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X. Xu et al.
PAPER
purified by chromatography (silica gel) to give 6 (667 mg, 88%) as
a colorless solid; ratio a/b 3:1).
Hz, J6a¢,6b¢ = 12.4 Hz, 1 H, H6a¢), 4.63 (d, J1¢,2¢ = 8.4 Hz, 1 H, H1¢),
4.96 (dd, J2¢,3¢ = 10.0 Hz, J2¢,1¢ = 1.6 Hz, 1 H, H2¢), 5.02 (dd,
J1,2 = 3.6 Hz, J1,3 = 2.0 Hz, 1 H, H1), 5.08 (dd, J4,3 = 9.2 Hz,
J4,5 = 9.6 Hz, 1 H, H4), 5.21 (dd, J3¢,2¢ = 9.2 Hz, J3¢,4¢ = 9.9 Hz, 1 H,
H3¢), 5.80 (ddd, J2,1 = 3.6 Hz, J2,3 = 10.0 Hz, J2,4 = 2.0 Hz, 1 H, H2),
6.22 (ddd, J3,1 = 2.0 Hz, J3,2 = 10.0 Hz, J3,4 = 9.2 Hz, 1 H, H3).
a-Isomer 6a
Mp 52–54 °C; Rf = 0.30 (hexane–EtOAc, 1:1); [a]D24 –5.50 (c 0.94,
CHCl3) [Lit.19 [a]D24 +16 (c 1, CHCl3)].
IR (KBr): 3437, 2963, 1751, 1635, 1437, 1373, 1230, 1169, 1125,
1079, 1051, 980, 913, 740, 602 cm–1.
13C NMR (100 MHz, CDCl3): d = 20.5, 20.6, 20.6, 20.7, 20.8 (5
COCH3), 61.8 (C6a, 6b, 6b¢), 62.2 (C6a¢), 62.7 (C1), 68.2 (C4), 71.2
(C2¢), 71.7 (C4¢), 72.0 (C5), 72.5 (C5¢, C3¢), 101.6 (C1¢), 115.8
(CN), 122.8 (C2), 132.0 (C3), 169.2, 169.3, 170.2, 170.4, 170.5 (5
COCH3).
1H NMR (400 MHz, CDCl3): d = 1.99, 2.06, 2.09, 2.11, 2.14 (5
COCH3), 3.9–4.0 (m, 2 H, H5, H5¢), 4.1–4.2 (m, 4 H, H4, H6a,
H6a¢, H6b¢), 4.37 (dd, J6b,5 = 2.0 Hz, J6b,6a = 12.0 Hz, 1 H, H6b),
4.60 (d, J1¢,2¢ = 8.0 Hz, 1 H, H1¢), 5.01 (dd, J3¢,4¢ = 3.6 Hz, J3¢,2¢ = 10.8
Hz, 1 H, H3¢), 5.03 (d, J1,2 = 3.6 Hz, 1 H, H1), 5.22 (d, J2¢,3¢ = 10.8
Hz, J2¢,1¢ = 8.4 Hz, 1 H, H2¢), 5.40 (dd, J4¢,3¢ = 3.4 Hz, J4¢,5¢ = 1.2 Hz,
1 H, H4¢), 5.80 (ddd, J2,1 = 3.6 Hz, J2,3 = 10.2 Hz, J2,4 = 2.0 Hz, 1 H,
H2), 6.25 (dt, J3,1 = 2.0 Hz, J3,2 = 10.4 Hz, J3,4 = 2.0 Hz, 1 H, H3).
13C NMR (100 MHz, CDCl3): d = 20.5, 20.6, 20.7 (5 COCH3), 61.3
(C6a¢, 6b¢, 6b), 62.2 (C6a), 62.6 (C3¢), 66.8 (C4¢), 68.6 (C2¢), 70.7
(C1), 70.9 (C5¢), 71.7 (C4), 72.5 (C5), 102.2 (C1¢), 115.5 (CN),
122.6 (C2), 132.0 (C3), 169.3, 170.0, 170.1, 170.3, 170.5 (5
COCH3).
MS (ESI+): m/z = 550.41 [M + Na]+.
Anal Calcd for C23H29O13N: C, 52.37; H, 5.54; N, 2.66. Found: C,
52.20; H, 5.57; N, 2.65.
b-Isomer 7b
Colorless solid; mp 141–142 °C; Rf = 0.36 (hexane–EtOAc, 1:1);
[a]D26 +91.35 (c 0.8, CHCl3) [Lit.19 [a]D25 +10 (c 1, CHCl3)].
IR (KBr): 3431, 2965, 2892, 1747, 1635, 1437, 1374, 1250, 1230,
1045, 908, 811 cm–1.
