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I. Wenzl et al.
1 h at room temperature. The reaction mixture was neutralized with Dowex 50 W (H ), ®ltered, and
evaporated in vacuo to dryness. Column chromatography gave 0.118 g 4 (31%) as yellow crystals.
TLC (ethyl acetate/hexane, 4:1): Rf 0.32; m.p.: 195ꢁC (decomposition); [ꢁ]D20 202.58
(c 1.24, CH3OH); IR: ꢃ 3294.3, 1648.2, 1549.4 cm ꢂ1
;
1H NMR (250 MHz, D2O/CD3OD):
ꢂ 5.94 (m, 1H, H20), 5.26 (m, 2H, H30), 4.88 (d, 1H, J1,2 3.34, H1), 4.85 (m, 1H, H5), 4.45 (dd,
1H, J2,3 10.96, J3,4 4.79, H3), 4.35 (dd, 1H, H2), 4.22 (m, 1H, H10), 4.10 (dd, 1H, J4.5 2.74,
H4), 4.02 (m, 1H, H10), 3.43 (dd, 1H, J6a,5 4.57, J6a,6b 11.88, H6a), 3.24 (dd, 1H, J6b,5 1.37,
H6b), 1.99 (s, 3H, NHCOCH3) ppm; 13C NMR (62.9 MHz, D2O/CD3OD): ꢂ 135.37, 117.73, 99.08,
75.82, 69.70, 66.80, 66.76, 51.57, 44.45, 22.61 ppm; MS (FI, 7 kV, 3 mA, 120ꢁC): m/z (rel.
intensity) 291.1 (100), 267.2 (18).
Allyl S-(2,3,4,6-tetra-O-acetyl-ꢀ-D-galactopyranosyl)-(1!4)-2-acetamido-4-thio-6-thiocyanato-
2,4,6-trideoxy-ꢁ-D-galactopyranoside (6; C26H36N2O13S2) and Allyl O-(2,3,4,6-tetra-O-acetyl-
ꢀ-D-galactopyranosyl)-(1!3)-(S-(2,3,4,6-tetra-O-acetyl-ꢀ-D-galactopyranosyl)-(1!4))-2-
acetamido-4-thio-6-thiocyanato-2,4,6-trideoxy-ꢁ-D-galactopyranoside (7; C40H54N2O22S2)
A mixture of 122 mg 4 (0.42 mmol), 210 mg Hg(CN)2 (0.84 mmol), 30 mg HgBr2 (0.084 mmol), and
3
ꢁ
Ê
4.0 g molecular sieves (4 A) in 12 cm 1:1 toluenenitromethane was stirred at 60 C. After 1 h, a
solution of 424 mg tetra-O-acetyl-ꢁ-D-galactopyranosyl bromide 5 (1.03 mmol) in 6 cm3
nitromethane was added dropwise over a period of 2 h. The mixture was stirred at 60ꢁC for further
18 h. TLC (toluene/acetone, 2:1) indicated complete disappearance of 4. The molecular sieve was
®ltered off. The solution was diluted with dichloromethane and washed three times with saturated
aqueous NH4Cl solution. The organic layer was separated, dried (MgSO4), and concentrated.
Puri®cation by column chromatography (toluene/acetone, 3:1! 1:1) gave 124 mg 6 (45%) and
72 mg 7 (17%) as colorless crystals.
