Job/Unit: O20242
/KAP1
Date: 12-07-12 17:03:15
Pages: 12
O-Glycosylation of d-Glucal-Derived β- and α-Vinyl Oxiranes
116.5, 95.6, 74.7, 73.6, 69.7, 62.7 ppm. HRMS (ESI): calcd. for
C19H20NaO4 [M + Na]+ 335.1254; found 335.1250.
= +40.17 (c = 1.4, CH Cl ). IR (neat): ν
= 3434, 3062, 3030,
˜
2
2
max
2916, 2865, 1495, 1453, 1367, 1158, 1098, 1045, 738, 697 cm–1. H
NMR (400 MHz, CDCl3): δ = 7.37–7.25 (m, 20 H, ArH), 6.08–
6.05 (m 1 H), 5.72 (d, J = 10.24 Hz, 1 H, -OCHPh), 5.25 (br. s, 1
H), 4.88 (br. s, 2 H), 4.78 (d, J = 12.20 Hz, 1 H, -OCHPh), 4.63
(d, J = 12.20 Hz, 1 H, -OCHPh), 4.62 (d, J = 12.20 Hz, 1 H,
-OCHPh), 4.59 (d, J = 3.64 Hz, 1 H), 4.53–4.47 (m, 3 H), 3.98–
3.86 (m, 3 H), 3.83–3.78 (m, 1 H), 3.72–3.67 (m, 2 H), 3.64–3.46
(m, 4 H), 3.36 (br. s, 3 H), 2.48 (d, J = 10.52 Hz, 1 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 139.0, 138.2, 138.1, 137.7, 131.3,
130.4, 128.3–127.3 (m, Ar-C), 98.1, 98.0, 80.7, 79.5, 77.2, 75.6, 74.9,
74.7, 73.8, 73.4, 70.5, 69.3, 68.1, 62.0, 55.1 ppm. HRMS (ESI):
calcd. for C41H46NaO9 [M + Na]+ 705.3034; found 705.3039.
1
Benzyl 6-O-Benzyl-2,3-dideoxy-β-
Yield: 86% (36 mg); Rf = 0.4 (hexane/ethyl acetate, 4:1); yellow
liquid; [α]2D8 = +12.0 (c = 1.0, CH Cl ). IR (neat): ν
= 3417,
D-threo-hex-2-enopyranoside (20):
˜
max
2
2
3030, 2920, 2859, 1725, 1598, 1496, 1453, 1378, 1321, 1255, 1208,
1157, 1116, 1051, 1020, 849, 788, 736, 697 cm–1. 1H NMR
(500 MHz, CDCl3): δ = 7.37–7.25 (m, 10 H, ArH), 6.15–6.12 (m,
1 H), 5.87 (d, J = 10.10 Hz, 1 H), 5.16 (d, J = 1.40 Hz, 1 H), 4.90
(d, J = 11.95 Hz, 1 H), 4.66 (d, J = 11.95 Hz, 1 H), 4.61 (br. s, 2
H), 3.98–3.95 (m, 1 H), 3.87–3.81 (m, 2 H), 3.76–3.73 (m, 1 H),
2.04 (br. s, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 138.1,
137.4, 130.9, 130.8, 128.5–127.8 (m, Ar-C), 96.8, 74.5, 73.7, 70.1,
69.9, 63.0 ppm. HRMS (ESI): calcd. for C20H22NaO4 [M + Na]+
349.1410; found 349.1419.
Methyl
anosyl)-2,4,6-tri-O-benzyl-α-
(52 mg); colorless liquid; Rf = 0.45 (hexane/ethyl acetate, 3:2);
[α]2D8 = +15.0 (c = 0.6, CH Cl ). IR (neat): νmax = 3466, 3030, 2864,
3-O-(6Ј-O-Benzyl-2Ј,3Ј-dideoxy-β-
D-threo-hex-2Ј-enopyr-
D-glucopyranoside (25): Yield: 60%
Cyclohexyl 6-O-Benzyl-2,3-dideoxy-β-
(21): Yield: 79% (32 mg); Rf = 0.45 (hexane/ethyl acetate, 3:2);
[α]2D8 = –90.34 (c = 1.45, CH Cl ). IR (neat): ν
= 3041, 3032,
D-threo-hex-2-enopyranoside
˜
2
2
1496, 1453, 1369, 1161, 1090, 1048, 906, 849, 737, 698 cm–1. 1H
NMR (400 MHz, CDCl3): δ = 7.39–7.24 (m, 20 H, ArH), 6.17–
6.13 (m, 1 H), 5.90 (d, J = 10.04 Hz, 1 H), 5.54 (br. s, 1 H), 5.06
(d, J = 10.48 Hz, 1 H, -OCHPh), 4.73 (d, J = 11.96 Hz, 1 H,
-OCHPh), 4.67–4.62 (m, 3 H), 4.58–4.48 (m, 3 H), 4.44 (d, J =
10.72 Hz, 1 H, -OCHPh), 4.33 (t, J = 9.28 Hz, 1 H), 3.99–3.94 (m,
1 H), 3.82–3.72 (m, 3 H), 3.69–3.63 (m, 3 H), 3.60–3.53 (m, 2 H),
3.39 (s, 3 H), 1.75 (d, J = 10.00 Hz, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 138.6, 138.1, 137.9, 137.8, 131.5, 130.3,
128.5–127.4 (m, Ar-C), 99.3, 97.7, 80.0, 79.6, 77.2, 76.8, 76.1, 74.5,
74.0, 73.4, 73.1, 69.9, 68.9, 68.5, 62.3 ppm. HRMS (ESI): calcd. for
C41H46NaO9 [M + Na]+ 705.3034; found 705.3044.