1H NMR (400 MHz, CDCl3): d = 1.98, 2.02, 2.04, 2.08, 2.11 (5
COCH3), 3.63 (ddd, J5,4 = 8.6 Hz, J5,6b = 6.0 Hz, J5,6a = 2.0 Hz, 1 H,
H5), 3.73 (ddd, J5¢,4¢ = 8.0 Hz, J5¢,6a¢ = 2.4 Hz, J5¢,6b¢ = 5.2 Hz, 1 H,
H5¢), 4.07 (dd, J6b,5 = 6.0 Hz, J6b,6a = 12.4 Hz, 1 H, H6b), 4.13 (dq,
J4,2 = 2.0 Hz, J4,3 = 2.4 Hz, J4,5 = 8.6 Hz, J4,1 = 2.0 Hz, 1 H, H4),
4.2–4.3 (m, 2 H, H6a¢, H6b¢), 4.35 (dd, J6a,5 = 2.0 Hz, J6a,6b = 12.4
Hz, 1 H, H6a), 4.62 (d, J1¢,2¢ = 8.0 Hz, 1 H, H1¢), 4.97 (dd, J2¢,1¢ = 8.0
Hz, J2¢,3¢ = 9.6 Hz, 1 H, H2¢), 5.07 (dd, J4¢,3¢ = 9.6 Hz, J4¢,5¢ = 8.0 Hz,
1 H, H4¢), 5.08 (dd, J1,2 = 2.0 Hz, J1,3 = 2.4 Hz, 1 H, H1), 5.19 (t,
MS (ESI+): m/z = 550.21 [M + Na]+, 565.77 [M + K]+.
Anal. Calcd for C23H29NO13: C, 52.37; H, 5.54; N, 2.66. Found: C,
52.49; H, 5.62; N, 2.81.
b-Isomer 6b
Mp 154–156 °C (Lit.19 147–149 °C); Rf = 0.40 (hexane–EtOAc,
1:1); [a]D23 +104.2 (c 0.8, CHCl3) [Lit.19 [a]D +134 (c 1, CHCl3)].
IR (KBr): 3437, 2982, 2894, 1752, 1636, 1435, 1372, 1232, 1168,
J3¢,2¢ = 9.6 Hz, J3¢,4¢ = 9.6 Hz, 1 H, H3¢), 5.80 (dt, J2,1 = 2.0 Hz,
1051, 950, 913, 810, 603 cm–1.
J2,3 = 10.4 Hz, J2,4 = 2.0 Hz, 1 H, H2), 6.24 (dt, J3,1 = 2.4 Hz,
J3,2 = 10.4 Hz, J3,4 = 2.4 Hz, 1 H, H3).
1H NMR (400 MHz, CDCl3): d = 1.98, 2.07, 2.13, 2.16 (5 COCH3),
3.66 (ddd, J5,4 = 10.6 Hz, J5,6a = 6.0 Hz, J5,6b = 2.0 Hz, 1 H, H5),
3.95 (t, J5¢,6a¢ = 6.8 Hz, J5¢,6b¢ = 6.4 Hz, 1 H, H5¢), 4.07–4.23 (m, 4 H),
4.34 (dd, J6b,5 = 2.0 Hz, J6a,6b = 12.4 Hz, 1 H, H6b), 4.59 (d,
13C NMR (100 MHz, CDCl3): d = 20.5, 20.6, 20.6, 20.7, 20.8 (5
COCH3), 61.82 (C6a¢, 6b¢), 62.5 (C6a, C1), 63.5 (C6b), 68.2 (C4¢),
71.2 (C2¢), 71.8 (C4), 72.1 (C5¢), 72.5 (C3¢), 75.1 (C5), 102.1 (C1¢),
115.8 (CN), 123.0 (C2), 131.5 (C3), 169.3, 170.1, 170.4, 170.5 (5
COCH3).
J1¢,2¢ = 8.0 Hz, 1 H, H1¢), 5.01 (dd, J3¢,2¢ = 10.2 Hz, J3¢,4¢ = 3.6 Hz, 1
H, H3¢), 5.08 (q, J1,2 = 2.8 Hz, J1,3 = 2.4 Hz, J1,4 = 2.0 Hz, 1 H, H1),
5.19 (dd, J2¢,1¢ = 8.0 Hz, J2¢,3¢ = 10.2 Hz, 1 H, H2¢), 5.39 (d, J4¢,3¢ = 3.6
Hz, 1 H, H4¢), 5.82 (dt, J2,1 = 1.6 Hz, J2,3 = 10.4 Hz, J2,4 = 1.6 Hz, 1
H, H2), 6.26 (dt, J3,1 = 2.0 Hz, J3,2 = 10.4 Hz, J3,4 = 2.0 Hz, 1 H,
H3).
MS (ESI+): m/z = 550.19 [M + Na]+, 566.01 [M + K]+.
Anal. Calcd for C23H29O13N; C, 52.37; H, 5.54; N, 2.66. Found: C,
52.30; H, 5.67; N, 2.77.
