Triethylamine-methanol mediated selective removal of oxophenylacetyl ester in saccharides

Article abstract of DOI:10.1039/d0ob02192j

A highly selective, mild, and efficient method for the cleavage of oxophenylacetyl ester protected saccharides was developed using triethylamine in methanol at room temperature. The reagent proved successful against different labile groups like acetal, ketal, and PMB and also generated good yields of the desired saccharides bearing lipid esters. Further, we also observed DBU in methanol as an alternative reagent for the deprotection of acetyl, benzoyl, and oxophenylacetyl ester groups. This journal is

Full text of DOI:10.1039/d0ob02192j

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DOI: 10.1039/D0OB02192J
ARTICLE
Triethylamine-Methanol Mediated Selective Removal of
Oxophenylacetyl Ester in Saccharides
Javeed Ur Rasool,a,c Atul Kumar,a,b,c Asif Ali,d and Qazi Naveed Ahmeda
Received 00th January 20xx,
Accepted 00th January 20xx
A highly selective, mild, and efficient method for the cleavage of oxophenylacetyl ester protected saccharides was
developed using triethylamine in methanol at room temperature. The reagent proved successful against different labile
groups like acetal, ketal, and PMB and also generated good yields of the desired saccharides bearing lipid esters. Further,
we also observed DBU in methanol as an alternative reagent for the deprotection of acetyl, benzoyl, and oxophenylacetyl
ester groups.
DOI: 10.1039/x0xx00000x
a) Previous work:
Introducing Oxophenylacetyl ester (OPAc) as a New Protecting
Group for Carbohydrates
Introduction
OH
OOPAc
AcPOO
O
O
KHSO5 (10.0 mmol)
dry MeOH-DCM (1:1)
HO
Owing to the presence of multiple hydroxyl groups in
saccharides and the need for controlled unmasking
(orthogonality) of protecting groups in the chemical synthesis
of oligosaccharides, careful manipulations are needed to
obtain good selectivity and yield for the removal of a
protecting group (PG).1-5 The difficulty obviously arises from
the presence of more groups with similar reactivity.6-8 As a
result, methods that can achieve high selectivity and good
yields are indispensable.9-12 Recently, we developed
oxophenylacetyl ester (OPAc) as a new protecting group for
carbohydrates and demonstrated its divergent base sensitivity
profiles against benzoyl (Bz) and acetyl (Ac) groups.13 Further,
KHSO5/AcCl in methanol was identified as an efficient
deprotecting reagent for its removal in the presence of
different protecting groups such as Bn, Bz, Ac, Me, TIPS,
TBDMS, All, Nap, Levulinyl, Pivolyl, etc (Scheme 1a). However,
acetal, ketal and PMB based protections were found sensitive
to both reagents and, with the lipidated model saccharides,
generated the desired product in lower yields with poor
selectivity (Scheme 1b). To address this limitation and to
improvise the better selectivity/yields, we envisage the
possibility of testing different amine bases against OPAc. The
key inspiration for this work is the enhanced electrophilic
character of CO group in OPAc that might assist us to examine
O
O
7
7
7
7
O
O
O
OMe
OMe
O
10 h, 65 o
C
7
7
7
7
69%
O
O
b) Limitaion:
In oxone/ AcCl environment, groups like acetal, ketal and PMB were found sensitive.
Substrates containing lipid chain gave low yields and generated mixture of products.
c) This work:
TEA as an alternative reagent for better selective cleavage of OPAc
PG
PG
PG= Bn, Bz, Ac, Me, TIPS,
TBDMS, All, NAP, acetal,
ketal, PMB, lipids etc
TEA
O
O
HO
n(AcPO)O
n
MeOH:DCM (8:2)
rt, 1-2 h
4
3
Scheme 1: Summary of this work.
different reagents against time and concentration.14 In this
study, we established that different saccharides when treated
with a fixed concentration of triethylamine in methanol
selectively lead to the cleavage of OPAc in presence of other
protecting groups in efficient yields (Scheme 1c). The method
also proved to be very successful for the selective cleavage of
OPAc against different labile groups like acetal, ketal and PMB,
as well as lipidated saccharides and in our case, no unwanted
ester or acyl migration was observed during the cleavage of
OPAc. Further, DBU in methanol was observed as an
alternative mild reagent for the efficient deprotection of
acetyl, benzoyl and oxophenylacetyl ester groups.
Results and discussion
Initially, model substrate 1a (1 mmol) was stirred with 0.3 mmol of
TEA in methanol for 30 m (Table 1, entry 1) resulting in the selective
cleavage of OPAc to afford the desired product 2a in 37% yield.
a.Medicinal Chemistry Division, Council of Scientific and Industrial
Research-Indian Institute of Integrative Medicine (CSIR-IIIM), Jammu- Further, investigation against time led to the generation of the
180001 India and Academy of scientific and innovative research,
Council of Scientific and Industrial Research-Indian Institute of
desired product 2a in 84% yield in 90 m with the same
concentration of TEA (entry 3). However, continuous stirring for
more time resulted in the mixture of other products 2c and 2d
(entries 4-6). Further, screening of base concentration (entry 7) and
solvents did not improve the selectivity and yield of the reaction
Integrative Medicine (CSIR-IIIM), Jammu-180001 India.
b.Department of Chemistry and Chemical Sciences, Central University of
Jammu, Rahya-Suchani (Bagla), District Samba, Jammu-180001, India.
c. Both authors contributed equally.
dCSIR-Traditional Knowledge Digital Library (TKDL) 14-Satsang Vihar,
Vigyan Suchna Bhawan, New Delhi-110067
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ARTICLE
Journal Name
OBz
OBz
Table 1. Optimization of the reaction.
2
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OH
OH
OAc
OAc
O
O
DOI: 10.1039/D0OB02192J
HO
HO
AcPOO
O
O
HO
O
O
AcO
AcPOO
HO
reagent AcO
AcPOO
+
+
HO
HO
HO
solvent,
time
BzO
BzO
BzO
HO
OMe
OMe
BzO
BzO
OMe
88
91
OMe
OMe
OMe
1b
2b
1a
2a
2c
2d
OOPAc
O
OH
3
entry
reagent (mmol)
time
yield (%)
O
O
AcPOO
AcPOO
HO
HO
(min)
solvent
2a
2c
2d
BzO
1
2
TEA(0.3)
TEA(0.3)
TEA (0.3)
TEA(0.3)
TEA(0.3)
TEA(0.3)
TEA (0.5)
TEA(0.3)
TEA(0.3)
TEA(0.3)
30
60
90
120
180
240
90
90
90
90
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeCN
DCM
Acetone:
H2O (9:1)
DMF
MeOH
MeOH
37
63
84
69
52
35
83
57
46
77
-
-
7
22
33
21
14
-
-
-
-
-
12
34
-
-
-
-
BzO
OH
OMe
OMe
OMe
1c
2c
a3
4
OOPAc
O
4
5
5
6
7
8
9
10
AcPOO
AcPOO
HO
HO
89
93
AcPOO
HO
OMe
1d
2d
2e
-
13
OOPAc
OH
O
O
BnO
BnO
BnO
BnO
11
12
b13
14
15
16
17
18
19
20
TEA(0.3)
DIPEA(0.3)
DBU(0.3)
90
90
90
27
71
-
12
9
-
7
83
BnO
BnO
OH
OMe
OMe
trace
1e
TMEDA(0.3)
NH2NH3+.-OAc(0.3)
BnNH2(0.3)
90
60
60
15
90
90
90
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
69
76
79
-
43
35
57
23
14
10
-
-
-
-
-
-
-
-
-
87
-
-
-
-
-
OOPAc
O
6
7
8
O
AcPOO
BnO
HO
BnO
NaOMe(0.3)
BnO
Piperidine(0.3)
PEG-400(0.3)
NH4.OAc(0.3)
NH2NH3+.-OAc(0.3)
BnNH2 (0.3)
BnO
OMe
OMe
OMe
92
89
89
1f
2f
OH
OOPAc
O
21
22
90
90
DMF
THF
-
-
O
HO
LevO
AcPOO
LevO
PivO
PivO
OMe
Reaction condition: a) For selective OPAc cleavage: 1a (1 mmol), TEA (0.3
mmol) in 3 mL of MeOH at 35C for 90 min. At rt. b) For deacylation
reaction: 1a (1 mmol), DBU (0.3 mmol) in 3 mL of MeOH at rt for 90 min.
at 35C.
1g
2g
OTIPS
O
OTIPS
O
HO
HO
AcPOO
AcPOO
BzO
BzO
OMe
OMe
(entries 8-11). Mixture of products was obtained after employing
other hindered bases like DIPEA, DBU and TMEDA (entries 12-14).
