Glycosyl alkoxythioimidates as complementary building blocks for chemical glycosylation

Article abstract of DOI:10.1021/ol1023079

It is reported that S-glycosyl O-methyl phenylcarbamothioates (SNea carbamothioates) have a fully orthogonal character in comparison to S-benzoxazolyl (SBox) glycosides. This complete orthogonality was revealed by performing competitive glycosylation expe

Full text of DOI:10.1021/ol1023079

Supporting information
Glycosyl thiocarbamates as complementary
building blocks for chemical glycosylation
Sneha C. Ranade, Sophon Kaeothip, and Alexei V. Demchenko*
Department of Chemistry and Biochemistry, University of Missouri – St. Louis, One University
Boulevard, St. Louis, MO 63121, USA; E-mail: demchenkoa@umsl.edu
Content:
General remarks
S2
S2
S3
S4
Synthesis of 3,4,6ꢀtriꢀOꢀbenzoylꢀ2ꢀOꢀbenzylꢀαꢀDꢀglucopyranosyl bromide (12)
Synthesis of 3,4,6ꢀtriꢀOꢀbenzoylꢀ2ꢀOꢀbenzylꢀβꢀDꢀglucopyranosyl thiocyanate (1a)
Synthesis of Oꢀmethyl phenylcarbamothioate
Synthesis of 2,3,4,6ꢀtetraꢀOꢀacetylꢀ1ꢀthioꢀβꢀDꢀglucopyranosyl Oꢀmethyl
phenylcarbamothioate (13)
S4
Synthesis of 2,3,4,6ꢀtetraꢀOꢀbenzoylꢀ1ꢀthioꢀβꢀDꢀglucopyranosyl Oꢀmethyl
phenylcarbamothioate (4c)
S5
Characterization data for glycosyl acceptors 2, 5ꢀ7
General procedures for glycosylation
S6
S8
General procedure for competitive glycosylations
Characterization data for disaccharides 8ꢀ11
NMR spectra
S9
S10
S12
S36
References
S1

General remarks.
Column chromatography was performed on silica gel 60 (EM Science, 70ꢀ230 mesh), reactions
were monitored by TLC on Kieselgel 60 F254 (EM Science). The compounds were detected by
examination under UV light and by charring with 10% sulfuric acid in methanol. Solvents were
o
removed under reduced pressure at < 40 C. CH2Cl2 and ClCH2CH2Cl were distilled from CaH2
directly prior to application. Methanol was dried by refluxing with magnesium methoxide,
distilled and stored under argon. Acetonitrile and pyridine were dried by refluxing with CaH2
and then distilled and stored over molecular sieves (3 Å). Acetone was dried by refluxing with
K2CO3 and then distilled and stored over molecular sieves (3 Å). KSCN was dried in vacuo at
150 oC for 24 h. Molecular sieves (3 Å or 4 Å), used for reactions, were crushed and activated in
vacuo at 390 °C during 8 h in the first instance and then for 2ꢀ3 h at 390 °C directly prior to
application. AgOTf was coꢀevaporated with toluene (3 x 10 mL) and dried in vacuo for 2ꢀ3 h
directly prior to application. Cu(OTf)2 was dried in vacuo for 1ꢀ2 h before using for
1
glycosylation. Optical rotations were measured at ‘Jasco Pꢀ1020’ polarimeter. Hꢀn.m.r. spectra
were recorded in CDCl3 at 300 MHz, 13CꢀNMR spectra were recorded in CDCl3 at 75 MHz
(Bruker Avance). HRMS determinations were made with the use of JEOL MStation (JMSꢀ700)
Mass Spectrometer.
3,4,6ꢀTriꢀOꢀbenzoylꢀ2ꢀOꢀbenzylꢀαꢀDꢀglucopyranosyl bromide (12).
A solution of acetyl bromide (4 mL, 54.29 mmol) and methanol (2.1 mL, 54.29 mmol) in
dichloromethane (25 mL) was added to a solution of 1,3,4,6ꢀtetraꢀOꢀbenzoylꢀ2ꢀOꢀbenzylꢀDꢀ
S2

