M. Matwiejuk, J. Thiem
FULL PAPER
16.0 mmol), MeI (1.6 mL, 25.7 mmol), absolute DMF (50 mL); Methyl 4-O-Benzyl-2,3-di-O-methyl-α-
D-galactopyranoside (30):
yield 94% (1.64 g, 6.25 mmol), colourless syrup, Rf = 0.27 (petro-
Cleavage of the triphenylmethyl group was performed according to
ref.[12] Compound 29 (4.6 g, 8.3 mmol), trifluoroacetic acid (90%,
17 mL); yield 93% (2.4 g, 7.7 mmol), yellow syrup, Rf = 0.31 (EA),
leum ether/EA, 1:1), [α]2D5 = +157.8 (c = 0.5, CHCl3) {ref.[32] [α]2D5
1
= +142 (c = 1.7, CHCl3)}. H NMR (400 MHz, CDCl3): δ = 4.84
(d, 3J1,2 = 3.5 Hz, 1 H, 1-H), 4.24 (dd, 3J2,3 = 7.8 Hz, 3J3,4 = 5.5 Hz, [α]2D5 = +0.81 (c = 0.29, H2O). 1H NMR (400 MHz, CDCl3): δ =
1 H, 3-H), 4.14 (dd, 3J3,4 = 5.5 Hz, 3J4,5 = 2.6 Hz, 1 H, 4-H), 4.13–
7.45–7.30 (m, 5 H, Harom.), 4.96 (d, JA,AЈ = 11.8 Hz, 1 H,
2
3
2
4.08 (m, 1 H, 5-H), 3.67–3.63 (m, 2 H, 6-H), 3.51, 3.42, 3.41 (s, 3 OCH2Ph-A), 4.93 (d, J1,2 = 3.5 Hz, 1 H, 1-H), 4.63 (d, JA,AЈ
=
3
3
H, OCH3) 3.34 (dd, J1,2 = 3.5 Hz, J2,3 = 7.8 Hz, 1 H, 2-H), 1.52,
11.8 Hz, 1 H, OCH2Ph-AЈ), 3.95–3.91 (m, 1 H, 4-H), 3.81–3.71 (m,
1.32 (s, 3 H, CH3) ppm. 13C NMR (101 MHz, CDCl3): δ = 109.2
3 H, 2-H, 5-H, 6a-H), 3.60 (dd, J2,3 = 10.0, J3,4 = 2.8 Hz, 1 H,
3
3
[(CH3)2COO], 97.7 (C-1), 79.3 (C-2), 75.9 (C-3), 73.8 (C-4), 72.1 3-H), 3.57–3.52 (m, 1 H, 6b-H), 3.55, 3.54, 3.42 (s, 3 H, OCH3)
(C-6), 66.4 (C-5), 59.3, 58.7, 55.5 (OCH3), 28.3, 26.3 (CH3) ppm.
ppm. 13C NMR (101 MHz, CDCl3): δ = 138.2 (Carom.), 128.5, 127.9
(CHarom.), 98.0 (C-1), 80.9 (C-3), 78.1 (C-2), 74.5 (OCH2Ph-A),
73.8 (C-4), 70.3 (C-5), 62.5 (C-6), 58.9, 58.6, 55.3 (OCH3) ppm.
HRMS (ESI): calcd. for C16H24O6 [M + Na]+ 335.1465; found
335.1470.
Methyl 4,6-O-Benzylidene-2,3-di-O-methyl-α- -galactopyranoside
D
(27): Methylation of the hydroxy groups was performed according
to ref.[12] Compound 26 (4.00 g, 14.2 mmol), NaH (2.56 g,
64.0 mmol), MeI (4.0 mL, 64 mmol), absolute DMF (60 mL); yield
97% (4.28 g, 13.8 mmol), colourless solid, Rf = 0.42 (EA), m.p.
114–115 °C (ref.[29] m.p. 123–124 °C), [α]2D5 = +162.3 (c = 0.21,
CHCl3) {ref.[29] [α]2D5 = +170 (CHCl3)}. 1H NMR (400 MHz,
CDCl3): δ = 7.57–7.51 (m, 2 H, Harom.), 7.40–7.31 (m, 3 H, Harom.),
Methyl 4-O-Benzyl-2,3,6-tri-O-methyl-α-D-galactopyranoside (31):
Methylation of the hydroxy group was performed according to
ref.[12] Compound 30 (2.3 g, 7.4 mmol), NaH (750 mg, 18.8 mmol),
MeI (1.2 mL, 19 mmol), absolute DMF (40 mL); yield 88% (2.2 g,
6.6 mmol), colourless syrup, Rf = 0.36 (PE/EA, 1:1), [α]2D5 = +110.5
(c = 0.32, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.42–7.25 (m,
3
5.56 (s, 1 H, PhCHOO), 5.01 (d, J1,2 = 3.5 Hz, 1 H, 1-H), 4.38–
3
2
4.34 (m, 1 H, 4-H), 4.28 (dd, J5,6a = 1.2, J6a,6b = 12.6 Hz, 1 H,
3
2
2
6a-H), 4.09 (dd, J5,6b = 1.3, J6a,6b = 12.6 Hz, 1 H, 6b-H), 3.81
5 H, Harom.), 4.93 (d, JA,AЈ = 11.6 Hz, 1 H, OCH2Ph-A), 4.91 (d,
3
3
3
3J1,2 = 3.8 Hz, 1 H, 1-H), 4.61 (d, 2JA,AЈ = 11.6 Hz, 1 H, OCH2Ph-
(dd, J1,2 = 3.5, J2,3 = 10.1 Hz, 1 H, 2-H), 3.70 (dd, J2,3 = 10.1,
3J3,4 = 3.5 Hz, 1 H, 3-H), 3.67–3.64 (m, 1 H, 5-H), 3.54, 3.53, 3.46
(s, 3 H, OCH3) ppm. 13C NMR (101 MHz, CDCl3): δ = 137.6
(Carom.), 128.9, 128.1, 126.4 (CHarom), 101.3 (PhCHOO), 98.6 (C-
1), 77.5 (C-3), 77.3 (C-2), 73.8 (C-4), 69.4 (C-6), 62.6 (C-5), 59.1,
57.8, 55.5 (OCH3) ppm.