13C NMR (100 MHz, CDCl3): d = 20.5, 20.60, 20.62, 20.7 (5
COCH3), 61.3 (C6a), 62.5 (C6b, 6a¢, 6b¢), 63.4 (C1), 66.8 (C4¢),
68.6 (C2¢), 70.7 (C3¢), 71.0 (C5¢), 71.8 (C4), 75.0 (C5), 102.7 (C1¢),
115.8 (CN), 123.0 (C2), 131.5 (C3), 169.4, 170.0, 170.1, 170.3,
170.5 (5 COCH3).
6-O-Acetyl-1,2,3-trideoxy-4-(2,3,4,6-tetra-O-acetyl-a-D-glu-
copyranosyl)-a/b-D-erythro-hex-2-enopyranosyl Cyanide (8)
Following the typical procedure for 6 using hexa-O-acetyl-D-maltal
3 gave 8 in 90% yield; ratio a/b 2:3.
MS (ESI+): m/z = 550.21 [M + Na]+, 565.77 [M + K]+.
a-Isomer 8a
Colorless solid; mp 132–133 °C (Lit.19 130–132 °C); Rf 0.28 (hex-
ane–EtOAc, 1:1); [a]D24 +185.1 (c 1.67, CHCl3) [Lit.19 [a]D +105 (c
1, CHCl3)].
Anal. Calcd for C23H29NO13: C, 52.37; H, 5.54; N; 2.66. Found: C,
52.14; H, 5.54; N, 2.71.
6-O-Acetyl-1,2,3-trideoxy-4-(2,3,4,6-tetra-O-acetyl-b-d-gluco-
pyranosyl)-a/b-D-erythro-hex-2-enopyranosyl Cyanide (7)
Following the typical procedure for 6 using hexa-O-acetyl-D-cello-
bial 2 gave 7 in 88% yield; ratio a/b 1:1.
IR (KBr): 3545, 3468, 3416, 2962, 2358, 2120, 1749, 1636, 1618,
1435, 1370, 1233, 1139, 1040, 942, 898, 783, 602 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.03, 2.05, 2.10, 2.11, 2.13 (5
COCH3), 3.98 (ddd, J5,6a = 3.2 Hz, J5,4 = 7.2 Hz, J5,6b = 5.1 Hz, 1 H,
H5), 4.07 (ddd, J5¢,4¢ = 9.3 Hz, J5¢,6a¢ = 2.4 Hz, J5¢,6b¢ = 4.2 Hz, 1 H,
H5¢), 4.08 (dd, J6a¢,5 = 2.1 Hz, J6a¢,6b¢ = 12.3 Hz, 1 H, H6a¢), 4.25 (1
H, H4), 4.27 (dd, J6b¢,5 = 4.2 Hz, J6b¢,6a¢ = 12.3 Hz, 1 H, H6b¢), 4.43
(dd, J6b,5 = 5.1 Hz, J6b,6a = 12.3 Hz, 1 H, H6b), 4.46 (dd, J6a,5 = 2.1
Hz, J6b,6a = 12.3 Hz, 1 H, H6a), 4.85 (dd, J2¢,3¢ = 10.5 Hz, J2¢,1¢ = 4.2
Hz, 1 H, H2¢), 5.04 (q, J1,2 = 2.1 Hz, J1,3 = 2.1 Hz, J1,4 = 2.1 Hz, 1
H, H1), 5.08 (t, J4¢,3¢ = 10.2 Hz, J4¢,5¢ = 10.2 Hz, 1 H, H4¢), 5.33 (d,
a-Isomer 7a
Colorless solid; mp 156–158 °C; Rf = 0.27 (hexane–EtOAc, 1:1);
[a]D26 –3.15 (c 0.8, CHCl3).
IR (KBr): 3435, 2948, 2889, 1746, 1635, 1431, 1376, 1259, 1231,
1092, 1067, 1048, 910, 830 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.01, 2.04, 2.07, 2.10, 2.13 (5
COCH3), 3.73 (ddd, J5,6a = 3.2 Hz, J5,4 = 9.6 Hz, J5,6b = 4.0 Hz, 1 H,
H5), 3.95 (ddd, J5¢,3¢ = 2.0 Hz, J5¢,4¢ = 9.0 Hz, J5¢,6¢ = 5.6 Hz, 1 H,
H5¢), 4.2–4.3 (m, 4 H, H4¢, H6b, H6a, H6b¢), 4.38 (dd, J6a¢,5¢ = 2.0
J1¢,2¢ = 3.9 Hz, 1 H, H1¢), 5.42 (dd, J3¢,4¢ = 9.9 Hz, J3¢,2¢ = 9.9 Hz, 1 H,
Synthesis 2008, No. 5, 770–776 © Thieme Stuttgart · New York