, J
= 2.6, 10.7 Hz, 1H), 3.79 (dd, J = 3.6, 10.7 Hz, 1H, H-2), 3.63 – 4.18 Cholesteryl 2-Azido-3,4,6-tri ‐ O‐ benzyl-2-deoxy ‐ α-D ‐
3.53 (m, 2H), 3.51 – 3.43 (m, 1H), 2.41 – 2.28 (m, 2H), 2.06 –
1.89 (m, 3H), 1.90 – 1.78 (m, 2H), 1.63 – 0.84 (m, 33H), 0.68 (s,
3H); 13C NMR (125 MHz, CDCl3): δ 140.6, 138.4, 137.9, 137.7,
128.5, 128.4, 128.3, 128.1, 127.9, 127.8, 127.8, 127.7, 127.6,
121.9, 96.8 (C-1, JCH = 168.5 Hz), 78.2, 77.4, 74.8, 73.6, 73.5,
72.2, 69.6, 68.8, 59.7 (C-2), 56.8, 56.1, 50.1, 42.3, 40.0, 39.8,
39.5, 37.0, 36.7, 36.2, 35.8, 31.9, 31.9, 28.2, 28.0, 27.9, 24.3,
23.8, 22.8, 22.6, 21.0, 19.4, 18.7, 11.9. HRMS-ESI (m/z): [M +
glucopyranoside (39). α-Anomer of cholesteryl 2-azido-2-
deoxyglucoside 39 was (43 mg, 58%) synthesized as a white
greasy solid from reaction of cholesterol 33 (33 mg, 0.085 mmol)
with 2-azido-2-deoxythioglucoside donor 31 (100 mg, 0.17
mmol) according to one-pot in situ adduct transformation and
glycosylation procedure (Table 3, entry 5 in main text). For α-
[ ]35
anomer 39, Rf 0.6 (hexanes/EtOAc 5/1);
훼
+22 (c 0.8,
D
CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.39 – 7.25 (m, 13H, Ar-
H), 7.17 – 7.14 (m, 2H, Ar-H), 5.30 (d, J = 4.7 Hz, 1H), 5.08 (d,
J = 3.5 Hz, 1H, H-1), 4.88 (q, J = 10.7 Hz, 2H), 4.81 (d, J = 10.8
Hz, 1H), 4.63 (d, J = 12.0 Hz, 1H), 4.53 – 4.46 (m, 2H), 4.06 –
4.00 (m, 1H, H-3), 3.97 – 3.91 (m, 1H), 3.80 – 3.75 (m, 1H),
3.73 – 3.68 (m, 1H), 3.68 – 3.63 (m, 1H), 3.55 – 3.46 (m, 1H),
3.30 (dd, J = 3.5, 10.3 Hz, 1H, H-2), 2.40 – 2.30 (m, 2H), 2.04
– 1.91 (m, 3H), 1.90 – 1.78 (m, 2H), 1.62 – 1.31 (m, 13H), 1.20
– 1.02 (m, 9H), 0.95 – 0.84 (m, 11H)., 0.68 (s, 3H); 13C NMR
(125 MHz, CDCl3): δ 140.5, 138.04, 137.95, 137.8, 128.434,
128.425, 128.36, 128.0, 127.9, 127.82, 127.80, 127.7, 122.0,
+
Na]+ calcd for C54H73N3NaO5 , 866.5442; found, 866.5443.