glucopyranose1 (2.3 g, 3.393 mmol) in dichloromethane (15 mL) at 0 oC. The resulting reaction
mixture was stirred for 2 h at 0 oC and then washed with water (1 x 15 mL), sat. aq. NaHCO3 (15
mL), and water (3 x 15 mL). The organic layer was separated, dried with MgSO4, concentrated
in vacuo and dried to afford the title compound in 78% (1.7 g) yield, which was used directly in
subsequent synthesis of 1a. Spectral data of 12 was the same as reported previously.2
3,4,6ꢀTriꢀOꢀbenzoylꢀ2ꢀOꢀbenzylꢀβꢀDꢀglucopyranosyl thiocyanate (1a).
The title compound was obtained in accordance with the method reported previously.3 18ꢀ
Crownꢀ6 (85 mg, 0.3 mmol) and KSCN (312 mg, 3.0 mmol) were added to a stirred solution of
bromide 12 (690 mg, 1.0 mmol) in dry acetone (2.6 mL) and the reaction mixture was stirred
under argon for 2.5 h at rt. After that, the mixture was diluted with acetone (20 mL), the solid
was filtered off, rinsed with acetone (3 x 5 mL) and the combined filtrate was concentrated in
vacuo. The residue was purified by column chromatography on silica gel (ethyl acetateꢀhexane
gradient elution) to afford the title compound as a white foam in 65% (435 mg) yield. Analytical
22
1
data for 1a: Rf = 0.48 (ethyl acetate/hexanes, 3/7, v/v); [α]D 21.1o (c = 0.9, CHCl3); H n.m.r.:
δ, 4.14 (dd, 1H, J2,3 = 9.2 Hz, Hꢀ2), 4.24 (m, 1H, J5,6a = 5.0, J5,6b = 2.9 Hz, Hꢀ5), 4.56 (dd, 1H,
J6a,6b = 12.3 Hz, Hꢀ6a), 4.68 (dd, Hꢀ6b), 4.83 (dd, 2H, J2 = 10.7 Hz, CH2Ph), 4.94 (d, 1H, J1,2
=
9.3 Hz, Hꢀ1), 5.70 (dd, 1H, J4,5 = 9.8 Hz, Hꢀ4), 5.93 (dd, 1H, J3,4 = 9.4 Hz, Hꢀ3), 7.27ꢀ8.12 (m,
25H, aromatic) ppm; 13C n.m.r.: δ, 62.9, 68.9, 75.4, 75.9, 77.1, 79.1, 84.3, 108.5, 128.5 (x 3),
128.6 (x 2), 128.61 (x 2), 128.7 (x 6), 128.9, 129.6, 129.9 (x 2), 130.0 (x 4), 133.3, 133.6, 136.3,
165.3, 165.6, 166.2 ppm, HRꢀFAB MS[M+Na]+ calcd for C35H29NO8SNa+ 646.1512, found
646.1501.
S3

OꢀMethyl phenylcarbamothioate.
A solution of NaOMe in methanol (1M, 22.2 mL) was added to phenyl isothiocyanate (1.7 mL,
14.7 mmol) and the resulting mixture was stirred for 15 min at rt. After that, conc. HCl was
added till the pH ~ 4ꢀ5. The resulting white precipitate was filtered off and the filtrate was
concentrated in vacuo. The crude residue containing the title compound was used directly in
subsequent reactions with glycosyl bromides. The analytical data of the title compound were the
same as described previously.4
2,3,4,6ꢀTetraꢀOꢀacetylꢀ1ꢀthioꢀβꢀDꢀglucopyranosyl Oꢀmethyl phenylcarbamothioate (13).
OꢀMethyl phenylcarbamothioate (HSNea, 61 mg, 0.364 mmol) and NaOH (9.7 mg, 0.243 mmol)
were added to a stirring solution of 2,3,4,6ꢀtetraꢀOꢀacetylꢀαꢀDꢀglucopyranosyl bromide5 (100
mg, 0.243 mmol) in dry acetonitrile (1.2 mL) and the resulting reaction mixture was stirred for 1
h at rt. After that, the solid was filtered off and filtrate was washed with sat. aq. NaHCO3 (5 mL)
and water (3 x 5 mL). The organic layer was separated, dried with MgSO4 and concentrated in
vacuo. The residue was purified by column chromatography on silica gel (ethyl acetateꢀtoluene
gradient elution) to afford the title compound as a white foam in 60% (73 mg) yield. Analytical
data for 13: Rf = 0.42 (ethyl acetate/hexanes, 3/7, v/v); [α]D25 ꢀ1.9o (c = 1, CHCl3); Hꢀn.m.r.: δ,
1
1.99, 2.01, 2.03, 2.09 (4s, 12H, 4 x COCH3), 3.77 (m, 1H, J5,6a = 2.3 Hz, J5,6b = 4.7 Hz, Hꢀ5),
4.01 (s, 3H, OCH3), 4.14 (dd, 1H, J6a,6b = 12.4 Hz, Hꢀ6a), 4.25 (dd, 1H, Hꢀ6b), 4.99 (dd, 1H, J2,3
= 9.2 Hz, Hꢀ2), 5.07 (dd, 1H, J4,5 = 9.7 Hz, Hꢀ4), 5.22 (dd, 1H, J3,4 = 9.3 Hz, Hꢀ3), 5.24 (dd, 1H,
S4

