M. Matwiejuk, J. Thiem
FULL PAPER
H), 2.96 (dd, J1β,2β = 7.6 Hz, J2β,3β = 8.9 Hz, 1 H, 2β-H), 3.63,
3.54, 3.52, 3.40 (s, 3 H, OCH3-α), 3.63, 3.61, 3.52, 3.40 (s, 3 H,
OCH3-β) ppm. 13C NMR (101 MHz, CDCl3): δ = 97.1 (C-1β), 90.7
3
3
DMF (80 mL). Yield: 84% (9.66 g, 17.4 mmol), colourless oil, Rf
= 0.23 (PE/EA, 4:1), [α]2D5 = +29.2 (c = 0.5, CHCl3), 1H NMR
(400 MHz, CDCl3): δ = 7.41–7.21 (m, 20 H, Harom.), 4.94 (d, 2JA,AЈ
2
(C-1α), 86.4 (C-3β), 84.8 (C-2β), 83.1 (C-3α), 82.0 (C-2α), 79.6 (C- = 11.5 Hz, 1 H, OCH2Ph-A), 4.84 (d, JB,BЈ = 11.9 Hz, 1 H,
2
4β), 79.5 (C-4α), 74.4 (C-5β), 71.6 (C-6β), 71.3 (C-6α), 70.0 (C-
5α), 60.8, 60.4, 59.1, 58.8 (OCH3-α), 60.7, 60.4, 60.3, 59.2 (OCH3-
β) ppm.
OCH2Ph-B), 4.83 (d, JC,CЈ = 12.2 Hz, 1 H, OCH2Ph-C), 4.72 (d,
2
2JB,BЈ = 11.9 Hz, 1 H, OCH2Ph-BЈ), 4.68 (d, JC,CЈ = 12.2 Hz, 1 H,
3
2
OCH2Ph-CЈ), 4.68 (d, J1,2 = 3.6 Hz, 1 H, 1-H), 4.56 (d, JA,AЈ
=
2
11.5 Hz, 1 H, OCH2Ph-AЈ), 4.47 (d, JD,DЈ = 11.7 Hz, 1 H,
2,3,4,6-Tetra-O-methyl-α/β-D-galactopyranose (51): Prepared ac-
2
OCH2Ph-D), 4.38 (d, JD,DЈ = 11.7 Hz, 1 H, OCH2Ph-DЈ), 4.03
cording to procedure C1. Compound 48 (7.49 g, 29.9 mmol), 0.5 m
HCl (200 mL). Yield: 81% (5.8 g, 25 mmol), α/β ratio = 3.2:1,
colourless oil, Rf = 0.16 (EA), [α]2D5 = +113.0 (c = 0.26, H2O)
{ref.[28] [α]2D3 = +118.0 (c = 1.9, H2O)}. 1H NMR (400 MHz,
3
3
(dd, J1,2 = 3.6 Hz, J2,3 = 10.9 Hz, 1 H, 2-H), 3.95–3.86 (m, 3 H,
3-H, 4-H, 5-H), 3.54–3.47 (m, 2 H, 6-H), 3.36 (s, 3 H, OCH3) ppm.
13C NMR (101 MHz, CDCl3): δ = 138.8, 138.6, 138.5, 138.0 (Ca-
rom.), 128.4, 128.3, 128.2, 128.2, 128.1, 127.7, 127.7, 127.7, 127.6,
127.5 (CHarom.), 98.8 (C-1), 79.1 (C-3), 76.4 (C-2), 75.1 (C-4), 74.7
(OCH2Ph-A), 73.6 (OCH2Ph-B), 73.5 (OCH2Ph-D), 73.3
(OCH2Ph-C), 69.2 (C-5), 69.1 (C-6) ppm. HRMS (ESI): calcd. for
C35H38O6 [M + Na]+ 577.2561; found 577.2579.