4.16 Methyl 2-Azido-3,4,6-tri-
pyranosyl-(1 6)-2,3,4-tri- -benzyl-α-
(37). α-Anomer of disaccharide 37 was (30 mg, 55%) obtained
from glycosylation of glucosyl acceptor (28 mg, 0.06 mmol)
O
-benzyl-2-deoxy-α-
D-gluco-

O
D
-glucopyranoside
4
with 2-azido-2-deoxythioglucoside donor 31 (70 mg, 0.12 mmol)
using the one-pot in situ adduct transformation and glycosylation
procedure with 2-azido-2-deoxythioglucoside donor (Table 3,
entry 3 in main text). For α-anomer 37, Rf 0.3 (hexanes/EtOAc
[ ]25
+46.8 (c 0.513, CHCl3); 1H NMR (500 MHz,
D
2.5/1);
훼
96.3 (C-1, JCH = 168.0 Hz), 80.2, 78.4, 78.2, 75.3, 75.1, 73.5,

CDCl3): δ 7.37 – 7.24 (m, 28H, Ar-H), 7.15 – 7.17 (m, 2H, Ar-
H), 5.00 (d, J = 3.5 Hz, 1H, H-1), 4.98 (d, J = 10.8 Hz, 1H), 4.94
(d, J = 11.2 Hz, 1H, benzyl-H), 4.85 (d, J = 3.0 Hz, 2H), 4.81 –
4.78 (m, 2H), 4.77 (d, J = 2.7 Hz, 1H), 4.66 (d, J = 12.0 Hz, 1H,
benzyl-H), 4.61 – 4.55 (m, 3H including H-1), 4.48 (d, J = 11.0
Hz, 1H, benzyl-H), 4.42 (d, J = 12.1 Hz, 1H, benzyl-H), 4.00 (t,
J = 9.3 Hz, 1H, H-3), 3.92 (dd, J = 8.6, 10.2 Hz, 1H, H-3), 3.82
(dd, J = 4.5, 11.3 Hz, 1H, H-6), 3.79 – 3.72 (m, 2H), 3.72 – 3.66
(m, 2H), 3.63 (dd, J = 3.3, 10.8 Hz, 1H, H-6), 3.59 – 3.51 (m,
70.7, 68.4, 63.3, 56.8, 56.2, 50.1, 42.3, 40.0, 39.8, 39.5, 37.0,
36.7, 36.2, 35.8, 31.93, 31.87, 28.2, 28.0, 27.8, 24.3, 23.82, 22.81,
22.6, 21.0, 19.4, 18.7, 11.9; HRMS-ESI (m/z): [M + Na]+ calcd
+
for C54H73N3NaO5 , 866.5442; found, 866.5433.
4.19 4-Azido-2,3-di-
yl-(1 6)-1,2:3,4-di-
O
-benzyl-4,6-dideoxy-α-
D-fucopyranos-

O
-isopropylidene-α- -galactopyranose
D
(40). α-Anomer of disaccharide 40 (53 mg, α only, 76%) was
synthesized from reaction of galactosyl acceptor 15 (41 mg,
0.158 mmol) with Fuc4N3 donor 32 (50 mg, 0.105 mmol) using
the one-pot in situ adduct transformation and glycosylation
procedure (Table 3, entry 6 in main text). For α-anomer of 40, Rf
3H), 3.37 (s, 3H, OCH3), 3.33 (dd, J = 3.5, 10.3 Hz, 1H); 13
C
NMR (125 MHz, CDCl3): δ 138.7, 138.3, 138.1, 138.0, 137.9,
137.8, 128.43, 128.38, 128.37, 128.35, 128.14, 128.10, 128.05,
128.03, 127.96, 127.87, 127.85, 127.82, 127.76, 127.71, 127.69,
[ ]35
1
0.48 (Hexanes/ EtOAc = 2/1);
훼
+3.32 (c 2.85, CHCl3); H
퐷
127.65, 127.63, 127.61, 127.60, 98.2 (C-1, JCH = 171.3 Hz),

NMR (500 MHz, CDCl3): δ = 7.41 – 7.27 (m, 10H, Ar-H), 5.52
(d, J = 5.0 Hz, 1H, H-1), 4.87 (d, J = 3.5 Hz, 1H, H-1), 4.83 (d,
J = 11.5 Hz, 1H, benzyl-H), 4.76 (d, J = 11.5, 1H, benzyl-H),
4.74 (d, J = 11.5, 1H, benzyl-H), 4.70 (d, J = 11.5, 1H, benzyl-
H), 4.58 (dd, J = 2.5, 8.0 Hz, 1H), 4.31 (dd, J = 2.4 Hz, 1H), 4.28
(dd, J = 2.0, 8.0 Hz, 1H), 4.07 – 3.99 (m, 3H), 3.84 (dd, J = 3.5,
10.0 Hz, 1H), 3.73 (d, J = 3.5, 2H), 3.72 (d, J = 3.6, 1H), 1.51 (s,
3H, CH3), 1.44 (s, 3H, CH3), 1.33 (s, 3H, CH3), 1.31 (s, 3H, CH3),
1.22 (d, J = 6.4 Hz, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ
138.5, 138.3, 128.4, 128.3, 127.7, 127.7, 127.6, 109.3, 109.3,
108.53, 108.5, 97.4 (C-1), 96.3 (C-1), 78.0, 75.9, 73.1, 72.9,
71.0, 70.7, 70.6, 66.7, 66.2, 65.0, 64.5, 26.1, 26.0, 24.9, 24.6,
17.3; HRMS (ESI): calcd for C32H41N3O9Na+ [M + Na]+ requires
634.2735, found 634.2757 m/z. The α-anomer of disaccharide 40
was obtained as the only anomer and no HPLC analysis was
performed for this reaction.