Meanwhile, during screening we also observed that stirring of 1a (1
mmol) against DBU (0.3 mmol) predominantly generated 2d in 83%
yield (entry 13). The reaction was also performed with previously
known reagents used for anomeric deacetylation.15 It was found
that ammonium acetate and benzylamine in methanol (entry 15
and 16) were good to some extent, however, not much
improvisation in the yield was observed. Other reagents tested
(entries 17-20) were found very less efficient as compared with TEA
in methanol. Lastly, reaction of 1a was performed with hydrazine
acetate and benzylamines in DMF and THF respectively. However
they failed to form any products (entries 21 and 22) which indicates
that the reaction pathway most likely follows transesterification
mechanism rather than simple aminolysis.16
2h
1h
OOPAc
O
OH
9
O
HO
PMBO
AcPOO
PMBO
PMBO
O
PMBO
OMe
OMe
91
92
2i
Ph
1i
Ph
10
11
O
O
O
O
O
HO
AcPOO
AcPOO
HO
OMe
OMe
1j
2j
O
O
O
O
O
O
O
O
O
O
AcPOO
HO
89
90
1k
2k
12
AcPOO
AcPOO
BzO
HO
O
O
HO
BzO
Table 2. Scope of the reaction.
BzO
BzO
OMe
OMe
O
O
1l
2l
TEA
AcPOO
HO
MeOH, rt, 1-2 h
1
2
Reaction condition: 1 (1 mmol), TEA (0.3 mmol) in 3 mL of MeOH at rt
for 90 min.
entry
substrate
product
yield(%)
84
OAc
O
OAc
1
O
After establishing the conditions for deprotection, we investigated
the scope of the reaction by removing OPAc in presence of different
protecting groups at the different positions of saccharides (Table 2).
Primarily, orthogonality of OPAc was tested in presence of different
acyl groups (OAc and Bz) under the optimized conditions which lead
AcO
AcO
HO
AcPOO
BzO
BzO
OMe
OMe
1a
2a
2 | J. Name., 2012, 00, 1-3
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ARTICLE
to the selective cleavage of OPAc in all of the five substrates anchored saccharides through ester linkages. Interestingly, all the
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DOI: 10.1039/D0OB02192J
(entries 1-3, 8 and 12). Further, a reaction with tetra-OPAc substrates provided the corresponding OPAc deprotected
protected saccharide 1d lead to the formation of desired product saccharides (4a-4e) between 89-94% yields (Table 3). These
2d in 89% yield. The selectivity of the optimized reaction condition examples further validated our results and could serve as an asset
was further tested with different saccharides containing protecting in the total synthesis of glycolipids like glycosylphosphatidylinositol
groups like Bn, TIPS, Levulinyl and Pivaloyl. As expected, OPAc was GPI and gangliosides.
cleaved against OBn protected saccharides to form 2e and 2f while
as Pivolyl, Levulinyl and TIPS were found very stable and formed 2g
and 2h respectively in appreciable yields (entries 5-8). Later on, we
focused towards the acid sensitive groups like PMB, benzylidine and
The commonly encountered problem in saccharides with acyl/ester
groups like OAc and OBz is their tendency to migrate towards
neighbouring hydroxyl groups especially under basic conditions.17
Thinking of this possibility, 2D-NMR analysis of 2l and 4a was
acetal (entries 9-11) and no interference with the aforementioned
carried out. In both the cases no acyl migration was noted (See the
sensitive groups while employing TEA in methanol was observed.
supporting information page: 54-58).
Thus, the orthogonal stability of these groups was achieved in
Further, as depicted in optimization table (Table 1, entry 13) DBU in
methanol was found to be an alternative mild reagent that
simultaneously resulted in the unmasking of all acetyl protections
like OAc, OBz and OPAc in saccharide 1a to form 2d in 83% yield. In
order to validate its generality four different reactions were carried
out and deacylated products (2d, 6a and 6b) were obtained in 87-
93% yields (Table 4).
better yields by selective removal of OPAc (entries 9-11).
Table 3. Scope against lipidated saccharides.
Lipid
Lipid
TEA
O
O
HO
n(AcPO)O
n
MeOH:DCM (8:2)
rt, 1-2 h
4
3
entry
1
substrate
AcPOO
AcPOO
O
product
yield(%)
93
HO
O
HO
O
O
O
Table 4. Scope against DBU promoted deacylation reactions.
O
11
OMe
11
OMe
O
O
O
DBU (0.5 eq.)
O
PO
HO
O
11
13
MeOH, rt,
30-90 min
O
11
6
5, 2b
P = OPAc, Bz, Ac
4a
3a
HO
HO
O
2
AcPOO
entry
1
substrate
product
O
yield (%)
91
O
O
O
O
AcPOO
BzO
HO
HO
HO
HO
HO
89
91
O
O
13
OMe
OMe
13
O
O
OH
O
BzO
OMe
OMe
O
13
4b
2b
2d
3b
AcO
AcO
AcO
HO
HO
HO
O
O
2
3
4
3
4
C8H18
C8H18
O
O
O
7
7
O
O
O
AcPOO
BnO
O
HO
AcO
HO
OOPAc
OH
93
87
89
BnO
5a
6a
BnO
BnO
OMe
OMe
AcO
AcO
AcO
HO
HO
HO
3c
O
4c
C5H11
AcO
HO
OH
OH
C5H11
O
O
O
5b
6a
6
AcPOO
HO
HO
HO
6
O
O
O
AcPOO
AcPOO
O
HO
BnO
O
SPhMe
SPhMe
AcPOO
BnO
94
93
AcPOO
HO
BnO
OH
OMe
BnO
OM
5c
6b
4d
3d
OOPAc
O
5
Reaction condition: 5, 2b (1 mmol), DBU (0.3 mmol) in 3 mL of
MeOH at rt for 90 min.
HO
O
AcPOO
O
O
7
7
7
7
7
O
O
O
O
O
OMe
OMe
7
7
7
O
3e
4e
Conclusion
Reaction condition: 3 (1 mmol), TEA (0.3 mmol) in 3 mL of
In conclusion, TEA was demonstrated as a better, selective
deprotecting reagent for the cleavage of OPAc. In addition, cleavage
of OPAc with TEA was successfully established in the saccharides
bearing different labile groups like acetal, ketal and PMB. Further,
saccharide bearing lipid esters were obtained with improvised
yields (>90%). These optimized conditions did not lead to any
unwanted migration of ester or acyl groups. Meanwhile, it was
observed that DBU in MeOH was an alternative reagent for the
deprotection of Bz, Ac and OPAc groups. The reaction more likely
MeOH:DCM (8:2) at rt for 90 min.
With these established conditions in hand we proceeded to check
the application of our reaction for the selective deprotection of
OPAc in lipidated saccharides (Table 3, entries 1-5). In order to
achieve better solubility we slightly modified our conditions (for
details see supporting information, Page 1). For this purpose,
different commonly used unsaturated lipids like mysitic acid (3a),
palmitic acid (3b), oleic acid (3c, 3e) and linolenic acid (3d)
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follows transesterification mechanism, a cleaner reaction than was evaporated under reduced pressure. The resulting reaction
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DOI: 10.1039/D0OB02192J
simple aminolysis.
mixture was then extracted with EtOH. The gummy solid
compounds (2a-2k) thus obtained were purified through column
chromatography by EtOH and n-Hexane.
Experimental
D. General Procedure for oxobenzoyl protection of lipid Sugars.
(Series 3). To a stirred solution of sugar alcohol (1.0 eq.) was added
DIC (1.2eq.), Lipid (1.2eq.) and DMAP (1.2eq.) in dry DCM under
nitrogen atmosphere. The reaction was allowed to continue for 3-4
h at 35 oC and monitored by thin layer chromatography. The
reaction mixture was dissolved in EtOAc and washed thrice with 3%
aqueous HCl followed by NaHCO3 wash. The organic layer was
collected and dried over Na2SO4, and evaporated on vacuum. The
products (3a-3e) were purified by column chromatography on silica
gel using EtOAc/Hexane as eluting agents.
A. General Information.
Solvents were purified according to standard procedures, and
reagents used were of highest purity available. All reactions were
performed in flame-dried glass apparatus under argon/nitrogen
atmosphere unless mentioned otherwise. Anhydrous solvents like
CH2Cl2, CH3OH, CH3CN, DMF, pyridine, and Et3N were freshly dried
using standard methods. NMR measurements (1H, 13C, 2D H-1H-
1
1
COSY and H-13C HMBC, HMQC, and NOESY) were recorded on a
400 and 500 MHz spectrometer fitted with pulse-field gradient
probe, and trimethylsilane (TMS) or residual resonance of
deuterated solvent were used as internal reference. 13C NMR
spectra were broadband 1H decoupled or inverse HMQC
experiments. Chemical shifts are expressed in ppm and coupling
constants J in Hz. High-resolution mass spectral data were obtained
from Q-ToF Mass Spectrometer coupled LC system. The following
conditions were used: capillary voltage 3500 V, capillary
temperature 350 οC, auxiliary gas flow rate 7.0 L/min, spray voltage
4.5 kV, mass range 100-1000 amu (maximum resolution 30000).
Optical rotations were measured on a digital polarimeter. Analytical
TLC was performed on 60 F254 plates, and compounds visualized by
methanol-sulphuric acid/ceric-sulfate developing reagent. Silica
column chromatography was carried out with silica gel 60 (60-120
mesh) or flash silica gel (230-400 mesh). Analytical and semi-
preparative HPLC purification were carried out on reversed-phase
(C18, 250 X 10 mm, L i.d.) column connected to an binary pump and
monitored using an photodiode array detector.
