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2633
alkane), 1725 (s, C@O ester), 1601, 1451 (m, ArC@C),
1265, 1108 (s, C–O), 1176 (w, C–N); dH (400 Hz, CDCl3)
(mixture of rotamers) 2.30–2.36 (1H, m, Hypb-HAHB),
2.58–2.63 (1H, m, Hypb-HAHB), 3.73–3.91 (2H, m,
Hypd-H2), 4.44–4.73 (10H, m, H-5, H-6A, H-6B,
Hypa-H, Hypc-H, CH2CH@CH2, Fmoc CH2, Fmoc
CH), 5.20–5.36 (3H, m, H-3, CH@CH2), 5.91 (1H, s,
H-1), 5.78–5.92 (2H, m, H-2, CH@CH2), 6.12 (1H, q,
J 9.8 Hz, H-4), 7.25–8.10 (28H, m, Bz ArH, Fmoc
ArH). dC (100 Hz, CDCl3) (mixture of rotamers) 36.4,
37.5 (Hypb-C), 47.1, 47.2 (Fmoc CH), 51.4, 51.36
(Hypd-C), 57.8, 58.2 (Hypa-C), 62.8 (C6), 65.9
(CH2CH@CH2), 66.8, 66.9 (C5), 67.8 (Fmoc CH2),
69.6 (C4), 70.3, 70.5 (C3, C2), 74.8, 76.7 (Hypd-C),
96.8, 97.5 (C1), 118.7, 119.9 (CH@CH2), 119.9, 125.0,
127.1, 127.7 (Fmoc ArCH), 128.3, 128.4, 128.5, 128.6,
129.7, 129.8 (Bz ArCH), 131.4, 131.6 (CH@CH2),
133.2, 133.2, 133.5, 133.6 (Bz ArCH), 141.3, 143.7,
143.9, 144.0 (quat., Fmoc C), 154.3, 154.7 (quat., Fmoc
C@O), 165.2, 165.4, 166.1 (quat., CO2Bz), 171.7, 171.8
(quat., COOH); m/z (FAB, %) 972 (MH+, 1), 579 (9),
178 (19), 154 (100), 105 (57).
ArCH), 140.9, 141.0, 143.4, 143.5 (quat., Fmoc C),
154.3, 154.8 (quat., Fmoc C@O), 169.6, 169.7 (quat.,
COCH3), 169.8 (quat. COCH3), 170.5 (quat., COCH3),
175.1, 175.4 (quat., COOH), 175.1 (quat., COCH3);
m/z (FAB, %) 684 (MH+, 3), 331 (3), 178 (15), 154
(100), 89 (20).
1.8. Na-Fluorenylmethoxycarbonyl-trans-4-hydroxy-4-O-
[(2,3,4,6-tetra-O-benzoyl)-a-D-mannopyranosyl]-L-proline
(17)
Using the procedure described above, Na-fluorenyl-
methoxycarbonyl-trans-4-hydroxy-4-O-[(2,3,4,6-tetra-O-
benzoyl)-a-D-mannopyranosyl]-L-proline allyl ester 3
(370 mg, 0.38 mmol) was treated with tetrakis(triphenyl-
phosphine)palladium(0) (0.025 equiv) and phenylsilane
(2 equiv) to give after flash chromatography using hex-
ane–ethyl acetate (2:1) + 10% acetic acid, glycoside 17
(179 mg, 50%) as a thick, viscous oil: (Found: MH+,
20
932.2928, C54H46NO14 requires 932.2918); ½aꢁD ꢀ32.8
(c 0.90, CHCl3); vmax (film)/cmꢀ1 3438 (br s, O–H),
3063 (s, ArC–H), 2959 (s, C–H alkane), 1728 (s, C@O
ester, acid), 1601, 1451 (m, ArC@C), 1265, 1108 (s, C–
O), 1068 (s, C–N); dH (300 Hz, CDCl3) (mixture of rota-
mers) 2.38–2.44 (1H, m, Hypb-HAHB), 2.61–2.67 (1H,
m, Hypb-HAHB), 3.73–3.90 (2H, m, Hypd-H2), 4.16–
4.76 (8H, m, H-5, H-6A, H-6B, Hypa-H, Hypc-H, Fmoc
CH2, Fmoc CH), 5.23 (1H, d, J 1.3 Hz, H-1), 5.73 (1H,