6: TLC (ethyl acetate): Rf 0.35; m.p.: 56±57ꢁC; [ꢁ]D20 67.73 (c 0.75, CH2Cl2); IR:
ꢃ 3369.9, 2929.6, 2155.5, 1750.8 cmꢂ1; 1H NMR (400 MHz): ꢂ 5.84 (m, 2H, H200, NHAc), 5.40
0
00
0
0
0
0
0
0
(dd, 1H, J4 ,5 0.62, H4 ), 5.30 (m, 2H, H3 ), 5.14 (t, 1H, J2 ,3 9.97, H2 ), 5.00 (dd, 1H,
0
0
0
0
0
J3 ,4 3.33, H3 ), 4.805 (d, 1H, J1 ,2 9.96, H1 ), 4.795 (d, 1H, J1,2 3.95, H1), 4.26 (m, 3H, H2,
H5, H100), 4.07 (m, 3H, H3, H60b, H60a), 4.00 (m, 1H, H100), 3.88 (m, 1H, H50), 3.59 (d, 1H,
JOH,3 7.68, OH), 3.41 (dd, 1H, J3,4 3.73, J4,5 1.66, H4), 3.35 (dd, 1H, J5,6a 8.51,
J6a,6b 13.91, H6a), 3.17 (dd, 1H, J5,6b 4.35, H6b), 2.10 (s, 6H, COCH3), 2.00 (s, 6H, COCH3),
1.91 (s, 3H, COCH3) ppm; 13C NMR (100 MHz): ꢂ 172.56, 170.35, 170.16, 170.14, 169.90, 132.70
(C200), 119.04 (C300), 111.98 (-SCN), 96.38 (C1), 85.03 (C10), 74.55 (C50), 71.57 (C30), 71.54 (C3),
69.05 (C5), 68.65 (C100), 67.68 (C20), 67.29 (C40), 61.62 (C60), 52.61 (C4), 51.43 (C2), 36.29 (C6),
23.22, 20.77, 20.68, 20.64, 20.50 ppm; MALDI MS (16 kV): m/z 687.3 (MK, 100%).
7: TLC (ethyl acetate): Rf 0.50; m.p.: 100±102ꢁC; [ꢁ]D20 53.44 (c 0.90, CH2Cl2); IR:
ꢃ 2934.4, 2155.3, 1751.2 cmꢂ1
;
1H NMR (400 MHz): ꢂ 5.90 (m, 1H, H2000), 5.51 (d, 1H,
0
00
0
0
00 00
JNH,2 9.7, NHAc), 5.42 (dd, 1H, J4 ,5 0.75, H4 ), 5.41 (dd, 1H, J4 ,5 1.1, H4 ), 5.29 (m, 2H,
H30a00, H3e000), 5.14 (dd, 1H, J2 ,3 9.8, H2 ), 5.11 (dd, 1H, J2 ,3 10.6, H2 ), 5.00 (d, 1H,
0
00
0
0
00 00
00 00
0
0
00
0
0
0
0
J1 ,2 10.6, H1 ), 5.00 (dd, 1H, J3 ,4 3.3, H3 ), 4.98 dd, 1H, J3 ,4 3.7, H3 ), 4.76 (d, 1H,
00
00 00
J1,2 3.9, H1), 4.64 (d, 1H, J1 ,2 7.9, H1 ), 4.60 (dd, 1H, J2,3 10.6, H2), 4.27 (dd, 1H,
J6 a,6 b 11.4, H6a00), 4.27 (ddd, 1H, J5,6a 8.3, J5,6b 4.4, H5), 4.24 (m, 1H, H1000), 4.17 (dd, 1H,
00
00
J6 a,6 b 11.0, H60b), 4.09 (dd, 1H, H60a), 4.03 (dd, 1H, H60b0), 4.00 (m, 1H, H1000), 3.95 (ddd, 1H,
0
0
J5 ,6 b 6.5, J5 ,6 a 7.0, H50), 3.91 (ddd, 1H, J5 ,6 b 5.9, J5 ,6 a 6.9, H500), 3.90 (dd, 1H,
J3,4 3.6, H3), 3.58 (dd, 1H, J4,5 1.8, H4), 3.28 (dd, 1H, J6a,6b 14.2, H6a), 3.17 (dd, 1H, H6b),
2.21 (s, 3H, COCH3), 2.14 (s, 3H, COCH3), 2.14 (s, 3H, COCH3), 2.03 (s, 3H, COCH3), 2.02 (s, 3H,
COCH3), 2.01 (s, 3H, COCH3), 1.97 (s, 3H, COCH3), 1.96 (s, 3H, COCH3), 1.95 (s, 3H, COCH3)
ppm; 13C NMR (100 MHz): ꢂ 171.04, 170.28, 170.14, 170.10, 170.06, 170.05, 169.06, 168.81,
132.83 (C2000), 119.24 (C3000), 112.01 (-SCN), 102.59 (C100), 97.04 (C1), 84.01 (C10), 78.62 (C3),
74.20 (C50), 72.25 (C30), 71.52 (C500), 70.48 (C300), 68.85 (C5), 68.80 (C1000), 68.54 (C200), 67.13
0
0
0
0
00 00
00 00