E. General Procedure for oxobenzoyl deprotection of lipid Sugars.
(Series 4). The oxobenzoyl protected lipidated saccharide was
dissolved in dry MeOH/DCM (8:2) and triethyl amine (TEA) was
added in stoichiometric portions. For each hydroxyl group of the
saccharide 0.5 equiv of TEA was added. The reaction was carried at
an ambient temperature (35oC) under nitrogen atmosphere and
monitored by TLC. After the reaction was completed, the reaction
was quenched by 0.1 N HCl and the solvent were evaporated under
reduced pressure. The resulting reaction mixture was then
extracted with EtOH. The compounds (4a-4e) obtained were
purified through column chromatography by EtOH and n-Hexane as
eluting agents.
F. General Procedure for overall deprotection of OPAc, OAc, OBz
and Lipid protected sugars. (Series 5). The protected saccharide
was dissolved in dry MeOH and 0.5 equiv of DBU was added for
each protected hydroxyl group of the sugar. The lipidated
saccharides were dissolved in dry MeOH/DCM (8:2). The reaction
was carried openly at an ambient temperature (30oC) and
monitored by TLC. All the reactions were completed within 1/2 to1h
time scale. The reaction was quenched by 0.1 N HCl and the solvent
were evaporated under reduced pressure. The resulting reaction
mixture was then extracted with EtOH. The compounds (6a-6c)
obtained were purified through column chromatography by EtOH
and n-Hexane as eluting agents.
B. General Procedure for oxobenzoyl protection of sugars. (Series
1)
For each of the hydroxyl group present, 1.2 mmol DIC,
Phenylglyoxalic acid and DMAP was utilized. To a stirred solution of
sugar alcohol (1.0 eq.) was added DIC (1.2eq.), phenylglyoxalic acid
(1.2 eq.) and DMAP (1.2eq.) in dry DCM under nitrogen atmosphere
o
and then stirred for 3 h at 35 C. The reaction was monitored by
thin layer chromatography. The reaction mixture was dissolved in
EtOAc and washed thrice with 3% aqueous HCl (20 mL), followed by
NaHCO3 wash. The organic layer was collected and dried over
Na2SO4, and evaporated on vacuum. The products (1a-1k) were
purified by column chromatography on silica gel using EtOAc and n-
Hexane as eluting agents.
G. Procedure for some starting material synthesis.
1. General Procedure for the synthesis of starting compound of 3a,
3b and 3e.
To a solution of Methyl α-D-glucopyranoside (1.0 equiv) in
anhydrous MeCN (50 mL) was added Benzaldehyde dimethyl acetal
(1.1 equiv) and camphorsulfonic acid (0.2 equiv) in catalytic
amount. The reaction mixture was stirred at room temperature for
4 h. After completion of the reaction confirmed by TLC, the reaction
mixture was extracted with ethyl acetate after which the combined
organic layer was washed with brine, dried over Na2SO4, and
concentrated in vaccum. The residue was dissolved in dry DCM and
added lipid acids (mysitic acid for 3a, palmitic acid for 3b, and oleic
acid for 3e) (2.2 equiv), DIC (2.2 equiv), and DMAP (2.2 equiv). The
reaction mixture was stirred at room temperature for 4 h. After the
C. General Procedure for oxobenzoyl deprotection of sugars.
(Series 2)
The oxophenylacetyl ester protected sugar was dissolved in dry
MeOH and triethyl amine (TEA) was added stoichiometrically. For
each hydroxyl group of the sugar 0.5 equiv of TEA was added. The
reaction was carried at an ambient temperature (35 oC) under
nitrogen atmosphere and monitored by TLC. After the reaction was
completed, the reaction was quenched by 0.1 N HCl and the solvent
4 | J. Name., 2012, 00, 1-3
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130.14, 129.81, 129.80, 129.58, 129.07, 128.74, 128.68, 128.61, 128.49,
completion of the reaction, the reaction mixture was extracted with
ethyl acetate and 2N HCl (2-3 times), dried over Na2SO4, and then
concentrated in vaccum. In the last step the deprotection of
benzylidene was carried out using catalytic amount of P-TSA in
methanol to obtain the desired product (Methyl- 4, 6-di-O-2, 3-
mesytyl-α-D-glucopyranoside, Methyl- 4, 6-di-O-2, 3-dipalmyl-α-D-
glucopyranoside and Methyl-2, 3-di-O-oleoyl-α-D-glucopyranoside).
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96.87, 71.81, 71.32, 69.50, 67.35, 62.02, 55.82. (ref 13)
DOI: 10.1039/D0OB02192J
1c. Methyl-3, 4, 6-tri-O-oxobenzoyl-2-O-benzoyl-α-D-glucopyranoside
(Starting material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.13 – 8.10 (m, 2H), 8.07 – 8.00 (m, 4H), 7.73
(dd, J = 8.3, 1.1 Hz, 2H), 7.67 – 7.60 (m, 3H), 7.54 – 7.43 (m, J = 16.3, 7.8 Hz,
7H), 7.08 (t, J = 7.9 Hz, 2H), 6.15 (t, J = 9.8 Hz, 1H), 5.56 (t, J = 9.8 Hz, 1H),
5.26 (d, J = 3.6 Hz, 1H), 5.20 (dd, J = 10.2, 3.6 Hz, 1H), 4.71 – 4.61 (m, J =
12.2, 3.8 Hz, 2H), 4.41 – 4.36 (m, J = 10.1, 4.6, 2.9 Hz, 1H), 3.45 (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 185.51, 185.36, 184.95, 165.37, 163.25, 163.12,
162.25, 135.32, 135.07, 134.98, 133.84, 132.34, 131.83, 131.74, 130.28,
130.15, 129.78, 129.14, 128.96, 128.80, 128.75, 128.71, 96.83, 71.69, 71.05,
2. General Procedure for the synthesis of starting compound of 3a,
3c and 3d.
To a solution of Methyl α-D-glucopyranoside (1.0 equiv) in 69.65, 67.00, 63.12, 55.97. (ref 13)
1d. Methyl-2, 3, 4, 6-tetra-O-oxobenzoyl-α-D-glucopyranoside (Starting
anhydrous MeCN (50 mL) was added benzaldehyde dimethyl acetal
(1.1 equiv) and camphorsulfonic acid in catalytic amount. The
reaction mixture was stirred at room temperature for 4 h. After
completion of the reaction confirmed by TLC, the reaction mixture
was extracted with ethylacetate after which the combined organic
layer was washed with brine, dried over Na2SO4, and concentrated
material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.07 – 7.95 (m, 6H), 7.92 – 7.86 (m, 2H), 7.68 –
7.60 (m, 3H), 7.56 – 7.44 (m, J = 21.4, 13.1, 6.0 Hz, 7H), 7.40 (t, J = 7.8 Hz,
2H), 6.08 (t, J = 9.8 Hz, 1H), 5.56 (t, J = 9.8 Hz, 1H), 5.37 (d, J = 3.5 Hz, 1H),
5.23 (dd, J = 10.2, 3.6 Hz, 1H), 4.66 (qd, J = 12.3, 3.7 Hz, 2H), 4.43 – 4.35 (m, J
= 10.1, 4.5, 2.8 Hz, 1H), 3.53 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 185.49,
185.11, 184.81, 184.75, 163.20, 162.66, 162.42, 162.15, 135.42, 135.36,
in vaccum. Benzyl bromide (2.2 equiv) was added to the residue in
o
DMF and the reaction was stirred at 0 C and NaH (4.0 equiv) was 135.22, 132.24, 131.99, 131.73, 131.71, 130.28, 130.18, 130.08, 130.05,
129.16, 129.10, 129.06, 129.02, 96.19, 72.60, 70.47, 69.66, 67.00, 62.93,
56.06. (ref 13)
added gradually in small quantities for some time. After the
addition of NaH, the reaction mixture was stirred at room
temperature for 3 h to get the dibenzylated product. The reaction
mixture was quenched with cold water and extracted with DCM,
dried over Na2SO4, and concentrated in vaccum. The product was
used without column chromatography for the deprotection of
benzylidene group in presence of the catalytic amount of P-TSA to
1e. Methyl-6-O-oxobenzoyl-2, 3, 4-tri-O-benzyl-α-D-glucopyranoside
(Starting material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.03 – 7.94 (m, 2H), 7.64 (t, J = 7.4 Hz, 1H), 7.45
(t, J = 7.8 Hz, 2H), 7.36 – 7.26 (m, 15H), 5.00 (d, J = 10.9 Hz, 1H), 4.91 (d, J =
11.0 Hz, 1H), 4.81 (t, 2H), 4.67 – 4.58 (m, J = 14.0, 10.9 Hz, 4H), 4.51 – 4.44
(m, J = 11.7, 5.1 Hz, 1H), 4.03 (t, J = 9.2 Hz, 1H), 3.96 – 3.90 (m, J = 10.0, 5.0,
obtain Methyl-2,3-di-O-benzyl-α-D-glucopyranoside. To the solution 2.0 Hz, 1H), 3.54 – 3.49 (m, J = 9.7, 3.2 Hz, 2H), 3.37 (s, 3H). 13C NMR (101
MHz, CDCl3) δ 185.89, 163.55, 138.59, 138.07, 137.86, 134.91, 132.43,
130.06, 128.85, 128.51, 128.43, 128.10, 127.99, 127.96, 127.94, 127.68,
98.15, 81.84, 79.91, 77.56, 75.79, 75.16, 73.43, 68.58, 64.38, 55.38. (ref 13)
1f. Methyl-4, 6-di-O-oxobenzoyl-2, 3-di-O-benzyl-α-D-glucopyranoside
(Starting material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.03 (dd, J = 8.3, 1.1 Hz, 2H), 7.93 (dd, J = 8.3, 1.1
Hz, 2H), 7.66 – 7.58 (m, 2H), 7.47 (t, J = 7.8 Hz, 2H), 7.37 – 7.23 (m, 12H),
5.27 (t, 1H), 4.96 (d, J = 11.2 Hz, 1H), 4.80 (d, J = 12.1 Hz, 1H), 4.72 – 4.58 (m,
of Methyl-2,3-di-O-benzyl-α-D-glucopyranoside in dry DCM was
added lipid acid (oleic acid for 3c and linolenic acids for 3d in 1.1
equiv), DIC (1.1 equiv) and DMAP (1.1 equiv). The reaction was
stirred at room temperature for 4 h. After completion of the
reaction confirmed by TLC, the reaction mixture was extracted with
ethylacetate after which the combined organic layer was washed
with brine, dried over Na2SO4, and concentrated in vaccum. The
product was isolated by column chromatography by using ethyl 4H), 4.49 (dd, J = 12.1, 2.6 Hz, 1H), 4.20 – 4.07 (m, 2H), 3.66 (dd, J = 9.6, 3.5
Hz, 1H), 3.40 (s, 3H).13C NMR (101 MHz, CDCl3) δ 185.66, 185.48, 163.39,
162.70, 138.14, 137.74, 135.08, 134.96, 132.37, 132.09, 130.21, 130.10,
acetate and hexane as an eluent.