97.9 (C-1, JCH = 167.4 Hz), 82.0, 80.1, 79.8, 78.2, 77.7, 75.8,
75.2, 74.9, 735, 73.4, 70.7, 69.9, 68.1, 66.4, 63.5, 55.2 (OCH3).
+
HRMS-ESI (m/z): [M + Na]+ calcd for C55H59N3NaO10
,
944.4093; found, 944.4094.
4.17 2-Azido-3,4,6-tri-
O
-benzyl-2-deoxy-α-
D-glucopyranos-
yl-(1 6)-1,2:3,4-di- -isopropylidene-α-D

O
-galactopyranose
(38). α-Anomer of disaccharide 38 was (27 mg, 84%)
synthesized from galactosyl acceptor 15 (12 mg, 0.045 mmol)
with 2-azido-2-deoxythioglucoside donor 31 (50 mg, 0.09 mmol)
according to one-pot in situ adduct transformation and
glycosylation procedure (Table 3, entry 4 in article). For α-
[ ]25
anomer of 38, Rf 0.2 (hexanes/EtOAc 3/1);
훼
+37.4 (c 0.64,
D
1
CHCl3); H NMR (500 MHz, CDCl3): δ 7.39 – 7.23 (m, 13H,
ArH), 7.18 – 7.13 (m, 2H, Ar-H), 5.51 (d, J = 5.0 Hz, 1H, H-1),
4.99 (d, J = 3.5 Hz, 1H, H-1), 4.86 (s, 2H), 4.79 (d, J = 10.9 Hz,
1H, benzyl-H), 4.66 – 4.59 (m, 2H), 4.52 (d, J = 10.8 Hz, 1H,
benzyl-H), 4.48 (d, J = 12.1 Hz, 1H, benzyl-H), 4.34 – 4.29 (m,
2H), 4.03 – 3.97 (m, 2H including H-3), 3.90 – 3.86 (m, 1H),
3.82 (dd, J = 6.4, 10.3 Hz, 1H), 3.80 – 3.73 (m, 2H), 3.71 (dd, J
= 5.0, 8.7 Hz, 1H), 3.66 (dd, J = 1.8, 10.8 Hz, 1H), 3.33 (dd, J =
3.5, 10.3 Hz, 1H, H-2), 1.53 (s, 3H, CH3), 1.43 (s, 3H, CH3),
4.20 Methyl 4-Azido-2,3-di-
O
-benzyl-4,6-dideoxy-α-
D-fuco-
pyranosyl-(1 3)-4- -benzyl-2,6-dideoxy-α-D-
ranoside (41). Disaccharide 41 (71 mg, 70%, α only) was

O
ribo-hexopy-
synthesized from glycosylation of methyl α-digitoside acceptor
34 (40.6 mg, 0.161 mmol) with 4-azido-4-deoxy-1-thio-
D-
fucopyranosyl donor 32 (91.8 mg, 0.193 mmol) by using the one-
1.34 (s, 3H, CH3), 1.33 (s, 3H, CH3); 13C NMR (125 MHz, pot in situ adduct transformation and glycosylation procedure
CDCl3): δ 138.0, 137.8, 128.40, 128.36, 128.35, 128.0, 127.9,
(Table 3, entry 7 in main text). For 41, Rf 0.30 (Hexanes/EtOAc
127.81, 127.77, 127.71, 127.68, 109.2, 108.6, 98.2 (C-1, JCH
=
[ ]35
= 5/1); 훼
+75.1 (c 1.75, CHCl3); 1H NMR (500 MHz,
퐷

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CDCl3): δ 7.38 (t, J = 8.5 Hz, 4H, Ar-H), 7.34 – 7.22 (m, 11H, imidinium ion adduct, methyl mannoside acceptor 44 (104.5 mg,
0.225 mmol) was added. The mixture was stirred at -20 °C for
24 h. The reaction was quenched by addition of NaHCO3.