J1,2 = 10.4 Hz, Hꢀ1), 6.83ꢀ7.27 (m, 5H, aromatic) ppm; 13C n.m.r.: δ, 20.7 (x 3), 20.9, 56.8, 62.2,
68.2, 69.9, 74.1, 76.3, 81.4, 121.5 (x 2), 124.4, 129.3 (x 2), 146.3, 154.5, 169.3, 169.5, 170.4,
170.8 ppm; HRꢀFAB MS[M+Na]+ calcd for C22H27NO10SNa+ 520.1253, found 520.1263.
2,3,4,6ꢀTetraꢀOꢀbenzoylꢀ1ꢀthioꢀβꢀDꢀglucopyranosyl Oꢀmethyl phenylcarbamothioate (4c).
A solution of NaOMe in methanol (1M, ~0.1 mL) was added dropwise to a solution of
thiocarbamate 12 (72 mg, 0.145 mmol) in methanol (1.0 mL) till pH ~ 9 and the resulting
reaction mixture was kept for 1 h at rt. After that, Dowex (H+) was added till pH ~ 7, the resin
was filtered off and washed successively with methanol (5 x 5 mL). The combined filtrate was
concentrated in vacuo and dried. The residue was dissolved in pyridine (1 mL) and benzoyl
o
chloride (0.1 mL, 0.87 mmol) was added dropwise at 0 C under argon. The external cooling
was removed, the reaction mixture was allowed to warm to rt and stirred for 4 h total. After that,
methanol (1 mL) was added, the volatiles were evaporated in vacuo, and the residue was coꢀ
evaporated with toluene (3 x 5 mL). The resulting residue was diluted with dichloromethane
(100 mL) and washed with 1N aq. HCl (25 mL), water (25 mL), sat. aq. NaHCO3 (25 mL), and
water (3 x 25 mL). The organic layer was separated, dried with MgSO4 and concentrated in
vacuo. The residue was purified by column chromatography on silica gel (ethyl acetate ꢀ toluene
gradient elution) to afford the title compound as a white foam in 83% (90 mg) yield. Analytical
data for 4c: Rf = 0.37 (ethyl acetate/toluene, 1.5/8.5, v/v); [α]D21 0.35o (c = 1, CHCl3); Hꢀn.m.r.:
1
δ, 3.90 (s, 3H, OCH3), 4.25 (m, 1H, J5,6a = 5.7 Hz, J5,6b = 2.9 Hz, Hꢀ5), 4.49 (dd, 1H, J6a,6b = 12.2
Hz, Hꢀ6a), 4.64 (dd, 1H, Hꢀ6b), 5.54 (dd, 1H, J2,3 = 9.2 Hz, Hꢀ2), 5.62 (d, 1H, J1,2 = 10.2 Hz, Hꢀ
1), 5.64 (dd, 1H, J4,5 = 9.8 Hz, Hꢀ4), 5.95 (dd, J3,4 = 9.2 Hz, Hꢀ3), 6.72ꢀ8.06 (m, 25H, aromatic)
S5

