(1 H, m, 2-H), 3.8 (1 H, m, 5-H), 3.85 (1 H, dd, Jα,β 3.0, Jβ,βЈ 10.4,
β-H), 4.1 (1 H, dd, J6,5 2.4, J6,6Ј 12.4, 6-H), 4.15–4.27 (3 H, m, α-
H, 6-HЈ, CH of Fmoc), 4.35–4.55 (3 H, m, β-HЈ, CH2 of
Fmoc), 4.6–4.7 (3 H, br d, 1-H, CH2O of allyl), 5.01 (1 H, dd,
(NCO), 166.17, 169.34, 170.56 and 170.67 (OCO); FAB-MS of
C39H34Cl3F5N2O14 (M, 956) m/z 993/995 (M ϩ K)ϩ, 977/979
(M ϩ Na)ϩ and 955/957 (M ϩ H)ϩ.
Compound 13a (1.5 g. 1.57 mmol) was treated with zinc (0.75
g) and acetic anhydride (10 ml) at room temperature for 6 h.
The mixture was filtered through a Celite bed and washed with
dry dichloromethane. The filtrate was evaporated to dry-
ness and the residue was purified by flash chromatography
(anhydrous silica gel) using ethyl acetate–light petroleum (7:3)
to afford title compound 14a (1.07 g, 83%), [α]D Ϫ11.07 (c 1.21,
CHCl3) (lit.,4 Ϫ10.0); mp 186–187 ЊC (lit.,5 184 ЊC); δH (600
MHz; CDCl3) 1.87 (3 H, s, NAc), 2.01 and 2.03 (9 H, 2 s,
3 × OAc), 3.68 (1 H, m, 5-H), 3.74 (1 H, ddd, J2,N H 6.45, J2,1 8.2,
J2,3 10.02, 2-H), 3.97 (1 H, dd, Jβ,α 2.78, Jβ,βЈ 10.57, β-H), 4.12
(1 H, dd, J6,5 2.4, J6,6Ј 12.4, 6-H), 4.2 (1 H, dd, J6Ј,5 4.8, J6Ј,6 12.4,
6-HЈ), 4.23 (1 H, dd, J1 6.97, J2 7.34, CH of Fmoc), 4.39 (1 H,
dd, Jα,βЈ 4.0, Jβ,βЈ 10.57, β-HЈ), 4.40 (1 H, dd, J1 7.6, J2 10.63,
CHH of Fmoc), 4.48 (1 H, dd, J1 7.13, J2 10.63, CHH of
Fmoc), 4.83 (1 H, d, J 8.2, 1-H), 4.86 (1 H, ddd, Jα,β 2.8, Jα,βЈ 4.0,
Jα,NH 7.51, α-H), 5.05 (1 H, dd, J4,3 = J4,5 = 9.6, 4-H), 5.27 (1 H,
dd, J3,4 9.6, J3,2 10.02, 3-H), 5.6 (1 H, d, J 6.45, 2-NH), 6.1 (1 H,
d, J 7.27, NH), 7.3 (2 H, m), 7.38 (2 H, m), 7.64 (2 H, dd, J1 5.3,
J2 7.41) and 7.75 (2 H, d, J 7.27) (together ArH); δC(62.68;
CDCl3) 20.58, 20.65, 23.21 (CH3 of NAc), 47.11 (CH of Fmoc),
54.3 (α-C), 54.9 (2-C), 61.9 (6-C), 67.22 (CH2 of Fmoc), 68.25
(β-C), 68.37 (4-C), 71.91 (3-C), 72.12 (5-C), 100.58 (1-C),
119.98, 125.15, 127.77, 141.3, 143.66, 143.72, 156.04, 166.28,
169.35, 170.62, 170.89 and 170.95; FAB-MS of C38F5H35N2O13
(M, 822) m/z 995 (M ϩ NaI ϩ Na)ϩ, 861 (M ϩ K)ϩ, 845
(M ϩ Na)ϩ and 823 (M ϩ H)ϩ.
J4,3 9.6, J4,5 9.5, 4-H), 5.15–5.4 (3 H, m, 3-H, CH᎐CH of allyl),
᎐
2
5.5 (1 H, d, J 8.3, NH), 5.79 (1 H, d, JN H ,2 9.0, 2-NH), 5.9 (1 H,
m, CH᎐CH of allyl), 7.27–7.41 (4 H, m), 7.36 (2 H, d, J 6.2)
᎐
2
and 7.76 (2 H, d, J 7.2) (together ArH); δC(62.68 MHz; CDCl3)
20.59, 20.65, 20.68, 23.15 (CH3 of NAc), 47.22 (CH of Fmoc),
54.24 (α-C), 54.55 (2-C), 62.01 (6-C), 66.27 (CH2 of Fmoc),
66.84, 68.47 (4-C), 71.99 (3-C), 72.14 (5-C), 100.82 (1-C),
118.66, 119.98, 125.09, 127.14, 127.76, 131.42, 141.32, 143.69,
143.83 (arom C of Fmoc), 169.26 (NCO), 169.34, 170.51,
170.61 and 170.84 (OCO); FAB-MS of C35H40N2O13 (M, 696)
m/z 735 (M ϩ K)ϩ and 719 (M ϩ Na)ϩ.