3
3
AЈ), 3.94 (dd, J3,4 = 2.3, J4,5 = 1.0 Hz, 1 H, 4-H), 3.88–3.82 (m,
3
3
1 H, 5-H), 3.76 (dd, J1,2 = 3.8, J2,3 = 10.0 Hz, 1 H, 2-H), 3.58
3
3
(dd, J2,3 = 10.0, J3,4 = 2.3 Hz, 1 H, 3-H), 3.49–3.41 (m, 2 H, 6-
H), 3.53, 3.51, 3.42, 3.31 (s, 3 H, OCH3) ppm. 13C NMR
(101 MHz, CDCl3): δ = 138.6 (Carom.), 128.2, 127.6 (CHarom.), 97.8
(C-1), 80.7 (C-3), 77.9 (C-2), 74.7 (OCH2Ph-A), 73.8 (C-4), 71.5
(C-6), 69.1 (C-5), 59.1, 58.8, 58.3, 55.3 (OCH3) ppm. HRMS (ESI):
calcd. for C17H26O6 [M + Na]+ 349.1622; found 349.1623.
Methyl 2,3-Di-O-methyl-6-O-triphenylmethyl-α-D-galactopyranos-
ide (28): Tritylation of OH-6 was performed according to ref.[12]
Compound 18 (2.2 g, 10 mmol), chlorotriphenylmethane (3.1 g,
11 mmol), catalytic amount of DMAP (approx. 20 mg), pyridine
(30 mL); yield 95% (4.5 g, 9.6 mmol), colourless solid, Rf = 0.53
(EA), m.p. 70–71 °C (ref.[33] m.p. 77–80 °C), [α]2D5 = +70.5 (c = 0.2
in CHCl3) {ref.[33] [α]2D5 = +68.0 (CHCl3)}. 1H NMR (400 MHz,
MeOD): δ = 7.50–7.42 (m, 6 H, Harom.), 7.33–7.19 (m, 9 H, Harom.),
Methyl 2,3-O-Isopropylidene-4,6-di-O-methyl-α-D-mannopyranoside
(35): Methylation of the hydroxy groups was performed according
to ref.[12] Compound 34 (1.88 g, 8.04 mmol), NaH (1.30 g,
32.1 mmol), MeI (2.0 mL, 32 mmol), absolute DMF (40 mL); yield
94% (1.98 g, 7.54 mmol), colourless syrup, Rf = 0.50 (petroleum
ether/EA, 1:1), [α]2D5 = +42.7 (c = 0.21, CHCl3). 1H NMR
3
4.91 (d, J1,2 = 3.8 Hz, 1 H, 1-H), 4.02–3.98 (m, 1 H, 4-H), 3.82–
3
3
3.76 (m, 1 H, 5-H), 3.54 (dd, J1,2 = 3.8 Hz, J2,3 = 10.1 Hz, 1 H,
3
(400 MHz, CDCl3): δ = 4.91 (s, 1 H, 1-H), 4.17 (dd, J2,3 = 5.8,
3
2-H), 3.44–3.38 (m, 2 H, 3-H, 6a-H), 3.23 (dd, J5,6b = 4.6 Hz,
3
3J3,4 = 6.8 Hz, 1 H, 3-H), 4.09 (d, J2,3 = 5.8 Hz, 1 H, 2-H), 3.66–
2J6a,6b = 10.0 Hz, 1 H, 6b-H), 3.46, 3.45, 3.40 (s, 3 H, OCH3) ppm.
13C NMR (101 MHz, MeOD): δ = 145.7 (Carom.), 130.0, 128.9,
128.3 (CHarom.), 99.0 (C-1), 88.2 (Ph3CO), 80.8 (C-3), 78.9 (C-2),
71.1 (C-5), 67.7 (C-4), 65.2 (C-6), 59.0, 57.4, 55.5 (OCH3) ppm.
MS (MALDI-TOF): m/z = 488.3 [M + Na]+.