128.97, 128.89, 128.59, 128.47, 128.37, 128.15, 127.61, 127.55, 98.19,
79.60, 78.39, 75.44, 73.59, 71.88, 67.04, 63.69, 55.69. (ref 13)
1g. Methyl-4, 6-di-O-oxobenzoyl-3-O-levulinyl-2-O-pivaloyl-α-D-glucopyran
oside (Starting material was synthesized from literature13).
H. Characterization Data:
1a. Methyl-3-O-oxobenzoyl-2-benzoyl-4, 6- diacetyl-α-D glucopyra-
noside (Starting material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 7.8 Hz, 2H), 7.66 (d, J = 7.9 Hz, 2H),
7.61 (t, J = 7.4 Hz, 1H), 7.46 (dd, J = 14.9, 7.4 Hz, 3H), 7.08 (t, J = 7.7 Hz, 2H),
5.96 (t, J = 9.9 Hz, 1H), 5.26 (t, J = 9.9 Hz, 1H), 5.18 – 5.10 (m, 2H), 4.29 (dd, J
= 12.3, 4.6 Hz, 1H), 4.16 – 4.06 (m, 2H), 3.41 (s, 3H), 2.09 (d, J = 7.3 Hz, 6H).
13C NMR (101 MHz, CDCl3) δ 185.78, 170.69, 169.44, 165.43, 163.82, 135.01,
133.80, 131.76, 130.10, 129.94, 129.69, 128.93, 128.77, 128.72, 128.59,
96.91, 71.79, 71.51, 68.04, 67.50, 61.92, 55.73, 20.74, 20.54. (ref 13)
1H NMR (400 MHz, CDCl3) δ 8.05 – 7.98 (m, 2H), 7.99 – 7.92 (m, 2H), 7.64 (t,
J = 7.4 Hz, 2H), 7.50 (t, J = 7.7 Hz, 4H), 5.71 (t, J = 9.8 Hz, 1H), 5.30 (t, J = 9.8
Hz, 1H), 5.00 (d, J = 3.6 Hz, 1H), 4.82 (dd, J = 10.2, 3.7 Hz, 1H), 4.58 (qd, J =
12.2, 3.7 Hz, 2H), 4.27 – 4.19 (m, J = 10.2, 4.6, 2.7 Hz, 1H), 3.37 (s, 3H), 2.74 –
2.61 (m, 2H), 2.52 (dd, J = 9.9, 4.0 Hz, 2H), 2.07 (s, 3H), 1.17 (s, 9H). 13C NMR
(101 MHz, CDCl3) δ 205.74, 185.56, 184.82, 177.67, 171.44, 163.31, 162.38,
135.19, 135.11, 132.27, 132.07, 130.12, 130.07, 129.03, 128.97, 96.85,
70.78, 70.43, 69.45, 66.72, 63.25, 55.90, 38.77, 37.67, 29.62, 27.88, 26.84.
(ref 13)
1h. Methyl-3, 4-O-dioxobenzoyl-2-O-benzoyl-6-O-(triisopropylsilyl) α-D-
glucopyranoside (Starting material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 7.4 Hz, 2H), 8.06 (d, J = 7.4 Hz, 2H),
7.77 (d, J = 7.4 Hz, 2H), 7.64 (dd, J = 11.8, 7.3 Hz, 2H), 7.50 (d, J = 7.3 Hz, 5H),
7.08 (t, J = 7.8 Hz, 2H), 6.16 (s, 1H), 5.65 (t, J = 9.8 Hz, 1H), 5.23 (d, J = 1.9 Hz,
2H), 4.13 – 4.07 (m, 1H), 3.99 (d, J = 3.0 Hz, 2H), 3.45 (s, 3H), 1.10 (d, J = 5.4
1b.
Methyl-3,4-di-O-oxobenzoyl-2,6-di-O-benzoyl-α-D-glucopyranoside
(Starting material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.12 (dd, J = 7.7, 6.5 Hz, 4H), 8.03 (dd, 2H), 7.76
(dd, J = 8.3, 1.2 Hz, 2H), 7.64 (ddd, 2H), 7.58 – 7.55 (m, J = 7.8, 1.6 Hz, 1H),
7.52 – 7.45 (m, 7H), 7.12 – 7.07 (m, J = 8.2, 7.6 Hz, 2H), 6.18 (td, 1H), 5.72 (t,
J = 9.9 Hz, 1H), 5.27 – 5.22 (m, J = 7.3, 3.6 Hz, 2H), 4.72 (dd, J = 12.5, 2.3 Hz,
1H), 4.54 (dd, J = 12.5, 4.2 Hz, 1H), 4.41 – 4.37 (m, J = 10.2, 4.0, 2.3 Hz, 1H),
3.47 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 185.42, 184.93, 166.05, 165.41,
163.16, 162.06, 135.19, 134.95, 133.79, 133.26, 131.93, 131.77, 130.25,
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Organic & Biomolecular Chemistry
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ARTICLE
Journal Name
Hz, 18H). 13C NMR (101 MHz, CDCl3) δ 185.71, 185.51, 165.50, 163.53, 1H NMR (400 MHz, MeOD) δ 7.98 (d, 2H), 7.51 (t, J = 7.4 Hz,V1ieHw),A7rt.ic3l8e O(tn,liJn=e
162.27, 135.20, 134.98, 133.80, 132.03, 131.81, 130.24, 130.16, 129.82, 7.7 Hz, 2H), 4.90 (d, J = 3.6 Hz, 1H), 4.79 – 4.71 (m, 3H), 3.90 (t, J = 9.4 Hz,
DOI: 10.1039/D0OB02192J
129.10, 128.77, 128.72, 96.65, 72.14, 71.87, 70.14, 69.40, 61.94, 55.43, 1H), 3.80 – 3.76 (m, 1H), 3.67 – 3.62 (m, 1H), 3.55 – 3.51 (m, 1H), 3.38 (t, J =
17.95, 12.03. LCMS (ESI-TOF): m/z [M + H]+ Calcd for C39H49O10Si, 705.31; 9.1 Hz, 1H), 3.29 (s, 3H). 13C NMR (101 MHz, MeOD) δ 166.38, 133.07,
found: 705.35
129.79, 129.46, 128.17, 97.11, 74.16, 72.17, 71.15, 70.51, 61.19, 54.21. (ref
1i. Methyl-4,6-di-O-oxobenzoyl-2,3- di-O- (4-methoxybenzyl) -α-D- 13)
glucopyranoside (Starting material was synthesized from literature13).
2d. Methyl-α-D-glucopyranoside.