˜
max
2
2
2931, 2855, 1650, 1495, 1452, 1373, 1316, 1259, 1177, 1163, 1119,
1044, 1024, 963, 890, 869, 848, 785, 736, 697 cm–1. 1H NMR
(500 MHz, CDCl3): δ = 7.34–7.25 (m, 5 H, ArH), 6.11–6.08 (m, 1
H), 5.80 (d, J = 9.65 Hz, 1 H), 5.16 (d, J = 1.40 Hz, 1 H), 4.59 (s,
2 H), 3.90 (br. s, 1 H), 3.83–3.77 (m, 2 H), 3.74–3.67 (m, 2 H),
2.03–1.90 (m, 3 H), 1.74–1.70 (m, 2 H), 1.58–1.52 (m, 1 H), 1.41–
1.19 (m, 5 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 138.1, 131.7,
130.4, 128.3–127.6 (m, Ar-C), 96.0, 74.5, 73.5, 69.9, 62.8, 33.7, 32.1,
25.5–24.1 (m) ppm. HRMS (ESI): calcd. for C19H26NaO4 [M +
Na]+ 341.1723; found 341.1727.
6-O-(6Ј-O-Benzyl-2Ј,3Ј-dideoxy-β-
1,2,3,4-di-O-isopropylidene-α- -galactopyranose (22): Yield: 65%
(40 mg); Rf = 0.4 (hexane/ethyl acetate, 7:3); colorless liquid; [α]2D8
= –86.66 (c = 0.9, CH Cl ). IR (neat): ν = 3459, 2987, 2924,
D-threo-hex-2Ј-enopyranosyl)-
L
-Tyrosine N-[(1,1-Dimethylethoxy)carbonyl]-O-(6-O-benzyl-2,3-di-
deoxy-β- -threo-hex-2-enopyranosyl) Methyl Ester (26): Yield: 65%
(43 mg); yellow liquid; Rf = 0.5 (hexane/ethyl acetate, 1:1); [α]2D8
+92.85 (c = 0.7, CH Cl ). IR (neat): νmax = 3424, 3063, 3027, 2977,
D
D
=
˜
max
2
2
˜
2
2
1725, 1647, 1445, 1382, 1308, 1256, 1212, 1168, 1070, 1002, 918,
1
899, 863 cm–1. H NMR (500 MHz, CDCl3): δ = 7.34–7.25 (m, 5
2927, 2867, 1743, 1712, 1610, 1556, 1509, 1452, 1393, 1367, 1229,
1165, 1108, 1051, 1017, 854, 738, 698 cm–1. 1H NMR (500 MHz,
CDCl3): δ = 7.35–7.25 (m, 5 H, ArH), 7.04–7.00 (m, 4 H, ArH),
6.24–6.21 (m, 1 H), 5.97 (d, J = 10.10 Hz, 1 H), 5.65 (s, 1 H), 4.94
(d, J = 7.95 Hz, 1 H), 4.61–4.53 (m, 3 H), 4.02–3.99 (m, 2 H), 3.86–
3.69 (m, 5 H), 3.04–3.01 (m, 2 H), 2.07 (d, J = 9.80 Hz, 1 H), 1.40
(br. s, 9 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 172.4, 156.1,
155.2, 138.0, 131.5, 130.4–127.8 (m, Ar-C), 116.6, 95.8, 80.0, 74.7,
73.7, 69.8, 62.7, 54.5, 52.3, 37.5, 28.3 ppm. HRMS (ESI): calcd. for
C28H39N2O8 [M + NH4]+ 531.2701; found 531.2709.
H, ArH), 6.13–6.10 (m, 1 H), 5.89 (d, J = 10.00 Hz, 1 H), 5.53 (d,
J = 4.90 Hz, 1 H), 5.15 (d, J = 1.45 Hz, 1 H), 4.59–4.57 (m, 3 H),
4.31–4.29 (m, 1 H), 4.21 (dd, J = 1.40, 1.75 Hz, 1 H), 4.02–3.98
(m, 2 H), 3.92 (br. s, 1 H), 3.82–3.76 (m, 3 H), 3.70–3.68 (m, 1 H),
2.22 (br. s, 1 H), 1.52 (br. s, 3 H), 1.43 (br. s, 3 H), 1.31 (br. s, 6
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 138.1, 130.8, 130.7,
128.5, 127.8 (m, Ar-C), 109.4, 108.7, 98.5, 96.4, 74.5, 73.6, 71.3,
70.7, 70.4, 69.7, 68.3, 67.8, 62.8, 26.1, 26.0, 25.0, 24.5 ppm. HRMS
(ESI): calcd. for C25H34NaO9 [M + Na]+ 501.2095; found 501.2108.