d, J 1.5 Hz, H-2), 5.94 (1H, dd, J 10.1, 2.7 Hz, H-3),
6.12–6.20 (1H, m, H-4), 7.14–8.11 (28H, m, Bz ArH,
Fmoc ArH). dC (75 Hz, CDCl3) (mixture of rotamers)
36.1, 37.3 (Hypb-C), 46.9, 47.0 (Fmoc CH), 51.3, 51.5
(Hypd-C), 57.4, 57.6 (Hypa-C), 62.8 (C6), 66.4, 66.8
(C5), 67.9 (Fmoc CH2), 69.4 (C4), 69.5, 69.6 (C3),
70.2, 70.4 (C2), 75.0, 76.7 (Hypc-C), 96.9, 97.4 (C1),
119.7, 119.8, 124.9, 126.9, 127.0, 127.5, 127.6 (Fmoc
ArCH), 128.1, 128.3, 128.4, 128.4, 128.5, 128.5, 132.9,
133.0, 133.4, 133.5 (Bz ArCH), 141.0, 141.1, 143.6,
143.7 (quat., Fmoc C), 154.5, 155.0 (quat., Fmoc
C@O), 165.1 (quat., COBz), 165.2, 165.3 (quat., COBz),
166.0 (quat., COBz), 176.0, 176.3 (quat., COBz), 176.6
(quat., COOH); m/z (FAB, %) 932 (MH+, 2), 579 (4),
178 (19), 154 (100), 105 (45).
1.7. Na-Fluorenylmethoxycarbonyl-trans-4-hydroxy-4-O-
[(2,3,4,6-tetra-O-acetyl)-a-D-mannopyranosyl]-L-proline
(16)
Na-fluorenylmethoxycarbonyl-trans-4-hydroxy-4-O-[(2,
3,4,6-tetra-O-acetyl)-a-D-mannopyranosyl]-L-proline
allyl ester 2 (350 mg, 0.48 mmol) was dissolved in dis-
tilled dichloromethane (8 mL) and degassed with argon
for 15 min. Tetrakis(triphenylphosphine)palladium(0)
(0.025 equiv) and phenylsilane (2 equiv) were added
and the reaction mixture was left to stir for 2 h. The
reaction mixture was concentrated in vacuo and the
crude product was purified by flash chromatography
using hexane–ethyl acetate (1:1) + 10% acetic acid to
afford glycoside 16 (203 mg, 61%) as a thick, viscous
oil: (Found: MH+, 684.2288, C34H38NO14 requires
20
684.2288); ½aꢁD ꢀ2.85 (c 1.35, CHCl3); vmax (film)/
cmꢀ1 3478 (br s, O–H), 3060 (s, ArC–H), 2956 (s, C–
H alkane), 1755 (s, C@O ester, acid), 1435, 1477 (m,
ArC@C), 1227, 1132 (s, C–O), 1047 (s, C–N); dH
(300 Hz, CDCl3) (mixture of rotamers) 1.99, 2.05,
2.08, 2.14 (4 · 3H, s, COCH3), 2.28–2.32 (1H, m,
Hypb-HAHB), 2.48–2.53 (1H, m, Hypb-HAHB), 3.57–
3.79 (2H, m, Hypd-H2), 4.04–4.53 (8H, m, H-5, H-6A,
H-6B, Hypa-H, Hypc-H, Fmoc CH2, Fmoc CH), 4.91
(1H, s, H-1), 5.23–5.36 (3H, m, H-2, H-3, H-4), 7.22–
7.75 (8H, m, Fmoc ArH). dC (75 Hz, CDCl3) (mixture
of rotamers) 20.3, 20.5, 20.5, 20.7 (4 · COCH3), 35.6,
36.9 (Hypb-C), 46.7, 46.8 (Fmoc CH), 51.2, 51.3
(Hypd-C), 57.3, 57.7 (Hypa-C), 62.4 (C6), 65.9, 66.0
(C5), 67.6, 67.7 (Fmoc CH2), 68.5 (C4), 68.8, 69.0
(C3), 69.2, 69.3 (C2), 74.7, 76.6 (Hypc-C), 96.6, 97.2
(C1), 119.6, 119.7, 124.8, 126.9, 127.3, 127.4 (Fmoc
References
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