1H NMR (400 MHz, CDCl3) δ 7.93 (dd, J = 21.8, 7.4 Hz, 4H), 7.58 (t, J = 7.0 Hz, 1H NMR (400 MHz, MeOD) δ 3.55 (s, 3H), 3.34 (d, J = 11.6 Hz, 1H), 2.50 (d, J =
2H), 7.39 (dt, J = 25.5, 7.8 Hz, 4H), 7.22 (d, J = 9.3 Hz, 2H), 7.13 (d, J = 8.5 Hz, 11.6 Hz, 1H), 2.40 – 2.26 (m, 1H), 2.26 – 2.16 (m, 1H), 2.08 (d, J = 8.7, 4.6 Hz,
2H), 6.82 (d, J = 8.5 Hz, 2H), 6.70 (d, J = 8.5 Hz, 2H), 5.16 (t, J = 9.8 Hz, 1H), 2H), 2.03 – 1.91 (m, J = 20.8, 11.3 Hz, 1H).13C NMR (101 MHz, MeOD) δ
4.79 (d, J = 10.7 Hz, 1H), 4.70 (d, J = 11.8 Hz, 1H), 4.53 (t, J = 4.4 Hz, 2H), 4.12 103.84, 77.73, 76.15, 76.11, 74.38, 65.29, 58.11. (ref 13)
– 4.05 (m, J = 7.8, 5.3 Hz, 1H), 4.01 (t, J = 9.4 Hz, 1H), 3.75 (d, J = 8.4 Hz, 3H), 2e. Methyl-2, 3, 4-tri-O-benzyl-α-D-glucopyranoside.
3.70 (s, 3H), 3.34 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 185.68, 185.37, 1H NMR (400 MHz, CDCl3) δ 7.43 – 7.26 (m, 15H), 5.00 (d, J = 10.9 Hz, 1H),
163.39, 162.53, 159.58, 159.16, 135.11, 134.99, 132.27, 132.08, 130.28, 4.92 – 4.79 (m, 3H), 4.67 (dd, J = 11.6, 6.2 Hz, 2H), 4.60 (d, J = 3.5 Hz, 1H),
130.16, 129.82, 129.34, 128.98, 128.89, 113.98, 113.76, 98.27, 79.06, 78.09, 4.03 (t, J = 9.2 Hz, 1H), 3.80 – 3.64 (m, 3H), 3.57 – 3.50 (m, 2H), 3.38 (s, 3H).
75.21, 73.27, 71.85, 66.95, 63.66, 55.69, 55.29, 55.22. LRMS (ESI-TOF): m/z 13C NMR (101 MHz, CDCl3) δ 138.84, 138.24, 138.20, 128.49, 128.41, 128.13,
[M + Na]+ Calcd for C39H38NaO12, 721.2261; found: 721.10
128.03, 127.96, 127.86, 127.61, 98.25, 82.00, 80.12, 77.57, 75.74, 75.04,
1j. Methyl-2, 3-di-O-oxobenzoyl-4,6-O-benzylidene-α-D-glucopyranoside 73.43, 70.77, 61.94, 55.21. (ref 13)
(Starting material was synthesized from literature13).
2f. Methyl-2, 3-di-O-benzyl-α-D-glucopyranoside.
1H NMR (400 MHz, CDCl3) δ 8.00 (dd, 2H), 7.86 (dd, 2H), 7.65 (t, J = 7.4 Hz, 1H NMR (400 MHz, CDCl3) δ 7.40 – 7.25 (m, 10H), 5.00 (d, J = 11.5 Hz, 2H),
1H), 7.57 – 7.48 (m, 5H), 7.43 – 7.38 (m, J = 6.5, 3.6 Hz, 3H), 7.19 (t, J = 7.9 4.73 (q, J = 13.5, 11.9 Hz, 1H), 4.64 (d, J = 12.1 Hz, 1H), 4.59 (d, J = 3.5 Hz,
Hz, 2H), 6.00 (t, J = 9.9 Hz, 1H), 5.56 (s, 1H), 5.31 (dd, J = 9.9, 3.7 Hz, 1H), 1H), 3.82 – 3.68 (m, 3H), 3.62 – 3.55 (m, 1H), 3.55 – 3.44 (m, 2H), 3.36 (s,
5.22 (d, J = 3.7 Hz, 1H), 4.38 (dd, J = 10.4, 4.9 Hz, 1H), 4.12 – 4.04 (m, J = 9.9, 3H), 2.67 (s, 1H), 2.21 (s, 1H).13C NMR (101 MHz, CDCl3) δ 138.80, 138.06,
4.9 Hz, 1H), 3.83 (td, J = 10.0, 4.7 Hz, 2H), 3.52 (s, 3H). 13C NMR (101 MHz, 128.61, 128.51, 128.10, 128.00, 127.96, 127.88, 98.25, 81.40, 79.90, 75.40,
CDCl3) δ 185.99, 185.42, 163.23, 163.03, 136.69, 135.22, 134.92, 132.05, 73.16, 70.82, 70.49, 62.41, 55.26. (ref 13)
130.12, 130.06, 129.38, 129.15, 128.81, 128.39, 126.34, 102.10, 97.33, 2g. Methyl-3-O-levulinyl-2-O-pivaloyl-α-D-glucopyranoside.
79.18, 72.41, 70.39, 68.84, 62.45, 55.80. (ref 13)
1k. 1, 2:5, 6-di-O-isopropylidene-3-O-oxobenzoyl-α-D-glucofuranoside
(Starting material was commercially available).
1H NMR (400 MHz, CDCl3) δ 5.32 (t, 1H), 4.82 (d, J = 3.6 Hz, 1H), 4.63 (dd, J =
10.2, 3.7 Hz, 1H), 4.12 (s, 1H), 3.78 (s, 2H), 3.72 – 3.59 (m, 2H), 3.31 (s, 3H),
3.16 (s, 1H), 2.79 – 2.37 (m, 4H), 2.11 (s, 3H), 1.09 (s, 9H). 13C NMR (101
1H NMR (400 MHz, CDCl3) δ 8.10 – 7.97 (m, 2H), 7.67 (t, J = 7.5 Hz, 1H), 7.50 MHz, CDCl3) δ 207.90, 177.95, 172.54, 96.88, 73.11, 71.19, 70.88, 68.90,
(t, J = 7.8 Hz, 2H), 5.93 (d, J = 3.7 Hz, 1H), 5.65 (d, J = 3.0 Hz, 1H), 4.64 (d, J = 61.58, 55.35, 38.68, 37.96, 29.80, 27.97, 26.82. (ref 13)
3.7 Hz, 1H), 4.27 (dd, J = 8.6, 3.0 Hz, 1H), 4.20 – 4.12 (m, J = 8.5, 5.8, 4.6 Hz, 2h. Methyl-2-O-benzoyl-6-O-triisopropylsilyl –α-D-glucopyranoside.
1H), 4.12 – 4.06 (m, J = 8.7, 6.0 Hz, 1H), 4.05 – 3.97 (m, J = 8.8, 4.5 Hz, 1H), 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 7.3 Hz, 2H), 7.50 (t, J = 7.4 Hz, 1H),
1.54 (s, 3H), 1.46 (s, 3H), 1.33 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 185.64, 7.38 (d, J = 7.7 Hz, 2H), 4.97 (d, J = 3.5 Hz, 1H), 4.87 (dd, J = 10.0, 3.6 Hz, 1H),
162.49, 135.16, 132.30, 130.11, 128.93, 112.47, 109.56, 105.36, 83.28, 4.12 (t, J = 9.2 Hz, 1H), 3.98 – 3.90 (m, 2H), 3.88 (s, 1H), 3.78 – 3.48 (m, 4H),
80.20, 77.27, 72.34, 67.60, 26.92, 26.74, 26.23, 25.23. (ref 13)
3.33 (s, 3H), 1.08 (t, J = 6.0 Hz, 18H). 13C NMR (101 MHz, CDCl3) δ 166.49,
1l. Methyl-2,6- di-O-oxobenzoyl-2, 3-di-O- benzoyl-α-D-glucopyranoside.
133.18, 129.94, 129.73, 128.34, 97.07, 73.93, 72.96 (s), 71.70, 70.68, 64.61,
1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 9.8 Hz, 2H), 8.01 (dd, J = 15.5, 7.8 Hz, 55.06. LCMS (ESI-TOF): m/z [M + H]+ Calcd for C23H41O6Si, 441.26; found:
4H), 7.68 (d, J = 7.5 Hz, 3H), 7.59 – 7.48 (m, 5H), 7.45 – 7.35 (m, J = 15.0, 7.5 441.20
Hz, 4H), 7.14 (t, J = 7.5 Hz, 2H), 6.14 (t, J = 10.2 Hz, 1H), 5.65 (t, J = 9.8 Hz, 2i. Methyl-2, 3-di-O-4-methoxybenzoyl -α-D-glucopyranoside.