N á-(Fluoren-9-ylmethoxycarbonyl)-O-(2-acetamido-3,4,6-tri-O-
acetyl-2-deoxy-â-D-glucopyranosyl)-L-threonine allyl ester 11b
Compound 10b (0.2 g, 0.23 mmol) was treated with zinc (0.1 g)
and acetic anhydride (5 ml) for 6 h at room temperature. After
the usual work-up and purification title compound 11b (0.13 g,
81%) was obtained; [α]D Ϫ12.86 (c 0.51, CHCl3) (Found: C,
60.57; H, 6.08; N, 3.71. C36H42N2O13 requires C, 60.8; H, 5.97;
N, 3.94%); δH (250 MHz; CDCl3) 1.22 (3 H, d, J 6.3, γ-H3), 1.92
(3 H, s, NAc), 2.00, 2.02 and 2.04 (total 9 H, 3 s, 3 × OAc),
3.62–3.73 (2 H, m, 2- and 5-H), 4.22 (1 H, dd, J6,5 2.4, J6,6Ј 12.4,
6-H), 4.25–4.28 (2 H, m, 6-HЈ, CH of Fmoc), 4.3–4.45 (4 H, m,
CH2 of Fmoc, β- and α-H), 4.62 (2 H, br s, CH2O of allyl), 4.7
(1 H, d, J1,2 8.2, 1-H), 5.02 (1 H, dd, J4,5 9.5, J4,3 9.6, 4-H), 5.23
(1 H, dd, J3,2 10.4, J3,4 9.6, 3-H), 5.29 (2 H, m, CH ᎐CH of
᎐
2
allyl), 5.54 (1 H, d, J 8.3, NH), 5.75 (1 H, d, J2,N H 9.0, 2-NH),
5.9 (1 H, m, CH᎐CH of allyl), 7.26–7.41 (4 H, m), 7.61–7.65 (2
N á-(Fluoren-9-ylmethoxycarbonyl)-O-(2-acetamido-3,4,6-tri-
O-acetyl-2-deoxy-â-D-glucopyranosyl)-L-threonine pentafluoro-
phenyl ester 14b
᎐
2
H, m) and 7.74 (2 H, d, J 7.2) (together ArH); δC(62.68 MHz;
CDCl3) 16.84 (γ-C), 20.6, 20.67, 23.2 (CH3 of NAc), 47.2 (CH
of Fmoc), 55.26 (2-C), 58.24 (α-C), 61.96 (6-C), 66.06 (CH2
of Fmoc), 67.2, 68.51 (4-C), 71.72 (3-C), 71.9 (5-C), 74.27
(β-C), 98.49 (1-C), 118.49, 119.43, 125.24, 127.07, 127.09,
127.69, 131.71 (arom C of Fmoc), 141.29, 143.78, 143.99,
156.81, 169.37, 169.81, 170.27 and 170.62; FAB-MS of
C36H42N2O13 (M, 710) m/z 883 (M ϩ NaI ϩ Na)ϩ, 749
(M ϩ K)ϩ and 733 (M ϩ Na)ϩ.
To a stirred solution of compounds 3 (0.6 g, 1.0 mmol) and 12b
(0.5 g, 1.0 mmol) in dry dichloromethane (10 ml) was added
dropwise TMSOTf (1.6 µl in 1 ml of dichloromethane) at room
temperature. After 1 h of stirring at room temperature the mix-
ture was concentrated under reduced pressure and the residue
was purified by flash chromatography (anhydrous silica gel)
using ethyl acetate–light petroleum (3:7) as eluent to afford
compound 13b (0.77 g, 80%) (Found: C, 49.36; H, 3.69; N, 3.01.
C40H36Cl3F5N2O14 requires C, 49.52; H, 3.74; N, 2.88%); [α]D
Ϫ22.2 (c 1.0, CHCl3); δH (250 MHz; CDCl3) 1.30 (3 H, d, J 6.2,
γ-H), 1.99, 2.01 and 2.04 (total 9 H, 3 s, 3 × OAc), 3.65 (2 H, m,
2- and 5-H), 4.12 (1 H, dd, J6,5 2.4, J6,6Ј 12.3, 6-H), 4.16–4.38
(3 H, m, 6-HЈ, CH of Fmoc, β-H), 4.49 (1 H, dd, J1 7.6, J2
10.1, CHH of Fmoc), 4.6–4.8 (4 H, m, α-H, CH2 of Teoc,
CHH of Fmoc), 4.72 (1 H, d, J1,2 8.1, 1-H), 5.06 (1 H, dd, J4,5
9.6, J4,3 9.9, 4-H), 5.23 (1 H, dd, J3,4 9.9, J3,2 10.2, 3-H), 5.37 (1
H, d, J 8.3, NH), 5.96 (1 H, d, J 9.0, NH), 7.26–7.4 (4 H, m),
7.65 (2 H, m) and 7.75 (2 H, d, J 7.2) (together ArH); δC(62.68;
CDCl3) 16.28 (γ-C), 20.36, 20.51, 20.58, 47.04 (CH of Fmoc),
56.28 (2-C), 58.60 (α-C), 61.75 (6-C), 67.56 (CH2 of Fmoc),
68.37 (4-C), 71.49 (3-C) 71.72 (5-C), 72.77, 74.51 (β-C), 98.02
(1-C), 119.93, 125.13, 127.07, 127.72, 141.20, 141.23 (Pfp),
143.60, 154.27, 156.56 (NCO), 166.40, 169.29, 170.57 and
170.93; FAB MS of C40H36Cl3F5N2O14 (M, 970) m/z 991/993
(M ϩ Na)ϩ.