ppm; 13Cꢀn.m.r.: δ, 56.8, 63.4, 69.6, 70.6, 74.3, 77.4, 81.9, 121.5 (x 2), 124.2, 128.5 (x 2), 128.6
(x 6), 128.7 (x 2), 128.9 (x 2), 129.1, 129.2 (x 2), 129.8, 129.9 (x 3), 130.0 (x 3), 133.4, 133.5,
133.6, 133.7, 146.3, 154.5, 165.1, 165.4, 165.9, 166.3 ppm; HRꢀFAB MS[M+Na]+ calcd for
C42H35NO10SNa+ 768.1879, found 768.1896.
Characterization data for glycosyl acceptors 2, 5ꢀ7
Methyl 2,3,4ꢀtriꢀOꢀbenzylꢀαꢀDꢀglucopyranoside (2).6
Analytical data for 2: 1H n.m.r.: δ, 3.33 (s, 3H, OCH3), 3.45ꢀ3.52 (m, 2H, Hꢀ2, 4), 3.59ꢀ3.76 (m,
3H, Hꢀ5, 6a, 6b), 3.98 (dd, 1H, J3,4 = 9.2 Hz, Hꢀ3), 4.53 (d, 1H, J1,2 = 3.5 Hz, Hꢀ1), 4.70 (dd, 2H,
J2 = 12.1 Hz, CH2Ph), 4.73 (dd, 2H, J2 = 11.0 Hz, CH2Ph), 4.89 (dd, 2H, J2 = 10.9 Hz, CH2Ph),
7.21ꢀ7.34 (m, 15H, aromatic) ppm; 13C n.m.r.: δ, 55.12, 61.76, 70.55, 73.33, 74.93, 77.24, 79.82,
81.83, 98.01, 127.42, 127.68, 127.74, 127.76 (x 3), 127.83 (x 2), 127.92 (x 2), 128.20 (x 2),
128.27 (x 4), 137.87, 138.48 ppm.
Methyl 2,3,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀglucopyranoside (5).7
1
Analytical data for 5: H n.m.r.: δ, 3.34 (s, 3H, OCH3), 3.52 (dd, 1H, J2,3 = 8.5 Hz, Hꢀ2), 3.56ꢀ
3.69 (m, 4H, Hꢀ4, 5, 6a, 6b), 3.74 (dd, 1H, J3,4 = 9.0 Hz, Hꢀ3), 4.52 (dd, 2H, J2 = 12.2 Hz,
CH2Ph), 4.59 (d, 1H, J1,2 = 3.7 Hz, Hꢀ1), 4.63 (dd, 2H, J2 = 12.4 Hz, CH2Ph), 4.84 (dd, 2H, J2 =
13
11.4 Hz, CH2Ph), 7.22ꢀ7.22 (m, 15H, aromatic) ppm; C n.m.r.: δ, 55.36, 69.57, 70.02, 70.80,
S6