1H), 5.27 (d, J = 6.5 Hz, 2H), 4.68 (d, J = 10.6 Hz, 2H), 4.43 (d, J = 10.1 Hz, 1H), 1H NMR (400 MHz, CDCl3) δ 7.28 (t, J = 7.7 Hz, 4H), 6.87 (d, J = 6.9 Hz, 4H),
3.45 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 185.59, 185.10, 165.77, 165.33, 4.92 (d, J = 11.1 Hz, 1H), 4.79 – 4.49 (m, J = 23.8, 21.2, 7.3 Hz, 4H), 3.79 (d, J
163.31, 162.64, 135.08, 133.56, 133.50, 132.38, 131.66, 130.20, 129.99, = 2.5 Hz, 6H), 3.58 (d, J = 9.5 Hz, 1H), 3.51 – 3.43 (m, 2H), 3.36 (s, 3H). 13C
129.80, 129.05, 128.98, 128.88, 128.81, 128.58, 128.48, 97.10, 71.93, 70.06, NMR (101 MHz, CDCl3) δ 159.47, 159.37, 130.89, 130.16, 129.72, 129.64,
69.99, 66.93, 63.22, 55.91. LCMS (ESI-TOF): m/z [M + H2O]+ Calcd for 114.03, 113.91, 98.30, 80.97, 79.46, 75.00, 72.80, 70.77, 70.39, 62.38, 55.27,
C37H32O13, 684.18; found: 684.25
2a. Methyl -2-benzoyl-4, 6- diacetyl-α-D-glucopyranoside.
1H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 7.3 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 2j. Methyl-4, 6-O-benzylidine -α-D-glucopyranoside.
55.27, 55.24. LCMS (ESI-TOF): m/z [M + Na]+ Calcd for C23H30NaO8, 457.18;
found: 457.30
7.45 (t, J = 7.7 Hz, 2H), 5.09 – 4.97 (m, 3H), 4.34 – 4.08 (m, 3H), 3.99 (ddd, J = 1H NMR (400 MHz, CDCl3) δ 7.55 – 7.50 (m, 2H), 7.40 (d, J = 4.4 Hz, 3H), 5.55
10.1, 4.7, 2.1 Hz, 1H), 3.40 (d, J = 4.6 Hz, 3H), 2.12 (d, J = 6.2 Hz, 6H). 13C NMR (s, 1H), 4.79 (d, J = 3.7 Hz, 1H), 4.31 (dd, J = 9.6, 4.2 Hz, 1H), 3.94 (t, J = 9.2
(101 MHz, CDCl3) δ 170.79, 170.71, 166.32, 133.44, 129.96, 129.45, 128.56, Hz, 1H), 3.83 – 3.78 (m, 2H), 3.63 (s, 1H), 3.53 (d, J = 9.2 Hz, 1H), 3.47 (d,
128.47, 97.23, 73.99, 71.09, 70.24, 67.34, 62.28, 55.56, 20.85, 20.75. (ref 13)
3H), 2.81 (s, 1H), 2.20 (s, 1H). 13C NMR (101 MHz, CDCl3) δ 137.17, 129.25,
2b. Methyl-2, 6-di-O-benzyl-α-D-glucopyranoside.
128.33, 126.40, 101.95, 99.94, 99.88, 81.04, 72.85, 71.53, 71.50, 68.97,
1H NMR (400 MHz, CDCl3) δ 8.14 – 8.04 (m, 4H), 7.58 (td, J = 7.4, 1.1 Hz, 2H), 62.44, 55.53, 30.90. (ref 13)
7.45 (q, J = 8.0 Hz, 4H), 5.07 (d, J = 3.7 Hz, 1H), 4.98 (dd, J = 10.0, 3.7 Hz, 1H), 2k. 1, 2:5, 6-di-O-isopropylidene-α-D-glucofuranoside.
4.73 (dd, J = 12.1, 4.8 Hz, 1H), 4.59 (dd, J = 12.1, 2.0 Hz, 1H), 4.22 (t, J = 9.4 1H NMR (400 MHz, CDCl3) δ 5.95 (d, J = 3.3 Hz, 1H), 4.54 (d, J = 3.3 Hz, 1H),
Hz, 1H), 3.97 (ddd, J = 9.9, 4.7, 1.9 Hz, 1H), 3.88 (s, 1H), 3.65 (t, J = 9.4 Hz, 4.38 – 4.29 (m, J = 12.9, 5.1 Hz, 2H), 4.17 (t, 1H), 4.07 (d, J = 5.6 Hz, 1H), 3.99
1H), 3.41 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 167.23, 166.48, 133.40, (dd, J = 8.4, 5.4 Hz, 1H), 2.63 (d, J = 3.5 Hz, 1H), 1.47 (d, J = 21.5 Hz, 6H), 1.35
133.36, 129.97, 129.84, 129.61, 129.50, 128.49, 128.45, 97.30, 73.74, 71.62, (d, J = 18.0 Hz, 6H).13C NMR (101 MHz, CDCl3) δ 111.85, 109.68, 105.32,
70.75, 69.56, 63.76, 55.38. (ref 13)
85.13, 81.20, 75.25, 73.50, 67.70, 26.88, 26.78, 26.21, 25.17. (ref 13)
2c. Methyl-2-O-benzoyl -α-D-glucopyranoside.
2l. Methyl- 2, 3-di-O- benzoyl-α-D-glucopyranoside.
6 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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1H NMR (400 MHz, CDCl3) δ 7.96 (t, J = 7.6 Hz, 4H), 7.49 – 7.43 (m, J = 16.6, (m, 4H), 2.02 (s, 6H), 1.59 (dd, J = 14.0, 6.9 Hz, 4H), 1.30 (d, J = 9.8 Hz, 42H),
7.6 Hz, 2H), 7.35 – 7.29 (m, J = 16.0, 8.0 Hz, 4H), 5.81 (t, J = 9.6 Hz, 1H), 5.20 0.90 (t, J = 6.6 Hz, 6H). 13C NMR (101 MHz, CDCl ) δ 185.52,V1ie8w4.A8r0ti,cl1e7O2n.l9in0e,
3DOI: 10.1039/D0OB02192J
(dd, J = 10.0, 3.3 Hz, 1H), 5.13 (d, J = 3.4 Hz, 1H), 4.00 (d, J = 9.5 Hz, 1H), 3.95 172.38, 163.30, 162.47, 135.24, 135.08, 132.31, 132.00, 130.15, 130.06,
(d, J = 3.2 Hz, 2H), 3.89 – 3.85 (m, 1H), 3.41 (s, 3H). 13C NMR (101 MHz, 130.02, 129.98, 129.69, 129.66, 129.05, 128.97, 96.92, 70.78, 70.54, 69.07,
CDCl3) δ 167.16, 166.10, 133.35, 133.30, 129.89, 129.82, 129.43, 129.15, 66.74, 63.25, 55.74, 34.11, 34.03, 31.92, 29.78, 29.72, 29.67, 29.64, 29.54,
128.40, 128.38, 97.17, 73.96, 71.85, 71.54, 69.56, 61.89, 55.41. LCMS (ESI- 29.37, 29.34, 29.27, 29.18, 29.13, 29.12, 29.04, 27.24, 27.19, 24.88, 24.80,
TOF): m/z [M + Na]+ Calcd for C21H22NaO8, 425.12; found: 425.15
22.69, 14.11. (ref 13)
3a. Methyl- 4, 6-di-O- oxobenzoyl-2, 3-mesytyl-α-D-glucopyranoside.
4a. Methyl- 4, 6-di-O-2, 3-mesytyl-α-D-glucopyranoside.
1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 7.3 Hz, 2H), 7.95 (d, J = 7.3 Hz, 2H), 1H NMR (400 MHz, CDCl3) δ 5.32 – 5.25 (m, 1H), 4.90 (d, J = 3.6 Hz, 1H), 4.86
7.67 (t, 2H), 7.52 (q, J = 7.1 Hz, 4H), 5.69 (t, 1H), 5.30 (t, J = 3.4 Hz, 1H), 5.01 – 4.78 (m, 1H), 3.92 – 3.78 (m, 3H), 3.68 (d, J = 7.6 Hz, 2H), 3.38 (s, 3H), 2.38
(d, J = 3.5 Hz, 1H), 4.92 (dd, J = 10.2, 3.6 Hz, 1H), 4.65 – 4.54 (m, J = 2.6 Hz, – 2.24 (m, 6H), 2.16 (s, 1H), 1.58 (s, 3H), 1.24 (s, 38H), 0.87 (t, J = 6.8 Hz, 6H).
2H), 4.30 – 4.23 (m, J = 8.9 Hz, 1H), 3.41 (s, 3H), 2.38 – 2.20 (m, 5H), 2.17 (s, 13C NMR (101 MHz, CDCl3) δ 96.95, 73.34, 71.36, 70.63, 70.07, 62.10, 55.29,
2H), 1.58 (s, 5H), 1.24 (d, J = 11.7 Hz, 36H), 0.88 (t, 6H).13C NMR (101 MHz, 34.37, 34.15, 31.94, 29.70, 29.68, 29.51, 29.37, 29.30, 29.13, 29.11, 25.02,
CDCl3) δ 185.53, 184.81, 172.95, 172.41, 163.30, 162.47, 135.23, 135.07, 24.97, 22.69, 14.09. LCMS (ESI-TOF): m/z [M + Na]+ Calcd for C35H66NaO8,
134.44, 132.33, 132.01, 130.15, 129.98, 129.75, 129.04, 129.01, 128.96, 637.46; found: 637.70
96.93, 70.78, 70.57, 69.07, 66.75, 63.27, 55.74, 34.14, 34.06, 31.93, 29.69, 4b. Methyl- 4, 6-di-O-2, 3-dipalmyl-α-D-glucopyranoside.