3
3
CDCl3): δ = 5.40 (d, J1α,2α = 3.8 Hz, 1 H, 1α-H), 4.55 (d, J1β,2β
= 7.6 Hz, 1 H, 1β-H), 4.16–4.10 (m, 1 H, 5α-H), 3.71–3.69 (m, 1
H, 4α-H), 3.66–3.59 (m, 2 H, 2α-H, 4β-H), 3.58–3.50 (m, 6 H, 5β-
3
3
H, 3α-H, 6α-H, 6β-H), 3.29 (dd, J1β,2β = 7.6 Hz, J2β,3β = 9.9 Hz,
3
3
1 H, 2β-H), 3.17 (dd, J2β,3β = 9.9 Hz, J3β,4β = 3.1 Hz, 1 H, 3β-
H), 3.57, 3.53, 3.52, 3.39 (s, 3 H, OCH3-α), 3.63, 3.55, 3.50, 3.39
(s, 3 H, OCH3-β) ppm. 13C NMR (101 MHz, CDCl3): δ = 97.6 (C-
1β), 91.1 (C-1α), 84.0 (C-3β), 82.0 (C-2β), 80.0 (C-3α), 78.1 (C-2α),
76.0 (C-4α), 75.1 (C-4β), 73.3 (C-5β), 71.4 (C-6α), 71.1 (C-6β), 69.1
(C-5α), 61.2, 60.8, 59.1, 58.2 (OCH3-β), 61.2, 59.1, 58.9, 58.0
(OCH3-α) ppm. HRMS (ESI): calcd. for C10H20O6 [M + Na]+
425.1152; found 259.1157.
2,3,4,6-Tetra-O-benzyl-α-D-mannopyranose (55): Prepared accord-
ing to procedure C2. Compound 53 (5.31 g, 9.57 mmol), glacial
acetic acid (85 mL), 1 n H2SO4 (42 mL). Yield: 54% (2.79 g,
5.16 mmol), α/β ratio: 3:1, yellow oil, Rf = 0.52 (DCM/MeOH, 6:1).
1H NMR (400 MHz, CDCl3): δ = 7.43–7.25 (m, 36 H, Harom.),
7.25–7.13 (m, 4 H, Harom.), 5.29 (d, J1α,2α = 0.5 Hz, 1 H, 1α-H),
5.13 (d, JAα,AЈα = 11.7 Hz, 1 H, OCH2Ph-Aα), 4.95–4.46 (m, 16
3
2
2,3,4,6-Tetra-O-methyl-α/β-D-mannopyranose (52): Prepared ac-
H, 1β-H, OCH2Ph-AЈα, Bα, BЈα, Cα, CЈα, Dα, DЈα, Aβ, AЈβ, Bβ,
cording to procedure C1. Compound 49 (2.25 g, 9.00 mmol), 0.5 m
BЈβ, Cβ, CЈβ, Dβ, DЈβ), 4.09–4.02 (m, 1 H, 5α-H), 4.02–3.94 (m, 2
3
HCl (50 mL). Yield: 77% (1.65 g, 6.97 mmol), α/β ratio = 5:1, H, 3α-H, 4β-H), 3.94–3.85 (m, 2 H, 4α-H, 2β-H), 3.84 (dd, J1α,2α
colourless oil, Rf = 0.11 (EA), [α]2D5 = +12.0 (c = 0.2, H2O). 1H
= 0.5 Hz, J2α,3α = 3.1 Hz, 1 H, 2α-H), 3.80–3.75 (m, 2 H, 6aβ-H,
3
3
3
NMR (400 MHz, CDCl3): δ = 5.31 (d, J1α,2α = 1.3 Hz, 1 H, 1α- 6bβ-H), 3.75–3.68 (m, 3 H, 6aα-H, 6bα-H, 2β-H), 3.64 (dd, J2β,3β
H), 4.67 (d, 3J1β,2β = 1.3 Hz, 1 H, 1β-H), 3.91 (ddd, 3J4α,5α = 9.5 Hz,
= 2.8 Hz, J3β,4β = 9.4 Hz, 1 H, 3β-H), 3.51–3.45 (m, 1 H, 5β-
3
3
3J5α,6aα = 2.3 Hz, J5α,6bα = 6.9 Hz, 1 H, 5α-H), 3.64–3.59 (m, 6 H,
