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F. Chéry et al./Carbohydrate Research 417 (2015) 117–124
4.7.1. Methyl 2,3-di-O-benzyl-6-O-vinyl-β-D-galactopyranoside
H-6b), 4.07 (dd, 1H, J1′–2′Z = 6.8, H-2′Z), 4.27 (ddd, 1H, J1–3 = 1.3, H-3),
4.28 (dd, 1H, J2′E–2′Z =2.3, H-2′E), 4.74 (dd, 1H, J2–3 = 1.7, H-2), 6.35 (dd,
1H, J1–2 = 5.9, H-1), 6.51 (dd, 1H, J1–2′E = 14.3, H-1′); 13C NMR δ 67.0
(C-6), 70.2 (C-3), 70.5 (C-4), 76.4 (C-5), 87.7 (C-2′), 102.9 (C-2), 144.6
(C-1), 151.7 (C-1′); MS IS m/z = 173.0 [M + H]+, 195.0 [M + Na]+; IR
1
Amorphous solid (58 mg, 29% yield); [α]D +7 (c = 0.8, CHCl3); H
NMR δ 3.49–3.52 (m, 1H, H-5), 3.53 (dd, 1H, J3–4 = 3.4, H-3), 3.57 (s,
3H, OMe), 3.63 (dd, 1H, J2–3 = 9.4, H-2), 3.94 (t, 1H, J5–6b =5.9, H-6b),
4.00 (dd, 1H, J5–6a =1.7, Jgem = 10.5, H-6a), 4.01 (m, 1H, H-4), 4.04 (dd,
1H, J1′–2′Z=6.6, H-2′Z), 4.26 (dd, 1H, J2′E–2′Z=2.1, H-2′E), 4.29 (d, 1H, J1-2 = 7.4,
H-1), 4.72 and 4.90 (2d, AB system, 2H, Jgem = 11.1, PhCH2O), 4.73 (s,
2H, PhCH2O), 6.48 (dd, 1H, J1′–2′E = 14.3, H-1′), 7.28–7.41 (m, 10H, H—Ar);
13C NMR δ 57.5 (OMe), 67.0 (C-4), 67.3 (C-6), 72.8 (C-5), 72.9, 75.5
(2PhCH2O), 79.3 (C-2), 80.8 (C-3), 87.7 (C-2′), 105.1 (C-1), 128.1, 128.3,
128.4, 128.7, 128.9 (CH—Ar), 138.1, 139.0 (2CIV—Ar), 152.0 (C-1′);
(film) 3500 (OH), 1625, 1613 (C
=C), 1013, 995 (=C—OR); HRMS:
C8H12O4: calcd. 172.0736; found 172.0751.
4.8.3. 1,5-Anhydro-2-deoxy-4-O-vinyl-D-arabino-hex-1-enitol
Colorless gum (19 mg, 20% yield), [α]D +13 (c = 0.8, CHCl3); 1H
NMR δ 1.95 (t, 1H, OH-6), 2.28 (d, 1H, OH-3), 3.79–4.04 (m, 4H, H-4,
H-5, H-6a, H-6b), 4.12 (dd, 1H, J1′–2′Z = 6.4, H-2′Z), 4.40 (m, 1H, H-3),
4.49 (dd, 1H, J2′E–2′Z =2.2, H-2′E), 4.79 (d, 1H, J2–3 = 2.6, H-2), 6.39 (dd,
1H, J1–2 = 5.9, J1–3 = 1.3, H-1), 6.48 (dd, 1H, J1′–2′E =13.8, H-1′); 13C NMR
δ 61.4 (C-6), 67.9, 76.8, 78.0 (C-3, C-4, C-5), 90.2 (C-2′), 102.7 (C-
IR (film) 3500 (OH), 2977, 2931 (
=CH2), 1639, 1624 (C=C), 1075,
1021, 972 (=
C—OR); MS IS m/z = 418.5 [M + NH4]+, 423.5 [M + Na]+,
439.5 [M + K]+; HRMS: C23H28O6: calcd. 400.1886; found 400.1872.