Workup procedure: NaHCO3 and Na2S2O3(s) were added to the
mixture, followed by stirring until the deep red color of the
reacting solution changed to pale yellow. The resulting mixture
was dried (over MgSO4), filtered, and concentrated for flash
chromatography purification (Elution: hexanes/EtOAc 1/0 to 5/1)
to furnish disaccharide 43 (91 mg, 61%, α:β >19:1 from NMR)
as a white amorphous solid. For α-anomer 45, Rf 0.28
Ar-H), 5.11 (d, J = 3.0 Hz, 1H, H-1), 4.83 (d, J = 12.0 Hz, 1H),
4.80 (d, J =12.0 Hz, 1H), 4.71 (d, J = 11.5 Hz, 1H), 4.66 (d, J =
12.0 Hz, 1H), 4.62 (d, J = 2.5 Hz, 1H, H-1), 4.59 (dd, J = 7.0,
12.0 Hz, 2H), 3.91 (dd, J = 6.5, 13.5 Hz, 1H), 3.87 (dd, J = 3.0,
9.5 Hz, 1H), 3.55 (d, J = 2.5 Hz, 1H, ), 3.21 (s, 3H, OCH3), 3.18
(dd, J = 2.5, 8.5 Hz, 1H), 2.24 (dd, J = 2.0, 15.0 Hz, 1H, H-2eq),
1.72 (dt, J = 4.0, 15.0 Hz, 1H, H-2ax), 1.27 (d, J = 6.5 Hz, 1H,
CH3), 1.04 (d, J = 6.5 Hz, 1H, CH3); 13C NMR (100 MHz,
CDCl3): δ 138.9, 138.4, 138.3, 128.3, 128.2, 128.1, 127.6, 127.6,
127.5, 127.3, 127.2, 127.2, 97.2 (C-1), 93.8 (C-1), 79.9, 77.4,
76.1, 73.0, 71.8, 71.4, 67.34, 65.1, 64.4, 63.3, 54.9, 31.3, 17.97,
17.2; HRMS (ESI): calcd for C34H41N3O7Na+ [M + Na]+ requires
626.2837, found 626.2864 m/z. The α-anomer of disaccharide 41
was obtained as the only anomer and no HPLC analysis was
performed for this reaction.
[ ]17
1
(hexanes/EtOAc 3/1);
훼
+90.0 (c 0.33, CHCl3); H NMR
D
(400 MHz, CDCl3): δ 7.37 – 7.20 (m, 25H, Ar-H), 7.17 – 7.10
(m, 10H, Ar-H), 5.48 (d, J = 3.6 Hz, 1H, anomeric-H), 4.90 (d, J
= 10.8 Hz, 1H), 4.83 (d, J = 10.8 Hz, 1H), 4.78 (d, J = 11.6 Hz,
1H), 4.75 (d, J = 2.4 Hz, 1H, anomeric-H), 4.70 (d, J = 10.8 Hz,
1H), 4.66 (s, 1H), 4.63 (d, J = 2.8 Hz, 1H), 4.60 (s, 1H), 4.54 –
4.42 (m, 4H), 4.34 (d, J = 10.8 Hz, 1H), 4.20 (t, J = 2.0 Hz, 1H),
4.03 (q, J = 19.2 Hz, 2H), 3.94 – 3.87 (m, 2H), 3.83 – 3.79 (m,
1H), 3.75 – 3.65 (m, 4H), 3.60 (t, J = 9.2 Hz, 1H), 3.54 (dd, J =
3.6, 9.6 Hz, 1H), 3.30 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3):
δ 139.0, 138.7, 138.6, 138.4, 138.2, 138.0, 128.5, 128.43, 128.37,
128.32, 128.31, 128.29, 128.1, 128.04, 127.96, 127.85, 127.81,
127.76, 127.70, 127.62, 127.50, 127.48, 127.4, 127.2, 100.1
(1JCH = 168.9 Hz), 97.2 (1JCH = 169.8 Hz), 81.5, 80.6, 79.7, 77.5,
75.6, 75.1, 75.0, 74.9, 73.5, 73.45, 73.1, 72.7, 72.3, 71.2, 70.7,
69.4, 68.6, 54.7; HRMS-ESI (m/z): [M + Na]+ calcd for
C62H66NaO11+, 1009.4503; found, 1009.4548.