H) ppm. 13C NMR (101 MHz, CDCl3): δ = 138.5, 138.4, 138.3,
3
2α-H, 3α-H, 6aα-H, 6β-H, 2β-H), 3.57 (dd, J5α,6bα = 6.9 Hz, 138.2, 138.1 (Carom. α,β), 128.5, 128.3, 127.9, 127.8, 127.6, 127.6
3
3
2J6aα,6bα = 10.0 Hz, 1 H, 6bα-H), 3.44 (dd, J3β,4β = 9.4 Hz, J4β,5β
(CHarom. α,β), 93.7 (C-1β), 92.8 (C-1α), 83.1 (C-3β), 79.7 (C-4α),
3
= 9.5 Hz, 1 H, 4β-H), 3.36–3.29 (m, 1 H, 4α-H), 3.28 (ddd, J4β,5β 76.0 (C-2β), 75.2 (C-5β), 75.2 (C-2α), 75.0 (OCH2Ph-α), 74.7 (C-
= 9.5 Hz, 3J5β,6aβ = 5.0 Hz, 3J5β,6bβ = 2.3 Hz, 1 H, 5β-H), 3.23 (dd,
5α), 74.6 (OCH2Ph-β), 74.3 (C-4β), 73.5 (OCH2Ph-β), 73.4
(OCH2Ph-α), 72.9 (OCH2Ph-β), 72.7(OCH2Ph-α), 72.2 (OCH2Ph-
3J2β,3β = 3.0 Hz, J3β,4β = 9.4 Hz, 1 H, 3β-H) 3.65, 3.53, 3.52, 3.39
3
(s, OCH3-β), 3.51, 3.50, 3.49, 3.38 (s, 3 H, OCH3-α) ppm. 13C α), 71.7 (C-3α), 69.6 (C-6α), 69.0 (C-6β) ppm. HRMS (ESI): calcd.
NMR (101 MHz, CDCl3): δ = 93.9 (C-1β), 91.2 (C-1α), 85.0 (C- for C34H36O6 [M + Na]+ 563.2404; found 563.2407.
3β), 80.8 (C-3α), 78.0 (C-2β), 77.4 (C-2α), 77.0 (C-4α), 76.0 (C-4β),
2,3,4,6-Tetra-O-benzyl-α-D-galactopyranose (56): Prepared accord-
74.8 (C-5β), 72.2 (C-6α), 71.4 (C-6β), 70.8 (C-5α), 60.6, 59.1, 59.0,
57.7 (OCH3-α), 61.6, 60.5, 59.2, 58.1 (OCH3-β) ppm. HRMS (ESI):
calcd. for C10H20O6 [M + Na]+ 259.1152; found 259.1161.
ing to procedure C2. Compound 54 (6.02 g, 10.8 mmol), glacial
acetic acid (105 mL), 1 n H2SO4 (52 mL). Yield: 60% (3.51 g,
6.50 mmol), α/β ratio: 2.5:1, colourless solid, Rf = 0.54 (DCM/
MeOH, 6:1). 1H NMR (400 MHz, CDCl3): δ = 7.43–7.25 (m, 40
Methyl 2,3,4,6-Tetra-O-benzyl-α-D-mannopyranoside (53): Prepared
according to procedure A2. Compound 46 (5.00 g, 25.7 mmol),
NaH (5.63 g, 141 mmol), BnBr (17.2 mL, 141 mmol), DMF
(90 mL). Yield: 86% (12.3 g, 22.2 mmol), colourless oil, Rf = 0.43
(PE/EA, 2:1), [α]2D5 = +43.2 (c = 0.5, CHCl3) {ref.[29] [α]2D3 = +23.4
(c = 1.0, CH2Cl2)}. 1H NMR (400 MHz, CDCl3): δ = 7.44–7.15
(m, 20 H, Harom.), 4.91 (d, 2JA,AЈ = 10.8 Hz, 1 H, OCH2Ph-A), 4.80
3
H, Harom.), 5.29 (d, J1α,2α = 3.6 Hz, 1 H, H-1α), 4.98–4.91 (m, 2
2