4.7.2. Methyl
2), 144.4 (C-1), 152.1 (C-1′); IR (film) 3489 (OH), 1615, 1610 (C
=C),
1023, 985 (
=
C—OR); MS IS m/z = 173.0 [M + H]+, 195.0 [M + Na]+;
2,3-di-O-benzyl-4,6-O-ethylidene-β-D-galactopyranoside
Colorless gum (60 mg, 31% yield); [α]D −3 (c = 1.0, CHCl3); 1H NMR
δ 1.46 (d, 3H, Jvic = 5.2, CH3CH), 3.21 (ddd, 1H, J5–6a = 1.5, H-5), 3.48
(dd, 1H, J3–4 = 3.8, H-3), 3.57 (s, 3H, OMe), 3.79 (dd, 1H, J2–3 = 9.8, H-2),
3.81 (t, 1H, J5–6b = 1.9, H-6b), 3.90 (dd, 1H, J3–4 = 3.8, H-4), 4.16 (dd,
1H, Jgem = 12.3, H-6a), 4.26 (d, 1H, J1–2 = 7.7, H-1), 4.71 (q, 1H, H-7),
4.73 and 4.79 (2d, AB system, 2H, Jgem = 12.3, PhCH2O), 4.78 and 4.91
(2d, AB system, 2H, Jgem = 10.8, PhCH2O), 7.25–7.42 (m, 10H, H—Ar);
13C NMR δ 21.5 (CH3CH), 57.5 (OMe), 66.7 (C-5), 69.1 (C-6), 72.7, 75.7
(2PhCH2O), 74.0 (C-4), 79.0 (C-2), 79.3 (C-3), 99.8 (C-7), 105.1 (C-
1), 127.9, 128.1, 128.3, 128.5, 128.7 (CH—Ar), 138.7, 139.3 (2CIV—Ar);
MS IS m/z = 418.5 [M + NH4]+, 423.5 [M + Na]+, 439.5 [M + K]+; HRMS:
C23H28O6: calcd. 400.1886; found 400.1879.
HRMS: C8H12O4: calcd. 172.0736; found 172.0733.
4.9. Reductive ring cleavage of methyl 2,3-anhydro-4,6-O-
(2-phenylsulfonyl)ethylidene-α-D-allopyranoside (11)3
From 171 mg (0.50 mmol) the following were successively ob-
tained from chromatography.
4.9.1. Methyl 2,3-anhydro-4,6-O-ethylidene-α-D-allopyranoside
Crystalline solid (34 mg, 34% yield), mp 124 °C (126–128 °C21),
[α]D +72 (c = 0.7, CHCl3); 1H NMR δ 1.37 (d, 3H, Jvic = 5.1, CH3CH),
3.42–3.50 (m, 3H, H-2, H-3, H-6b), 3.44 (s, 3H, OMe), 3.72 (dd, 1H,
J3–4 = 1.2, H-4), 3.91 (dt, 1H, J4–5 = 9.1, J5–6b = 10.2, H-5), 4.06 (dd, 1H,
J5–6a = 4.9, Jgem = 10.2, H-6a), 4.77 (q, 1H, H-7), 4.84 (d, 1H, J1–2 = 2.3,
H-1); 13C NMR δ 20.6 (CH3CH), 50.8 (C-3), 53.2 (OMe), 56.0 (C-2),
60.1 (C-5), 68.5 (C-6), 76.7 (C-4), 95.4 (C-1), 100.6 (C-7); MS IS
m/z = 203.0 [M + H]+, 220.0 [M + NH4]+, 225.0 [M + Na]+; HRMS:
C9H14O5: calcd. 202.0841; found 202.0829.
4.7.3. Methyl 2,3-di-O-benzyl-4-O-vinyl-β-D-galactopyranoside
Colorless gum (54 mg, 28% yield); [α]D +26 (c = 1.0, CHCl3); 1H
NMR δ 3.52 (m, 1H, H-5), 3.54 (dd, 1H, J3–4 = 2.9, H-3), 3.58 (s, 3H,
OMe), 3.69 (m, 1H, H-6b), 3.72 (dd, 1H, J2–3 = 9.8, H-2), 3.83 (t, 1H,
J5–6a = 1.9, Jgem = 12.5, H-6a), 4.04 (dd, 1H, J1–2′Z = 6.4, H-2′Z), 4.09 (dd,
1H, J4–5 = 0.8, H-4), 4.31 (d, 1H, J1–2 = 7.7, H-1), 4.45 (dd, 1H, J2′E–2′Z =1.9,
H-2′E), 4.71 and 4.76 (2d, AB system, 2H, Jgem = 11.9, PhCH2O), 4.74
and 4.88 (2d, AB system, 2H, Jgem = 10.8, PhCH2O), 6.39 (dd, 1H,
J1′–2′E =13.8, H-1′), 7.28–7.37 (m, 10H, H—Ar); 13C NMR δ 57.7 (OMe),
61.9 (C-6), 73.3, 75.7 (2PhCH2O), 74.7 (C-5), 75.4 (C-4), 79.9 (C-2),
80.5 (C-3), 89.1 (C-2′), 105.3 (C-1), 128.0, 128.2, 128.4, 128.7, 128.8
(CH—Ar), 138.5, 139.1 (2CIV—Ar), 153.2 (C-1′); IR (film) 3491 (OH),
4.9.2. Methyl 2,3-anhydro-6-O-vinyl-α-D-allopyranoside
Colorless amorphous solid (32 mg, 32% yield), [α]D +75 (c = 1.0,
CHCl3); 1H NMR δ 3.46 (s, 3H, OMe), 3.50 (dd, 1H, J3–4 = 1.9, H-3),
3.59 (dd, 1H, J2–3 = 4.2, H-2), 3.78–3.84 (m, 1H, H-5), 3.93 (m, 2H,
H-6a, H-6b), 4.02–4.05 (m, 1H, H-4), 4.05 (dd, 1H, J1′–2′Z =6.8, H-2′Z),
4.25 (dd, 1H, J2′E–2′Z =2.1, H-2′E), 4.93 (d, 1H, J1–2 = 3.2, H-1), 6.50 (dd,
1H, J1–2′E = 14.3, H-1′); 13C NMR δ 54.1 (OMe), 55.9 (C-3), 56.0 (C-2),
65.9 (C-4), 67.2 (C-6), 67.7 (C-5), 87.4 (C-2′), 94.7 (C-1), 151.8 (C-
2984, 2931 (=CH2), 1633, 1625 (C=C),1078, 1027, 969 (=C—OR);
MS IS m/z = 418.5 [M + NH4]+, 423.5 [M + Na]+, 439.5 [M + K]+; HRMS:
C23H28O6: calcd. 400.1886; found 400.1870.