29.66, 29.63, 29.50, 29.46, 29.36, 29.26, 29.15, 29.07, 24.89, 24.81, 22.69, 1H NMR (400 MHz, CDCl3) δ 5.28 (t, J = 8.6 Hz, 1H), 4.90 (s, 1H), 4.84 (d, J =
18.64, 14.10. LCMS (ESI-TOF): m/z [M + H2O]+ Calcd for C51H76O13, 896.52; 7.4 Hz, 1H), 3.91 – 3.78 (m, 2H), 3.70 (s, 2H), 3.39 (s, 3H), 2.31 (d, J = 6.0 Hz,
found: 896.70
6H), 1.25 (s, 50H), 0.88 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 174.89, 173.10,
3b. Methyl- 4, 6-di-O-2, 3-dipalmyl-α-D-glucopyranoside.
96.93, 73.41, 71.33, 70.58, 70.13, 62.12, 55.27, 37.11, 34.36, 34.14, 31.93,
1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 7.4 Hz, 2H), 7.95 (d, J = 7.4 Hz, 2H), 30.04, 29.70, 29.67, 29.50, 29.49, 29.36, 29.28, 29.11, 29.09, 27.09, 25.01,
7.66 (t, J = 7.4 Hz, 2H), 7.51 (dd, J = 13.8, 7.3 Hz, 4H), 5.69 (t, J = 9.8 Hz, 1H), 24.96, 23.44, 22.68, 19.73, 14.08. LCMS (ESI-TOF): m/z [M + H2O]+ Calcd for
5.31 (t, J = 9.8 Hz, 1H), 5.01 (d, J = 3.4 Hz, 1H), 4.92 (dd, J = 10.2, 3.5 Hz, 1H), C39H76O9, 688.54; found: 688.60
4.65 – 4.53 (m, 2H), 4.30 – 4.21 (m, 1H), 3.40 (s, 3H), 2.34 – 2.24 (m, 4H), 4c Methyl- 2, 3-dibenzyl-4-O-6-oleoyl-α-D-glucopyranoside.
1.61 – 1.50 (m, 6H), 1.24 (d, J = 11.3 Hz, 46H), 0.88 (t, J = 6.6 Hz, 6H).13C NMR 1H NMR (400 MHz, CDCl3) δ 7.37 – 7.21 (m, J = 14.8, 7.1 Hz, 10H), 5.36 (s,
(101 MHz, CDCl3) δ 185.54, 184.82, 172.95, 172.43, 163.32, 162.48, 135.26, 2H), 4.98 (d, 1H), 4.78 (d, J = 11.3 Hz, 2H), 4.69 – 4.62 (m, J = 12.9, 7.4 Hz,
135.10, 132.31, 132.00, 130.17, 129.99, 129.06, 128.98, 96.93, 70.77, 70.54, 2H), 4.38 (dd, J = 4.8 Hz, 1H), 4.26 (d, J = 11.9 Hz, 1H), 3.81 (t, 1H), 3.52 (t,
69.06, 66.75, 63.25, 55.75, 34.14, 34.07, 31.96, 29.73, 29.70, 29.66, 29.53, 1H), 3.39 (s, 3H), 2.33 (t, J = 7.4 Hz, 2H), 2.03 (d, J = 5.2 Hz, 4H), 1.62 (s, 2H),
29.49, 29.40, 29.30, 29.17, 29.09, 24.91, 24.83, 22.72. LCMS (ESI-TOF): m/z 1.29 (s, 20H), 0.91 (t, J = 5.2 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 174.05,
[M + H]+ Calcd for C55H83O12, 935.58; found: 935.70
3c. Methyl- 2, 3-dibenzyl-4-O-oxobenzoyl-6-oleoyl-α-D-glucopyranoside.
138.74, 138.06, 129.99, 129.73, 128.53, 128.47, 128.08, 128.03, 127.96,
127.82, 98.19, 81.26, 79.62, 75.56, 73.21, 70.15, 69.46, 65.11, 63.16, 55.18,
1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.7 Hz, 2H), 7.60 (t, J = 7.4 Hz, 1H), 41.89, 37.13, 34.13, 32.64, 31.94, 31.55, 29.79, 29.72, 29.70, 29.56, 29.35,
7.41 – 7.22 (m, 12H), 5.32 (dd, J = 18.4, 8.5 Hz, 3H), 4.95 (d, J = 11.1 Hz, 1H), 29.18, 29.12, 29.11, 28.97, 27.25, 27.20, 27.12, 24.89, 22.71, 14.15. LCMS
4.81 (d, J = 12.0 Hz, 1H), 4.73 (d, J = 11.1 Hz, 1H), 4.70 – 4.64 (m, 2H), 4.34 (ESI-TOF); m/z: [M + H]+ Calcd for C39H59O7, 639.42; found: 639.70
(dd, J = 12.3, 4.5 Hz, 1H), 4.18 (dd, J = 12.3, 2.2 Hz, 1H), 4.08 (dd, J = 16.4, 6.9 4d. Methyl- 2, 3-dibenzyl-4-O-6-linolyl-α-D-glucopyranoside.
Hz, 2H), 3.67 (dd, J = 9.5, 3.5 Hz, 1H), 3.41 (s, 3H), 2.37 (d, J = 3.3 Hz, 2H), 1H NMR (400 MHz, CDCl3) δ 7.34 (dd, J = 15.8, 5.2 Hz, 10H), 5.35 (dd, J =
2.02 (d, J = 2.9 Hz, 2H), 1.68 – 1.58 (m, 2H), 1.29 (d, J = 6.6 Hz, 22H), 0.89 (t, J 12.2, 5.8 Hz, 4H), 4.99 (dd, J = 11.3, 5.6 Hz, 1H), 4.84 – 4.60 (m, 4H), 4.40
= 6.4 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 185.54, 173.40, 162.51, 138.20, (dd, J = 11.9, 5.0 Hz, 1H), 4.23 (d, J = 12.1 Hz, 1H), 3.86 – 3.67 (m, 2H), 3.50
137.82, 134.95, 132.22, 130.11, 129.98, 129.78, 128.92, 128.56, 128.36, (dd, J = 9.5, 3.6 Hz, 1H), 3.40 (dd, J = 13.1, 7.8 Hz, 3H), 2.77 (d, J = 5.3 Hz,
128.14, 128.11, 127.67, 127.61, 98.25, 79.64, 78.58, 75.49, 73.57, 71.80, 2H), 2.33 (dd, J = 9.0, 5.7 Hz, 2H), 2.17 (d, J = 5.9 Hz, 2H), 2.05 (d, J = 5.5 Hz,
67.19, 62.08, 55.52, 34.03, 31.92, 29.78, 29.71, 29.53, 29.33, 29.17, 29.13, 4H), 1.30 (s, 14H), 0.92 – 0.84 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 185.56,
27.24, 27.20, 25.67, 24.80, 22.69, 14.11, 11.12. LCMS (ESI-TOF): m/z [M + 173.40, 162.53, 138.21, 137.84, 134.97, 132.23, 130.23, 130.13, 130.08,
H]+ Calcd for C47H63O9, 771.45; found: 771.55
3d. Methyl- 2, 3-dibenzyl-4-O-oxobenzoyl-6-linolyl-α-D-glucopyranoside.
128.94, 128.58, 128.38, 128.15, 128.08, 127.98, 127.69, 127.64, 98.27,
79.73, 78.59, 75.51, 73.59, 71.80, 67.20, 62.09, 55.54, 34.04, 31.56, 29.74,
1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.9 Hz, 2H), 7.61 (t, J = 7.2 Hz, 1H), 29.64, 29.38, 29.19, 29.13, 27.24, 25.69, 24.81, 22.72, 22.60, 14.09, 14.08.
7.41 – 7.30 (m, 10H), 7.27 (d, J = 5.9 Hz, 2H), 5.45 – 5.28 (m, 5H), 4.96 (d, J = LCMS (ESI-TOF): m/z [M + H]+ Calcd for C39H57O7, 637.41; found; 637.40
11.0 Hz, 1H), 4.82 (d, J = 12.1 Hz, 1H), 4.74 (d, J = 11.1 Hz, 1H), 4.67 (d, J = 4e. Methyl-2,3-di-O-oleoyl-α-D-glucopyranoside.