4.21 Methyl 2,3,4,6-Tetra-
4)-2,3,6-tri- -benzyl-α-
-glucopyranoside (43).17 Mixture of
thioglucoside donor (100 mg, 0.15 mmol) and flame-dried
molecular sieve (4Å , 300 mg) was suspended in dried CH2Cl2 (3
mL) such that the final concentration of was 50 mM. Then,
O-benzyl-α-D-glucopyranosyl-(1
O
D
2
2
NFM (60 μL, 0.6 mmol) was added to the mixture. The resulting
mixture was stirred at room temperature for 10 min and at 0 °C
for additional 20-30 min, followed by addition of NIS (50.6 mg,
0.225 mmol) and TMSOTf (27 μL, 0.15 mmol). The formation
of NFM imidinium adduct was monitored by TLC. Upon
complete formation of the imidinium adduct intermediate,
methyl glucoside acceptor 42 (104.5 mg, 0.225 mmol) was added.
The mixture was stirred at 0 °C. Upon completion of the
4.23 Methyl 2,3,6-Tri-
O
-benzyl-α-
D
-glucopyranosyl-(1
(46) For

6)-
α-
2,3,4-tri- -benzyl-α- -glucopyranoside
O
D
:
[ ]30
glycosylation reaction (~24 h), the reaction was quenched by disaccharide 46, Rf 0.43 (hexanes/EtOAc/CH2Cl2 2/1/1);
addition of Et3N. Workup procedure: NaHCO3 and Na2S2O3(s) +55.3 (c 1.012, CHCl3); H NMR (500 MHz, CDCl3): δ 7.33-
훼
D
1
were added to the mixture, followed by stirring until the deep red 7.20 (m, 30H, Ar-H), 4.98-4.94 (m, 3H, including anomeric-H),
color of the reacting solution changed to pale yellow. The
4.92 (dd, J = 2.0, 11.0 Hz, 1H), 4.82 (dd, J = 2.5, 11.0 Hz, 1H),
resulting mixture was dried (over MgSO4), filtered, and 4.73 – 4.63 (m, 5H), 4.55 – 4.52 (m, 3H, including anomeric-H),
concentrated for flash chromatography purification over silica 4.48 (d, J = 12.0 Hz, 1H) , 3.99 (td, J = 2.5, 9.0 Hz, 1H), 3.84 –
gel (Elution: hexanes/EtOAc 7:1) to furnish the glycosylation 3.73 (m, 5H), 3.70 (d, J = 11.5 Hz, 1H) , 3.66 (dd, J = 3.5, 9.5
product. The disaccharide 43 (106 mg, 0.11 mmol, 70%, α:β 16:1
Hz, 1H), 3.62 – 3.57 (m, 3H), 3.51 (dt, J = 2.5, 9.5 Hz, 1H), 3.43
from NMR) was obtained as a glassy solid. For α-anomer of 43
,
(dt, J = 2.5, 9.5 Hz, 1H), 3.34 (s, 3H, CH3); 13C NMR (125 MHz,
1H NMR (400 MHz, CDCl3): δ 7.27 – 7.18 (m, 33H, Ar-H), 7.11 CDCl3): δ 138.8, 138.7, 138.4, 138.3, 138.1, 138.0, 128.5,
– 7.08 (m, 2H, Ar-H), 5.69 (d, J = 3.6 Hz, 1H, H-1ʹ), 5.02 (d, J = 128.38, 128.36, 128.33, 128.31, 128.30, 128.04, 127.95, 127.8,
127.7, 127.63, 127.56, 98.0 (1JCH = 166.4 Hz), 97.2 (1JCH = 168.1
11.6 Hz, 1H), 4.87 (d, J = 10.8 Hz, 1H), 4.81 – 4.75 (m, 4H),
4.69 (d, J = 12.0 Hz, 1H), 4.60 (d, J = 3.6 Hz, 1H), 4.58 (d, J = Hz), 82.1, 80.6, 80.1, 79.6, 77.8, 75.8, 75.7, 75.6, 75.1, 75.01,
1.2 Hz, 1H, H-1), 4.54 (s, 1H), 4.52 (d, J = 3.6 Hz, 1H), 4.49 (d, 74.96, 73. 5, 73.43, 73.37, 73.33, 73.30, 72.14, 72.10, 72.07, 70.6,
J = 2.8 Hz, 2H), 4.42 (d, J = 10.8 Hz, 1H), 4.27 (d, J = 12.0 Hz, 70.3, 70.1, 69.5, 66.1, 55.1; HRMS-ESI (m/z): [M + Na]+ calcd
for C55H60NaO11+, 919.4028; found, 919.4041.