L
-Serine N-[(1,1-Dimethylethoxy)carbonyl]-O-(6-O-benzyl-2,3-dide-
oxy-β- -threo-hex-2-enopyranosyl) Methyl Ester (27): Yield: 62%
(35 mg); Rf = 0.6 (hexane/ethyl acetate, 1:1); colorless liquid; [α]2D8
= –38.46 (c = 1.3, CH Cl ). IR (neat): ν = 3386, 2976, 2931,
Methyl
anosyl)-2,3,4-tri-O-benzyl-α-
(54 mg); Rf = 0.4 (hexane/ethyl acetate, 3:2); [α]2D8 = +25.41 (c =
1.2, CH Cl ). IR (neat): νmax = 3428, 3030, 2918, 1597, 1496, 1453,
6-O-(6Ј-O-Benzyl-2Ј,3Ј-dideoxy-β-
D-threo-hex-2Ј-enopyr-
D
D-glucopyranoside (23): Yield: 62%
˜
max
˜
2
2
2
2
1385, 1257, 1159, 1048, 912, 871, 737, 697 cm–1. 1H NMR
(500 MHz, CDCl3): δ = 7.35–7.25 (m, 20 H, ArH), 6.11–6.09 (m,
1 H), 5.76 (d, J = 9.75 Hz, 1 H), 4.99 (d, J = 8.00 Hz, 1 H), 4.97
(d, J = 2.30 Hz, 1 H), 4.87 (d, J = 12.60 Hz, 1 H), 4.81 (d, J =
11.45 Hz, 1 H), 4.78 (d, J = 12.60 Hz, 1 H), 4.65–4.53 (m, 5 H),
4.04 (d, J = 8.60 Hz, 1 H), 3.98 (t, J = 9.15 Hz, 1 H), 3.89 (br. s, 1
H), 3.78–3.71 (m, 4 H), 3.64–3.52 (m, 3 H), 3.35 (s, 3 H), 1.83 (d,
J = 10.0 Hz, 1 H) ppm. 13C NMR (125 MHz): δ = 138.7, 138.3,
138.2, 138.1, 130.8, 130.6, 128.3–127.5 (m, Ar-C), 98.1, 98.1, 82.1,
79.7, 75.7, 74.8, 74.5, 74.5, 73.5, 73.3, 69.6, 69.6, 66.5, 62.6,
55.1 ppm. HRMS (ESI): calcd. for C41H46NaO9 [M + Na]+
705.3034; found 705.3047.
2875, 1748, 1713, 1509, 1454, 1438, 1391, 1367, 1296, 1249, 1212,
1
1164, 1119, 1053, 867, 850, 812, 781 cm–1. H NMR (500 MHz): δ
= 7.34–7.25 (m, 5 H, ArH), 6.16–6.13 (m, 1 H), 5.77 (d, J =
10.35 Hz, 1 H), 5.50 (d, J = 8.55 Hz, 1 H), 5.09 (br. s, 1 H), 4.58
(d, J = 2.75 Hz, 2 H), 4.45–4.41 (m, 1 H), 4.19–4.15 (m, 1 H), 3.95
(br. s, 1 H), 3.85–3.81 (m, 2 H), 3.78–3.75 (m, 1 H), 3.73 (s, 3 H),
3.69–3.66 (m, 1 H), 2.08 (d, J = 9.45 Hz, 1 H), 1.44 (br. s, 9 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 171.0, 155.5, 138.0, 131.4, 130.0,
128.5–127.8 (m, Ar-C), 97.4, 80.1, 74.4, 73.7, 69.6, 67.7, 62.6, 53.9,
52.6, 28.4 ppm. HRMS (ESI): calcd. for C22H31NNaO8 [M +
Na]+ 460.1942; found 460.1942.
L
-Threonine N-[(1,1-Dimethylethoxy)carbonyl]-O-(6-O-benzyl-2,3-
dideoxy-β- -threo-hex-2-enopyranosyl) Methyl Ester (28): Yield:
61% (35 mg); colorless liquid; Rf = 0.5 (hexane/ethyl acetate, 1:1);
Methyl
anosyl)-2,3,6-tri-O-benzyl-α-
(50 mg); Rf = 0.5 (hexane/ethyl acetate, 3:2); colorless liquid; [α]2D8
4-O-(6Ј-O-Benzyl-2Ј,3Ј-dideoxy-β-D-threo-hex-2Ј-enopyr-
D
D-glucopyranoside (24): Yield: 58%
[α]2D8 = –51.11 (c = 0.45, CH Cl ). IR (neat): ν
= 3430, 3063,
˜
2
2
max
Eur. J. Org. Chem. 0000, 0–0
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www.eurjoc.org
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