73.28, 73.69, 75.55, 79.71, 81.59, 98.32, 127.80 (x 3), 128.02, 128.14, 128.18 (x 2), 128.31 (x 2),
128.54 (x 2), 128.66 (x 2), 128.77 (x 2), 138.19, 138.24, 138.99 ppm.
Methyl 2,4,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀglucopyranoside (6).8
27
1
Analytical data for 6: Rf = 0.35 (ethyl acetate/toluene, 2/8, v/v); [α]D +36o (c = 1, CHCl3); H
n.m.r.: δ, 3.29 (s, 3H, OCH3), 3.36 (dd, 1H, J1,2 = 3.5 Hz, J2,3 = 9.6 Hz, Hꢀ2), 3.51 (dd, 1H, J4,5
=
9.3 Hz, Hꢀ4), 3.58ꢀ3.7 (m, 3H, Hꢀ5, 6a, 6b), 4.02 (dd, 1H, J3,4 = 9.1 Hz, Hꢀ3), 4.50 (dd, 2H, J2 =
12.1 Hz, CH2Ph), 4.61 (d, 1H, J1,2 = 3.5 Hz, Hꢀ1), 4.62 (dd, 2H, J2 = 11.1 Hz, CH2Ph), 4.64 (dd,
2H, J2 = 12.1 Hz, CH2Ph), 7.15ꢀ7.33 (m, 15H, aromatic) ppm; 13C n.m.r.: δ, 55.21, 68.51, 69.65,
73.11, 73.54, 73.63, 74.60, 77.29, 79.51, 97.60, 127.73, 127.76, 127.91 (x 2), 127.99 (x 2),
128.13, 128.17 (x 2), 128.42 (x 4), 128.61 (x 2), 137.94, 138.01, 138.45 ppm.
Methyl 3,4,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀglucopyranoside (7).9
OBn
O
BnO
BnO
HO
OMe
1
Analytical data for 7: H n.m.r.: δ, 3.43 (s, 3H, OCH3), 3.62ꢀ3.80 (m, 6H, Hꢀ2, 3, 4, 5, 6a, 6b),
4.58 (dd, 2H, J2 = 12.1 Hz, CH2Ph), 4.67 (dd, J2 = 10.8 Hz, ½ CH2Ph), 4.81 (d, 1H, J1,2 = 3.2 Hz,
Hꢀ1), 4.88 (m, 2H, J2 = 11.2 Hz, CH2Ph), 7.14ꢀ7.30 (m, 15H, aromatic) ppm. 13C n.m.r.: δ,
55.32, 68.60, 70.54, 73.03, 73.64, 75.48, 77.60, 83.38, 99.53, 127.84, 127.97 (x 2), 128.03 (x 5),
128.51 (x 4), 128.57 (x 3), 138.05, 138.30, 138.79 ppm.
S7

General procedures for glycosylation
In the presence of MeOTf (Method A). A mixture of a glycosyl donor (0.04 mmol), glycosyl
acceptor (0.032 mmol), and freshly activated molecular sieves (3 Å, 90 mg) in 1,2ꢀ
dichloroethane (0.5 mL) was stirred under argon at rt for 1.5 h. MeOTf (10 ꢁL, 0.08 mmol) was
added and the reaction mixture was stirred at rt for 22ꢀ48 h. After that, the solid was filtered off
and the filtrate was washed successively with sat. aq. NaHCO3 (5 mL) and water (3 x 5 mL). The
organic layer was separated, dried with MgSO4 and concentrated in vacuo. The residue was
purified by column chromatography on silica gel (ethyl acetateꢀtoluene gradient elution) to
afford the corresponding disaccharide.
In the presence of AgOTf (Method B): A mixture of glycosyl donor (0.04 mmol), glycosyl
acceptor (0.032 mmol), and freshly activated molecular sieves (3 Å, 90 mg) in 1,2ꢀ
dichloroethane (0.5 mL) was stirred under argon for 1.5 h. AgOTf (12.3 mg, 0.048 mmol) was
added and the reaction mixture was stirred for 24 h. Upon completion, the solid was filtered off
and the filtrate was washed with NaHCO3 (5 mL) and water (3 x 5 mL). The organic layer was
separated, dried with MgSO4 and concentrated in vacuo. The residue was purified by silica gel
column chromatography (ethyl acetateꢀtoluene gradient elution) to afford the corresponding
oligosaccharide.
In the presence of AgBF4 (Method C): A mixture of glycosyl donor (0.04 mmol), glycosyl
acceptor (0.032 mmol), and freshly activated molecular sieves (3 Å, 90 mg) in 1,2ꢀ
dichloroethane (0.5 mL) was stirred under argon for 1.5 h. AgBF4 (9.3 mg, 0.048 mmol) was
added and the reaction mixture was stirred for 5 min ꢀ 24 h. Upon completion, the solid was
filtered off and the filtrate was washed with NaHCO3 (5 mL) and water (3 x 5 mL). The organic
layer was separated, dried with MgSO4 and concentrated in vacuo. The residue was purified by
S8