12.3 Hz, 2H), 4.36 (dd, J = 12.3, 4.2 Hz, 1H), 4.17 (d, J = 11.0 Hz, 1H), 4.10 (t, J 1H NMR (400 MHz, CDCl3) δ 5.41 – 5.28 (m, 5H), 4.92 (d, J = 3.6 Hz, 1H), 4.84
= 9.5 Hz, 1H), 4.04 (d, J = 9.9 Hz, 1H), 3.67 (dd, J = 9.5, 3.2 Hz, 1H), 3.41 (s, (dd, J = 10.2, 3.6 Hz, 1H), 3.92 – 3.83 (m, 2H), 3.76 – 3.68 (m, J = 13.6, 5.4 Hz,
3H), 2.78 (t, J = 6.0 Hz,21H), 2.37 (td, J = 7.3, 3.6 Hz, 2H), 2.09 – 2.02 (m, 4H), 2H), 3.41 (s, 3H), 2.37 – 2.28 (m, 4H), 2.06 – 2.00 (m, J = 12.4, 6.4 Hz, 6H),
1.29 (d, J = 10.7 Hz, 16H), 0.90 (t, J = 6.2 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 1.61 (s, 4H), 1.29 (d, J = 9.6 Hz, 42H), 0.90 (t, J = 8.7, 4.8 Hz, 6H). 13C NMR
174.04, 138.76, 138.10, 130.22, 130.03, 128.57, 128.49, 128.12, 128.08, (126 MHz, CDCl3) δ 174.69, 173.17, 130.03, 129.65, 96.85, 73.02, 71.29,
128.05, 127.97, 127.86, 98.23, 81.29, 79.70, 75.57, 73.22, 70.21, 69.49, 70.61, 69.73, 61.89, 55.26, 34.33, 34.09, 31.92, 29.77, 29.73, 29.55, 29.39,
63.19, 55.22, 34.16, 31.55, 29.72, 29.62, 29.37, 29.17, 29.12, 29.11, 28.88, 29.34, 29.23, 29.22, 29.15, 29.09, 29.05, 27.23, 27.18, 25.62, 24.99, 24.92,
27.23, 25.69, 24.91, 22.71, 22.59, 14.08. LCMS (ESI-TOF); m/z [M + H]+ Calcd 22.70, 14.14. (ref 13)
for C47H61O9, 769.43; found: 769.50
3e. Methyl-4, 6-di-O-oxobenzoyl-2, 3-di-O-oleoyl-α-D-glucopyranoside.
5a. 1-O-oxobenzoyl- 2, 3, 4, 6-penta-O-acetyl α-D-glucopyranoside (Starting
material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 8.1 Hz, 2H), 7.98 (d, J = 8.0 Hz, 2H), 1H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 7.8 Hz, 1H), 7.89 (d, J = 7.8 Hz, 1H),
7.69 (t, J = 7.4 Hz, 2H), 7.54 (dd, J = 13.9, 7.5 Hz, 4H), 5.72 (t, J = 9.8 Hz, 1H), 7.75 – 7.61 (m, 1H), 7.61 – 7.43 (m, J = 23.2, 7.7 Hz, 2H), 6.56 (dd, J = 32.3,
5.43 – 5.29 (m, 5H), 5.04 (d, J = 3.5 Hz, 1H), 4.95 (dd, J = 10.2, 3.5 Hz, 1H), 3.5 Hz, 1H), 5.61 – 5.42 (m, J = 43.3 Hz, 1H), 5.34 (dd, J = 3.6 Hz, 1H), 5.22 –
4.63 (qd, J = 12.2, 3.6 Hz, 2H), 4.33 – 4.25 (m, 1H), 3.43 (s, 3H), 2.37 – 2.27
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Organic & Biomolecular Chemistry
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Journal Name
5.16 (m, 1H), 4.28 (td, J = 12.9, 3.9 Hz, 1H), 4.17 (dd, J = 9.4, 4.2 Hz, 1H), 4.13
– 4.05 (m, 1H), 2.10 – 1.97 (m, 12H).
5b. 1, 2, 3, 4, 6-Penta O-acetyl α-D-glucopyranoside (Starting material was
synthesized from literature13).
6
7
8
Jian G.; Xin-Shan, Y.; Molecules 2010, 15, 7235-7265.
DOI: 10.1039/D0OB02192J
Swarts, B. M.; Guo, Z.; Chem. Sci. 2011, 2, 2342-2352.
Lloyd, D.; Bylsma, M.; Bright, D. K.; Chen, X.; Bennett,
C. S. J. Org. Chem. 2017, 82, 3926-3934.
View Article Online
1H NMR (400 MHz, CDCl3) δ 5.48 (t, J = 9.8 Hz, 1H), 5.39 (d, J = 2.5 Hz, 1H),
5.03 (t, J = 9.5 Hz, 2H), 4.82 (dd, J = 10.2, 3.4 Hz, 1H), 4.24 – 4.17 (m, 2H),
4.07 (d, J = 10.6 Hz, 1H), 2.04 (d, J = 4.2 Hz, 6H), 1.98 (d, J = 7.3 Hz, 6H).
5c. (4-methyl) Phenyl-2, 3, 4, 6-tetra-O-oxobenzoyl-1-deoxy-1-thio-α-D-
glucopyranoside (Starting material was synthesized from literature13).
1H NMR (400 MHz, CDCl3) δ 8.16 (dd, 2H), 8.08 – 8.02 (m, 2H), 7.97 (d, J = 8.3
Hz, 4H), 7.85 (d, J = 8.3 Hz, 2H), 7.63 (m, J = 15.7, 12.4, 7.6, 1.4 Hz, 7H), 7.50
(t, J = 7.8 Hz, 2H), 7.46 – 7.37 (m, 4H), 7.28 (s, 1H), 5.92 (dd, J = 9.4 Hz, 1H),
5.70 (t, J = 9.5 Hz, 1H), 5.40 (t, J = 9.8 Hz, 1H), 4.86 (s, 1H), 4.65 (dd, J = 12.6,
2.4 Hz, 1H), 4.55 (dd, J = 12.6, 4.4 Hz, 1H), 4.23 – 4.12 (m, J = 10.0, 4.2, 2.4
Hz, 1H), 2.36 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 185.23, 184.40, 184.35,
184.24, 162.99, 162.00, 161.59, 161.19, 146.53, 135.49, 135.32, 135.23,
134.72, 133.86, 132.13, 132.05, 131.65, 131.59, 130.93, 130.65, 130.52,
130.27, 130.16, 129.96, 129.88, 129.21, 129.13, 129.03, 128.94, 128.34,
88.08, 75.58, 73.73, 68.47, 68.10, 62.05, 21.74.
9
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6a. β-D-Glucose
1H NMR (400 MHz, D2O) δ 5.10 (d, J = 3.7 Hz, 1H), 4.51 (d, J = 7.9 Hz, 1H),
3.78 – 3.55 (m, 6H), 3.40 (dd, J = 9.8, 3.7 Hz, 1H), 3.33 (D, J = 11.2, 5.5 Hz,
1H), 3.27 (M, J = 9.4, 4.4 Hz, 2H), 3.11 (t, J = 8.6 Hz, 1H).
6b. (4-methyl) Phenyl-1-deoxy-1-thio-α-D-glucopyranoside.
1H NMR (400 MHz, DMSO-D6) δ 7.37 (d, J = 8.1 Hz, 2H), 7.12 (d, J = 8.0 Hz,
2H), 5.24 (d, J = 6.0 Hz, 1H), 5.08 (d, J = 4.9 Hz, 1H), 4.97 (d, J = 5.3 Hz, 1H),
4.61 – 4.42 (m, 2H), 3.75 – 3.63 (m, 1H), 3.49 – 3.40 (m, J = 11.9, 6.0 Hz, 1H),
3.27 – 3.12 (m, J = 9.5, 4.0 Hz, 2H), 3.13 – 2.94 (m, 2H), 2.27 (s, 3H). 13C NMR
(101 MHz, MeOD) δ 137.60, 132.38, 132.24, 129.52, 129.25, 88.22, 80.54,
78.20, 72.29, 69.97, 61.48, 19.78. (ref 13)
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
J. R is thankful to the Council of Scientific and Industrial
Research (CSIR) for the award of SRF and A.K is thankful to the
DST-SERB for the award of NPDF (PDF/2019/000348). This
work was generously supported by CSIR network project
through grant no. HCP-0008. IIIM communication no.
IIIM/2241/2018.
Notes and references
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1998, 120, 7137–7138.
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Wunberg, T.; Kallus, C.; Opatz, T.; Henke, S.; Schmidt,
W.; Kunz, H. Angew. Chem., Int. Ed. 1998, 37, 2503–
2505.
3
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Zhu, T.; Boons, G. J. Tetrahedron Asymmetry 2000, 11,
199–205.
Arranz, E.; Boons, G. J. Tetrahedron Lett. 2001, 42,
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Tanaka, H.; Amaya, T.; Takahashi, T.; Tetrahedron Lett.
2003, 44, 3053–3057.
8 | J. Name., 2012, 00, 1-3
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Page 9 of 9
Organic & Biomolecular Chemistry
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DOI: 10.1039/D0OB02192J
Triethylamine-Methanol Mediated Selective Removal of Oxophenylacetyl
Ester in Saccharides
Javeed Ur Rasool,a,c Atul Kumar,a,b,c Asif Ali,d and Qazi Naveed Ahmed a
A highly selective, mild and efficient method for the cleavage of oxophenylacetyl ester
protected saccharides was developed using triethylamine in methanol at room temperature.
The reagent proved successful against different labile groups like acetal, ketal and PMB and also
generated good yields of the desired saccharides bearing lipid esters. Further, we also observed
DBU in methanol as an alternative reagent for the deprotection of acetyl, benzoyl and
oxophenylacetyl ester groups.
OP
OP
TEA (0.3 mmol)
MeOH, rt, 1-2 h
O
O
HO
n(AcPO)O
n = 1-4
n
P = Bz, Ac, PMB, TIPS,
Bn, lipid, Acetals