H, OCH2Ph-Aβ, Bβ), 4.95 (d, JAα,AЈα = 11.5 Hz, 1 H, OCH2Ph-
Aα), 4.86–4.70 (m, 7 H, H-1α, OCH2Ph-Bα, BЈα, Cα, CЈα, AЈβ,
3
2
BЈβ, Cβ), 4.67 (d, J1β,2β = 7.4 Hz, 1 H, H-1β), 4.62 (d, JCβ,CЈβ
=
2
11.7 Hz, 1 H, OCH2Ph-CЈβ), 4.60 (d, JAα,AЈα = 11.5 Hz, 1 H,
OCH2Ph-AЈα), 4.51–4.40 (m, 2 H, OCH2Ph-Dβ, DЈβ), 4.49 (d,
3
(d, J1,2 = 1.8 Hz, 1 H, 1-H), 4.78–4.72 (m, 2 H, OCH2Ph-B, D),
2JDα,DЈα = 12.0 Hz, 1 H, OCH2Ph-Dα), 4.42 (d, 2JDα,DЈα = 12.0 Hz,
2
4.72–4.61 (m, 3 H, OCH2Ph-C, BЈ, DЈ), 4.58 (d, JC,CЈ = 12.0 Hz,
3
1 H, OCH2Ph-DЈα), 4.20–4.13 (m, 1 H, H-5α), 4.05 (dd, J1α,2α
=
2
1 H, OCH2Ph-CЈ), 4.53 (d, JA,AЈ = 10.8 Hz, 1 H, OCH2Ph-AЈ),
3.6 Hz, 3J2α,3α = 9.7 Hz, 1 H, H-2α), 3.99–3.96 (m, 1 H, H-4α), 3.93
3
3
4.03–3.97 (m, 1 H, 4-H), 3.92 (dd, J2,3 = 3.3 Hz, J3,4 = 9.3 Hz, 1
H, 3-H), 3.84–3.74 (m, 4 H, 2-H, 5-H, 6-H), 3.35 (s, 3 H,
OCH3) ppm. 13C NMR (101 MHz, CDCl3): δ = 138.5, 138.5, 138.4,
138.3 (Carom.), 128.3, 128.3, 128.3, 127.9, 127.8, 127.7, 127.6, 127.4
(CHarom.), 98.9 (C-1), 80.2 (C-3), 75.0 (OCH2Ph-A), 74.9 (C-4),
74.5 (C-5), 73.3 (OCH2Ph-C), 72.5 (OCH2Ph-B), 72.1 (OCH2Ph-
D), 71.7 (C-2), 69.3 (C-6), 54.7 (OCH3) ppm.
3
3
(dd, J2α,3α = 9.7 Hz, J3α,4α = 2.8 Hz, 1 H, H-3α), 3.91–3.89 (m, 1
3
3
H, H-4β), 3.78 (dd, J1β,2β = 7.4 Hz, J2β,3β = 9.7 Hz, 1 H, H-2β),
3.65–3.57 (m, 2 H, H-5β, H-6aβ), 3.58–3.46 (m, 4 H, H-6α, H-6bβ,
H-3β) ppm. 13C NMR (101 MHz, CDCl3): δ = 138.6, 138.5, 138.2,
137.8 (Carom.,α), 138.5, 138.4, 138.3, 137.7 (Carom.,β), 128.4, 128.4,
128.3, 128.2, 128.2, 128.2, 128.0, 127.9, 127.8, 127.8, 127.7, 127.6,
127.6, 127.5, 127.5 (CHarom. α,β), 97.8 (C-1β), 91.9 (C-1α), 82.2 (C-
3β), 80.7 (C-2β), 78.7 (C-3α), 76.6 (C-2α), 75.1, 74.5, 72.9
(OCH2Ph-β), 74.6, 73.5, 73.4, 72.9 (OCH2Ph-α), 74.6 (C-4α), 73.6
(C-4β), 73.6 (C-5β), 69.5 (C-5α), 69.0 (C-6α), 68.9 (C-6β) ppm.
Methyl 2,3,4,6-Tetra-O-benzyl-α-D-galactopyranoside (54): Pre-
pared according to procedure A2. Compound 45 (4.02 g,
20.7 mmol), NaH (4.60 g, 115 mmol), BnBr (14.0 mL, 115 mmol),
5874
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Eur. J. Org. Chem. 2011, 5860–5878