silica gel column chromatography (ethyl acetateꢀtoluene gradient elution) to afford the
corresponding oligosaccharide.
In the presence of Cu(OTf)2 (Method D): A mixture of glycosyl donor (0.04 mmol), glycosyl
acceptor (0.032 mmol), and freshly activated molecular sieves (4 Å, 90 mg) in 1,2ꢀ
dichloroethane (0.5 mL) was stirred under argon for 1.5 h. Cu(OTf)2 (17 mg, 0.048 mmol) was
added and the reaction mixture was stirred for 10 min ꢀ 24 h. Upon completion, the solid was
filtered off and the filtrate was washed with NaHCO3 (5 mL) and water (3 x 5 mL). The organic
layer was separated, dried with MgSO4 and concentrated in vacuo. The residue was purified by
silica gel column chromatography (ethyl acetateꢀtoluene gradient elution) to afford the
corresponding disaccharide.
General Procedure for Competitive Glycosylations
A mixture of glycosyl donor 4b (47 mg, 0.0645 mmol), glycosyl donor 4c (48 mg, 0.0645
mmol), glycosyl acceptor 2 (20 mg, 0.043 mmol), and freshly activated molecular sieves (4 Å for
Cu(OTf)2 or 3 Å for MeOTfꢀpromoted reactions, 140 mg) in 1,2ꢀdichloroethane (1 mL) was
stirred under argon at rt for 1h. Cu(OTf)2 (28 mg, 0.0774 mmol) or MeOTf (16 µL, 0.129 mmol)
was added and the resulting reaction mixture was stirred at rt. The reaction was monitored by
TLC (ethyl acetate / toluene, 1/4, v/v); upon disappearance of the glycosyl acceptor 2 (1ꢀ1.5 h),
the solid was filtered off, rinsed with CH2Cl2 (3 x 5 mL), and the combined filtrate was washed
with sat. aq. NaHCO3 (5 mL) and water (3 x 5 mL). The organic layer was separated, dried with
MgSO4, filtered and concentrated in vacuo.
The residue was purified by column
chromatography on silica gel (ethyl acetate – hexanes gradient elution) to afford disaccharide 8
in 88ꢀ97% yield and unreacted glycosyl donors.
S9

Characterization data for disaccharides 8ꢀ11
Methyl
6ꢀOꢀ(2,3,4,6ꢀtetraꢀOꢀbenzoylꢀβꢀDꢀglucopyranosyl)ꢀ2,3,4ꢀtriꢀOꢀbenzylꢀαꢀDꢀ
glucopyranoside (8).10
The title compound was synthesized by method D from glycosyl donor 4c (30 mg, 0.04 mmol)
and glycosyl acceptor 2 (15 mg, 0.032 mmol) in 90% (30 mg) yield. Analytical data for 8 was in
agreement with that reported previously.10
Methyl
4ꢀOꢀ(2,3,4,6ꢀtetraꢀOꢀbenzoylꢀβꢀDꢀglucopyranosyl)ꢀ2,3,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀ
glucopyranoside (9).10
The title compound was synthesized by method D from glycosyl donor 4c (30 mg, 0.04 mmol)
and glycosyl acceptor 5 (15 mg, 0.032 mmol) in 78% (26 mg) yield. Analytical data for 9 was in
agreement with that reported previously.10
Methyl
3ꢀOꢀ(2,3,4,6ꢀtetraꢀOꢀbenzoylꢀβꢀDꢀglucopyranosyl)ꢀ2,4,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀ
glucopyranoside (10).
The title compound was synthesized by method D from glycosyl donor 4c (30 mg, 0.04 mmol)
and glycosyl acceptor 6 (15 mg, 0.032 mmol) in 74% (25 mg) yield. Analytical data for 10: Rf =
S10