1H), 4.12 – 4.01 (m, 2H), 3.93 – 3.81 (m, 3H), 3.73 – 3.64 (m,
3H), 3.59 (dd, J = 3.6, 8.8 Hz, 1H), 3.49 (dd, J = 3.6, 10.0 Hz,
2H), 3.40 (d, J = 1.6 Hz, 1H), 3.37 (s, 3H, CH3); 13C NMR (100
MHz, CDCl3): δ 139.0, 138.8, 138.6, 138.2, 138.1, 138.04,
138.00, 128.5, 128.37, 128.35, 128.30, 128.27, 128.25, 128.1,
128.0, 127.87, 127.86, 127.75, 127.67, 127.61, 127.5, 127.4,
127.3, 127.1, 126.8, 97.8 (1JCH = 166.2 Hz), 96.70 (1JCH = 168.4
Hz), 82.10, 82.08, 80.3, 79.5, 77.7, 75.6, 75.0, 74.5, 73.5, 73.4,
73.3, 73.2, 72.4, 71.0, 69.6, 69.1, 68.3, 55.2.
4.24 Methyl 2,3,4,6-Tetra-
4)-2,3,6-tri- -benzyl-α- -glucopyranosyl-(1
benzyl-α- -glucopyranoside (47): Trisaccharide 47 was (48 mg,
60%) synthesized from glycosylation of disaccharide 46 (100 mg,
0.12 mmol) with donor (109 mg, 0.17 mmol) according to the
O
-benzyl-α-
D
-glucopyranosyl-(1

O-
O
D

6)-2,3,4-tri-
D
2
glycosylation protocol for preparation of 43. The trisaccharide
47 was obtained as a white glassy solid by flash chromatography
purification (Elution: hexanes/EtOAc 7/1 to 5/1) and no other
4.22 Methyl 2,3,4,6-Tetra-
2)-3,4,6-tri- -benzyl-α- -mannopyranoside (45). Mixture of
donor (100 mg, 0.15 mmol) and flame-dried molecular sieve
(4Å ) (0.3 mg) was suspended in dried CH2Cl2 (3 mL). Then,
NFM (120 μL, 1.2 mmol) was added to the mixture. The
resulting mixture was stirred at room temperature for 10 min and
at -20 °C for additional 20-30 min followed by addition of NIS
(50.6 mg, 0.225 mmol) and TMSOTf (27 μL, 0.15 mmol). The
reaction was monitored by TLC. Upon complete formation of
O-benzyl-α-D-glucopyranosyl-(1
anomer was obtained. For trisaccharide 47
,
Rf 0.19
[ ]30
1
O
D
(hexanes/EtOAc 3/1);
훼
+71.6 (c 0.475, CHCl3); H NMR
D
2
(500 MHz, CDCl3): δ 7.33 – 7.19 (m, 43H, Ar-H), 7.14 – 7.10
(m, 7H, Ar-H), 5.68 (d, J = 3.5 Hz, 1H, anomeric-H), 4.99 – 4.92
(m, 4H, including anomeric-H), 4.86 – 4.73 (m, 5H), 4.70 – 4.67
(m, 2H), 4.61 – 4.41 (m, 10H, including one anomeric-H), 4.27
(dd, J = 3.0, 12.0 Hz, 1H), 4.07 – 3.97 (m, 3H), 3.90-3.87 (m,
2H), 3.81 – 3.79 (m, 3H), 3.74 – 3.70 (m, 2H), 3.66 – 3.56 (m,
4H), 3.48 – 3.42 (m, 3H), 3.38 – 3.35 (m, 4H, including CH3);
10 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C7OB00839B