1′); IR (film) 3495 (OH), 2987, 2936 (=CH2), 1637, 1621 (C=C), 1079,
4.8. Reductive ring cleavage of 1,5-anhydro-4,6-O-
1025, 978 (=
C—OR); MS IS m/z = 171.0 [M-OMe]+, 203.0 [M + H]+,
(2-phenylsulfonyl)ethylidene-D-arabino-hex-1-enitol (10)3
220.0 [M + NH4]+, 225.0 [M + Na]+; HRMS: C9H14O5: calcd. 202.0841;
found 202.0832.
From 169 mg (0.54 mmol) the following were successively ob-
tained from chromatography.
4.9.3. Methyl 2,3-anhydro-6-O-tert-butyldimethylsilyl-4-O-
vinyl-α-D-allopyranoside
4.8.1. 1,5-Anhydro-2-deoxy-4,6-O-ethylidene-D-arabino-hex-1-enitol
Colorless gum (32.5 mg, 35% yield), [α]D −6 (c = 3.3, CHCl3); 1H
NMR δ 1.36 (d, 3H, J = 4.9, CH3CH), 2.61 (d, 1H, OH), 3.56 (dd, 1H,
J3–4 = 7.4, H-4), 3.57 (t, 1H, J5–6b =10.4, H-6b), 3.75 (dt, 1H, J4–5 = 10.4,
H-5), 4.17 (dd, J5–6a = 4.9, Jgem = 10.4, H-6a), 4.40 (bdd, 1H, J1–3 = 1.5,
H-3), 4.72 (dd, 1H, J2–3 = 2.1, H-2), 4.78 (q, 1H, H-7), 6.28 (dd, 1H,
J1–2 = 5.9, H-1); 13C NMR δ 20.5 (CH3CH), 66.7 (C-3), 67.9 (C-6), 68.5
(C-5), 80.2 (C-4), 99.7 (C-7), 103.8 (C-2), 144.2 (C-1); MS IS
m/z = 173.0 [M + H]+, 195.0 [M + Na]+; HRMS: C8H12O4: calcd.
172.0736; found 172.0744.
Isolated via selective 6-O-silylation from the mixture of
regioisomeric alcohols (52 mg, 33% over two steps), colorless gum;
[α]D +111 (c = 0.8, CHCl3); 1H NMR δ 0.09 (s, 6H, Me2Si), 1.25 (s, 9H,
t-BuSi), 3.41 (dd, 1H, J2–3 = 4.2, H-2), 3.45 (s, 3H, OMe), 3.55 (dd, 1H,
J3–4 = 1.4, H-3), 3.71–3.84 (m, 3H, H-5, H-6a, H-6b), 4.12 (dd, 1H,
J1′–2′Z =6.6, H-2′Z), 4.26 (dd, 1H, J4–5 = 9.1, H-4), 4.44 (dd, 1H, J2′E–2′Z =1.9,
H-2′E), 4.90 (d, 1H, J1–2 = 2.9, H-1), 6.45 (dd, 1H, J1′–2′E = 14.3, H-1′);
13C NMR δ −4.8 (Me2Si), 18.5 (CIV—tBuSi), 26.1 (Me3CSi), 51.5 (C-3),
54.8 (C-2), 55.7 (OMe), 62.0 (C-6), 67.8 (C-5), 71.7 (C-4), 89.7 (C-
2′), 94.7 (C-1), 150.6 (C-1′); IR (film) 2981, 2933 (=CH2), 1632, 1623
4.8.2. 1,5-Anhydro-2-deoxy-6-O-vinyl-D-arabino-hex-1-enitol
Colorless gum (21 mg, 23% yield), [α]D +30 (c = 0.4, CHCl3); 1H
NMR δ 3.79 (dd, 1H, J4–5 = 9.4, H-4), 3.97–4.06 (m, 3H, H-5, H-6a,
(C=C), 1078, 1022, 977 (=
C—OR); MS IS m/z = 317.5 [M + H]+, 334.5
[M + NH4]+, 339.5 [M + Na]+; HRMS: C15H28O5Si: calcd. 316.1706; found
316.1730.