27
1
0.4 (ethyl acetate / toluene, 1/5, v/v), [α]D ꢀ12.8o (c = 1, CHCl3), Hꢀn.m.r.: δ, 3.15 (s, 3H,
OCH3), 3.25 (dd, 1H, J2,3 = 9.6 Hz, Hꢀ2), 3.44ꢀ3.58 (m, 4H, Hꢀ4, 5, 6a, 6b), 4.03ꢀ4.07 (m, 1H, Hꢀ
5’), 4.19 (d, 1H, J1,2 = 3.4 Hz, Hꢀ1), 4.28 (dd, 1H, J3,4 = 9.7 Hz, Hꢀ3), 4.30 (dd, 2H, J2 = 12.2 Hz,
CH2Ph), 4.30ꢀ4.50 (m, 2H, Hꢀ6a’, 6b’), 4.70 (dd, 2H, J2 = 10.8 Hz, CH2Ph), 5.43 (d, 1H, J1’,2’
=
8.0 Hz, Hꢀ1’), 5.57 (dd, 1H, J2’,3’ = 9.7 Hz, Hꢀ2’), 5.63 (dd, 1H, J4’,5’ = 9.7 Hz, Hꢀ4’), 5.86 (dd,
13
1H, J3’,4’ = 9.6 Hz, Hꢀ3’), 7.0ꢀ7.94 (m, 35H, aromatic) ppm; C n.m.r.: δ, 55.19, 63,46, 68.59,
69.71, 70.05, 72.08, 72.68, 73.32, 73.66, 74.01, 75.07, 75.58, 79.51, 80.97, 97.84, 101.19,
127.62, 127.88, 128.07 (x 2), 128.14 (x 2), 128.25 (x 4), 128.29 (x 2), 128.38 (x 2), 128.46 (x 2),
128.54 (x 4), 128.64 (x 2), 128.67 (x 2), 128.99, 129.57, 129.79, 129.89 (x 2), 129.99 (x 4),
130.03 (x 2), 133.07, 133.39, 133.46, 133.54, 138.04, 138.11, 138.66, 165.34, 165.43, 166.02,
166.28 ppm; HRꢀFAB MS[M+Na]+ calcd for C62H58O15Na+ 1065.3673, found 1065.3673.
Methyl
2ꢀOꢀ(2,3,4,6ꢀtetraꢀOꢀbenzoylꢀβꢀDꢀglucopyranosyl)ꢀ3,4,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀ
glucopyranoside (11).11
The title compound was synthesized by method D from glycosyl donor 4c (30 mg, 0.04 mmol)
and glycosyl acceptor 7 (15 mg, 0.032 mmol) in 75% (25 mg) yield. Analytical data for 11 was
in agreement with that reported previously.11
S11

ꢁMR spectra
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
2.074.15
9.90 5.06
7.5
1.00 0.99
1.94 2.22 1.04
5.0 4.5
2.52
8.0
7.0
6.5
6.0
5.5
4.0
Chemical Shift (ppm)
CDCl3 at 300 MHz
160
150
140
130
120
110
100
90
80
70 ppm
CDCl3 at 75 MHz
S12

ppm
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 ppm
CDCl3 at 300 MHz
S13

2
CDCl3 at 300 MHz
CDCl3 at 75 MHz
S14

2
CDCl3 at 300 MHz
S15

0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
2.17 2.27 2.23 2.08
8.0
16.16
7.5
1.08 1.15 1.10
6.0
1.00
1.08 1.13
4.5
1.07
7.0
6.5
5.5
5.0
Chemical Shift (ppm)
CDCl3 at 300 MHz
160 150 140 130 120 110 100 90
80
70
ppm
CDCl3 at 300 MHz
S16

ppm
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 ppm
CDCl3 at 300 MHz
S17

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
2.07 4.06 2.04 3.25 7.33 2.97 2.02 0.99 1.96
8.0 7.5 7.0
1.00
1.06 1.97
5.5
1.00 1.01
4.5
1.01
2.92
4.0
6.5
6.0
Chemical Shift (ppm)
5.0
CDCl3 at 300 MHz
160
150
140
130
120
110
100
90
80
70
60 ppm
CDCl3 at 75 MHz
S18

ppm
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5
CDCl3 at 300 MHz
ppm
S19

5
CDCl3 at 300 MHz
CDCl3 at 75 MHz
S20

5
CDCl3 at 300 MHz
S21

6
CDCl3 at 300 MHz
CDCl3 at 75 MHz
S22

6
CDCl3 at 300 MHz
S23

OBn
O
BnO
BnO
HO
OMe
7
CDCl3 at 300 MHz
CDCl3 at 75 MHz
S24

OBn
O
BnO
BnO
HO
OMe
7
CDCl3 at 300 MHz
S25

8
CDCl3 at 300 MHz
CDCl3 at 75 MHz
S26

8
CDCl3 at 300 MHz
S27

9
CDCl3 at 300 MHz
CDCl3 at 75 MHz
S28

9
CDCl3 at 300 MHz
S29

10
CDCl3 at 300 MHz
CDCl3 at 75 MHz
S30