Page 11 of 12
Journal Name
Organic & Biomolecular Chemistry
ARTICLE
13C NMR (125 MHz, CDCl3): δ 139.1, 138.9, 138.8, 138.6, 138.4,
138.3, 138.24, 138.19, 138.16, 138.0, 128.5, 128.44, 128.38,
128.34, 128.29, 128.25, 128.19, 128.03, 127.99, 127.93, 127.87,
127.85, 127.83, 127.74, 127.65, 127.60, 127.58, 127.52, 127.48,
127.38, 127.29, 127.0, 126.9, 98.0 (1JCH = 165.5 Hz), 96.8 (1JCH
= 172.3 Hz), 96.8 (1JCH = 168.6 Hz), 82.2, 82.1, 81.7, 80.2, 80.1,
79.5, 77.8, 77.7, 75.8, 75.5, 75.1, 75.0, 74.1, 73.5, 73.4, 73.2,
73.1, 72.9, 72.3, 71.0, 70.5, 69.9, 69.2, 68.3, 65.9, 55.3. HRMS-
ESI (m/z): [M + Na]+ calcd for C89H94NaO16+, 1441.6434; found,
1441.6431.
8. L. Yang, Q. Qin, X.-S. Ye, Asian J. Org. Chem. 2013,
2, 30-49.
9. S. Manabe, Y. Ito, Curr. Bioactive Compd. 2008, , 258-281.
4
10. S. K. Mulani, W.-C. Hung, A. B. Ingle, K.-S. Shiau, K.-K. T. Mong,
Org. Biomol. Chem. 2014, 12, 1184-1197.
11. a) R. U. Lemieux, K. B. Hendriks, R. V. Stick, K. James, J. Am. Chem.
Soc. 1975, 97, 4056-4062; b) R. U. Lemieux, H. Driguez, J. Am. Chem.
Soc. 1975, 97, 4063-4068.
12. a) M. J. Hadd, J. Gervay, Carbohydr. Res. 1999, 320, 61-69; b) S. N.
Lam, J. Gervay-Hague, Org. Lett. 2002, 4, 2039-2042; c) S. N. Lam,
J. Gervay-Hague, Carbohydr. Res. 2002, 337, 1953-1965; d) A. H.
Adam Chu, S. H. Nguyen, J. A. Sisel, A. Minciunescu, C. S. Bennett,
Org. Lett. 2013, 15, 2566-2569 (TBAI).
4.25 Methyl
D-Glucopyranosyl-(14)-α-D-glucopyranosyl-
(1 6)-α- -glucopyranoside (48): Protected trisaccharide 47

D
(147 mg, 0.10 mmol) dissolved in 4:1:0.5 MeOH/EtOAc/AcOH
solvent mixture was treated with Pd/C (100 mg) under H2 (1 atm).
The reaction mixture was stirred at RT for 2 days and then filter
(over celite) to remove Pd/C. The resulting filtrate was
concentrated and purified by FPLC (Elution: 1:1 MeOH:H2O,
flow rate 0.5 mL/min) to obtain the trisaccharide 48 as a white
glassy solid (30 mg, 56%). For 48, Rf 0.09 (CH2Cl2/MeOH/H2O
13. U. Schmid, H. Waldmann, Eur. J. Org. Chem. 1997, 2573-2577 (LiI).
14. S. Koto et al. Bull. Chem. Soc. Jpn. 1999, 72, 765-777.
15. T. Mukaiyama, S. Suda, Chem. Lett. 1990, 143-146.
16. J. Park, S. Kawatkar, J. H. Kim, G. J. Boons, Org. Lett. 2007, 9, 1959-
1962.