3.56 (m, 3 H, 6-H, 5-H), 3.50, 3.41, 3.38 (s, 3 H, OCH3), 3.32–3.25
(m, 1 H, 4-H), 1.53, 1.34 (s, 3 H, CH3) ppm. 13C NMR (101 MHz,
CDCl3): δ = 109.2 [(CH3)2COO], 98.4 (C-1), 78.5 (C-3), 77.8 (C-
4), 75.8 (C-2), 71.6 (C-6), 68.1 (C-5), 59.3, 59.2, 54.9 (OCH3), 28.0,
26.2 (CH3) ppm. HRMS (ESI): calcd. for C12H22O6 [M + Na]+
285.1309; found 285.1313.
Methyl 4-O-Benzyl-2,3-di-O-methyl-6-O-triphenylmethyl-α-D-galac-
topyranoside (29): Benzylation of the hydroxy group was performed
according to ref.[12] Compound 28 (4.4 g, 9.4 mmol), NaH (940 mg,
23.6 mmol), BnBr (2.80 mL, 23.6 mmol), absolute DMF (45 mL);
yield 89% (4.7 g, 8.4 mmol), colourless solid, Rf = 0.14 (petroleum
Methyl 2-O-Benzyl-β-D-glucopyranoside (39): Cleavage of the
benzylidene group was performed according to ref.[12] Compound
38 (1.63 g, 4.38 mmol), MeOH (40 mL), H2O (3 mL), 1 n HCl
(1 mL); yield 70% (870 mg, 3.06 mmol), colourless solid, Rf = 0.11
(EA); m.p. 130 °C, [α]2D5 = +20.5 (c = 0.2, CHCl3). 1H NMR
ether/EA, 3:1), m.p. 51–52 °C, [α]2D5 = +0.59 (c = 0.21, MeOH). H
1
NMR (400 MHz, MeOD): δ = 7.43–7.37 (m, 6 H, Harom.), 7.32–
2
(400 MHz, CDCl3): δ = 7.42–7.29 (m, 5 H, Harom.), 4.95 (d, JA,AЈ
3
7.18 (m, 12 H, Harom.), 7.13–7.08 (m, 2 H, Harom.), 4.85 (d, J1,2
=
2
= 11.4 Hz, 1 H, OCH2Ph-A), 4.64 (d, JA,AЈ = 11.4 Hz, 1 H,
2
3.5 Hz, 1 H, 1-H), 4.72 (d, JA,AЈ = 11.1 Hz, 1 H, OCH2Ph-A),
3
3
OCH2Ph-AЈ), 4.37 (d, J1,2 = 7.8 Hz, 1 H, 1-H), 3.93 (dd, J5,6a
=
=
2
3
4.41 (d, JA,AЈ = 11.1 Hz, 1 H, OCH2Ph-AЈ), 3.95 (dd, J3,4 = 3.0,
2
3
2
3.5, J6a,6b = 11.8 Hz, 1 H, 6a-H), 3.82 (dd, J5,6b = 4.8, J6a,6b
3J4,5 = 0.8 Hz, 1 H, 4-H), 3.78–3.72 (m, 1 H, 5-H), 3.59 (dd, J1,2
3
11.8 Hz, 1 H, 6b-H), 3.61–3.53 (m, 2 H, 3-H, 4-H), 3.42–3.35 (m,
1 H, 5-H), 3.23–3.17 (m, 1 H, 2-H), 3.35 (s, 3 H, OCH3) ppm. 13C
NMR (101 MHz, CDCl3): δ = 138.3 (Carom.), 128.6, 128.1, 128.0
(CHarom.), 104.6 (C-1), 80.9 (C-2), 76.0 (C-3), 75.0 (C-5), 74.4
(OCH2Ph), 70.5 (C-4), 62.6 (C-6), 57.2 (OCH3) ppm. HRMS (ESI):
calcd. for C14H20O6 [M + Na]+ 307.1152; found 307.1158.
3
3
3
= 3.5, J2,3 = 10.4 Hz, 1 H, 2-H), 3.50 (dd, J2,3 = 10.4, J3,4
=
3.0 Hz, 1 H, 3-H), 3.43–3.36 (m, 1 H, 6a-H), 3.13 (dd, 3J5,6b = 5.8,
2J6a,6b = 9.9 Hz, 1 H, 6b-H), 3.46, 3.45, 3.41 (s, 3 H, OCH3) ppm.
13C NMR (101 MHz, MeOD): δ = 145.5, 139.9 (Carom.), 130.0,
129.4, 129.3, 129.0, 128.8, 128.3 (CHarom.), 99.1 (C-1), 88.4
(Ph3CO), 81.9 (C-3), 79.5 (C-2), 75.9 (OCH2Ph-A), 75.8 (C-4), 71.1
(C-5), 64.9 (C-6), 59.1, 58.6, 55.5 (OCH3) ppm. HRMS (ESI):
calcd. for C35H38O6 [M + Na]+ 577.2561; found 577.2562.
Methyl 2-O-Benzyl-3,4,6-tri-O-methyl-β-
D-glucopyranoside (40):
Methylation of the hydroxy groups was performed according to
2186
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Eur. J. Org. Chem. 2012, 2180–2187