Compound 13b (0.51 g, 0.51 mmol) was treated with acti-
vated zinc (0.25 g) and acetic anhydride (2 ml) at room temper-
ature for 6 h. After the usual work-up and purification using
anhydrous silica gel column chromatography [ethyl acetate–
light petroleum (7:3)] compound 14b (0.34 g, 80%) was
obtained, δH (250 MHz; CDCl3) 1.28 (3 H, d, J 6.3, γ-H3), 1.93
(3 H, s, NAc), 1.98, 2.01 and 2.03 (total 9 H, 3 s, 3 × OAc), 3.65
(1 H, ddd, J5,6 2.3, J5,6Ј 4.7, J5,4 9.7, 5-H), 3.75 (1 H, ddd, J2,N H
8.04, J2,1 8.2, J2,3 10.2, 2-H), 4.05 (1 H, dd, J5,6 2.3, J6,6Ј 12.2, 6-
H), 4.2 (1 H, dd, J6Ј,5 4.7, J6Ј,6 12.2, 6-HЈ), 4.24 (1 H, dd, J1 7.1,
J2 7.4, CH of Fmoc), 4.35–4.5 (2 H, m, CH2 of Fmoc), 4.56 (1
N á-(Fluoren-9-ylmethoxycarbonyl)-O-(2-acetamido-3,4,6-tri-O-
acetyl-2-deoxy-â-D-glucopyranosyl)-L-serine pentafluorophenyl
ester 14a
To a stirred solution of compounds 3 (1.25 g, 2.0 mmol) and 12a
(1.0 g, 2.0 mmol) in dry dichloromethane (20 ml) at room tem-
perature was added TMSOTf (3.2 µl in 1 ml of dichloromethane)
dropwise. The mixture was stirred for 1 h at room temperature
and then concentrated under reduced pressure to give a thick
syrup, which was purified by flash chromatography (anhydrous
silica gel) with ethyl acetate–light petroleum (3:7) to afford
compound 13a (1.66 g, 87%); [α]D Ϫ9.06 (c 1.17, CHCl3)
(Found: C, 48.78; H, 3.49; N, 3.08. C39H34Cl3F5N2O14 requires
C, 48.99; H, 3.58; N, 2.93%); δH (600 MHz; CDCl3) 2.02 (9 H, s,
3 × OAc), 3.6 (1 H, ddd, J2,N H 6.54, J2.1 8.2, J2,3 10.2, 2-H), 3.66
(1 H, ddd, J6,5 2.4, J5,4 9.6, 5-H), 3.97 (1 H, dd, Jβ,α 2.8, Jβ,βЈ 10.2,
β-H), 4.12 (1 H, dd, J6,5 2.4, J6,6Ј 12.3, 6-H), 4.2 (1 H, dd, J6Ј,5
4.7, J6Ј,6 12.3, 6-HЈ), 4.23 (1 H, dd, J1 7.1, J2 7.6, CH of Fmoc),
4.35 (1 H, dd, J1 7.1, J2 10.1, CHH of Fmoc), 4.42 (1 H, dd, JβЈ,α
3.5, JβЈ,β, β-HЈ), 4.52 (1 H, dd, J1 7.6, J2 10.1, CHH of Fmoc),
4.57 (1 H, br s, CHH of Teoc), 4.67 (2 H, br d, J1,2 8.2, 1-H and
CHH of Teoc), 4.88 (1 H, m, α-H), 5.06 (1 H, dd, J4,5 9.6, J4,3
9.9, 4-H), 5.2 (1 H, br s, NH), 5.23 (1 H, dd, J3,4 9.9, J3,2 10.2, 3-
H), 5.93 (1 H, br s, NH), 7.28–7.31 (2 H, m), 7.36–7.39 (2 H, m),
7.59–7.61 (2 H, m) and 7.74 (2 H, d, J 7.2) (together ArH);
δC(62.68 MHz; CDCl3) 20.52, 47.05 (CH of Fmoc), 54.11 (α-C),
56.12 (2-C), 61.83 (6-C), 67.23 (CH2 of Fmoc), 68.43 (4-C),
71.63 (3-C), 71.98 (5-C), 100.51 (1-C), 120.0, 127.12, 127.78,
143.52, 143.65 (arom C of Fmoc), 141.26 (Pfp), 154.25, 155.95
J. Chem. Soc., Perkin Trans. 1, 1997
1859