17. S.-R. Lu, Y.-H. Lai, J.-H. Chen, C.-Y. Liu, K.-K. T. Mong, Angew.
Chem., Int. Ed. 2011, 50, 7315-7320
[ ]35
1
2/1/0.05);
훼
+28.8 (c 0.35, MeOH); H NMR (500 MHz,
D
CD3OD): δ 5.15 (d, J = 4.0 Hz, 1H, anomeric H), 4.85 (d, J = 4.0
Hz, 1H, anomeric H overlapped with residual H2O signals), 4.67
(d, J = 4.0 Hz, 1H, H-1), 3.92 – 3.88 (m, 2H), 3.86 – 3.64 (m,
8H), 3.61 (td, J = 3.0, 9.5 Hz, 2H), 3.54 (t, J = 9.5 Hz, 1H), 3.47
– 3.43 (m, 2H), 3.42 (s, 3H, CH3), 3.41 (m, 1H), 3.35 (dd, J =
10.0, 11.5 Hz, 1H), 3.27 (t, J = 9.0 Hz, 1H);13C NMR (125 MHz,
CD3OD): δ 103.0 (1JCH = 172.5 Hz), 101.5 (1JCH = 171.3 Hz),
100.0 (1JCH = 168.85 Hz), 81.8, 75.4, 75.2, 75.1, 74.9, 74.4, 73.5,
72.3, 72.1, 72.0, 71.6, 67.8, 62.9, 62.1, 56.0 (OCH3); HRMS-ESI
(m/z): [M + Na]+ calcd for C19H34NaO16+, 541.1739; found,
541.1745.
18. A. B. Ingle, C.-S. Chao, W.-C. Hung, K.-K. T. Mong, Org. Lett. 2013,
15, 5290-5293.
19. For preparation of compounds 1-4 and related references, see ESI
20. G. H. Veeneman, S. H. van Leeuwen, J. H. van Boom, Tetrahedron
Lett. 1990, 31, 1331-1334.
21. The stereocenter of acceptor
3 was found undergoing racemization at
higher reaction temperature and/or prolonged reaction time; therefore
it was not suitable for glycosylation study at higher temperature and
the reason for using the donor
2 is its simpler preparation procedure.
22. R. Caputo, H. Kunz, D. Mastroianni, G. Palumbo, S. Pedatella, F. Solla,
Eur. J. Org. Chem. 1999, 3147-3150 (NMR iodide).
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J. Gervay, T. N. Nguyen, M. J. Hadd, Carbohydr. Res. 1997, 300, 119-
125.
Acknowledgements
Thanks are given to the Ministry of Science and Technology
(MOST) of Taiwan for financial support (105–2627-M-009-012).
Notes and references
24. B. Cao, X.-Q. Chen, Y. Yamaryo-Botte, M. B. Richardson, K. L.
Martin, G. N. Khairallah, T. W. T. Rupasinghe, R. M. O'Flaherty, R.
A. J. O'Hair, J. E. Ralton, P. K. Crellin, R. L. Coppel, M. J. McConville,
S. J. Williams, J. Org. Chem. 2013, 78, 2175-2190 (long reaction time
for iodide).
a
Applied Chemistry Department, National Chiao Tung University of
Taiwan, 1001, University Road, Hsinchu, Taiwan, Republic of China.
E-mail: tmong@mail.ncut.edu.tw; Fax: +886-3-5723764.
b Institute of Biological Chemistry, Academia Sinica, Room 802, 128,
Academia Road Sec. 2, Nankang, Taipei 115, Taiwan, Republic of China.
25. Y. F. Yen, R. C. Sawant, S. Y. Luo, Synthesis, 2013, 45, 511 (heat).
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9083 (Micorwave).
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spectroscopic data for preparation of building blocks
1, 2a, 2a, 2b, 3, 4-
27. Preparation of 14 was given in supporting information.
28. H.-J. Lin, A. K. Adak, L. V. Reddy, S.-H. Wu, C.-C. Lin, Chem. Eur.
J. 2013, 19, 7989-7998.
13, oligomannans 14 21 are available. See DOI: 10.1039/b000000x/
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, 497-
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3453.
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32. B. Ghosh, Y. H. Lai, Y. Y. Shih, T. K. Pradhan, C. H. Lin, K. K. T.
4. K. L. M. Hoang, X. W. Liu, Nature Commun. 2014, 5, 10.
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33. H. W. He, X. M. Zhu, Org. Lett. 2014, 16, 3102-3105 (α-disaccharide
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6
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This journal is © The Royal Society of Chemistry 2012
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Page 12 of 12
ARTICLE
Journal Name
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12 | J. Name., 2012, 00, 1-3
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